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Sample records for calculated electronic structure

  1. Towards scalable electronic structure calculations for alloys

    SciTech Connect

    Stocks, G.M.; Nicholson, D.M.C.; Wang, Y.; Shelton, W.A.; Szotek, Z.; Temmermann, W.M.

    1994-06-01

    A new approach to calculating the properties of large systems within the local density approximation (LDA) that offers the promise of scalability on massively parallel supercomputers is outlined. The electronic structure problem is formulated in real space using multiple scattering theory. The standard LDA algorithm is divided into two parts. Firstly, finding the self-consistent field (SCF) electron density, Secondly, calculating the energy corresponding to the SCF density. We show, at least for metals and alloys, that the former problem is easily solved using real space methods. For the second we take advantage of the variational properties of a generalized Harris-Foulkes free energy functional, a new conduction band Fermi function, and a fictitious finite electron temperature that again allow us to use real-space methods. Using a compute-node {R_arrow} atom equivalence the new method is naturally highly parallel and leads to O(N) scaling where N is the number of atoms making up the system. We show scaling data gathered on the Intel XP/S 35 Paragon for systems up to 512-atoms/simulation cell. To demonstrate that we can achieve metallurgical-precision, we apply the new method to the calculation the energies of disordered CuO{sub 0.5}Zn{sub 0.5} alloys using a large random sample.

  2. Multilevel domain decomposition for electronic structure calculations

    SciTech Connect

    Barrault, M. . E-mail: maxime.barrault@edf.fr; Cances, E. . E-mail: cances@cermics.enpc.fr; Hager, W.W. . E-mail: hager@math.ufl.edu; Le Bris, C. . E-mail: lebris@cermics.enpc.fr

    2007-03-01

    We introduce a new multilevel domain decomposition method (MDD) for electronic structure calculations within semi-empirical and density functional theory (DFT) frameworks. This method iterates between local fine solvers and global coarse solvers, in the spirit of domain decomposition methods. Using this approach, calculations have been successfully performed on several linear polymer chains containing up to 40,000 atoms and 200,000 atomic orbitals. Both the computational cost and the memory requirement scale linearly with the number of atoms. Additional speed-up can easily be obtained by parallelization. We show that this domain decomposition method outperforms the density matrix minimization (DMM) method for poor initial guesses. Our method provides an efficient preconditioner for DMM and other linear scaling methods, variational in nature, such as the orbital minimization (OM) procedure.

  3. Multigrid Methods in Electronic Structure Calculations

    NASA Astrophysics Data System (ADS)

    Briggs, Emil

    1996-03-01

    Multigrid techniques have become the method of choice for a broad range of computational problems. Their use in electronic structure calculations introduces a new set of issues when compared to traditional plane wave approaches. We have developed a set of techniques that address these issues and permit multigrid algorithms to be applied to the electronic structure problem in an efficient manner. In our approach the Kohn-Sham equations are discretized on a real-space mesh using a compact representation of the Hamiltonian. The resulting equations are solved directly on the mesh using multigrid iterations. This produces rapid convergence rates even for ill-conditioned systems with large length and/or energy scales. The method has been applied to both periodic and non-periodic systems containing over 400 atoms and the results are in very good agreement with both theory and experiment. Example applications include a vacancy in diamond, an isolated C60 molecule, and a 64-atom cell of GaN with the Ga d-electrons in valence which required a 250 Ry cutoff. A particular strength of a real-space multigrid approach is its ready adaptability to massively parallel computer architectures. The compact representation of the Hamiltonian is especially well suited to such machines. Tests on the Cray-T3D have shown nearly linear scaling of the execution time up to the maximum number of processors (512). The MPP implementation has been used for studies of a large Amyloid Beta Peptide (C_146O_45N_42H_210) found in the brains of Alzheimers disease patients. Further applications of the multigrid method will also be described. (in collaboration D. J. Sullivan and J. Bernholc)

  4. Electronic structure calculations in arbitrary electrostatic environments

    NASA Astrophysics Data System (ADS)

    Watson, Mark A.; Rappoport, Dmitrij; Lee, Elizabeth M. Y.; Olivares-Amaya, Roberto; Aspuru-Guzik, Alán

    2012-01-01

    Modeling of electronic structure of molecules in electrostatic environments is of considerable relevance for surface-enhanced spectroscopy and molecular electronics. We have developed and implemented a novel approach to the molecular electronic structure in arbitrary electrostatic environments that is compatible with standard quantum chemical methods and can be applied to medium-sized and large molecules. The scheme denoted CheESE (chemistry in electrostatic environments) is based on the description of molecular electronic structure subject to a boundary condition on the system/environment interface. Thus, it is particularly suited to study molecules on metallic surfaces. The proposed model is capable of describing both electrostatic effects near nanostructured metallic surfaces and image-charge effects. We present an implementation of the CheESE model as a library module and show example applications to neutral and negatively charged molecules.

  5. Electronic structure calculations on helical conducting polymers.

    PubMed

    Ripoll, Juan D; Serna, Andrei; Guerra, Doris; Restrepo, Albeiro

    2010-10-21

    We present a study of the electronic structure and derived properties of polyfurane (PFu), polypyrrol (PPy), and polythiophene (PTh). Two spatial arrangements are considered: trans chain (tc-PFu, tc-PPy, tc-PTh) and cis α-helical (α-PFu, α-PPy, α-PTh). Even at the small sizes considered here, helical conformations appear to be stable. Band gaps of pure, undoped oligomers fall into the semiconductor range. Density of states (DOS) analysis suggest dense valence and conduction bands. Bond length alternation analysis predicts almost complete delocalization of the π clouds in all spatial arrangements. Doping with electron donors or electron-withdrawing impurities reduces all band gaps close to the metallic regime in addition to increasing the DOS for the valence and conduction bands.

  6. Electronic Structure Calculations of Highly Charged Ions

    NASA Astrophysics Data System (ADS)

    Bromley, Steve; Ziolkowski, Marcin; Marler, Joan

    2016-05-01

    Exotic systems like Highly Charged Ions (HCIs) are attracting more attention based on their properties and possible interactions. Abundance of HCIs in the solar wind and their interaction with the upper atmosphere puts them in the attention of astro- and atmospheric physicists. Also, their unique properties originating in the high charge make them an excellent candidate for precision measurements and the next generation of atomic clocks. For a better understanding of the dynamics of processes involving HCIs a combined theoretical and experimental effort is needed to study their basic properties and interactions. Both theory and experiment need to be combined due to the extreme nature of these systems. We present preliminary insight into electronic structure of light HCIs, their interactions with neutral atoms and dynamics of charge transfer processes.

  7. Probing Actinide Electronic Structure through Pu Cluster Calculations

    DOE PAGES

    Ryzhkov, Mickhail V.; Mirmelstein, Alexei; Yu, Sung-Woo; Chung, Brandon W.; Tobin, James G.

    2013-02-26

    The calculations for the electronic structure of clusters of plutonium have been performed, within the framework of the relativistic discrete-variational method. Moreover, these theoretical results and those calculated earlier for related systems have been compared to spectroscopic data produced in the experimental investigations of bulk systems, including photoelectron spectroscopy. Observation of the changes in the Pu electronic structure as a function of size provides powerful insight for aspects of bulk Pu electronic structure.

  8. Multidomain decomposition approach to large scale electronic structure calculations

    NASA Astrophysics Data System (ADS)

    Varga, Kalman

    2010-03-01

    A first-principles electronic structure calculation is presented using a domain decomposition technique. The domain decomposition leads to block tridiagonal Hamiltonian and overlap matrices. With the help of an LDL decomposition the block tridiagonal structure can be exploited and the Kohn-Sham states and/or the electron density can be calculated in an computationally efficient way. The electron density can be calculated from the Green's function or from the eigensolution obtained using subspace iteration. In both cases, the calculation of the density is divided into a series of independent computations that can be done in parallel. This approach allows us to determine tens of thousands of eigenstates with any desired accuracy. If the Kohn-Sham states are not required, the density can be calculated from the Green's function in a linearly scaling fashion. The linear scaling is achieved by using the special structure resulting from the domain decomposition and not by truncation or cutoff.

  9. Parallel adaptive mesh refinement for electronic structure calculations

    SciTech Connect

    Kohn, S.; Weare, J.; Ong, E.; Baden, S.

    1996-12-01

    We have applied structured adaptive mesh refinement techniques to the solution of the LDA equations for electronic structure calculations. Local spatial refinement concentrates memory resources and numerical effort where it is most needed, near the atomic centers and in regions of rapidly varying charge density. The structured grid representation enables us to employ efficient iterative solver techniques such as conjugate gradients with multigrid preconditioning. We have parallelized our solver using an object-oriented adaptive mesh refinement framework.

  10. Electronic structure calculations of ESR parameters of melanin units.

    PubMed

    Batagin-Neto, Augusto; Bronze-Uhle, Erika Soares; Graeff, Carlos Frederico de Oliveira

    2015-03-21

    Melanins represent an important class of natural pigments present in plants and animals that are currently considered to be promising materials for applications in optic and electronic devices. Despite their interesting properties, some of the basic features of melanins are not satisfactorily understood, including the origin of their intrinsic paramagnetism. A number of experiments have been performed to investigate the electron spin resonance (ESR) response of melanin derivatives, but until now, there has been no consensus regarding the real structure of the paramagnetic centers involved. In this work, we have employed electronic structure calculations to evaluate the ESR parameters of distinct melanin monomers and dimers in order to identify the possible structures associated with unpaired spins in this biopolymer. The g-factors and hyperfine constants of the cationic, anionic and radicalar structures were investigated. The results confirm the existence of at least two distinct paramagnetic centers in melanin structure, identifying the chemical species associated with them and their roles in electrical conductivity.

  11. Exchange coupling in transition metal monoxides: Electronic structure calculations

    SciTech Connect

    Fischer, Guntram; Daene, Markus W; Ernst, Arthur; Bruno, Patrick; Lueders, Martin; Szotek, Zdzislawa; Temmerman, Walter M; Wolfam, Hergert

    2009-01-01

    An ab initio study of magnetic-exchange interactions in antiferromagnetic and strongly correlated 3d transition metal monoxides is presented. Their electronic structure is calculated using the local self-interaction correction approach, implemented within the Korringa-Kohn-Rostoker band-structure method, which is based on multiple scattering theory. The Heisenberg exchange constants are evaluated with the magnetic force theorem. Based on these the corresponding Neel temperatures TN and spin-wave dispersions are calculated. The Neel temperatures are obtained using mean-field approximation, random-phase approximation and Monte Carlo simulations. The pressure dependence of TN is investigated using exchange constants calculated for different lattice constants. All the calculated results are compared to experimental data.

  12. Electronic Structure and Molecular Dynamics Calculations for KBH4

    NASA Astrophysics Data System (ADS)

    Papaconstantopoulos, Dimitrios; Shabaev, Andrew; Hoang, Khang; Mehl, Michael; Kioussis, Nicholas

    2012-02-01

    In the search for hydrogen storage materials, alkali borohydrides MBH4 (M=Li, Na, K) are especially interesting because of their light weight and the high number of hydrogen atoms per metal atom. Electronic structure calculations can give insights into the properties of these complex hydrides and provide understanding of the structural properties and of the bonding of hydrogen. We have performed first-principles density-functional theory (DFT) and tight-binding (TB) calculations for KBH4 in both the high temperature (HT) and low temperature (LT) phases to understand its electronic and structural properties. Our DFT calculations were carried out using the VASP code. The results were then used as a database to develop a tight-binding Hamiltonian using the NRL-TB method. This approach allowed for computationally efficient calculations of phonon frequencies and elastic constants using the static module of the NRL-TB, and also using the molecular dynamics module to calculate mean-square displacements and formation energies of hydrogen vacancies.

  13. Linear Multigrid Techniques in Self-consistent Electronic Structure Calculations

    SciTech Connect

    Fattebert, J-L

    2000-05-23

    Ab initio DFT electronic structure calculations involve an iterative process to solve the Kohn-Sham equations for an Hamiltonian depending on the electronic density. We discretize these equations on a grid by finite differences. Trial eigenfunctions are improved at each step of the algorithm using multigrid techniques to efficiently reduce the error at all length scale, until self-consistency is achieved. In this paper we focus on an iterative eigensolver based on the idea of inexact inverse iteration, using multigrid as a preconditioner. We also discuss how this technique can be used for electrons described by general non-orthogonal wave functions, and how that leads to a linear scaling with the system size for the computational cost of the most expensive parts of the algorithm.

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

    PubMed

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

    2016-12-01

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

  15. Multi-million atom electronic structure calculations for quantum dots

    NASA Astrophysics Data System (ADS)

    Usman, Muhammad

    Quantum dots grown by self-assembly process are typically constructed by 50,000 to 5,000,000 structural atoms which confine a small, countable number of extra electrons or holes in a space that is comparable in size to the electron wavelength. Under such conditions quantum dots can be interpreted as artificial atoms with the potential to be custom tailored to new functionality. In the past decade or so, these nanostructures have attracted significant experimental and theoretical attention in the field of nanoscience. The new and tunable optical and electrical properties of these artificial atoms have been proposed in a variety of different fields, for example in communication and computing systems, medical and quantum computing applications. Predictive and quantitative modeling and simulation of these structures can help to narrow down the vast design space to a range that is experimentally affordable and move this part of nanoscience to nano-Technology. Modeling of such quantum dots pose a formidable challenge to theoretical physicists because: (1) Strain originating from the lattice mismatch of the materials penetrates deep inside the buffer surrounding the quantum dots and require large scale (multi-million atom) simulations to correctly capture its effect on the electronic structure, (2) The interface roughness, the alloy randomness, and the atomistic granularity require the calculation of electronic structure at the atomistic scale. Most of the current or past theoretical calculations are based on continuum approach such as effective mass approximation or k.p modeling capturing either no or one of the above mentioned effects, thus missing some of the essential physics. The Objectives of this thesis are: (1) to model and simulate the experimental quantum dot topologies at the atomistic scale; (2) to theoretically explore the essential physics i.e. long range strain, linear and quadratic piezoelectricity, interband optical transition strengths, quantum confined

  16. Supersampling method for efficient grid-based electronic structure calculations

    NASA Astrophysics Data System (ADS)

    Ryu, Seongok; Choi, Sunghwan; Hong, Kwangwoo; Kim, Woo Youn

    2016-03-01

    The egg-box effect, the spurious variation of energy and force due to the discretization of continuous space, is an inherent vexing problem in grid-based electronic structure calculations. Its effective suppression allowing for large grid spacing is thus crucial for accurate and efficient computations. We here report that the supersampling method drastically alleviates it by eliminating the rapidly varying part of a target function along both radial and angular directions. In particular, the use of the sinc filtering function performs best because as an ideal low pass filter it clearly cuts out the high frequency region beyond allowed by a given grid spacing.

  17. Efficient Execution of Electronic Structure Calculations on SMP Clusters

    SciTech Connect

    Ustemirov, Nurzhan

    2006-01-01

    Applications augmented with adaptive capabilities are becoming common in parallel computing environments. For large-scale scientific applications, dynamic adjustments to a computationally-intensive part may lead to a large pay-off in facilitating efficient execution of the entire application while aiming at avoiding resource contention. Application-specific knowledge, often best revealed during the run-time, is required to initiate and time these adjustments. In particular, General Atomic and Molecular Electronic Structure System (GAMESS) is a program for ab initio quantum chemistry that places significant demands on the high-performance computing platforms. Certain electronic structure calculations are characterized by high consumption of a particular resource, such as CPU, main memory, or disk I/O. This may lead to resource contention among concurrent GAMESS jobs and other programs in the dynamically changing environment. Thus, it is desirable to improve GAMESS calculations by means of dynamic adaptations. In this thesis, we show how an application- or algorithm-specific knowledge may play a significant role in achieving this goal. The choice of implementation is facilitated by a module-driven middleware easily integrated with GAMESS that assesses resource consumption and invokes GAMESS adaptations to the system environment. We show that the throughput of GAMESS jobs may be improved greatly as a result of such adaptations.

  18. Electronic structure calculations toward new potentially AChE inhibitors

    NASA Astrophysics Data System (ADS)

    de Paula, A. A. N.; Martins, J. B. L.; Gargano, R.; dos Santos, M. L.; Romeiro, L. A. S.

    2007-10-01

    The main purpose of this study was the use of natural non-isoprenoid phenolic lipid of cashew nut shell liquid from Anacardium occidentale as lead material for generating new potentially candidates of acetylcholinesterase inhibitors. Therefore, we studied the electronic structure of 15 molecules derivatives from the cardanol using the following groups: methyl, acetyl, N, N-dimethylcarbamoyl, N, N-dimethylamine, N, N-diethylamine, piperidine, pyrrolidine, and N-benzylamine. The calculations were performed at RHF level using 6-31G, 6-31G(d), 6-31+G(d) and 6-311G(d,p) basis functions. Among the proposed compounds we found that the structures with substitution by acetyl, N, N-dimethylcarbamoyl, N, N-dimethylamine, and pyrrolidine groups were better correlated to rivastigmine indicating possible activity.

  19. An Extensive Database of Electronic Structure Calculations between Transition Metals

    NASA Astrophysics Data System (ADS)

    Sayed, Shereef; Papaconstantopoulos, Dimitrios

    Density Functional Theory and its derived application methods, such as the Augmented Plane Wave (APW) method, have shown great success in predicting the fundamental properties of materials. In this work, we apply the APW method to explore the properties of diatomic pairs of transition metals in the CsCl structure, for all possible combinations. A total of 435 compounds have been studied. The predicted Density of States, and Band Structures are presented, along with predicted electron-phonon coupling and Stoner Criterion, in order to identify potential new superconducting or ferromagnetic materials. This work is performed to demonstrate the concept of ``high-throughput'' calculations at the crossing-point of ``Big Data'' and materials science. Us Dept of Energy.

  20. Reduced density matrix approach to calculation of electronic structure

    NASA Astrophysics Data System (ADS)

    Braams, Bastiaan J.; Jiang, Shidong; Nayakkankuppam, Madhu; Overton, Michael L.; Percus, Jerome K.

    1998-11-01

    The possibility of using the one-body and two-body reduced density matrices, rather than the many-body wavefunction, as the fundamental object of study for electronic structure calculations was actively explored in the 1960's and 1970's [1]-[3], but interest has waned since. In this approach the calculation of ground-state properties is reduced to a linear optimization problem subject to the representability conditions for the density matrices, which are a mixture of linear equalities and bounds on eigenvalues. We will review this approach, present a new family of representability conditions, and discuss our experience in using present-day methods for semi-definite programming for this application. [1] A. J. Coleman: Structure of fermion density matrices. Rev. Mod. Phys. 35 (1963) 668--689. [2] Claude Garrod and Jerome K. Percus: Reduction of the N-particle variational problem. J. Math. Phys. 5 (1964) 1756--1776. [3] M. Rosina and C. Garrod: The variational calculation of reduced density matrices. J. Comput. Phys. 18 (1975) 300--310.

  1. Electronic structure calculations of hexaborides and boron carbide

    SciTech Connect

    Ripplinger, H.; Schwarz, K.; Blaha, P.

    1997-10-01

    The electronic structures of several CaB{sub 6}-type hexaborides and boron carbide, B{sub 4}C, are studied by the full potential linearized-augmented plane-wave (LAPW) method within density functional theory. The hexaborides contain inter- and intra-octahedral boron-boron bonds, which under pressure decrease approximately linearly; however, the former shrinks more than the latter, consistent with Raman spectra and a simple spring constant model. The boron-boron dumbbell is stronger than the intraoctahedral bonds. For boron carbide several substitutions of the three-atom chain are simulated (BBC, BCB, CBC, CCB, and CCC). Trends in the charge distribution are analyzed and electric field gradient calculations compared to nuclear quadrupole coupling constant measurements show that B must be in the center position.

  2. Electronic structure calculations of group III nitride clusters

    NASA Astrophysics Data System (ADS)

    Kandalam, Anil Kumar

    2002-04-01

    Group III nitrides have become materials of choice in the manufacturing of devices used in opto-electronic and high-temperature high-power electronic industries. Hence, these materials received wide attention and have become the focus of several theoretical and experimental studies. Though these materials are studied in bulk and thin film forms, research at the cluster level is still lacking. Hence, a first principles calculation, based on the Generalized Gradient Approximation (GGA) to Density Functional Theory (DFT) was initiated to study the structural and electronic properties of AlnN n, GanNn, and InnNn, (n = 1--6) clusters. The calculated results show that the small polyatomic nitride clusters (monomer, triatomic and dimer) have a strong tendency to form N-N multiple bonds leading to the weakening of any existent metal-N or metal-metal bonds. In the absence of the N-N bonds, the metal-nitrogen bond dominates, forming short bond-lengths and large force constants. However, the strength of these heteronuclear bonds decreases in going from Al to Ga and In, whereas the weak metal-metal bond increases its strength from Al to Ga to In in the nitride clusters. Starting from the trimers M3N3, a distinct structural difference between the lowest energy configurations of AlnNn and that of GanNn, and In nNn, clusters has been observed. For AlnNn, clusters, the metal-nitrogen bond is found to dominate the lowest energy configurations. As the cluster size is increased from Al3N3 to Al 6N6, a transition from planar ring structures towards a bulk-like three dimensional configurations is seen. However, in GanN n, and InnNn clusters, no such trend is observed and the lowest energy configurations are dominated either by N2 or (N3)- sub-units. The segregation of N atoms within the stoichiometric clusters indicates the possibility of N2 and N3 based defects in the thin-film deposition process which may affect the quality of the thin-film devices based on Group III nitrides.

  3. Electronic structure from relativistic quasiparticle self-consistent GW calculations

    NASA Astrophysics Data System (ADS)

    Blügel, Stefan

    Most theoretical studies of topological insulators (TIs) are based on tight-binding descriptions and density functional theory (DFT). But recently, many-body calculations within the GW approximation attract much attention in the study of these materials. We present an implementation of the quasiparticle self-consistent (QS) GW method where the spin-orbit coupling (SOC) is fully taken into account in each iteration rather than added a posteriori. Within the all-electron FLAPW formalism, we show DFT, one-shot GW , and QS GW calculations for several, well-known TIs. We present a comparison of the calculations to photoemission spectroscopy and show that the GW corrected bands agree much better with experiment. For example, we show that Bi2Se3 is a direct gap semiconductor, in contrast to what was believed for many years by interpreting experimental results on the basis of DFT and that small strains in Bi can lead to a semimetal-to-semiconductor or trivial-to-topological transitions. Quasiparticle calculations for low-dimensional systems are still very demanding. In order to study the topological surface states with an approach based on GW , we use Wannier functions to construct a Hamiltonian that reproduces the many-body band structure of the bulk, and that is used to construct a slab Hamiltonian. With this approach, we discuss the effect of quasiparticle corrections on the surface states of TIs and on the interaction between bulk and surface states Work was funded by the Virtual Institute for Topological Insulators of the Helmholtz Association and carried out in collaboration with Irene Aguilera, Gustav Bihlmayer, and Christoph Friedrich.

  4. "Lagrange functions" for order(N) electronic structure calculations

    NASA Astrophysics Data System (ADS)

    Varga, Kalman; Zhang, Zhenyu; Pantelides, S. T.

    2004-03-01

    "Plane waves" have several highly desirable properties for electronic structure calculations, but effectively scale as N3, where N is the number of atoms, because they impose a uniform grid on which one must perform fast Fourier transforms (FFTs). To achieve near-order-N methods, it is imperative to adopt "real-space methods and non-uniform grids. The objective is usually pursued either by discretization or by adopting local basis sets, either numerical or analytical, with optimized short range. Here we report on a novel basis set, which we label "Lagrange functions" that are defined to satisfy the Lagrange interpolation condition and on a grid that corresponds to a Gaussian quadrature for integrations with optimized numerical accuracy. Lagrange functions combine the best attributes of plane waves and real-space methods. Just like plane waves, convergence is controlled by a single parameter in a systematic way, are orthonormal and defined analytically everywhere, but have the added flexibility of a weight function that controls the distribution of grid points and can be used to optimize the calculation for each system. They do not require FFTs and integrals are trivial and accurate since each Lagrange function is nonzero on a single grid point. The power of the method will be illustrated with several examples.

  5. Adaptations in Electronic Structure Calculations in Heterogeneous Environments

    SciTech Connect

    Talamudupula, Sai

    2011-01-01

    Modern quantum chemistry deals with electronic structure calculations of unprecedented complexity and accuracy. They demand full power of high-performance computing and must be in tune with the given architecture for superior e ciency. To make such applications resourceaware, it is desirable to enable their static and dynamic adaptations using some external software (middleware), which may monitor both system availability and application needs, rather than mix science with system-related calls inside the application. The present work investigates scienti c application interlinking with middleware based on the example of the computational chemistry package GAMESS and middleware NICAN. The existing synchronous model is limited by the possible delays due to the middleware processing time under the sustainable runtime system conditions. Proposed asynchronous and hybrid models aim at overcoming this limitation. When linked with NICAN, the fragment molecular orbital (FMO) method is capable of adapting statically and dynamically its fragment scheduling policy based on the computing platform conditions. Signi cant execution time and throughput gains have been obtained due to such static adaptations when the compute nodes have very di erent core counts. Dynamic adaptations are based on the main memory availability at run time. NICAN prompts FMO to postpone scheduling certain fragments, if there is not enough memory for their immediate execution. Hence, FMO may be able to complete the calculations whereas without such adaptations it aborts.

  6. Large Scale Electronic Structure Calculations using Quantum Chemistry Methods

    NASA Astrophysics Data System (ADS)

    Scuseria, Gustavo E.

    1998-03-01

    This talk will address our recent efforts in developing fast, linear scaling electronic structure methods for large scale applications. Of special importance is our fast multipole method( M. C. Strain, G. E. Scuseria, and M. J. Frisch, Science 271), 51 (1996). (FMM) for achieving linear scaling for the quantum Coulomb problem (GvFMM), the traditional bottleneck in quantum chemistry calculations based on Gaussian orbitals. Fast quadratures(R. E. Stratmann, G. E. Scuseria, and M. J. Frisch, Chem. Phys. Lett. 257), 213 (1996). combined with methods that avoid the Hamiltonian diagonalization( J. M. Millam and G. E. Scuseria, J. Chem. Phys. 106), 5569 (1997) have resulted in density functional theory (DFT) programs that can be applied to systems containing many hundreds of atoms and ---depending on computational resources or level of theory-- to many thousands of atoms.( A. D. Daniels, J. M. Millam and G. E. Scuseria, J. Chem. Phys. 107), 425 (1997). Three solutions for the diagonalization bottleneck will be analyzed and compared: a conjugate gradient density matrix search (CGDMS), a Hamiltonian polynomial expansion of the density matrix, and a pseudo-diagonalization method. Besides DFT, our near-field exchange method( J. C. Burant, G. E. Scuseria, and M. J. Frisch, J. Chem. Phys. 105), 8969 (1996). for linear scaling Hartree-Fock calculations will be discussed. Based on these improved capabilities, we have also developed programs to obtain vibrational frequencies (via analytic energy second derivatives) and excitation energies (through time-dependent DFT) of large molecules like porphyn or C_70. Our GvFMM has been extended to periodic systems( K. N. Kudin and G. E. Scuseria, Chem. Phys. Lett., in press.) and progress towards a Gaussian-based DFT and HF program for polymers and solids will be reported. Last, we will discuss our progress on a Laplace-transformed \\cal O(N^2) second-order pertubation theory (MP2) method.

  7. Complex wet-environments in electronic-structure calculations

    NASA Astrophysics Data System (ADS)

    Fisicaro, Giuseppe; Genovese, Luigi; Andreussi, Oliviero; Marzari, Nicola; Goedecker, Stefan

    The computational study of chemical reactions in complex, wet environments is critical for applications in many fields. It is often essential to study chemical reactions in the presence of an applied electrochemical potentials, including complex electrostatic screening coming from the solvent. In the present work we present a solver to handle both the Generalized Poisson and the Poisson-Boltzmann equation. A preconditioned conjugate gradient (PCG) method has been implemented for the Generalized Poisson and the linear regime of the Poisson-Boltzmann, allowing to solve iteratively the minimization problem with some ten iterations. On the other hand, a self-consistent procedure enables us to solve the Poisson-Boltzmann problem. The algorithms take advantage of a preconditioning procedure based on the BigDFT Poisson solver for the standard Poisson equation. They exhibit very high accuracy and parallel efficiency, and allow different boundary conditions, including surfaces. The solver has been integrated into the BigDFT and Quantum-ESPRESSO electronic-structure packages and it will be released as a independent program, suitable for integration in other codes. We present test calculations for large proteins to demonstrate efficiency and performances. This work was done within the PASC and NCCR MARVEL projects. Computer resources were provided by the Swiss National Supercomputing Centre (CSCS) under Project ID s499. LG acknowledges also support from the EXTMOS EU project.

  8. Electronic band structure calculations of bismuth-antimony nanowires

    NASA Astrophysics Data System (ADS)

    Levin, Andrei; Dresselhaus, Mildred

    2012-02-01

    Alloys of bismuth and antimony received initial interest due to their unmatched low-temperature thermoelectric performance, and have drawn more recent attention as the first 3D topological insulators. One-dimensional bismuth-antimony (BiSb) nanowires display interesting quantum confinement effects, and are expected to exhibit even better thermoelectric properties than bulk BiSb. Due to the small, anisotropic carrier effective masses, the electronic properties of BiSb nanowires show great sensitivity to nanowire diameter, crystalline orientation, and alloy composition. We develop a theoretical model for calculating the band structure of BiSb nanowires. For a given crystalline orientation, BiSb nanowires can be in the semimetallic, direct semiconducting, or indirect semiconducting phase, depending on nanowire diameter and alloy composition. These ``phase diagrams'' turn out to be remarkably similar among the different orientations, which is surprising in light of the anisotropy of the bulk BiSb Fermi surface. We predict a novel direct semiconducting phase for nanowires with diameter less than ˜15 nm, over a narrow composition range. We also find that, in contrast to the bulk and thin film BiSb cases, a gapless state with Dirac dispersion cannot be realized in BiSb nanowires.

  9. Atomic spectral methods for molecular electronic structure calculations.

    PubMed

    Langhoff, P W; Boatz, J A; Hinde, R J; Sheehy, J A

    2004-11-15

    Theoretical methods are reported for ab initio calculations of the adiabatic (Born-Oppenheimer) electronic wave functions and potential energy surfaces of molecules and other atomic aggregates. An outer product of complete sets of atomic eigenstates familiar from perturbation-theoretical treatments of long-range interactions is employed as a representational basis without prior enforcement of aggregate wave function antisymmetry. The nature and attributes of this atomic spectral-product basis are indicated, completeness proofs for representation of antisymmetric states provided, convergence of Schrodinger eigenstates in the basis established, and strategies for computational implemention of the theory described. A diabaticlike Hamiltonian matrix representative is obtained, which is additive in atomic-energy and pairwise-atomic interaction-energy matrices, providing a basis for molecular calculations in terms of the (Coulombic) interactions of the atomic constituents. The spectral-product basis is shown to contain the totally antisymmetric irreducible representation of the symmetric group of aggregate electron coordinate permutations once and only once, but to also span other (non-Pauli) symmetric group representations known to contain unphysical discrete states and associated continua in which the physically significant Schrodinger eigenstates are generally embedded. These unphysical representations are avoided by isolating the physical block of the Hamiltonian matrix with a unitary transformation obtained from the metric matrix of the explicitly antisymmetrized spectral-product basis. A formal proof of convergence is given in the limit of spectral closure to wave functions and energy surfaces obtained employing conventional prior antisymmetrization, but determined without repeated calculations of Hamiltonian matrix elements as integrals over explicitly antisymmetric aggregate basis states. Computational implementations of the theory employ efficient recursive

  10. Grid-based electronic structure calculations: The tensor decomposition approach

    NASA Astrophysics Data System (ADS)

    Rakhuba, M. V.; Oseledets, I. V.

    2016-05-01

    We present a fully grid-based approach for solving Hartree-Fock and all-electron Kohn-Sham equations based on low-rank approximation of three-dimensional electron orbitals. Due to the low-rank structure the total complexity of the algorithm depends linearly with respect to the one-dimensional grid size. Linear complexity allows for the usage of fine grids, e.g. 81923 and, thus, cheap extrapolation procedure. We test the proposed approach on closed-shell atoms up to the argon, several molecules and clusters of hydrogen atoms. All tests show systematical convergence with the required accuracy.

  11. Software abstractions and computational issues in parallel structure adaptive mesh methods for electronic structure calculations

    SciTech Connect

    Kohn, S.; Weare, J.; Ong, E.; Baden, S.

    1997-05-01

    We have applied structured adaptive mesh refinement techniques to the solution of the LDA equations for electronic structure calculations. Local spatial refinement concentrates memory resources and numerical effort where it is most needed, near the atomic centers and in regions of rapidly varying charge density. The structured grid representation enables us to employ efficient iterative solver techniques such as conjugate gradient with FAC multigrid preconditioning. We have parallelized our solver using an object- oriented adaptive mesh refinement framework.

  12. Calculations of Cleavage Processes, Surface Structures and Electronic Structure of Silicon and Germanium.

    NASA Astrophysics Data System (ADS)

    Chen, Bo.

    The cleavage processes, surface and step structures, and electronic structure of Si and Ge (111)2 x 1 surfaces were studied. The ab initio quantum chemistry programs KGNMOL-89 and DMol were used to study the cleavage of silicon and germanium clusters in the diamond structure. It was found that the potential energy of stretching and shearing glide planes increases much faster than for shuffle planes. The cleavage process is discussed and it is shown how glide -plane cleavage can occur, with consequences for surface structure models. The Keating strain-energy method has been applied to estimate the energies of surface and step structures on Si(111)2 x 1. Two minimum strain-energy TBS (Three -Bond Scission) model structures were obtained. Since angular strains are involved which go beyond the applicability limits of the Keating formula, a correction factor is used, derived by comparing Keating-type calculations of particular surface models of Si(111) with the results of more extensive calculations. The use of a simple correction factor gives results that agree with a calculation for the Pandey ( pi-bonded chain) model and one for the TBS model. Using this factor, a model for a 3-substep structure of the (322) step on Si is found to be quite stable, while the 2-substep structures are moderately stable. The surface band structure of the TBS and Pandey models have been computed using an ab initio HF LCAO program CRYSTAL-92. In the case of the TBS model, the results showed valence band dispersion that could be compatible with experiments. For the Pandey model, the calculated valence band dispersion seemed large. The surface band gap for both TBS and Pandey models was greatly overestimated. The significance is discussed. The surface electron density of states was calculated for the TBS model and the valence band generally matched experimental results from STM (scanning tunneling microscopy). The electron charge density of various surface regions was calculated. The

  13. Electronic Structure Calculations of delta-Pu Based Alloys

    SciTech Connect

    Landa, A; Soderlind, P; Ruban, A

    2003-11-13

    First-principles methods are employed to study the ground-state properties of {delta}-Pu-based alloys. The calculations show that an alloy component larger than {delta}-Pu has a stabilizing effect. Detailed calculations have been performed for the {delta}-Pu{sub 1-c}Am{sub c} system. Calculated density of Pu-Am alloys agrees well with the experimental data. The paramagnetic {yields} antiferromagnetic transition temperature (T{sub c}) of {delta}-Pu{sub 1-c}Am{sub c} alloys is calculated by a Monte-Carlo technique. By introducing Am into the system, one could lower T{sub c} from 548 K (pure Pu) to 372 K (Pu{sub 70}Am{sub 30}). We also found that, contrary to pure Pu where this transition destabilizes {delta}-phase, Pu{sub 3}Am compound remains stable in the antiferromagnetic phase that correlates with the recent discovery of a Curie-Weiss behavior of {delta}-Pu{sub 1-c}Am{sub c} at c {approx} 24 at. %.

  14. Electronic structure calculations on lithium battery electrolyte salts.

    PubMed

    Johansson, Patrik

    2007-03-28

    New lithium salts for non-aqueous liquid, gel and polymeric electrolytes are crucial due to the limiting role of the electrolyte in modern lithium batteries. The solvation of any lithium salt to form an electrolyte solution ultimately depends on the strength of the cation-solvent vs. the cation-anion interaction. Here, the latter is probed via HF, B3LYP and G3 theory gas-phase calculations for the dissociation reaction: LiX <--> Li(+) + X(-). Furthermore, a continuum solvation method (C-PCM) has been applied to mimic solvent effects. Anion volumes were also calculated to facilitate a discussion on ion conductivities and cation transport numbers. Judging from the present results, synthesis efforts should target heterocyclic anions with a size of ca. 150 A(3) molecule(-1) to render new highly dissociative lithium salts that result in electrolytes with high cation transport numbers. PMID:17356757

  15. Symmetry and equivalence restrictions in electronic structure calculations

    NASA Technical Reports Server (NTRS)

    Bauschlicher, Charles W., Jr.; Taylor, Peter R.

    1988-01-01

    A simple method for obtaining MCSCF orbitals and CI natural orbitals adapted to degenerate point groups, with full symmetry and equivalnece restrictions, is described. Among several advantages accruing from this method are the ability to perform atomic SCF calculations on states for which the SCF energy expression cannot be written in terms of Coulomb and exchange integrals over real orbitals, and the generation of symmetry-adapted atomic natural orbitals for use in a recently proposed method for basis set contraction.

  16. Efficient O(N) integration for all-electron electronic structure calculation using numeric basis functions

    SciTech Connect

    Havu, V. Blum, V.; Havu, P.; Scheffler, M.

    2009-12-01

    We consider the problem of developing O(N) scaling grid-based operations needed in many central operations when performing electronic structure calculations with numeric atom-centered orbitals as basis functions. We outline the overall formulation of localized algorithms, and specifically the creation of localized grid batches. The choice of the grid partitioning scheme plays an important role in the performance and memory consumption of the grid-based operations. Three different top-down partitioning methods are investigated, and compared with formally more rigorous yet much more expensive bottom-up algorithms. We show that a conceptually simple top-down grid partitioning scheme achieves essentially the same efficiency as the more rigorous bottom-up approaches.

  17. High Resolution Measurements and Electronic Structure Calculations of a Diazanaphthalene

    NASA Astrophysics Data System (ADS)

    Gruet, Sébastien; Goubet, Manuel; Pirali, Olivier

    2014-06-01

    Polycyclic Aromatic Hydrocarbons (PAHs) have long been suspected to be the carriers of so called Unidentified Infrared Bands (UIBs). Most of the results published in the literature report rotationally unresolved spectra of pure carbon as well as heteroatom-containing PAHs species. To date for this class of molecules, the principal source of rotational informations is ruled by microwave (MW) spectroscopy while high resolution measurements reporting rotational structure of the infrared (IR) vibrational bands are very scarce. Recently, some high resolution techniques provided interesting new results to rotationally resolve the IR and far-IR bands of these large carbonated molecules of astrophysical interest. One of them is to use the bright synchrotron radiation as IR continuum source of a high resolution Fourier transform (FTIR) spectrometer. We report the very complementary analysis of the [1,6] naphthyridine (a N-bearing PAH) for which we recorded the microwave spectrum at the PhLAM laboratory (Lille) and the high resolution far-infrared spectrum on the AILES beamline at synchrotron facility SOLEIL. MW spectroscopy provided highly accurate rotational constants in the ground state to perform Ground State Combinations Differences (GSCD) allowing the analysis of the two most intense FT-FIR bands in the 50-900 wn range. Moreover, during this presentation the negative value of the inertial defect in the GS of the molecule will be discussed. A. Leger, J. L. Puget, Astron. Astrophys. 137, L5-L8 (1984) L. J. Allamandola et al. Astrophys. J. 290, L25-L28 (1985). Z. Kisiel et al. J. Mol. Spectrosc. 217, 115 (2003) S. Thorwirth et al. Astrophys. J. 662, 1309 (2007) D. McNaughton et al. J. Chem. Phys. 124, 154305 (2011). S. Albert et al. Faraday Discuss. 150, 71-99 (2011) B. E. Brumfield et al. Phys. Chem. Lett. 3, 1985-1988 (2012) O. Pirali et al. Phys. Chem. Chem. Phys. 15, 10141 (2013).

  18. Simple extrapolation method to predict the electronic structure of conjugated polymers from calculations on oligomers

    DOE PAGES

    Larsen, Ross E.

    2016-04-12

    In this study, we introduce two simple tight-binding models, which we call fragment frontier orbital extrapolations (FFOE), to extrapolate important electronic properties to the polymer limit using electronic structure calculations on only a few small oligomers. In particular, we demonstrate by comparison to explicit density functional theory calculations that for long oligomers the energies of the highest occupied molecular orbital (HOMO), the lowest unoccupied molecular orbital (LUMO), and of the first electronic excited state are accurately described as a function of number of repeat units by a simple effective Hamiltonian parameterized from electronic structure calculations on monomers, dimers and, optionally,more » tetramers. For the alternating copolymer materials that currently comprise some of the most efficient polymer organic photovoltaic devices one can use these simple but rigorous models to extrapolate computed properties to the polymer limit based on calculations on a small number of low-molecular-weight oligomers.« less

  19. Electronic and structural properties of ultrathin tungsten nanowires and nanotubes by density functional theory calculation

    SciTech Connect

    Sun, Shih-Jye; Lin, Ken-Huang; Li, Jia-Yun; Ju, Shin-Pon

    2014-10-07

    The simulated annealing basin-hopping method incorporating the penalty function was used to predict the lowest-energy structures for ultrathin tungsten nanowires and nanotubes of different sizes. These predicted structures indicate that tungsten one-dimensional structures at this small scale do not possess B.C.C. configuration as in bulk tungsten material. In order to analyze the relationship between multi-shell geometries and electronic transfer, the electronic and structural properties of tungsten wires and tubes including partial density of state and band structures which were determined and analyzed by quantum chemistry calculations. In addition, in order to understand the application feasibility of these nanowires and tubes on nano-devices such as field emitters or chemical catalysts, the electronic stability of these ultrathin tungsten nanowires was also investigated by density functional theory calculations.

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

    NASA Astrophysics Data System (ADS)

    Zheng, Haoping

    2003-04-01

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

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

    NASA Astrophysics Data System (ADS)

    Zheng, Haoping

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

  2. First-principles calculation of electronic structure and optical absorption of BN ZnO

    NASA Astrophysics Data System (ADS)

    Zhang, Xiao; Schleife, Andre

    2015-03-01

    The α-BN structure of ZnO, a nonequilibrium phase with a transition pressure of 25 GPa, has been found in nano structures of ZnO. The structural difference between the BN structure and the equilibrium wurtzite structure can play an important role for applications of nanostructured ZnO. In order to understand the difference, first principles calculations have been performed on both phases. The electronic structure is computed using the GW method based on Density Functional Theory and HSE hybrid functional calculations. The GW method includes the quasiparticle effects due to the screened electron-electron interaction which gives an accurate description of the electronic band structure and density of states. After that, by solving the Bethe-Salpeter Equation for the optical polarization function, which take excitonic effects into account, we have achieved an accurate description of optical absorption spectra for both structures. We find a good agreement with experimental and previous computational results for WZ structure, and predict the absorption for the BN structure. The BN structure shows a larger band gap and we found a very large optical anisotropy: The gap for extraordinary light polarization is almost 0.7eV larger than that for ordinary light polarization.

  3. Structure and properties of electronic and hole centers in CsBr from theoretical calculations

    SciTech Connect

    Halliday, Matthew T.; Hess, Wayne P.; Shluger, Alexander L.

    2015-06-24

    The electronic structure, geometry, diffusion barriers and optical properties of fundamental defects of CsBr are calculated using hybrid functional DFT and TD- DFT methods. The B3LYP functional with a modified exchange contribution has been used in an embedded cluster scheme to model the structure and spectroscopic properties of self-trapped triplet exciton, interstitial Br atoms and ions, self-trapped holes and Br vacancies. The calculated migration barriers and positions of maxima of optical absorption bands are in good agreement with experiment, justifying the obtained defect geometries. The o*-center triplet exciton luminescence energy is also accurately calculated.

  4. First principles calculation of the structural, electronic, and magnetic properties of Au-Pd atomic chains

    SciTech Connect

    Dave, Mudra R.; Sharma, A. C.

    2015-06-24

    The structural, electronic and magnetic properties of free standing Au-Pd bimetallic atomic chain is studied using ab-initio method. It is found that electronic and magnetic properties of chains depend on position of atoms and number of atoms. Spin polarization factor for different atomic configuration of atomic chain is calculated predicting a half metallic behavior. It suggests a total spin polarised transport in these chains.

  5. Dissociative recombination of interstellar ions: electronic structure calculations for HCO/sup +/

    SciTech Connect

    Kraemer, W.P.; Hazi, A.U.

    1985-07-02

    The present study of the interstellar formyl ion HCO/sup +/ is the first attempt to investigate dissociative recombination for a triatomic molecular ion using an entirely theoretical approach. We describe a number of fairly extensive electronic structure calculations that were performed to determine the reaction mechanism of the e-HCO/sup +/ process. Similar calculations for the isoelectronic ions HOC/sup +/ and HN/sub 2//sup +/ are in progress. 60 refs.

  6. Ab initio calculations of the electronic structure of silicon nanocrystals doped with shallow donors (Li, P)

    SciTech Connect

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

    2013-12-15

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

  7. Investigating the Electronic Structure of Fluorite Oxides: Comparsion of EELS and First Principles Calculations

    SciTech Connect

    Aguiar, J; Asta, M; Gronbech-Jensen, N; Perlov, A; Milman, V; Gao, S; Pickard, C; Browning, N

    2009-06-05

    Energy loss spectra from a variety of cubic oxides are compared with ab-initio calculations based on the density functional plane wave method (CASTEP). In order to obtain agreement between experimental and theoretical spectra, unique material specific considerations were taken into account. The spectra were calculated using various approximations to describe core-hole effects and electronic correlations. All the calculations are based on the local spin density approximation to show qualitative agreement with the sensitive oxygen K-edge spectra in ceria, zirconia, and urania. Comparison of experimental and theoretical results let us characterize the main electronic interactions responsible for both the electronic structure and the resulting EEL spectra of the compounds in question.

  8. Electronic Structure Calculations for Heavy Elements: Radon (Z=86) and Francium (Z=87)

    NASA Astrophysics Data System (ADS)

    Koufos, Alexander; Papaconstantopoulos, Dimitrios

    2010-03-01

    Electronic structure calculations allow scientists to predict the properties of solids without the use of physical material. Although the ability to manipulate matter has improved dramatically within the past couple decades, some matter is still hard to study. Modern computers not only let us study this matter, but allow us to do it more quickly and just as accurately. The electronic structure of two rare and mostly unstudied elements, Radon (Z=86) and Francium (Z=87), has been calculated. The augmented plane wave (APW) method with local density approximation (LDA) functional as well as the linearized augmented plane wave (LAPW) method with both LDA and generalized gradient approximation (GGA) functionals were used to perform the calculations. Francium total energy calculations gave the fcc structure slightly below the bcc structure with a minimal energy difference of δE=0.33mRy. The difference found is consistent with other alkali metal total energy calculations which do not verify the bcc structure to be the ground state. Radon was predicted to be an insulator with a gap of 0.931 Ry similar to the other noble gases.

  9. Topological Insulators, Semi-Metals and Superconductors From First Principles Electronic Structure Calculations

    NASA Astrophysics Data System (ADS)

    Savrasov, Sergey

    2014-03-01

    Using first-principles electronic structure calculations we investigate novel phases that emerge from the interplay of electron correlations, strong spin-orbit coupling and electron-phonon interactions. We first focus on describing the topological semimetal, a three-dimensional phase of a magnetic solid, and argue that it may be realized in a class of pyrochlore iridates (such as Y2Ir2O7) based on calculations using the LDA + U method. This state is a three-dimensional analog of graphene with linearly dispersing excitations and provides a condensed-matter realization of Weyl fermions that obeys a two-component Dirac equation. It also exhibits remarkable topological properties manifested by surface states in the form of Fermi arcs, which are impossible to realize in purely two-dimensional band structures. We second predict that osmium compounds such as CaOs2O4 and SrOs2O4 can be stabilized in the geometrically frustrated spinel crystal structure. They show ferromagnetic order in a reasonable range of the on-site Coulomb correlation U and exotic electronic properties, in particular, a large magnetoelectric coupling characteristic of axion electrodynamics. Finally, the issue of topological superconductivity and the possibility of the odd pairing will be discussed in Cu doped Bi2Te3 materials where electron-phonon coupling constant is calculated for various pairing symmetries using density functional linear response approach.

  10. Ab Initio Electronic Structure Calculations of Cytochrome P450 -- Ligand Interactions

    NASA Astrophysics Data System (ADS)

    Segall, M. D.; Payne, M. C.; Ellis, S. W.; Tucker, G. T.

    1997-03-01

    The Cytochrome P450 superfamily of enzymes are of great interest in pharmacology as they participate in an enormous range of physiological processes including drug deactivation and xenobiotic detoxification. We apply ab initio electronic structure calculations to model the interactions of the haem molecule at the P450 active site with substrate and inhibitor ligands. These calculations, based on density function theory, were performed with the CETEP code which uses a plane wave basis set and pseudopotentials to perform efficient LDA, GGA and spin dependent calculations. A change in the spin state of the haem iron atom is observed on binding of a substrate molecule, consistent with the accepted reaction mechanism.

  11. First-Principles Electronic Structure Calculations of Zinc-Blende Chromium Monopnictides

    NASA Astrophysics Data System (ADS)

    Shirai, M.; Taguchi, H.; Akinaga, H.

    2003-03-01

    Electronic band-structure of zinc-blende (zb) chromium monopnictides, CrP, CrAs, and CrSb, is studied comparatively by using first-principles density-functional calculations. Effect of spin-orbit interaction on the spin-polarization near the Fermi-level is also investigated. It is found that zb-CrAs and CrSb are predicted to be the ferromagnets exhibiting highly spin-polarized electronic band-structure, even if the effect of the spin-orbit interaction is taken into account.

  12. Structural and electronic properties of solid naphthalene under pressure: density functional calculations

    NASA Astrophysics Data System (ADS)

    Xiao, Ling-Ping; Zeng, Zhi; Chen, Xiao-Jia

    2016-06-01

    The pressure effect on the geometrical and electronic structures of crystalline naphthalene is calculated up to 30 GPa by performing density functional calculations. The lattice parameters a, b, and c, decrease by 1.77 Å (-20.4%), 0.85 Å (-14.1%), and 0.91 Å (-8.2%), respectively, while the monoclinic angle β increases by 3.95° in this pressure region. At the highest pressure of 30 GPa the unit cell volume decreases by 62.7%. The detailed analysis of the molecular arrangement within crystal structure reveals that the molecular motion becomes more and more localized, and hints towards the evolution of intermolecular interaction with pressure. Moreover, the electronic structure of naphthalene under high pressure is also discussed. A pressure induced decrease of the band gap is observed.

  13. Density functional calculation of the structural and electronic properties of germanium quantum dots

    SciTech Connect

    Anas, M. M.; Gopir, G.

    2015-04-24

    We apply first principles density functional computational methods to study the structures, densities of states (DOS), and higher occupied molecular orbital (HOMO) – lowest unoccupied molecular orbital (LUMO) gaps of selected free-standing Ge semiconductor quantum dots up to 1.8nm. Our calculations are performed using numerical atomic orbital approach where linear combination of atomic orbital was applied. The surfaces of the quantum dots was passivized by hydrogen atoms. We find that surface passivation does affect the electronic properties associated with the changes of surface state, electron localization, and the energy gaps of germanium nanocrystals as well as the confinement of electrons inside the quantum dots (QDs). Our study shows that the energy gaps of germanium quantum dots decreases with the increasing dot diameter. The size-dependent variations of the computed HOMO-LUMO gaps in our quantum dots model were found to be consistent with the effects of quantum confinement reported in others theoretical and experimental calculation.

  14. Layers and tubes of fluorographene C4F: Stability, structural and electronic properties from DFTB calculations

    NASA Astrophysics Data System (ADS)

    Enyashin, A. N.; Ivanovskii, A. L.

    2013-06-01

    By means of the DFTB band structure calculations we have explored the layers' isomerism of fluorographene C4F. The relative stability, structural and electronic properties of the C4F layers and nanotubes have been revealed depending on the possible types of fluorine coverage: single-sided, double-sided or so-called non-uniform variants. Our main finding is that the aforementioned types of fluorine coverage are crucial for the morphology of these materials. At the non-uniform or single-sided coverage types the C4F structures aspire to the spontaneous folding in order to minimize their surface tension.

  15. Structural stabilities, elastic and electronic properties of chromium tetraboride from first-principles calculations

    NASA Astrophysics Data System (ADS)

    Xu, C.; Li, Q.; Liu, C. M.; Duan, M. Y.; Wang, H. K.

    2016-05-01

    First-principles calculations are employed to investigate the structural and elastic properties, formation enthalpies and chemical bonding features as well as hardness values of chromium tetraboride (CrB4) with different structures. The lattice parameters, Poisson’s ratio and B/G ratio are also derived. Our calculations indicate that the orthorhombic structure with Pnnm symmetry is the most energetically stable one for CrB4. Except for WB4P63/mmc structure with imaginary frequencies, another six new structures are investigated through the full phonon dispersion calculations. Their mechanical and thermodynamic stabilities are also studied by calculating the elastic constants and formation enthalpies. Our calculations show that the thermodynamic stabilities of all these CrB4 phases can be enhanced under high pressure. The large shear moduli, Young’s moduli and hardness values indicate that these CrB4 phases are potential hard materials. Analyses of the densities of states (DOSs) and electron localization functions (ELFs) provide further understandings of the chemical and physical properties of these CrB4 phases. It is observed that the large occupations and high strengths of the B-B covalent bonds are important for the stabilities, incompressibility and hardnesses of these CrB4 phases.

  16. The structural and electronic properties of amorphous HgCdTe from first-principles calculations

    NASA Astrophysics Data System (ADS)

    Zhao, Huxian; Chen, Xiaoshuang; Lu, Jianping; Shu, Haibo; Lu, Wei

    2014-01-01

    Amorphous mercury cadmium telluride (a-MCT) model structures, with x being 0.125 and 0.25, are obtained from first-principles calculations. We generate initial structures by computation alchemy method. It is found that most atoms in the network of amorphous structures tend to be fourfold and form tetrahedral structures, implying that the chemical ordered continuous random network with some coordination defects is the ideal structure for a-MCT. The electronic structure is also concerned. The gap is found to be 0.30 and 0.26 eV for a-Hg0.875Cd0.125Te and a-Hg0.75Cd0.25Te model structures, independent of the composition. By comparing with the properties of crystalline MCT with the same composition, we observe a blue-shift of energy band gap. The localization of tail states and its atomic origin are also discussed.

  17. Isolation, Structure, and Electronic Calculations of the Heterofullerene Salt K_6C59N

    NASA Astrophysics Data System (ADS)

    Prassides, Kosmas; Keshavarz-K., Majid; Hummelen, Jan Cornelis; Andreoni, Wanda; Giannozzi, Paolo; Beer, Ernst; Bellavia, Cheryl; Cristofolini, Luigi; Gonzalez, Rosario; Lappas, Alexandros; Murata, Yasuo; Malecki, Magdalena; Srdanov, Vojislav; Wudl, Fred

    1996-03-01

    An intercalation compound of azafullerene, K_6C59N, was prepared and structurally characterized. It is isostructural with the fullerene compound K_6C60, adopts a body-centered-cubic structure (lattice constant a = 11.31 angstroms), and consists of quasi-spherical monomeric (C59N)^6-ions. Density functional calculations of the structural and electronic properties confirm the similarity to K_6C60 but also suggest a sizable deformation, principally confined in the vicinity of the nitrogen atom, of both the molecular structure and the electron states. These results show that study of the intercalation chemistry of azafullerene promises to reveal a rich family of both n- and p-doped systems with novel conducting and magnetic properties, like their fullerene antecedents.

  18. Structural, elastic, vibrational and electronic properties of amorphous Al2O3 from ab initio calculations.

    PubMed

    Davis, Sergio; Gutiérrez, Gonzalo

    2011-12-14

    First-principles molecular dynamics calculations of the structural, elastic, vibrational and electronic properties of amorphous Al(2)O(3), in a system consisting of a supercell of 80 atoms, are reported. A detailed analysis of the interatomic correlations allows us to conclude that the short-range order is mainly composed of AlO(4) tetrahedra, but, in contrast with previous results, also an important number of AlO(6) octahedra and AlO(5) units are present. The vibrational density of states presents two frequency bands, related to bond-bending and bond-stretching modes. It also shows other recognizable features present in similar amorphous oxides. We also present the calculation of elastic properties (bulk modulus and shear modulus). The calculated electronic structure of the material, including total and partial electronic density of states, charge distribution, electron localization function and the ionicity for each species, gives evidence of correlation between the ionicity and the coordination for each Al atom.

  19. Multi-Center Electronic Structure Calculations for Plasma Equation of State

    SciTech Connect

    Wilson, B G; Johnson, D D; Alam, A

    2010-12-14

    We report on an approach for computing electronic structure utilizing solid-state multi-center scattering techniques, but generalized to finite temperatures to model plasmas. This approach has the advantage of handling mixtures at a fundamental level without the imposition of ad hoc continuum lowering models, and incorporates bonding and charge exchange, as well as multi-center effects in the calculation of the continuum density of states.

  20. Population analysis of plane-wave electronic structure calculations of bulk materials

    SciTech Connect

    Segall, M.D.; Shah, R.; Pickard, C.J.; Payne, M.C.

    1996-12-01

    {ital Ab} {ital initio} plane-wave electronic structure calculations are widely used in the study of bulk materials. A technique for the projection of plane-wave states onto a localized basis set is used to calculate atomic charges and bond populations by means of Mulliken analysis. We analyze a number of simple bulk crystals and find correlations of overlap population with covalency of bonding and bond strength, and effective valence charge with ionicity of bonding. Thus, we show that the techniques described in this paper may be usefully applied in the field of solid state physics. {copyright}{ital 1996 The American Physical Society.}

  1. The LDA+U calculation of electronic band structure of GaAs

    NASA Astrophysics Data System (ADS)

    Bahuguna, B. P.; Sharma, R. O.; Saini, L. K.

    2016-05-01

    We present the electronic band structure of bulk gallium arsenide (GaAs) using first principle approach. A series of calculations has been performed by applying norm-conserving pseudopotentials and ultrasoft non-norm-conserving pseudopotentials within the density functional theory. These calculations yield too small band gap as compare to experiment. Thus, we use semiemperical approach called local density approximation plus the multi-orbital mean-field Hubbard model (LDA+U), which is quite effective in order to describe the band gap of GaAs.

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

    NASA Astrophysics Data System (ADS)

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

    2005-12-01

    Lanthanum hexaboride ( LaB6 , NIST SRM-660a) is widely used as a standard reference material for calibrating the line position and line shape parameters of powder diffraction instruments. The accuracy of this calibration technique is highly dependent on how completely the reference material is characterized. Critical to x-ray diffraction, this understanding must include the valence of the La atomic position, which in turn will influence the x-ray form factor (f) and hence the diffracted intensities. The electronic structure and bonding properties of LaB6 have been investigated using ab initio plane-wave pseudopotential total energy calculations. The electronic properties and atomic bonding characteristics were analyzed by estimating the energy band structure and the density of states around the Fermi energy level. The calculated energy band structure is consistent with previously reported experimental findings; de Haas-van Alphen and two-dimensional angular correlation of electron-positron annihilation radiation. In addition, the bond strengths and types of atomic bonds in the LaB6 compound were estimated by analyzing the Mulliken charge density population. The calculated result revealed the coexistence of covalent, ionic, and metallic bonding in the LaB6 system and partially explains its high efficiency as a thermionic emitter.

  3. The Dirac equation in electronic structure calculations: Accurate evaluation of DFT predictions for actinides

    SciTech Connect

    Wills, John M; Mattsson, Ann E

    2012-06-06

    Brooks, Johansson, and Skriver, using the LMTO-ASA method and considerable insight, were able to explain many of the ground state properties of the actinides. In the many years since this work was done, electronic structure calculations of increasing sophistication have been applied to actinide elements and compounds, attempting to quantify the applicability of DFT to actinides and actinide compounds and to try to incorporate other methodologies (i.e. DMFT) into DFT calculations. Through these calculations, the limits of both available density functionals and ad hoc methodologies are starting to become clear. However, it has also become clear that approximations used to incorporate relativity are not adequate to provide rigorous tests of the underlying equations of DFT, not to mention ad hoc additions. In this talk, we describe the result of full-potential LMTO calculations for the elemental actinides, comparing results obtained with a full Dirac basis with those obtained from scalar-relativistic bases, with and without variational spin-orbit. This comparison shows that the scalar relativistic treatment of actinides does not have sufficient accuracy to provide a rigorous test of theory and that variational spin-orbit introduces uncontrolled errors in the results of electronic structure calculations on actinide elements.

  4. Linear algebraic calculation of the Green's function for large-scale electronic structure theory

    NASA Astrophysics Data System (ADS)

    Takayama, R.; Hoshi, T.; Sogabe, T.; Zhang, S.-L.; Fujiwara, T.

    2006-04-01

    A linear algebraic method named the shifted conjugate-orthogonal conjugate-gradient method is introduced for large-scale electronic structure calculation. The method gives an iterative solver algorithm of the Green’s function and the density matrix without calculating eigenstates. The problem is reduced to independent linear equations at many energy points and the calculation is actually carried out only for a single energy point. The method is robust against the round-off error and the calculation can reach the machine accuracy. With the observation of residual vectors, the accuracy can be controlled, microscopically, independently for each element of the Green’s function, and dynamically, at each step in dynamical simulations. The method is applied to both a semiconductor and a metal.

  5. A novel Gaussian-Sinc mixed basis set for electronic structure calculations

    NASA Astrophysics Data System (ADS)

    Jerke, Jonathan L.; Lee, Young; Tymczak, C. J.

    2015-08-01

    A Gaussian-Sinc basis set methodology is presented for the calculation of the electronic structure of atoms and molecules at the Hartree-Fock level of theory. This methodology has several advantages over previous methods. The all-electron electronic structure in a Gaussian-Sinc mixed basis spans both the "localized" and "delocalized" regions. A basis set for each region is combined to make a new basis methodology—a lattice of orthonormal sinc functions is used to represent the "delocalized" regions and the atom-centered Gaussian functions are used to represent the "localized" regions to any desired accuracy. For this mixed basis, all the Coulomb integrals are definable and can be computed in a dimensional separated methodology. Additionally, the Sinc basis is translationally invariant, which allows for the Coulomb singularity to be placed anywhere including on lattice sites. Finally, boundary conditions are always satisfied with this basis. To demonstrate the utility of this method, we calculated the ground state Hartree-Fock energies for atoms up to neon, the diatomic systems H2, O2, and N2, and the multi-atom system benzene. Together, it is shown that the Gaussian-Sinc mixed basis set is a flexible and accurate method for solving the electronic structure of atomic and molecular species.

  6. A novel Gaussian-Sinc mixed basis set for electronic structure calculations

    SciTech Connect

    Jerke, Jonathan L.; Lee, Young; Tymczak, C. J.

    2015-08-14

    A Gaussian-Sinc basis set methodology is presented for the calculation of the electronic structure of atoms and molecules at the Hartree–Fock level of theory. This methodology has several advantages over previous methods. The all-electron electronic structure in a Gaussian-Sinc mixed basis spans both the “localized” and “delocalized” regions. A basis set for each region is combined to make a new basis methodology—a lattice of orthonormal sinc functions is used to represent the “delocalized” regions and the atom-centered Gaussian functions are used to represent the “localized” regions to any desired accuracy. For this mixed basis, all the Coulomb integrals are definable and can be computed in a dimensional separated methodology. Additionally, the Sinc basis is translationally invariant, which allows for the Coulomb singularity to be placed anywhere including on lattice sites. Finally, boundary conditions are always satisfied with this basis. To demonstrate the utility of this method, we calculated the ground state Hartree–Fock energies for atoms up to neon, the diatomic systems H{sub 2}, O{sub 2}, and N{sub 2}, and the multi-atom system benzene. Together, it is shown that the Gaussian-Sinc mixed basis set is a flexible and accurate method for solving the electronic structure of atomic and molecular species.

  7. A novel Gaussian-Sinc mixed basis set for electronic structure calculations.

    PubMed

    Jerke, Jonathan L; Lee, Young; Tymczak, C J

    2015-08-14

    A Gaussian-Sinc basis set methodology is presented for the calculation of the electronic structure of atoms and molecules at the Hartree-Fock level of theory. This methodology has several advantages over previous methods. The all-electron electronic structure in a Gaussian-Sinc mixed basis spans both the "localized" and "delocalized" regions. A basis set for each region is combined to make a new basis methodology-a lattice of orthonormal sinc functions is used to represent the "delocalized" regions and the atom-centered Gaussian functions are used to represent the "localized" regions to any desired accuracy. For this mixed basis, all the Coulomb integrals are definable and can be computed in a dimensional separated methodology. Additionally, the Sinc basis is translationally invariant, which allows for the Coulomb singularity to be placed anywhere including on lattice sites. Finally, boundary conditions are always satisfied with this basis. To demonstrate the utility of this method, we calculated the ground state Hartree-Fock energies for atoms up to neon, the diatomic systems H2, O2, and N2, and the multi-atom system benzene. Together, it is shown that the Gaussian-Sinc mixed basis set is a flexible and accurate method for solving the electronic structure of atomic and molecular species. PMID:26277128

  8. The electronic structure and magnetism of CaFeAs2: First principles calculations

    NASA Astrophysics Data System (ADS)

    Wang, Guangtao; Shi, Xianbiao; Zhang, Lin; Yi, Xia

    2014-12-01

    The electronic structure, magnetism and Fermi surface (FS) nesting of the recently discovered superconductive parent material CaFeAs2 are studied by the first-principles, based on the GGA and GGA+U methods. In the nonmagnetic state, the density of states at the Fermi level are mostly derived from the dxy, dyz and dzx orbits, just like LaOFeAs. The Fermi surfaces consist of four hole like FS sheets around the Γ-point, two electron like sheets near the Brillouin zone corner M-point, and small pockets near X-point. The hole like Fermi surfaces will strongly overlap with the electron like FS sheets, if they are shifted by the q-vector q=(π, π, 0). Such FS nesting will induce the magnetic instability and spin density wave (SDW), which has been confirmed to be more stable than other states by the calculated total energy. The calculated bare susceptibility χ0(q) peaked at M-point, and was obviously suppressed with the electron doping. This explains the emergence of the superconductivity in the electron-doped compound Ca1-xLaxFeAs2, because the electron doping suppressed the SDW and induced the superconductivity.

  9. Electronic-structure calculations of praseodymium metal by means of modified density-functional theory

    SciTech Connect

    Svane, A.; Trygg, J.; Johansson, B.; Eriksson, O. |

    1997-09-01

    Electronic-structure calculations of elemental praseodymium are presented. Several approximations are used to describe the Pr f electrons. It is found that the low-pressure, trivalent phase is well described using either the self-interaction corrected (SIC) local-spin-density (LSD) approximation or the generalized-gradient approximation (GGA) with spin and orbital polarization (OP). In the SIC-LSD approach the Pr f electrons are treated explicitly as localized with a localization energy given by the self-interaction of the f orbital. In the GGA+OP scheme the f-electron localization is described by the onset of spin and orbital polarization, the energetics of which is described by spin-moment formation energy and a term proportional to the total orbital moment, L{sub z}{sup 2}. The high-pressure phase is well described with the f electrons treated as band electrons, in either the LSD or the GGA approximations, of which the latter describes more accurately the experimental equation of state. The calculated pressure of the transition from localized to delocalized behavior is 280 kbar in the SIC-LSD approximation and 156 kbar in the GGA+OP approach, both comparing favorably with the experimentally observed transition pressure of 210 kbar. {copyright} {ital 1997} {ital The American Physical Society}

  10. Pressure induced structural phase transition and electronic properties of actinide monophospides: Ab-initio calculations

    NASA Astrophysics Data System (ADS)

    Makode, Chandrabhan; Sanyal, Sankar P.

    2011-09-01

    We have investigated the structural and electronic properties of monophospides of thorium, uranium and neptunium. The total energy as a function of volume is obtained by means of the self-consistent tight binding linear muffin-tin-orbital (TB-LMTO) method within the local density approximation (LDA). From the present study with the help of total energy calculations it is found that ThP, UP and NpP are stable in NaCl-type structure at ambient pressure. The structural stability of ThP, UP and NpP changes under the application of pressure. We predict a structural phase transition from NaCl-type (B 1-phase) structure to CsCl-type (B 2-phase) structure for these phospides in the pressure range of 37.0-24.0 GPa (ThP-NpP). We also calculate lattice parameter ( a0), bulk modulus ( B0), band structure and density of states. From energy band diagram it is observed that ThP, UP and NpP exhibit metallic behavior. The calculated equilibrium lattice parameters and bulk modulus are in good agreement with experimental and theoretical work.

  11. Atomic and Molecular Complex Resonances from Real Eigenvalues Using Standard (Hermitian) Electronic Structure Calculations.

    PubMed

    Landau, Arie; Haritan, Idan; Kaprálová-Žd'ánská, Petra Ruth; Moiseyev, Nimrod

    2016-05-19

    Complex eigenvalues, resonances, play an important role in a large variety of fields in physics and chemistry. For example, in cold molecular collision experiments and electron scattering experiments, autoionizing and predissociative metastable resonances are generated. However, the computation of complex resonance requires modifications of standard electronic structure codes and methods, which are not always straightforward, in addition, application of complex codes requires more computational efforts. Here we show how resonance eigenvalues, positions and widths, can be calculated using the standard, widely used, electronic-structure packages. Our method enables the calculations of the complex resonance eigenvalues by using analytical continuation procedures (such as Padé). The key point in our approach is the existence of narrow analytical passages from the real axis to the complex energy plane. In fact, the existence of these analytical passages relies on using finite basis sets. These passages become narrower as the basis set becomes more complete, whereas in the exact limit, these passages to the complex plane are closed. As illustrative numerical examples we calculated the autoionization Feshbach resonances of helium, hydrogen anion, and hydrogen molecule. We show that our results are in an excellent agreement with the results obtained by other theoretical methods and with available experimental results.

  12. Electronic structure and defect properties of Tl6SeI4: Density functional calculations

    NASA Astrophysics Data System (ADS)

    Biswas, Koushik; Du, Mao-Hua; Singh, David J.

    2012-10-01

    We report density functional calculations of electronic structure, phase diagram, and dielectric, optical, and defect properties of Tl6SeI4. We discuss how electronic structure and defect properties affect resistivity and carrier mobility-lifetime (μτ) products in Tl6SeI4. We find large Born effective charges due to covalency involving Tl-6p states. High Born charges generally enhance the static dielectric constant. This provides a mechanism for effective screening of charged defects and impurities. We find that high resistivity can be obtained under near-stoichiometric growth conditions via Fermi level pinning near the middle of the band gap by shallow donors and acceptors, as opposed to deep traps that can give high resistivity, but at the expense of short carrier drift lengths. Defect calculations also reveal the presence of deep native donors that may cause electron trapping. The experimentally observed good μτ products may be explained by a combination of small effective masses and effective screening of charged defects. High resistivity and good μτ products make Tl6SeI4 a promising room-temperature radiation detector material. We also show the calculated defect diffusion barriers, which affect defect migration under external bias in a detector.

  13. Structural, electronic, and thermodynamic properties of UN: Systematic density functional calculations

    NASA Astrophysics Data System (ADS)

    Lu, Yong; Wang, Bao-Tian; Li, Rong-Wu; Shi, Hongliang; Zhang, Ping

    2010-11-01

    A systematic first-principle study is performed to calculate the lattice parameters, electronic structure, and thermodynamic properties of UN using the local-density approximation (LDA)+ U and the generalized gradient approximation (GGA)+ U formalisms. To properly describe the strong correlation in the U 5 f electrons, we optimized the U parameter in calculating the total energy, lattice parameters, and bulk modulus at the nonmagnetic (NM), ferromagnetic (FM), and antiferromagnetic (AFM) configurations. Our results show that by choosing the Hubbard U around 2 eV within the GGA+ U approach, it is promising to correctly and consistently describe the above mentioned properties of UN. The localization behavior of 5 f electrons is found to be stronger than that of UC and our electronic analysis indicates that the effective charge of UN can be represented as U 1.71+N 1.71-. As for the thermodynamic study, the phonon dispersion illustrates the stability of UN and we further predict the lattice vibration energy, thermal expansion, and specific heat by utilizing the quasiharmonic approximation. Our calculated specific heat is well consistent with experiments.

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

    NASA Astrophysics Data System (ADS)

    Correa, J. D.; Cisternas, E.

    2016-09-01

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

  15. Photoisomerization mechanism of 4-methylpyridine explored by electronic structure calculations and nonadiabatic dynamics simulations

    SciTech Connect

    Cao Jun; Fang Weihai; Fang Qiu

    2011-01-28

    In the present paper, different electronic structure methods have been used to determine stationary and intersection structures on the ground (S{sub 0}) and {sup 1}{pi}{pi}* (S{sub 2}) states of 4-methylpyridine, which is followed by adiabatic and nonadiabatic dynamics simulations to explore the mechanistic photoisomerization of 4-methylpyridine. Photoisomerization starts from the S{sub 2}({sup 1}{pi}{pi}*) state and overcomes a small barrier, leading to formation of the prefulvene isomer in the S{sub 0} state via a S{sub 2}/S{sub 0} conical intersection. The ultrafast S{sub 2}{yields} S{sub 0} nonradiative decay and low quantum yield for the photoisomerization reaction were well reproduced by the combined electronic structure calculation and dynamics simulation. The prefulvene isomer was assigned as a long-lived intermediate and suggested to isomerize to 4-methylpyridine directly in the previous study, which is not supported by the present calculation. The nonadiabatic dynamics simulation and electronic structure calculation reveal that the prefulvene isomer is a short-lived intermediate and isomerizes to benzvalene form very easily. The benzvalene form was predicted as the stable isomer in the present study and is probably the long-lived intermediate observed experimentally. A consecutive light and thermal isomerization cycle via Dewar isomer was determined and this cycle mechanism is different from that reported in the previous study. It should be pointed out that formation of Dewar isomer from the S{sub 2}({sup 1}{pi}{pi}*) state is not in competition with the isomerization to the prefulvene form. The Dewar structure observed experimentally may originate from other excited states.

  16. Including nuclear quantum effects into highly correlated electronic structure calculations of weakly bound systems.

    PubMed

    Aguirre, Néstor F; Villarreal, Pablo; Delgado-Barrio, Gerardo; Posada, Edwin; Reyes, Andrés; Biczysko, Malgorzata; Mitrushchenkov, Alexander O; de Lara-Castells, María Pilar

    2013-05-14

    An interface between the APMO code and the electronic structure package MOLPRO is presented. The any particle molecular orbital APMO code [González et al., Int. J. Quantum Chem. 108, 1742 (2008)] implements the model where electrons and light nuclei are treated simultaneously at Hartree-Fock or second-order Möller-Plesset levels of theory. The APMO-MOLPRO interface allows to include high-level electronic correlation as implemented in the MOLPRO package and to describe nuclear quantum effects at Hartree-Fock level of theory with the APMO code. Different model systems illustrate the implementation: (4)He2 dimer as a protype of a weakly bound van der Waals system; isotopomers of [He-H-He](+) molecule as an example of a hydrogen bonded system; and molecular hydrogen to compare with very accurate non-Born-Oppenheimer calculations. The possible improvements and future developments are outlined.

  17. Massively parallel full configuration interaction. Benchmark electronic structure calculations on the Intel Touchstone Delta

    SciTech Connect

    Harrison, R.J.; Stahlberg, E.A.

    1994-10-01

    We describe an implementation of the benchmark ab initio electronic structure full configuration interaction model on the Intel Touchstone Delta. Its performance is demonstrated with several calculations, the largest of which (95 million configurations, 418 million determinants) is the largest full-CI calculation yet completed. The feasibility of calculations with over one billion configurations is discussed. A sustained computation rate in excess of 4 GFLOP/s on 512 processors is achieved, with an average aggregate communication rate of 155 Mbytes/s. Data-compression techniques and a modified diagonalization method were required to minimize I/O. The object-oriented design has increased portability and provides the distinction between local and non-local data essential for use of a distributed-data model.

  18. Effect of tensile strain on the electronic structure of Ge: A first-principles calculation

    SciTech Connect

    Liu, Li; Zhang, Miao; Di, Zengfeng E-mail: shijin.zhao@shu.edu.cn; Hu, Lijuan; Zhao, Shi-Jin E-mail: shijin.zhao@shu.edu.cn

    2014-09-21

    Taking the change of L-point conduction band valley degeneracy under strain into consideration, we investigate the effect of biaxially tensile strain (parallel to the (001), (110), and (111) planes) and uniaxially tensile strain (along the [001], [110], and [111] directions) on the electronic structure of Ge using density functional theory calculations. Our calculation shows that biaxial tension parallel to (001) is the most efficient way to transform Ge into a direct bandgap material among all tensile strains considered. [111]-tension is the best choice among all uniaxial approaches for an indirect- to direct-bandgap transition of Ge. The calculation results, which are further elaborated by bond-orbital approximation, provide a useful guidance on the optical applications of Ge through strain engineering.

  19. Electronic structure of cubic ScF3 from first-principles calculations

    NASA Astrophysics Data System (ADS)

    Bocharov, D.; Žguns, P.; Piskunov, S.; Kuzmin, A.; Purans, J.

    2016-07-01

    The ground state properties of cubic scandium trifluoride (ScF3) perovskite were studied using first-principles calculations. The electronic structure of ScF3 was determined by linear combination of atomic orbital (LCAO) and plane wave projector augmented-wave (PAW) methods using modified hybrid exchange-correlation functionals within the density functional theory (DFT). The comprehensive comparison of the results obtained by two methods is presented. Both methods allowed us to reproduce the lattice constant found experimentally in ScF3 at low temperatures and to predict its electronic structure in good agreement with known experimental valence-band photoelectron and F 1s x-ray absorption spectra.

  20. ACRES: An Efficient Method for First-Principles Electronic Structure Calculations of Complex Systems

    SciTech Connect

    WAGHMARE,R.V.; KIM,HANCHUL; PARK,I.J.; MODINE,NORMAND A.; MARAGAKIS,P.; KAXIRAS,EFTHIMIOS

    2000-08-29

    The authors discuss their new implementation of the Adaptive Coordinate Real-space Electronic Structure (ACRES) method for studying the atomic and electronic structure of infinite periodic as well as finite systems, based on density functional theory. This improved version aims at making the method widely applicable and efficient, using high performance Fortran on parallel architectures. The scaling of various parts of an ACRES calculation is analyzed and compared to that of plane-wave based methods. The new developments that lead to enhanced performance, and their parallel implementation, are presented in detail. They illustrate the application of ACRES to the study of elemental crystalline solids, molecules and complex crystalline materials, such as blue bronze and zeolites.

  1. Structural and electronic phase transitions of ThS2 from first-principles calculations

    NASA Astrophysics Data System (ADS)

    Guo, Yongliang; Wang, Changying; Qiu, Wujie; Ke, Xuezhi; Huai, Ping; Cheng, Cheng; Zhu, Zhiyuan; Chen, Changfeng

    2016-10-01

    Thorium and its compounds have received considerable attention in recent years due to the renewed interest in developing the thorium fuel cycle as an alternative nuclear energy technology. There is pressing current need to explore the physical properties essential to the fundamental understanding and practical application of these materials. Here we report on a computational study of thorium disulfide (ThS2), which plays an important role in the thorium fuel reprocessing cycle. We have employed the density functional theory and evolutionary structure search methods to determine the crystal structures, electronic band structures, phonon dispersions and density of states, and thermodynamic properties of ThS2 under various pressure and temperature conditions. Our calculations identify several crystalline phases of ThS2 and a series of structural phase transitions induced by pressure and temperature. The calculated results also reveal electronic phase transitions from the semiconducting state in the low-pressure phases of ThS2 in the P n m a and F m 3 ¯m symmetry to the metallic state in the high-pressure phases of ThS2 in the P n m a and I 4 /m m m symmetry. These results explain the experimental observation of the thermodynamic stability of the P n m a phase of ThS2 at the ambient conditions and a pressure-induced structural phase transition in ThS2 around 40 GPa. Moreover, the present study reveals considerable additional information on the structural and electronic properties of ThS2 in a wide range of pressure and temperature. Such information provides key insights into the fundamental material behavior and the underlying mechanisms that lay the foundation for further exploration and application of ThS2.

  2. Exploring positron characteristics utilizing two new positron-electron correlation schemes based on multiple electronic structure calculation methods

    NASA Astrophysics Data System (ADS)

    Zhang, Wen-Shuai; Gu, Bing-Chuan; Han, Xiao-Xi; Liu, Jian-Dang; Ye, Bang-Jiao

    2015-10-01

    We make a gradient correction to a new local density approximation form of positron-electron correlation. The positron lifetimes and affinities are then probed by using these two approximation forms based on three electronic-structure calculation methods, including the full-potential linearized augmented plane wave (FLAPW) plus local orbitals approach, the atomic superposition (ATSUP) approach, and the projector augmented wave (PAW) approach. The differences between calculated lifetimes using the FLAPW and ATSUP methods are clearly interpreted in the view of positron and electron transfers. We further find that a well-implemented PAW method can give near-perfect agreement on both the positron lifetimes and affinities with the FLAPW method, and the competitiveness of the ATSUP method against the FLAPW/PAW method is reduced within the best calculations. By comparing with the experimental data, the new introduced gradient corrected correlation form is proved to be competitive for positron lifetime and affinity calculations. Project supported by the National Natural Science Foundation of China (Grant Nos. 11175171 and 11105139).

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

    NASA Astrophysics Data System (ADS)

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

    2014-03-01

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

  4. Bright and dark excitons in semiconductor carbon nanotubes: insights from electronic structure calculations.

    PubMed

    Kilina, Svetlana; Badaeva, Ekaterina; Piryatinski, Andrei; Tretiak, Sergei; Saxena, Avadh; Bishop, Alan R

    2009-06-01

    We review electronic structure calculations of finite-length semiconducting carbon nanotubes using time-dependent density functional theory (TD-DFT) and the time dependent Hartree-Fock (TD-HF) approach coupled with semi-empirical AM1 and ZINDO Hamiltonians. We specifically focus on the energy splitting, relative ordering, and localization properties of optically active (bright) and optically forbidden (dark) states from the lowest excitonic band of the nanotubes. These excitonic states are very important in competing radiative and non-radiative processes in these systems. Our analysis of excitonic transition density matrices demonstrates that pure DFT functionals overdelocalize excitons making an electron-hole pair unbound; consequently, excitonic features are not presented in this method. In contrast, the pure HF and AM1 calculations overbind excitons, inaccurately predicting the lowest energy state as a bright exciton. Changing the AM1 with the ZINDO Hamiltonian in TD-HF calculations predicts the bright exciton as the second state after the dark one. However, in contrast to AM1 calculations, the diameter dependence of the excitation energies obtained by ZINDO does not follow the experimental trends. Finally, the TD-DFT approach incorporating hybrid functionals with a moderate portion of the long-range HF exchange, such as B3LYP, has the most generality and predictive capacity providing a sufficiently accurate description of excitonic structure in finite-size nanotubes. These methods characterize four important lower exciton bands: the lowest state is dark, the upper band is bright, and the two other dark and nearly degenerate excitons lie in between. Although the calculated energy splittings between the lowest dark and the bright excitons are relatively large ( approximately 0.1 eV), the dense excitonic manifold below the bright exciton allows for fast non-radiative relaxation leading to the rapid population of the lowest dark exciton. This rationalizes the low

  5. Determination of Structural and Electronic Parameters of Antimony Complex, from Theoretical Calculations

    NASA Astrophysics Data System (ADS)

    Catikkas, Berna; Kosar, Ismail

    2016-06-01

    In this study, ground states of antimony (Sbv) with organic ligands complexes were studied by using density functional theory hybrid methods in order to obtain structural, electronic and vibrational spectral parameters. The mapping molecular electrostatic potential surface of the molecules computed to information about the charge density distribution of the molecules and its chemical reactivity. Frontier molecule orbital properties, HOMO and LUMO energies, global descriptors, and the total density of state diagram analysis were performed by using the time-dependent density functional theory. For the learning nonlinear optical properties, polarizability and hyperpolarizability tensors of the molecule were calculated.

  6. A Linear Scaling Three Dimensional Fragment Method for Large ScaleElectronic Structure Calculations

    SciTech Connect

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

    2007-07-26

    We present a novel linear scaling ab initio total energyelectronic structure calculation method, which is simple to implement,easily to parallelize, and produces essentially thesame results as thedirect ab initio method, while it could be thousands of times faster.Using this method, we have studied the dipole moments of CdSe quantumdots, and found both significant bulk and surface contributions. The bulkdipole contribution cannot simply be estimated from the bulk spontaneouspolarization value by a proportional volume factor. Instead it has ageometry dependent screening effect. The dipole moment also produces astrong internal electric field which induces a strong electron holeseparation.

  7. Calculation of cohesion and changes in electronic structure due to impurity segregation at boundaries in iron

    SciTech Connect

    Rez, P.; Alvarez, J.R.

    1999-11-12

    It is well known that impurities in iron which segregate to grain boundaries can dramatically change physical properties. Carbon and boron tend to increase ductility while phosphorus and sulfur lead to embrittlement. Cohesion at boundaries in iron can be understood by studying changes in the iron d states responsible for bonding. Since the effects are quite localized, relatively small systems can be used to model the electronic structure. Both FLAPW and LKKR calculations show that the average energy of the d band is lower for B and C impurities and higher for P and S impurities. These results are consistent with the macroscopic changes in cohesion.

  8. Functional renormalization group approach to electronic structure calculations for systems without translational symmetry

    NASA Astrophysics Data System (ADS)

    Seiler, Christian; Evers, Ferdinand

    2016-10-01

    A formalism for electronic-structure calculations is presented that is based on the functional renormalization group (FRG). The traditional FRG has been formulated for systems that exhibit a translational symmetry with an associated Fermi surface, which can provide the organization principle for the renormalization group (RG) procedure. We here advance an alternative formulation, where the RG flow is organized in the energy-domain rather than in k space. This has the advantage that it can also be applied to inhomogeneous matter lacking a band structure, such as disordered metals or molecules. The energy-domain FRG (ɛ FRG) presented here accounts for Fermi-liquid corrections to quasiparticle energies and particle-hole excitations. It goes beyond the state of the art G W -BSE , because in ɛ FRG the Bethe-Salpeter equation (BSE) is solved in a self-consistent manner. An efficient implementation of the approach that has been tested against exact diagonalization calculations and calculations based on the density matrix renormalization group is presented. Similar to the conventional FRG, also the ɛ FRG is able to signalize the vicinity of an instability of the Fermi-liquid fixed point via runaway flow of the corresponding interaction vertex. Embarking upon this fact, in an application of ɛ FRG to the spinless disordered Hubbard model we calculate its phase boundary in the plane spanned by the interaction and disorder strength. Finally, an extension of the approach to finite temperatures and spin S =1 /2 is also given.

  9. Linearly Scaling 3D Fragment Method for Large-Scale Electronic Structure Calculations

    SciTech Connect

    Wang, Lin-Wang; Lee, Byounghak; Shan, Hongzhang; Zhao, Zhengji; Meza, Juan; Strohmaier, Erich; Bailey, David H.

    2008-07-01

    We present a new linearly scaling three-dimensional fragment (LS3DF) method for large scale ab initio electronic structure calculations. LS3DF is based on a divide-and-conquer approach, which incorporates a novel patching scheme that effectively cancels out the artificial boundary effects due to the subdivision of the system. As a consequence, the LS3DF program yields essentially the same results as direct density functional theory (DFT) calculations. The fragments of the LS3DF algorithm can be calculated separately with different groups of processors. This leads to almost perfect parallelization on tens of thousands of processors. After code optimization, we were able to achieve 35.1 Tflop/s, which is 39percent of the theoretical speed on 17,280 Cray XT4 processor cores. Our 13,824-atom ZnTeO alloy calculation runs 400 times faster than a direct DFTcalculation, even presuming that the direct DFT calculation can scale well up to 17,280 processor cores. These results demonstrate the applicability of the LS3DF method to material simulations, the advantage of using linearly scaling algorithms over conventional O(N3) methods, and the potential for petascale computation using the LS3DF method.

  10. Excited-state dynamics of oxazole: A combined electronic structure calculations and dynamic simulations study

    NASA Astrophysics Data System (ADS)

    Cao, Jun; Xie, Zhi-Zhong; Yu, Xiaodong

    2016-08-01

    In the present work, the combined electronic structure calculations and surface hopping simulations have been performed to investigate the excited-state decay of the parent oxazole in the gas phase. Our calculations show that the S2 state decay of oxazole is an ultrafast process characterized by the ring-opening and ring-closure of the five-membered oxazole ring, in which the triplet contribution is minor. The ring-opening involves the Osbnd C bond cleavage affording the nitrile ylide and airine intermediates, while the ring-closure gives rise to a bicyclic species through a 2sbnd 5 bond formation. The azirine and bicyclic intermediates in the S0 state are very likely involved in the phototranspositions of oxazoles. This is different from the previous mechanism in which these intermediates in the T1 state have been proposed for these phototranspositions.

  11. Hybrid preconditioning for iterative diagonalization of ill-conditioned generalized eigenvalue problems in electronic structure calculations

    SciTech Connect

    Cai, Yunfeng; Bai, Zhaojun; Pask, John E.; Sukumar, N.

    2013-12-15

    The iterative diagonalization of a sequence of large ill-conditioned generalized eigenvalue problems is a computational bottleneck in quantum mechanical methods employing a nonorthogonal basis for ab initio electronic structure calculations. We propose a hybrid preconditioning scheme to effectively combine global and locally accelerated preconditioners for rapid iterative diagonalization of such eigenvalue problems. In partition-of-unity finite-element (PUFE) pseudopotential density-functional calculations, employing a nonorthogonal basis, we show that the hybrid preconditioned block steepest descent method is a cost-effective eigensolver, outperforming current state-of-the-art global preconditioning schemes, and comparably efficient for the ill-conditioned generalized eigenvalue problems produced by PUFE as the locally optimal block preconditioned conjugate-gradient method for the well-conditioned standard eigenvalue problems produced by planewave methods.

  12. Tensor decomposition in electronic structure calculations on 3D Cartesian grids

    SciTech Connect

    Khoromskij, B.N. Khoromskaia, V.; Chinnamsetty, S.R.; Flad, H.-J.

    2009-09-01

    In this paper, we investigate a novel approach based on the combination of Tucker-type and canonical tensor decomposition techniques for the efficient numerical approximation of functions and operators in electronic structure calculations. In particular, we study applicability of tensor approximations for the numerical solution of Hartree-Fock and Kohn-Sham equations on 3D Cartesian grids. We show that the orthogonal Tucker-type tensor approximation of electron density and Hartree potential of simple molecules leads to low tensor rank representations. This enables an efficient tensor-product convolution scheme for the computation of the Hartree potential using a collocation-type approximation via piecewise constant basis functions on a uniform nxnxn grid. Combined with the Richardson extrapolation, our approach exhibits O(h{sup 3}) convergence in the grid-size h=O(n{sup -1}). Moreover, this requires O(3rn+r{sup 3}) storage, where r denotes the Tucker rank of the electron density with r=O(logn), almost uniformly in n. For example, calculations of the Coulomb matrix and the Hartree-Fock energy for the CH{sub 4} molecule, with a pseudopotential on the C atom, achieved accuracies of the order of 10{sup -6} hartree with a grid-size n of several hundreds. Since the tensor-product convolution in 3D is performed via 1D convolution transforms, our scheme markedly outperforms the 3D-FFT in both the computing time and storage requirements.

  13. Molecular structure, vibrational, electronic and thermal properties of 4-vinylcyclohexene by quantum chemical calculations.

    PubMed

    Nagabalasubramanian, P B; Periandy, S; Karabacak, Mehmet; Govindarajan, M

    2015-06-15

    The solid phase FT-IR and FT-Raman spectra of 4-vinylcyclohexene (abbreviated as 4-VCH) have been recorded in the region 4000-100cm(-1). The optimized molecular geometry and vibrational frequencies of the fundamental modes of 4-VCH have been precisely assigned and analyzed with the aid of structure optimizations and normal coordinate force field calculations based on density functional theory (DFT) method at 6-311++G(d,p) level basis set. The theoretical frequencies were properly scaled and compared with experimentally obtained FT-IR and FT-Raman spectra. Also, the effect due the substitution of vinyl group on the ring vibrational frequencies was analyzed and a detailed interpretation of the vibrational spectra of this compound has been made on the basis of the calculated total energy distribution (TED). The time dependent DFT (TD-DFT) method was employed to predict its electronic properties, such as electronic transitions by UV-Visible analysis, HOMO and LUMO energies, molecular electrostatic potential (MEP) and various global reactivity and selectivity descriptors (chemical hardness, chemical potential, softness, electrophilicity index). Stability of the molecule arising from hyper conjugative interaction, charge delocalization has been analyzed using natural bond orbital (NBO) analysis. Atomic charges obtained by Mulliken population analysis and NBO analysis are compared. Thermodynamic properties (heat capacity, entropy and enthalpy) of the title compound at different temperatures are also calculated.

  14. Gas phase structures and charge localization in small aluminum oxide anions: Infrared photodissociation spectroscopy and electronic structure calculations.

    PubMed

    Song, Xiaowei; Fagiani, Matias R; Gewinner, Sandy; Schöllkopf, Wieland; Asmis, Knut R; Bischoff, Florian A; Berger, Fabian; Sauer, Joachim

    2016-06-28

    We use cryogenic ion trap vibrational spectroscopy in combination with quantum chemical calculations to study the structure of mono- and dialuminum oxide anions. The infrared photodissociation spectra of D2-tagged AlO1-4 (-) and Al2O3-6 (-) are measured in the region from 400 to 1200 cm(-1). Structures are assigned based on a comparison to simulated harmonic and anharmonic IR spectra derived from electronic structure calculations. The monoaluminum anions contain an even number of electrons and exhibit an electronic closed-shell ground state. The Al2O3-6 (-) anions are oxygen-centered radicals. As a result of a delicate balance between localization and delocalization of the unpaired electron, only the BHLYP functional is able to qualitatively describe the observed IR spectra of all species with the exception of AlO3 (-). Terminal Al-O stretching modes are found between 1140 and 960 cm(-1). Superoxo and peroxo stretching modes are found at higher (1120-1010 cm(-1)) and lower energies (850-570 cm(-1)), respectively. Four modes in-between 910 and 530 cm(-1) represent the IR fingerprint of the common structural motif of dialuminum oxide anions, an asymmetric four-member Al-(O)2-Al ring. PMID:27369513

  15. Gas phase structures and charge localization in small aluminum oxide anions: Infrared photodissociation spectroscopy and electronic structure calculations

    NASA Astrophysics Data System (ADS)

    Song, Xiaowei; Fagiani, Matias R.; Gewinner, Sandy; Schöllkopf, Wieland; Asmis, Knut R.; Bischoff, Florian A.; Berger, Fabian; Sauer, Joachim

    2016-06-01

    We use cryogenic ion trap vibrational spectroscopy in combination with quantum chemical calculations to study the structure of mono- and dialuminum oxide anions. The infrared photodissociation spectra of D2-tagged AlO1-4- and Al2O3-6- are measured in the region from 400 to 1200 cm-1. Structures are assigned based on a comparison to simulated harmonic and anharmonic IR spectra derived from electronic structure calculations. The monoaluminum anions contain an even number of electrons and exhibit an electronic closed-shell ground state. The Al2O3-6- anions are oxygen-centered radicals. As a result of a delicate balance between localization and delocalization of the unpaired electron, only the BHLYP functional is able to qualitatively describe the observed IR spectra of all species with the exception of AlO3-. Terminal Al-O stretching modes are found between 1140 and 960 cm-1. Superoxo and peroxo stretching modes are found at higher (1120-1010 cm-1) and lower energies (850-570 cm-1), respectively. Four modes in-between 910 and 530 cm-1 represent the IR fingerprint of the common structural motif of dialuminum oxide anions, an asymmetric four-member Al-(O)2-Al ring.

  16. Origin of resolution enhancement by co-doping of scintillators: Insight from electronic structure calculations

    SciTech Connect

    Åberg, Daniel Sadigh, Babak; Schleife, André; Erhart, Paul

    2014-05-26

    It was recently shown that the energy resolution of Ce-doped LaBr{sub 3} scintillator radiation detectors can be crucially improved by co-doping with Sr, Ca, or Ba. Here, we outline a mechanism for this enhancement on the basis of electronic structure calculations. We show that (i) Br vacancies are the primary electron traps during the initial stage of thermalization of hot carriers, prior to hole capture by Ce dopants; (ii) isolated Br vacancies are associated with deep levels; (iii) Sr doping increases the Br vacancy concentration by several orders of magnitude; (iv) Sr{sub La} binds to V{sub Br} resulting in a stable neutral complex; and (v) association with Sr causes the deep vacancy level to move toward the conduction band edge. The latter is essential for reducing the effective carrier density available for Auger quenching during thermalization of hot carriers. Subsequent de-trapping of electrons from Sr{sub La}–V{sub Br} complexes can activate Ce dopants that have previously captured a hole leading to luminescence. This mechanism implies an overall reduction of Auger quenching of free carriers, which is expected to improve the linearity of the photon light yield with respect to the energy of incident electron or photon.

  17. Theoretical calculations on structural and electronic properties of BGaAsBi alloys

    NASA Astrophysics Data System (ADS)

    Aslan, Metin; Yalcin, Battal G.; Ustundag, Mehmet; Bagci, Sadik

    2015-11-01

    The structural and electronic properties of cubic B x Ga1- x As1- y Bi y alloys with bismuth (Bi) concentration of 0.0625, 0.125, 0.1875 and 0.25 are studied with various boron (B) compositions by means of density functional theory (DFT) within the Wu-Cohen (WC) exchange correlation potential based on generalized gradient approximation (GGA). For all studied alloy structures, we have implemented geometric optimization before the volume optimization calculations. The obtained equilibrium lattice constants and band gap of studied quaternary alloys are investigated for the first time in literature. While the lattice constant behavior changes linearly with boron concentration, increasing small amount of bismuth concentration alter the lattice constant nonlinearly. The present calculation shows that the band gap decreases with increasing bismuth concentration and direct band gap semiconductor alloy became an indirect band gap with increasing boron concentration. From the band offset calculation we have shown that increasing B and Bi concentration in host GaAs reduced the valance band offset in a heterostructure formed by GaAs and studied alloys.

  18. Combined First Principles Electronic Structure Calculations and Thermodynamic Study of Binary Alloys

    NASA Astrophysics Data System (ADS)

    Guo, Xiaoqing

    In the past decade, density functional theory (DFT), combined with the highly precise computational methods and the increasing computer power, has become a most successful tool to study the physical properties of atoms, molecules, solids, surfaces and disordered systems. In this dissertation, we present a common framework, based on the density functional theory, to study the electronic structure, structural stability and the phase equilibria of both ordered compounds and solid solution of the binary alloys which usually have very small energy differences. As an illustrative example, we have made a systematic study on the Al-Li alloys which have become promising low density, high strength aerospace materials. The Al-Li ordered compounds are calculated by the all electron self-consistent, full potential linearized augmented plane wave (FLAPW) method within the local density approximation. All the stable and metastable phases are correctly predicted due to the high precision of the method. The phase stability in Al-Li alloys can be understood by our assumption that the Li atoms basically transfer their valence electrons in between the Al bonds and the resultant strengthened bonds stabilize the Al-Li compounds. The unusually high elastic modulus of the Al-Li alloys is due to the increased anisotropic Al bonding (decrease of the Poisson's ratio) with increasing Li content. Very good agreement with experiment is obtained. To utilize the existing highly precise band calculation method, we describe the Al-Li solid solution by a supercell method based on the "theory of locality". The relatively small size of a supercell is shown to give a very good description of Al-rich Al-Li solid solution. A thermodynamic model is proposed, as a first step, to calculate the phase diagrams of the binary alloys. The grand partition function, constructed from volume-dependent internal energies obtained from local-density total-energy supercell calculations, permits the determination of the

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

    SciTech Connect

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

    2015-06-24

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

  20. First Principles Calculations of the Electronic Structure of ZrN Allotropes

    NASA Astrophysics Data System (ADS)

    Yin, Li-Chang; Saito, Riichiro

    2011-11-01

    The atomic structures and electronic properties of different ZrN allotropes, including face-centered cubic ZrN (B1 ZrN), hypothetic wurtzite (w) ZrN, and hypothetic two-dimensional (2D) and three-dimensional (3D) layered hexagonal (h) ZrN, are investigated by systematic first-principles calculations. Although the cohesive energy calculation indicates that the B1 ZrN is more stable than the hypothetic w-ZrN and h-ZrN, we suggest that the monolayer h-ZrN may be stable on some substrates. Charge population analysis shows that the polar, covalent bonding character appears between N atoms and Zr atoms for all ZrN allotropes involved in this paper. A Van Hove singularity (VHS) with a high density of states (DOS) locating at 0.2 eV above the Fermi level appears for monolayer h-ZrN, which results from a saddle point of the partially occupied Zr-dz^{2 energy bands due to lack of interlayer interaction. Such a VHS observed in the monolayer h-ZrN indicates that this hypothetic monolayer material might be a potential candidate for new superconducting material by electron doping.

  1. Electronic structures of halogen-doped Cu2O based on DFT calculations

    NASA Astrophysics Data System (ADS)

    Zhao, Zong-Yan; Yi, Juan; Zhou, Da-Cheng

    2014-01-01

    In order to construct p—n homojunction of Cu2O-based thin film solar cells that may increase its conversion efficiency, to synthesize n-type Cu2O with high conductivity is extremely crucial, and considered as a challenge in the near future. The doping effects of halogen on electronic structure of Cu2O have been investigated by density function theory calculations in the present work. Halogen dopants form donor levels below the bottom of conduction band through gaining or losing electrons, suggesting that halogen doping could make Cu2O have n-type conductivity. The lattice distortion, the impurity formation energy, the position, and the band width of donor level of Cu2O1-xHx (H = F, Cl, Br, I) increase with the halogen atomic number. Based on the calculated results, chlorine doping is an effective n-type dopant for Cu2O, owing to the lower impurity formation energy and suitable donor level.

  2. Accelerating Atomic Orbital-based Electronic Structure Calculation via Pole Expansion plus Selected Inversion

    SciTech Connect

    Lin, Lin; Chen, Mohan; Yang, Chao; He, Lixin

    2012-02-10

    We describe how to apply the recently developed pole expansion plus selected inversion (PEpSI) technique to Kohn-Sham density function theory (DFT) electronic structure calculations that are based on atomic orbital discretization. We give analytic expressions for evaluating charge density, total energy, Helmholtz free energy and atomic forces without using the eigenvalues and eigenvectors of the Kohn-Sham Hamiltonian. We also show how to update the chemical potential without using Kohn-Sham eigenvalues. The advantage of using PEpSI is that it has a much lower computational complexity than that associated with the matrix diagonalization procedure. We demonstrate the performance gain by comparing the timing of PEpSI with that of diagonalization on insulating and metallic nanotubes. For these quasi-1D systems, the complexity of PEpSI is linear with respect to the number of atoms. This linear scaling can be observed in our computational experiments when the number of atoms in a nanotube is larger than a few hundreds. Both the wall clock time and the memory requirement of PEpSI is modest. This makes it even possible to perform Kohn-Sham DFT calculations for 10,000-atom nanotubes on a single processor. We also show that the use of PEpSI does not lead to loss of accuracy required in a practical DFT calculation.

  3. Density functional calculations for structural, electronic, and magnetic properties of gadolinium-oxide clusters

    NASA Astrophysics Data System (ADS)

    Yuan, H. K.; Chen, H.; Tian, C. L.; Kuang, A. L.; Wang, J. Z.

    2014-04-01

    Gadolinium-oxide clusters in various sizes and stoichiometries have been systematically studied by employing the density functional theory with the generalized gradient approximation. The clusters in bulk stoichiometry are relatively more stable and their binding energies increase with the increasing size. Stoichiometric (Gd2O3)n clusters of n = 1-3 prefer cage-like structures, whereas the clusters of n = 4-30 prefer compact structures layered by wedge-like units and exhibit a rough feature toward the bulk-like arrangement with small disorders of atomic positions. The polyhedral-cages analogous to carbon-fullerenes are stable isomers yet not the minimum energy configurations. Their stabilities can be improved by embedding one oxygen atom or a suitable cage to form core-shell configurations. The mostly favored antiferromagnetic couplings between adjacent Gd atoms are nearly degenerated in energy with their ferromagnetic couplings, resulting in super-paramagnetic characters of gadolinium-oxide clusters. The Ruderman-Kittel-Kasuya-Yosida (RKKY)-type mechanism together with the superexchange-type mechanism plays cooperation role for the magnetic interactions in clusters. We present, as a function of n, calculated binding energies, ionization potential, electron affinity, and electronic dipole moment.

  4. Density functional calculations for structural, electronic, and magnetic properties of gadolinium-oxide clusters

    SciTech Connect

    Yuan, H. K.; Chen, H. Tian, C. L.; Kuang, A. L.; Wang, J. Z.

    2014-04-21

    Gadolinium-oxide clusters in various sizes and stoichiometries have been systematically studied by employing the density functional theory with the generalized gradient approximation. The clusters in bulk stoichiometry are relatively more stable and their binding energies increase with the increasing size. Stoichiometric (Gd{sub 2}O{sub 3}){sub n} clusters of n = 1–3 prefer cage-like structures, whereas the clusters of n = 4–30 prefer compact structures layered by wedge-like units and exhibit a rough feature toward the bulk-like arrangement with small disorders of atomic positions. The polyhedral-cages analogous to carbon-fullerenes are stable isomers yet not the minimum energy configurations. Their stabilities can be improved by embedding one oxygen atom or a suitable cage to form core-shell configurations. The mostly favored antiferromagnetic couplings between adjacent Gd atoms are nearly degenerated in energy with their ferromagnetic couplings, resulting in super-paramagnetic characters of gadolinium-oxide clusters. The Ruderman-Kittel-Kasuya-Yosida (RKKY)-type mechanism together with the superexchange-type mechanism plays cooperation role for the magnetic interactions in clusters. We present, as a function of n, calculated binding energies, ionization potential, electron affinity, and electronic dipole moment.

  5. GPAW - massively parallel electronic structure calculations with Python-based software.

    SciTech Connect

    Enkovaara, J.; Romero, N.; Shende, S.; Mortensen, J.

    2011-01-01

    Electronic structure calculations are a widely used tool in materials science and large consumer of supercomputing resources. Traditionally, the software packages for these kind of simulations have been implemented in compiled languages, where Fortran in its different versions has been the most popular choice. While dynamic, interpreted languages, such as Python, can increase the effciency of programmer, they cannot compete directly with the raw performance of compiled languages. However, by using an interpreted language together with a compiled language, it is possible to have most of the productivity enhancing features together with a good numerical performance. We have used this approach in implementing an electronic structure simulation software GPAW using the combination of Python and C programming languages. While the chosen approach works well in standard workstations and Unix environments, massively parallel supercomputing systems can present some challenges in porting, debugging and profiling the software. In this paper we describe some details of the implementation and discuss the advantages and challenges of the combined Python/C approach. We show that despite the challenges it is possible to obtain good numerical performance and good parallel scalability with Python based software.

  6. Bridging experiment and theory: A template for unifying NMR data and electronic structure calculations

    DOE PAGES

    Brown, David M. L.; Cho, Herman; de Jong, Wibe A.

    2016-02-09

    Here, the testing of theoretical models with experimental data is an integral part of the scientific method, and a logical place to search for new ways of stimulating scientific productivity. Often experiment/theory comparisons may be viewed as a workflow comprised of well-defined, rote operations distributed over several distinct computers, as exemplified by the way in which predictions from electronic structure theories are evaluated with results from spectroscopic experiments. For workflows such as this, which may be laborious and time consuming to perform manually, software that could orchestrate the operations and transfer results between computers in a seamless and automated fashionmore » would offer major efficiency gains. Such tools also promise to alter how researchers interact with data outside their field of specialization by, e.g., making raw experimental results more accessible to theorists, and the outputs of theoretical calculations more readily comprehended by experimentalists.« less

  7. Electronic Structure of ABC-stacked Multilayer Graphene and Trigonal Warping:A First Principles Calculation

    NASA Astrophysics Data System (ADS)

    Yelgel, Celal

    2016-04-01

    We present an extensive density functional theory (DFT) based investigation of the electronic structures of ABC-stacked N-layer graphene. It is found that for such systems the dispersion relations of the highest valence and the lowest conduction bands near the K point in the Brillouin zone are characterised by a mixture of cubic, parabolic, and linear behaviours. When the number of graphene layers is increased to more than three, the separation between the valence and conduction bands decreases up until they touch each other. For five and six layer samples these bands show flat behaviour close to the K point. We note that all states in the vicinity of the Fermi energy are surface states originated from the top and/or bottom surface of all the systems considered. For the trilayer system, N = 3, pronounced trigonal warping of the bands slightly above the Fermi level is directly obtained from DFT calculations.

  8. Half-metallic ferromagnetism and electronic structures in zinc blende YC: The first-principles calculations

    NASA Astrophysics Data System (ADS)

    Wu, Qiao; Wang, Zhonglong; Fan, Shuaiwei; Yao, Kailun

    2014-11-01

    Applying the first-principles with the generalized gradient approximation and the modified Becke and Johnson potential plus the generalized gradient approximation potential as exchange correlation potential, the electronic structures, half-metallicity and the cohesive energy for hypothetical zinc blende YC compound are calculated. Obtained results show that the zinc blende YC is typical half-metallic with a large half-metallic gap of 0.67(2) eV and magnetic moment of 1.00 μB per molecule. Magnetic moments mainly come from the p orbital of C atom, where p-d hybridization mechanism plays a dominating role in the formation of half-metallicity. The relatively stable ferromagnetic ground state, large half-metallic gap, the robust half-metallicity with respect to the lattice constant compression, and negative cohesive energy indicate zinc blende YC would be a promising half metallic ferromagnet.

  9. Analysis of the valence electronic structures and calculation of the physical properties of Fe, Co, and Ni

    NASA Astrophysics Data System (ADS)

    Wu, Wenxia; Xue, Zhiyong; Hong, Xing; Li, Xiumei; Guo, Yongquan

    2009-06-01

    The valence electronic structures of Fe, Co and Ni have been investigated with Empirical Electron Theory of Solids and Molecules. The magnetic moments, Curie temperature, cohesive energy and melting point have been calculated according to the valence electronic structure. These calculations fit the experimental data very well. Based on the calculations, the magnetic moments are proportional to the number of 3d magnetic electrons. Curie temperatures are related to the magnetic electrons and the bond lengths between magnetic atoms. Cohesive energies increase with the increase of the number of covalent electrons, and the decrease of the number of magnetic and dumb pair electrons. The melting point is mainly related to the number of covalent electron pairs distributed in the strongest bond. The contribution from the lattice electrons is very small, the dumb pair electrons weaken the melting point; however, the contribution to melting point of the magnetic electrons can be neglected. It reveals that the magnetic and thermal properties are closely related to the valence electronic structures, and the changes or transitions between the electrons obviously affect the physical properties.

  10. Accelerating atomic orbital-based electronic structure calculation via pole expansion and selected inversion

    NASA Astrophysics Data System (ADS)

    Lin, Lin; Chen, Mohan; Yang, Chao; He, Lixin

    2013-07-01

    We describe how to apply the recently developed pole expansion and selected inversion (PEXSI) technique to Kohn-Sham density function theory (DFT) electronic structure calculations that are based on atomic orbital discretization. We give analytic expressions for evaluating the charge density, the total energy, the Helmholtz free energy and the atomic forces (including both the Hellmann-Feynman force and the Pulay force) without using the eigenvalues and eigenvectors of the Kohn-Sham Hamiltonian. We also show how to update the chemical potential without using Kohn-Sham eigenvalues. The advantage of using PEXSI is that it has a computational complexity much lower than that associated with the matrix diagonalization procedure. We demonstrate the performance gain by comparing the timing of PEXSI with that of diagonalization on insulating and metallic nanotubes. For these quasi-1D systems, the complexity of PEXSI is linear with respect to the number of atoms. This linear scaling can be observed in our computational experiments when the number of atoms in a nanotube is larger than a few hundreds. Both the wall clock time and the memory requirement of PEXSI are modest. This even makes it possible to perform Kohn-Sham DFT calculations for 10 000-atom nanotubes with a sequential implementation of the selected inversion algorithm. We also perform an accurate geometry optimization calculation on a truncated (8, 0) boron nitride nanotube system containing 1024 atoms. Numerical results indicate that the use of PEXSI does not lead to loss of the accuracy required in a practical DFT calculation.

  11. A brief comparison between grid based real space algorithms andspectrum algorithms for electronic structure calculations

    SciTech Connect

    Wang, Lin-Wang

    2006-12-01

    Quantum mechanical ab initio calculation constitutes the biggest portion of the computer time in material science and chemical science simulations. As a computer center like NERSC, to better serve these communities, it will be very useful to have a prediction for the future trends of ab initio calculations in these areas. Such prediction can help us to decide what future computer architecture can be most useful for these communities, and what should be emphasized on in future supercomputer procurement. As the size of the computer and the size of the simulated physical systems increase, there is a renewed interest in using the real space grid method in electronic structure calculations. This is fueled by two factors. First, it is generally assumed that the real space grid method is more suitable for parallel computation for its limited communication requirement, compared with spectrum method where a global FFT is required. Second, as the size N of the calculated system increases together with the computer power, O(N) scaling approaches become more favorable than the traditional direct O(N{sup 3}) scaling methods. These O(N) methods are usually based on localized orbital in real space, which can be described more naturally by the real space basis. In this report, the author compares the real space methods versus the traditional plane wave (PW) spectrum methods, for their technical pros and cons, and the possible of future trends. For the real space method, the author focuses on the regular grid finite different (FD) method and the finite element (FE) method. These are the methods used mostly in material science simulation. As for chemical science, the predominant methods are still Gaussian basis method, and sometime the atomic orbital basis method. These two basis sets are localized in real space, and there is no indication that their roles in quantum chemical simulation will change anytime soon. The author focuses on the density functional theory (DFT), which is the

  12. The linearly scaling 3D fragment method for large scale electronic structure calculations

    SciTech Connect

    Zhao, Zhengji; Meza, Juan; Lee, Byounghak; Shan, Hongzhang; Strohmaier, Erich; Bailey, David; Wang, Lin-Wang

    2009-07-28

    The Linearly Scaling three-dimensional fragment (LS3DF) method is an O(N) ab initio electronic structure method for large-scale nano material simulations. It is a divide-and-conquer approach with a novel patching scheme that effectively cancels out the artificial boundary effects, which exist in all divide-and-conquer schemes. This method has made ab initio simulations of thousand-atom nanosystems feasible in a couple of hours, while retaining essentially the same accuracy as the direct calculation methods. The LS3DF method won the 2008 ACM Gordon Bell Prize for algorithm innovation. Our code has reached 442 Tflop/s running on 147,456 processors on the Cray XT5 (Jaguar) at OLCF, and has been run on 163,840 processors on the Blue Gene/P (Intrepid) at ALCF, and has been applied to a system containing 36,000 atoms. In this paper, we will present the recent parallel performance results of this code, and will apply the method to asymmetric CdSe/CdS core/shell nanorods, which have potential applications in electronic devices and solar cells.

  13. The Linearly Scaling 3D Fragment Method for Large Scale Electronic Structure Calculations

    SciTech Connect

    Zhao, Zhengji; Meza, Juan; Lee, Byounghak; Shan, Hongzhang; Strohmaier, Erich; Bailey, David; Wang, Lin-Wang

    2009-06-26

    The Linearly Scaling three-dimensional fragment (LS3DF) method is an O(N) ab initio electronic structure method for large-scale nano material simulations. It is a divide-and-conquer approach with a novel patching scheme that effectively cancels out the artificial boundary effects, which exist in all divide-and-conquer schemes. This method has made ab initio simulations of thousand-atom nanosystems feasible in a couple of hours, while retaining essentially the same accuracy as the direct calculation methods. The LS3DF method won the 2008 ACM Gordon Bell Prize for algorithm innovation. Our code has reached 442 Tflop/s running on 147,456 processors on the Cray XT5 (Jaguar) at OLCF, and has been run on 163,840 processors on the Blue Gene/P (Intrepid) at ALCF, and has been applied to a system containing 36,000 atoms. In this paper, we will present the recent parallel performance results of this code, and will apply the method to asymmetric CdSe/CdS core/shell nanorods, which have potential applications in electronic devices and solar cells.

  14. The linearly scaling 3D fragment method for large scale electronic structure calculations

    NASA Astrophysics Data System (ADS)

    Zhao, Zhengji; Meza, Juan; Lee, Byounghak; Shan, Hongzhang; Strohmaier, Erich; Bailey, David; Wang, Lin-Wang

    2009-07-01

    The linearly scaling three-dimensional fragment (LS3DF) method is an O(N) ab initio electronic structure method for large-scale nano material simulations. It is a divide-and-conquer approach with a novel patching scheme that effectively cancels out the artificial boundary effects, which exist in all divide-and-conquer schemes. This method has made ab initio simulations of thousand-atom nanosystems feasible in a couple of hours, while retaining essentially the same accuracy as the direct calculation methods. The LS3DF method won the 2008 ACM Gordon Bell Prize for algorithm innovation. Our code has reached 442 Tflop/s running on 147,456 processors on the Cray XT5 (Jaguar) at OLCF, and has been run on 163,840 processors on the Blue Gene/P (Intrepid) at ALCF, and has been applied to a system containing 36,000 atoms. In this paper, we will present the recent parallel performance results of this code, and will apply the method to asymmetric CdSe/CdS core/shell nanorods, which have potential applications in electronic devices and solar cells.

  15. Real Space Multigrid (RMG) Open Source Software Suite for Multi-Petaflops Electronic Structure Calculations

    NASA Astrophysics Data System (ADS)

    Briggs, Emil; Hodak, Miroslav; Lu, Wenchang; Bernholc, Jerry; Li, Yan

    RMG is a cross platform open source package for ab initio electronic structure calculations that uses real-space grids, multigrid pre-conditioning, and subspace diagonalization to solve the Kohn-Sham equations. The code has been successfully used for a wide range of problems ranging from complex bulk materials to multifunctional electronic devices and biological systems. RMG makes efficient use of GPU accelerators, if present, but does not require them. Recent work has extended GPU support to systems with multiple GPU's per computational node, as well as optimized both CPU and GPU memory usage to enable large problem sizes, which are no longer limited by the memory of the GPU board. Additional enhancements include increased portability, scalability and performance. New versions of the code are regularly released at sourceforge.net/projects/rmgdft/. The releases include binaries for Linux, Windows and MacIntosh systems, automated builds for clusters using cmake, as well as versions adapted to the major supercomputing installations and platforms.

  16. Structural study of methyl isonicotinate by gas phase electron diffraction combined with ab initio calculations

    NASA Astrophysics Data System (ADS)

    Kiyono, Hajime; Kuze, Nobuhiko; Fujiwara, Hideo; Takeuchi, Hiroshi; Egawa, Toru; Konaka, Shigehiro

    1996-02-01

    The molecular structure of methyl isonicotinate was studied by gas phase electron diffraction combined with ab initio calculations. The molecular skeleton was assumed to be planar. The determined values of principal structure parameters ( rg and ∠ α) are as follows: r( NC) = 1.343(5) Å, r( C…C) ring = 1.401(3) Å, r( Cγ C) = 1.499(9) Å, r( C O) = 1.205(5) Å, r( C( O) O) = 1.331(8) Å, r( OC Me) = 1.430(8) Å, = 1.103(10) Å, ∠CNC = 117.6(9)°, ∠C βC γC β = 118.7(9)°, ∠C β,trans C γC(O) = 118.6(12), ∠C γCO = 121.4(12)°, ∠C γCO = 114.2(10)°, ∠COC = 115.4(15)°, where angled brackets denote average values and C γ,trans denotes the carbon atom which is trans to the carbonyl oxygen atom. Values in parentheses are the estimated limits of error (3σ) referring to the last significant digit. The structure of the ring in methyl isonicotinate agrees with that of pyridine within experimental error. In contrast, the structure parameters of the COOCH 3 group are significantly different from those of methyl acrylate and methyl acetate. These differences have been discussed in terms of hyperconjugation and steric effects.

  17. Investigating the electronic structure of fluorite-structured oxide compounds: comparison of experimental EELS with first principles calculations

    SciTech Connect

    Aguiar, Jeff; Ramasse, Q. M.; Asta, Mark D.; Browning, Nigel D.

    2012-06-27

    Energy loss spectra from fluorite-structured ZrO2, CeO2, and UO2 compounds are compared with theoretical calculations based on density functional theory (DFT) and its extensions, including the use of Hubbard-U corrections (DFT + U) and hybrid functionals. Electron energy loss spectra (EELS) were obtained from each oxide using a scanning transmission electron microscope (STEM). The same spectra were computed within the framework of the full-potential linear augmented plane-wave (FLAPW) method. The theoretical and experimental EEL spectra are compared quantitatively using non-linear least squares peak fitting and a cross-correlation approach, with the best level of agreement between experiment and theory being obtained using the DFT + U and hybrid computational approaches.

  18. A Fast Parallel Algorithm for Selected Inversion of Structured Sparse Matrices with Application to 2D Electronic Structure Calculations

    SciTech Connect

    Lin, Lin; Yang, Chao; Lu, Jiangfeng; Ying, Lexing; E, Weinan

    2009-09-25

    We present an efficient parallel algorithm and its implementation for computing the diagonal of $H^-1$ where $H$ is a 2D Kohn-Sham Hamiltonian discretized on a rectangular domain using a standard second order finite difference scheme. This type of calculation can be used to obtain an accurate approximation to the diagonal of a Fermi-Dirac function of $H$ through a recently developed pole-expansion technique \\cite{LinLuYingE2009}. The diagonal elements are needed in electronic structure calculations for quantum mechanical systems \\citeHohenbergKohn1964, KohnSham 1965,DreizlerGross1990. We show how elimination tree is used to organize the parallel computation and how synchronization overhead is reduced by passing data level by level along this tree using the technique of local buffers and relative indices. We analyze the performance of our implementation by examining its load balance and communication overhead. We show that our implementation exhibits an excellent weak scaling on a large-scale high performance distributed parallel machine. When compared with standard approach for evaluating the diagonal a Fermi-Dirac function of a Kohn-Sham Hamiltonian associated a 2D electron quantum dot, the new pole-expansion technique that uses our algorithm to compute the diagonal of $(H-z_i I)^-1$ for a small number of poles $z_i$ is much faster, especially when the quantum dot contains many electrons.

  19. Calculated electronic structure and transport properties of La{sub .67}Ca{sub .33}MnO{sub 3}

    SciTech Connect

    Butler, W.H.; Zhang, X.G.; MacLaren, J.M.

    1995-12-31

    We have calculated the electronic structure, total energy, magnetic moments, and electrical resistivities of LaMnO{sub 3} and La{sub . 67}Ca{sub .33}MnO{sub 3} using mean field band theory. The magnetic and structural properties seems to be in good agreement with experiment. Calculations predict that La{sub .67}Ca{sub .33}MnO{sub 3} is metallic for the majority spins and semiconducting for the minority spins.

  20. Electronic structure and optical properties of TbPO4: Experiment and density functional theory calculations

    NASA Astrophysics Data System (ADS)

    Khadraoui, Z.; Horchani-Naifer, K.; Ferhi, M.; Ferid, M.

    2015-09-01

    Single crystals of TbPO4 were grown by high temperature solid-state reaction and identified by means of X-ray diffraction, infrared and Raman spectroscopies analysis. The electronic properties of TbPO4 such as the energy band structures, density of states were carried out using density functional theory (DFT). We have employed the LDA+U functional to treat the exchange correlation potential by solving Kohn-Sham equation. The calculated total and partial density of states indicate that the top of valance band is mainly built upon O-2p states and the bottom of the conduction band mostly originates from Tb-5d states. The population analysis indicates that the P-O bond was mainly covalent and Tb-O bond was mainly ionic. The emission spectrum, color coordinates and decay curve were employed to reveal the luminescence properties of TbPO4. Moreover, the optical properties including the dielectric function, absorption spectrum, refractive index, extinction coefficient, reflectivity and energy-loss spectrum are investigated and analyzed. The results are discussed and compared with the available experimental data.

  1. A Novel Gaussian-Sinc mixed Basis Set for Electronic Structure calculations

    NASA Astrophysics Data System (ADS)

    Jerke, Jonathan; Lee, Young; Tymczak, C. J.

    2015-03-01

    A Gaussian-Sinc mixed basis set for the computation of the electronic structure of atoms and molecules is presented. Excellent bases functions are known for ``core'' and ``valence'' separately, such as Gaussians for the ``core'' wave functions and Plane-waves for ``valance'' wave functions, but as yet no method is known that can accurately deal with both regimes in a single basis. A Gaussian-Sinc mixed basis can do both. This method resolves several issues such as: i) the Sincs basis spans the same space as the plane-waves basis, yet are semi-local enough to define all interaction elements including Exchange; ii) the Gaussians span the spherically symmetric core states and can be mixed with the Sinc functions in a computationally efficient methodology; iii) together, this mixed basis set is a flexible, computationally efficient and a highly accurate method for solving atomic and molecular problems. This methodology has been implemented within the Hartree-Fock level of theory within ultra-strong magnetic fields. To demonstrate the utility of this new method, we calculated the ground state Hartree-Fock energies to five digits accuracy in ultra strong magnetic fields for Helium to Neon, Molecular Hydrogen, Water, Carbon dioxide and Benzene. Welch Foundation (Grant J-1675), the ARO (Grant W911Nf-13-1-0162), the Texas Southern University High Performance Computing Center (http:/hpcc.tsu.edu/; Grant PHY-1126251) and NSF-CREST CRCN project (Grant HRD-1137732).

  2. Unexpected electronic structure of the alloyed and doped arsenene sheets: First-Principles calculations

    NASA Astrophysics Data System (ADS)

    Liu, Ming-Yang; Huang, Yang; Chen, Qing-Yuan; Cao, Chao; He, Yao

    2016-07-01

    We study the equilibrium geometry and electronic structure of alloyed and doped arsenene sheets based on the density functional theory calculations. AsN, AsP and SbAs alloys possess indirect band gap and BiAs is direct band gap. Although AsP, SbAs and BiAs alloyed arsenene sheets maintain the semiconducting character of pure arsenene, they have indirect-direct and semiconducting-metallic transitions by applying biaxial strain. We find that B- and N-doped arsenene render p-type semiconducting character, while C- and O-doped arsenene are metallic character. Especially, the C-doped arsenene is spin-polarization asymmetric and can be tuned into the bipolar spin-gapless semiconductor by the external electric field. Moreover, the doping concentration can effectively affect the magnetism of the C-doped system. Finally, we briefly study the chemical molecule adsorbed arsenene. Our results may be valuable for alloyed and doped arsenene sheets applications in mechanical sensors and spintronic devices in the future.

  3. Unexpected electronic structure of the alloyed and doped arsenene sheets: First-Principles calculations

    PubMed Central

    Liu, Ming-Yang; Huang, Yang; Chen, Qing-Yuan; Cao, Chao; He, Yao

    2016-01-01

    We study the equilibrium geometry and electronic structure of alloyed and doped arsenene sheets based on the density functional theory calculations. AsN, AsP and SbAs alloys possess indirect band gap and BiAs is direct band gap. Although AsP, SbAs and BiAs alloyed arsenene sheets maintain the semiconducting character of pure arsenene, they have indirect-direct and semiconducting-metallic transitions by applying biaxial strain. We find that B- and N-doped arsenene render p-type semiconducting character, while C- and O-doped arsenene are metallic character. Especially, the C-doped arsenene is spin-polarization asymmetric and can be tuned into the bipolar spin-gapless semiconductor by the external electric field. Moreover, the doping concentration can effectively affect the magnetism of the C-doped system. Finally, we briefly study the chemical molecule adsorbed arsenene. Our results may be valuable for alloyed and doped arsenene sheets applications in mechanical sensors and spintronic devices in the future. PMID:27373712

  4. Theoretical study of the electronic structure with dipole moment calculations of barium monofluoride

    NASA Astrophysics Data System (ADS)

    Tohme, Samir N.; Korek, Mahmoud

    2015-12-01

    The potential energy curves have been investigated for the 41 lowest doublet and quartet electronic states in the 2s+1Λ± representation below 55,000 cm-1 of the molecule BaF via CASSCF and MRCI (single and double excitations with Davidson correction) calculations. Twenty-five electronic states have been studied here theoretically for the first time. The crossing and avoided crossing of 20 doublet electronic states have been studied in the region 30,000-50,000 cm-1. The harmonic frequency ωe, the internuclear distance Re, the rotational constant Be, the electronic energy with respect to the ground state Te, and the permanent and transition dipole moments have been calculated in addition to static dipole polarizability of the ground state. By using the canonical functions approach, the eigenvalue Ev, the rotational constant Bv, and the abscissas of the turning points Rmin and Rmax have been calculated for the electronic states up to the vibrational level v=98. The comparison of these values with the theoretical results available in the literature shows a very good agreement.

  5. Calculation of Electron Trajectories

    1982-06-01

    EGUN, the SLAC Electron Trajectory Program, computes trajectories of charged particles in electrostatic and magnetostatic focusing systems including the effects of space charge and self-magnetic fields. Starting options include Child''s Law conditions on cathodes of various shapes, user-specified initial conditions for each ray, and a combination of Child''s Law conditions and user specifications. Either rectangular or cylindrically symmetric geometry may be used. Magnetic fields may be specified using arbitrary configuration of coils, or the outputmore » of a magnet program, such as Poisson, or by an externally calculated array of the axial fields.« less

  6. Hydrostatic Pressure Effects on Structural and Electronic Properties of ETN and PETN from First-Principles Calculations.

    PubMed

    Fedorov, Igor A; Fedorova, Tatyana P; Zhuravlev, Yuriy N

    2016-05-26

    We studied the structural and electronic properties of pentaerythritol tetranitrate (PETN) and erythritol tetranitrate (ETN) crystals within the framework of density functional theory with van der Waals interactions. The computed lattice parameters have good agreement with experimental data. Electronic and structural properties of the crystals under 0-20 GPa hydrostatic pressure were studied. The parameters of equations of state calculated from the theoretical data show good agreement with experiment within the studied pressure intervals. We have also calculated the detonation velocity and pressure. PMID:27128718

  7. Structural, electronic, optical and bonding properties of strontianite, SrCO3: First-principles calculations

    NASA Astrophysics Data System (ADS)

    Hu, Zuowei; Li, Yun; Zhang, Chuanyu; Ao, Bingyun

    2016-11-01

    The first-principles calculations are performed within the density functional theory to investigate the crystal structure, energy band structure, density of states, optical properties, and bonding properties of strontianite. The optimized structure parameters and bonding results with the generalized gradient approximation (GGA) functional and the localized density approximation (LDA) functional are in good agreement with the earlier experimental data. The band structure, density of states and chemical bonding of strontianite have been calculated and analyzed. The indirect band gap of strontianite is estimated to be ~4.45 eV (GGA) or ~4.24 eV (LDA). The absorption, reflectivity, refractive index and extinction coefficient have been calculated using the imaginary part of the dielectric function. The calculated results of the optical properties show that strontianite has an optical anisotropy along [100] (or [010]) and [010] polarization directions of incoming light. Furthermore, the calculated results of the density of states and Mulliken population indicate that the interactions among atoms are both ionic and covalent bonding in strontianite.

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

    SciTech Connect

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

    2014-09-14

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

  9. CYANOMETHANIMINE ISOMERS IN COLD INTERSTELLAR CLOUDS: INSIGHTS FROM ELECTRONIC STRUCTURE AND KINETIC CALCULATIONS

    SciTech Connect

    Vazart, Fanny; Latouche, Camille; Skouteris, Dimitrios; Barone, Vincenzo; Balucani, Nadia

    2015-09-10

    New insights into the formation of interstellar cyanomethanimine, a species of great relevance in prebiotic chemistry, are provided by electronic structure and kinetic calculations for the reaction CN + CH{sub 2} = NH. This reaction is a facile formation route of Z,E-C-cyanomethanimine, even under the extreme conditions of density and temperature typical of cold interstellar clouds. E-C-cyanomethanimine has been recently identified in Sgr B2(N) in the Green Bank Telescope (GBT) PRIMOS survey by P. Zaleski et al. and no efficient formation routes have been envisaged so far. The rate coefficient expression for the reaction channel leading to the observed isomer E-C-cyanomethanimine is 3.15 × 10-10 × (T/300){sup 0.152} × e{sup (−0.0948/T)}. According to the present study, the more stable Z-C-cyanomethanimine isomer is formed with a slightly larger yield (4.59 × 10{sup −10} × (T/300){sup 0.153} × e{sup (−0.0871/T)}. As the detection of E-isomer is favored due to its larger dipole moment, the missing detection of the Z-isomer can be due to the sensitivity limit of the GBT PRIMOS survey and the detection of the Z-isomer should be attempted with more sensitive instrumentation. The CN + CH{sub 2} = NH reaction can also play a role in the chemistry of the upper atmosphere of Titan where the cyanomethanimine products can contribute to the buildup of the observed nitrogen-rich organic aerosols that cover the moon.

  10. Electronic band structure calculation of GaNAsBi alloys and effective mass study

    NASA Astrophysics Data System (ADS)

    Habchi, M. M.; Ben Nasr, A.; Rebey, A.; El Jani, B.

    2013-11-01

    Electronic band structures of GaNxAs1-x-yBiy dilute nitrides-bismides have been determined theoretically within the framework of the band anticrossing (BAC) model and k ṡ p method. We have developed computer codes based on our extended BAC model, denoted (16 × 16), in which the dimension of the used states basis was equal to 16. We have investigated the band gap and the spin orbit splitting as a function of Bi composition for alloys lattice matched to GaAs. We have found that the substitution of As element by N and Bi impurities leads to a significant reduction of band gap energy by roughly 198 meV/%Bi. Meanwhile, spin orbit splitting increases by 56 meV/%Bi regardless N content. There is an excellent agreement between the model predictions and experiment reported in the literature. In addition, alloys compositions and oscillator strengths of transition energies have been calculated for GaNAsBi alloys which represent active zone of temperature insensitive (1.55 μm and 1.3 μm) wavelength laser diodes intended for optical fiber communications. A crossover at about 0.6 eV has occurred between Eg and Δso of GaN.039As.893Bi.068. When the quaternary is lattice mismatched to GaAs, resonance energy increases with Bi content if N content decreases. On the other hand, effective mass behavior of carriers at Γ point has been discussed with respect to alloy composition, k-directions and lattice mismatch.

  11. Voronoi-cell finite difference method for accurate electronic structure calculation of polyatomic molecules on unstructured grids

    SciTech Connect

    Son, Sang-Kil

    2011-03-01

    We introduce a new numerical grid-based method on unstructured grids in the three-dimensional real-space to investigate the electronic structure of polyatomic molecules. The Voronoi-cell finite difference (VFD) method realizes a discrete Laplacian operator based on Voronoi cells and their natural neighbors, featuring high adaptivity and simplicity. To resolve multicenter Coulomb singularity in all-electron calculations of polyatomic molecules, this method utilizes highly adaptive molecular grids which consist of spherical atomic grids. It provides accurate and efficient solutions for the Schroedinger equation and the Poisson equation with the all-electron Coulomb potentials regardless of the coordinate system and the molecular symmetry. For numerical examples, we assess accuracy of the VFD method for electronic structures of one-electron polyatomic systems, and apply the method to the density-functional theory for many-electron polyatomic molecules.

  12. Nonrelativistic structure calculations of two-electron ions in a strongly coupled plasma environment

    SciTech Connect

    Bhattacharyya, S.; Saha, J. K.; Mukherjee, T. K.

    2015-04-01

    In this work, the controversy between the interpretations of recent measurements on dense aluminum plasma created with the Linac coherent light source (LCLS) x-ray free electron laser (FEL) and the Orion laser has been addressed. In both kinds of experiments, heliumlike and hydrogenlike spectral lines are used for plasma diagnostics. However, there exist no precise theoretical calculations for He-like ions within a dense plasma environment. The strong need for an accurate theoretical estimate for spectral properties of He-like ions in a strongly coupled plasma environment leads us to perform ab initio calculations in the framework of the Rayleigh-Ritz variation principle in Hylleraas coordinates where an ion-sphere potential is used. An approach to resolve the long-drawn problem of numerical instability for evaluating two-electron integrals with an extended basis inside a finite domain is presented here. The present values of electron densities corresponding to the disappearance of different spectral lines obtained within the framework of an ion-sphere potential show excellent agreement with Orion laser experiments in Al plasma and with recent theories. Moreover, this method is extended to predict the critical plasma densities at which the spectral lines of H-like and He-like carbon and argon ions disappear. Incidental degeneracy and level-crossing phenomena are being reported for two-electron ions embedded in strongly coupled plasma. Thermodynamic pressure experienced by the ions in their respective ground states inside the ion spheres is also reported.

  13. Electron correlation and relativistic effects in atomic structure calculations of Th+, Th2+ ions

    NASA Astrophysics Data System (ADS)

    Roy, S. K.; Prasad, Rajendra; Datta, Sambhu N.; Chandra, P.

    2012-10-01

    Relativistic two-component ab initio calculations through second-order Douglas-Kroll-Hess (DKH2) transformation are performed on Th+ and Th2+ ions. Spin-orbit-free calculations are done at SA-CASSCF and MS-CASPT2 levels. Spin-orbit coupled states are studied using effective mean-field operator. Spin-orbit states of Th+, below 23 000 cm-1 are compared with experimental values. Relative separations between various energy levels depend on the amount of electron correlation included in the calculation. For Th2+, spin-orbit energy levels below 20 000 cm-1 agree well with the experimental levels. Transition properties of several spin-orbit states in case of Th2+ ion are predicted.

  14. First principle calculations of structural phase transition and electronic properties in AmTe

    NASA Astrophysics Data System (ADS)

    Pataiya, Jagdeesh; Aynyas, Mahendra; Makode, C.; Singh, A.; Sanyal, S. P.

    2015-06-01

    The tight-binding linear muffin-tin orbital (TB-LMTO) with in the local density approximation is used to calculate total energy, lattice parameters, bulk modulus, density of states and energy band structure of americium telluride at ambient as well as at high pressure. It is found that AmTe is stable in NaCl - type structure under ambient pressure. The phase transition pressure was found to be 15.0 GPa from NaCl-type (B1-phase) structure to CsCl-type (B2-phase) structure for this compound. From energy band diagram it is observed that AmTe exhibit metallic behaviour. The calculated ground state properties such as lattice parameters and bulk modulus are in general good agreement with the available results.

  15. First principle calculations of structural phase transition and electronic properties in AmTe

    SciTech Connect

    Pataiya, Jagdeesh Makode, C.; Aynyas, Mahendra; Singh, A.; Sanyal, S. P.

    2015-06-24

    The tight-binding linear muffin-tin orbital (TB-LMTO) with in the local density approximation is used to calculate total energy, lattice parameters, bulk modulus, density of states and energy band structure of americium telluride at ambient as well as at high pressure. It is found that AmTe is stable in NaCl – type structure under ambient pressure. The phase transition pressure was found to be 15.0 GPa from NaCl-type (B{sub 1}-phase) structure to CsCl-type (B{sub 2}-phase) structure for this compound. From energy band diagram it is observed that AmTe exhibit metallic behaviour. The calculated ground state properties such as lattice parameters and bulk modulus are in general good agreement with the available results.

  16. Quantum-chemical calculations and electron diffraction study of the equilibrium molecular structure of vitamin K3

    NASA Astrophysics Data System (ADS)

    Khaikin, L. S.; Tikhonov, D. S.; Grikina, O. E.; Rykov, A. N.; Stepanov, N. F.

    2014-05-01

    The equilibrium molecular structure of 2-methyl-1,4-naphthoquinone (vitamin K3) having C s symmetry is experimentally characterized for the first time by means of gas-phase electron diffraction using quantum-chemical calculations and data on the vibrational spectra of related compounds.

  17. Molecular structure of cotinine studied by gas electron diffraction combined with theoretical calculations

    NASA Astrophysics Data System (ADS)

    Takeshima, Tsuguhide; Takeuchi, Hiroshi; Egawa, Toru; Konaka, Shigehiro

    2007-09-01

    The molecular structure of cotinine (( S)-1-methyl-5-(3-pyridinyl)-2-pyrrolidinone), the major metabolite of nicotine, has been determined at about 182 °C by gas electron diffraction combined with MP2 and DFT calculations. The diffraction data are consistent with the existence of the (ax, sc), (ax, ap), (eq, sp) and (eq, ap) conformers, where ax and eq indicate the configuration of the pyrrolidinone ring by means of the position (axial and equatorial) of the pyridine ring, and sc, sp and ap distinguish the isomers arising from the internal rotation around the bond connecting the two rings. The (CH 3)NCCC(N) dihedral angles, ϕ, of the (ax, sc) and (eq, sp) conformers were determined independently to be 158(12)° and 129(13)°, respectively, where the numbers in parentheses are three times the standard errors, 3 σ. According to the MP2 calculations, the corresponding dihedral angles for the (ax, ap) and (eq, ap) conformers were assumed to differ by 180° from their syn counterparts. The ratios x(ax, sc)/ x(ax, ap) and x(eq, sp)/ x(eq, ap) were taken from the theoretically estimated free energy differences, Δ G, where x is the abundance of the conformer. The resultant abundances of (ax, sc), (ax, ap), (eq, sp) and (eq, ap) conformers are 34(6)%, 21% (d.p.), 28% (d.p.), and 17% (d.p.), respectively, where d.p. represents dependent parameters. The determined structural parameters ( rg (Å) and ∠ α (°)) of the most abundant conformer, (ax, sc), are as follows: r(N sbnd C) pyrrol = 1.463(5); r(N sbnd C methyl) = 1.457(←); r(N sbnd C( dbnd O)) = 1.384(12); r(C dbnd O) = 1.219(5); < r(C sbnd C) pyrrol> = 1.541(3); r(C pyrrolsbnd C pyrid) = 1.521(←); < r(C sbnd C) pyrid> = 1.396(2); < r(C sbnd N) pyrid> = 1.343(←); ∠(CNC) pyrrol = 113.9(11); ∠CCC pyrrol(-C pyrid) = 103.6(←); ∠NCO = 124.1(13); ∠NC pyrrolC pyrid = 113.1(12); ∠C pyrrolC pyrrolC pyrid = 113.3(←); ∠(CNC) pyrid = 117.1(2); <∠(NCC) pyrid> = 124.4(←); ∠C methylNC( dbnd O) =

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

    SciTech Connect

    Hegde, Ganesh Bowen, R. Chris

    2015-10-15

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

  19. Dielectric-dependent Density Functionals for Accurate Electronic Structure Calculations of Molecules and Solids

    NASA Astrophysics Data System (ADS)

    Skone, Jonathan; Govoni, Marco; Galli, Giulia

    Dielectric-dependent hybrid [DDH] functionals have recently been shown to yield highly accurate energy gaps and dielectric constants for a wide variety of solids, at a computational cost considerably less than standard GW calculations. The fraction of exact exchange included in the definition of DDH functionals depends (self-consistently) on the dielectric constant of the material. In the present talk we introduce a range-separated (RS) version of DDH functionals where short and long-range components are matched using material dependent, non-empirical parameters. Comparing with state of the art GW calculations and experiment, we show that such RS hybrids yield accurate electronic properties of both molecules and solids, including energy gaps, photoelectron spectra and absolute ionization potentials. This work was supported by NSF-CCI Grant Number NSF-CHE-0802907 and DOE-BES.

  20. Indo Mo calculations of the electronic structures of pyrrole, imidazole, and derivatives

    NASA Astrophysics Data System (ADS)

    Pachler, Klaus G. R.; Pachter, Ruth

    INDO MO calculations on a series of N-substituted pyrroles and imidazoles have been analysed for substituent effects. Some of the basic characteristics of the σ I and or parameters are reflected in the calculated electron densities of the compounds studied. For example, good correlations are obtained between Δ qσN(1)/ΣΔ qσ parameters and σ I for the —R substituted compounds, as well as between ΣΔ qπ values and σ Ro for the +R derivatives. The +R substituents lead to an increased localization of the π-bonds, whereas —R substituted derivatives show an increased delocalization, i.e., the π-bond orders across C(2)-C(3) [or C(2)-N(3)] and C(4)-C(5) decrease and those across other bonds in the ring increase.

  1. Structural, electronic, thermodynamical and charge transfer properties of Chloramphenicol Palmitate using vibrational spectroscopy and DFT calculations

    NASA Astrophysics Data System (ADS)

    Mishra, Rashmi; Srivastava, Anubha; Sharma, Anamika; Tandon, Poonam; Baraldi, Cecilia; Gamberini, Maria Christina

    2013-01-01

    The global problem of advancing bacterial resistance to newer drugs has led to renewed interest in the use of Chloramphenicol Palmitate (C27H42Cl2N2O6) [Palmitic acid alpha ester with D-threo-(-),2-dichloro-N-(beta-hydroxy-alpha-(hydroxymethyl)-p-nitrophenethyl)acetamide also known as Detereopal]. The characterization of the three polymorphic forms of Chloramphenicol Palmitate (CPP) was done spectroscopically by employing FT-IR and FT-Raman techniques. The equilibrium geometry, various bonding features, and harmonic wavenumbers have been investigated for most stable form A with the help of DFT calculations and a good correlation was found between experimental data and theoretical values. Electronic properties have been analyzed employing TD-DFT for both gaseous and solvent phase. The theoretical calculation of thermodynamical properties along with NBO analysis has also been performed to have a deep insight into the molecule for further applications.

  2. The Electronic Structure and Formation Energies of Ni-doped CuAlO2 by Density Functional Theory Calculation

    NASA Astrophysics Data System (ADS)

    Xu, Ying; Li, Fei; Sheng, Wei; Nie, Guo-Zheng; Yuan, Ding-Wang

    2014-03-01

    The electronic structure and formation energies of Ni-doped CuAlO2 are calculated by first-principles calculations. Our results show that Ni is good for p-type doping in CuAlO2. When Ni is doped into CuAlO2, it prefers to substitute Al-site. NiAl is a shallow acceptor, while NiCu is a deep acceptor and its formation energy is high. Further electronic structure calculations show that strong hybridization happens between Ni-3d and O-2p states for Ni substituting Al-site, while localized Ni-3d states are found for Ni substituting Cu-site.

  3. Structural determination of vanillin, isovanillin and ethylvanillin by means of gas electron diffraction and theoretical calculations

    NASA Astrophysics Data System (ADS)

    Egawa, Toru; Kameyama, Akiyo; Takeuchi, Hiroshi

    2006-08-01

    The molecular structures of vanillin (4-hydroxy-3-methoxybenzaldehyde), isovanillin (3-hydroxy-4-methoxybenzaldehyde) and ethylvanillin (3-ethoxy-4-hydroxybenzaldehyde) were determined by means of gas electron diffraction. Among them, vanillin and ethylvanillin have a vanilla odor but isovanillin smells differently. The nozzle temperatures were 125, 173 and 146 °C, for vanillin, isovanillin and ethylvanillin, respectively. The results of MP2 and B3LYP calculations with the 6-31G** basis set were used as supporting information. The MP2 calculations predicted that vanillin and isovanillin have two stable conformers and ethylvanillin has four stable conformers. The electron diffraction data were found to be consistent with these conformational compositions. The determined structural parameters ( rg and ∠ α) of vanillin are as follows: < r(C-C) ring>=1.397(4) Å; r(C 1-C aldehyde)=1.471(←) Å; r(C 3-O Me)=1.374(9) Å; r(C 4-O H)=1.361(←) Å; r(O-C Me)=1.428(←) Å; r(C dbnd6 O)=1.214(8) Å; < r(C-H)>=1.110(11) Å; r(O-H)=0.991(←) Å; ∠C 6-C 1-C 2=120.6(2)°; ∠C 1-C 2-C 3=118.8(←)°; ∠C 1-C 6-C 5=120.1(←)°; ∠C 2-C 1-C aldehyde=122.7(18)°; ∠C 1-C dbnd6 O=119.4(16)°; ∠C 4-C 3-O Me=112.2(12)°; ∠C 3-C 4-O H=119.1(←)°; ∠C 3-O-C=121.7(29)°. Those of isovanillin are as follows: < r(C-C) ring>=1.402(4) Å; r(C 1-C aldehyde)=1.479(←) Å; r(C 4-O Me)=1.369(9) Å; r(C 3-O H)=1.357(←) Å; r(O-C Me)=1.422(←) Å; r(C dbnd6 O)=1.221(9) Å; < r(C-H)>=1.114(14) Å; r(O-H)=0.995(←) Å; ∠C 6-C 1-C 2=120.2(3)°; ∠C 1-C 2-C 3=119.0(←)°; ∠C 1-C 6-C 5=119.9(←)°; ∠C 2-C 1-C aldehyde=124.6(25)°; ∠C 1-C dbnd6 O=121.3(24)°; ∠C 3-C 4-O Me=114.4(12)°; ∠C 4-C 3-O H=121.2(←)°; ∠C 4-O-C=123.8(26)°. Those of ethylvanillin are as follows: < r(C-C) ring>=1.397(6) Å; r(C 1-C aldehyde)=1.471(←) Å; r(C 3-O Et)=1.365(13) Å; r(C 4-O H)=1.352(←) Å; r(O-C Et)=1.427(←) Å; r(C-C Et)=1.494(21) Å; r(C dbnd6 O)=1.206(9) Å; < r

  4. Electronic structures and magnetism for carbon doped CdSe: Modified Becke-Johnson density functional calculations

    NASA Astrophysics Data System (ADS)

    Fan, S. W.; Song, T.; Huang, X. N.; Yang, L.; Ding, L. J.; Pan, L. Q.

    2016-09-01

    Utilizing the full potential linearized augment plane wave method, the electronic structures and magnetism for carbon doped CdSe are investigated. Calculations show carbon substituting selenium could induce CdSe to be a diluted magnetic semiconductor. Single carbon dopant could induce 2.00 μB magnetic moment. Electronic structures show the long-range ferromagnetic coupling mainly originates from the p-d exchange-like p-p coupling interaction. Positive chemical pair interactions indicate carbon dopants would form homogeneous distribution in CdSe host. The formation energy implies the non-equilibrium fabricated technology is necessary during the samples fabricated.

  5. Electronic structures of Stone-Wales defective chiral (6,2) silicon carbide nanotubes: First-principles calculations

    NASA Astrophysics Data System (ADS)

    Song, Jiuxu; Liu, Hongxia; Guo, Yingna; Zhu, Kairan

    2015-11-01

    By using first-principle calculations based on density functional theory, the geometries and electronic structures of the Stone-Wales defective chiral (6,2) silicon carbide nanotubes (SiCNTs) are investigated. Independent on their orientations, Stone-Wales defects form two asymmetric pentagons and heptagons coupled in pairs (5-7-7-5) and a defect energy level in the band gap of the SiCNT. By applying transverse electric fields, significant differences in the electronic structures of the defective (6,2) SiCNTs are achieved, which may provide the foundation of identifying the orientation of Stone-Wales defects in chiral SiCNTs.

  6. Phase stability, electronic structure and equation of state of cubic TcN from first-principles calculations

    NASA Astrophysics Data System (ADS)

    Song, T.; Ma, Q.; Sun, X. W.; Liu, Z. J.; Fu, Z. J.; Wei, X. P.; Wang, T.; Tian, J. H.

    2016-09-01

    The phase transition, electronic band structure, and equation of state (EOS) of cubic TcN are investigated by first-principles pseudopotential method based on density-functional theory. The calculated enthalpies show that TcN has a transformation between zincblende and rocksalt phases and the pressure determined by the relative enthalpy is 32 GPa. The calculated band structure indicates the metallic feature and it might make cubic TcN a better candidate for hard materials. Particular attention is paid to the predictions of volume, bulk modulus and its pressure derivative which play a central role in the formulation of approximate EOSs using the quasi-harmonic Debye model.

  7. First-principles Electronic Structure Calculations for Scintillation Phosphor Nuclear Detector Materials

    NASA Astrophysics Data System (ADS)

    Canning, Andrew

    2013-03-01

    Inorganic scintillation phosphors (scintillators) are extensively employed as radiation detector materials in many fields of applied and fundamental research such as medical imaging, high energy physics, astrophysics, oil exploration and nuclear materials detection for homeland security and other applications. The ideal scintillator for gamma ray detection must have exceptional performance in terms of stopping power, luminosity, proportionality, speed, and cost. Recently, trivalent lanthanide dopants such as Ce and Eu have received greater attention for fast and bright scintillators as the optical 5d to 4f transition is relatively fast. However, crystal growth and production costs remain challenging for these new materials so there is still a need for new higher performing scintillators that meet the needs of the different application areas. First principles calculations can provide a useful insight into the chemical and electronic properties of such materials and hence can aid in the search for better new scintillators. In the past there has been little first-principles work done on scintillator materials in part because it means modeling f electrons in lanthanides as well as complex excited state and scattering processes. In this talk I will give an overview of the scintillation process and show how first-principles calculations can be applied to such systems to gain a better understanding of the physics involved. I will also present work on a high-throughput first principles approach to select new scintillator materials for fabrication as well as present more detailed calculations to study trapping process etc. that can limit their brightness. This work in collaboration with experimental groups has lead to the discovery of some new bright scintillators. Work supported by the U.S. Department of Homeland Security and carried out under U.S. Department of Energy Contract no. DE-AC02-05CH11231 at Lawrence Berkeley National Laboratory.

  8. The use of quadratic forms in the calculation of ground state electronic structures

    SciTech Connect

    Keller, Jaime; Weinberger, Peter

    2006-08-15

    There are many examples in theoretical physics where a fundamental quantity can be considered a quadratic form {rho}={sigma}{sub i}{rho}{sub i}=vertical bar {psi} vertical bar{sup 2} and the corresponding linear form {psi}={sigma}{sub i}{psi}{sub i} is highly relevant for the physical problem under study. This, in particular, is the case of the density and the wave function in quantum mechanics. In the study of N-identical-fermion systems we have the additional feature that {psi} is a function of the 3N configuration space coordinates and {rho} is defined in three-dimensional real space. For many-electron systems in the ground state the wave function and the Hamiltonian are to be expressed in terms of the configuration space (CS), a replica of real space for each electron. Here we present a geometric formulation of the CS, of the wave function, of the density, and of the Hamiltonian to compute the electronic structure of the system. Then, using the new geometric notation and the indistinguishability and equivalence of the electrons, we obtain an alternative computational method for the ground state of the system. We present the method and discuss its usefulness and relation to other approaches.

  9. Molecule-optimized basis sets and Hamiltonians for accelerated electronic structure calculations of atoms and molecules.

    PubMed

    Gidofalvi, Gergely; Mazziotti, David A

    2014-01-16

    Molecule-optimized basis sets, based on approximate natural orbitals, are developed for accelerating the convergence of quantum calculations with strongly correlated (multireferenced) electrons. We use a low-cost approximate solution of the anti-Hermitian contracted Schrödinger equation (ACSE) for the one- and two-electron reduced density matrices (RDMs) to generate an approximate set of natural orbitals for strongly correlated quantum systems. The natural-orbital basis set is truncated to generate a molecule-optimized basis set whose rank matches that of a standard correlation-consistent basis set optimized for the atoms. We show that basis-set truncation by approximate natural orbitals can be viewed as a one-electron unitary transformation of the Hamiltonian operator and suggest an extension of approximate natural-orbital truncations through two-electron unitary transformations of the Hamiltonian operator, such as those employed in the solution of the ACSE. The molecule-optimized basis set from the ACSE improves the accuracy of the equivalent standard atom-optimized basis set at little additional computational cost. We illustrate the method with the potential energy curves of hydrogen fluoride and diatomic nitrogen. Relative to the hydrogen fluoride potential energy curve from the ACSE in a polarized triple-ζ basis set, the ACSE curve in a molecule-optimized basis set, equivalent in size to a polarized double-ζ basis, has a nonparallelity error of 0.0154 au, which is significantly better than the nonparallelity error of 0.0252 au from the polarized double-ζ basis set.

  10. Plane-wave DFT-LDA calculation of the electronic structure and absorption spectrum of copper

    NASA Astrophysics Data System (ADS)

    Marini, Andrea; Onida, Giovanni; del Sole, Rodolfo

    2001-11-01

    We present an accurate, first-principles study of the electronic structure and absorption spectrum of bulk copper within density functional theory in the local density approximation, including the study of intraband transitions. We construct norm-conserving pseudopotentials (PP's) including the 3d shell (and optionally the underlying 3s and 3p shells) in the valence and requiring a relatively small plane-wave basis (60 and 140 Ry cutoff, respectively). As a consequence, these PP's are strongly nonlocal, yielding macroscopically wrong results in the absorption spectrum when momentum matrix elements are computed naively. Our results are compared with experimental photoemission, absorption, and electron energy loss data, and suggest nontrivial self-energy effects in the quasiparticle spectrum of Cu.

  11. Bonding in elemental boron: a view from electronic structure calculations using maximally localized Wannier functions

    NASA Astrophysics Data System (ADS)

    Ogitsu, Tadashi; Gygi, Francois; Reed, John; Schwegler, Eric; Galli, Giulia

    2007-03-01

    Boron exhibits the most complex structure of all elemental solids, with more than 300 atoms per unit cell arranged in interconnecting icosahedra, and some crystallographic positions occupied with a probability of less than one. The precise determination of the ground state geometry of boron---the so-called β-boron structure--has been elusive and its electronic and bonding properties have been difficult to rationalize. Using lattice model Monte Carlo optimization techniques and ab-initio simulations, we have shown that a defective, quasi-ordered β solid is the most stable structure at zero as well as finite T. In the absence of partially occupied sites (POS), the perfect β-boron crystal is unstable; the presence of POS lower its internal energy below that of an ordered α-phase, not mere an entropic effect. We present a picture of the intricate and unique bonding in boron based on maximally localized Wannier (MLWF) functions, which indicates that the presence of POS provides a subtle, yet essential spatial balance between electron deficient and fully saturated bonds. This work was performed under the auspices of the U.S. Dept. of Energy at the University of California/ LLNL under contract no. W-7405-Eng-48.

  12. Structural, electronic, mechanical, and thermodynamic properties of UN 2: Systematic density functional calculations

    NASA Astrophysics Data System (ADS)

    Lu, Yong; Wang, Bao-Tian; Li, Rong-Wu; Shi, Hong-Liang; Zhang, Ping

    2011-03-01

    We have performed a comparative study of UN 2 and β-U 2N 3using the generalized gradient approximation (GGA) and the GGA + U approaches based on the density functional theory (DFT). The lattice parameters obtained from the GGA + U calculations can be ameliorated appreciably, however, the density of states (DOS) is insensitive to Hubbard U for both compounds. Our Bader analysis shows that the effective charges increase with decreasing U:N ratio (from UN to UN 2). The f electrons in UN 2 and β-U 2N 3 seem less localized than that in UN phase. The effects of Hubbard U on mechanical properties is evident, while the phonon dispersion depends weakly on the changes of Hubbard U. Based on our phonon dispersion data, the lattice vibration energy, thermal expansion, and specific heat are obtained by utilizing the quasiharmonic approximation (QHA).

  13. Electronic structure calculations of PbS quantum rods and tubes

    SciTech Connect

    Pimachev, Artem; Dahnovsky, Yuri

    2014-01-28

    We study absorption spectra, optical and HOMO-LUMO gaps, and the density of states for PbS quantum rods (QRs) and tubes (QTs). We find some similarities and also differences in QR and QT properties. For both QRs and QTs, the optical and HOMO-LUMO gaps reach the plateaus for small lengths. We find that tubes are as stable as rods. The optical spectra exhibit a peak that can be due to the electron-hole interaction or be a prototype of an S{sub e}–S{sub h} transition in the effective mass approximation. We also calculate the density of states by the density functional theory (DFT) and time-dependent density functional theory (TDDFT) methods. The TDDFT density of states function is shifted towards the red side by 0.5 eV indicating the strong e-h interaction.

  14. Many-body electronic structure calculations of Eu-doped ZnO

    NASA Astrophysics Data System (ADS)

    Lorke, M.; Frauenheim, T.; da Rosa, A. L.

    2016-03-01

    The formation energies and electronic structure of europium-doped zinc oxide has been determined using DFT and many-body G W methods. In the absence of intrisic defects, we find that the europium-f states are located in the ZnO band gap with europium possessing a formal charge of 2+. On the other hand, the presence of intrinsic defects in ZnO allows intraband f -f transitions otherwise forbidden in atomic europium. This result corroborates with recently observed photoluminescence in the visible red region S. Geburt et al. [Nano Lett. 14, 4523 (2014), 10.1021/nl5015553].

  15. Synthesis, structure, and electronic structure calculation of a new centrosymmetric borate Pb2O[BO2(OH)] based on anion-centered OPb4 tetrahedra

    NASA Astrophysics Data System (ADS)

    Sun, Feng; Wang, Li; Stoumpos, Constantinos C.

    2016-08-01

    The synthesis, structure, and characterization of a new centrosymmetric borate Pb2O[BO2(OH)] based on anion-centered OPb4 tetrahedra are reported. Pb2O[BO2(OH)] crystallizes in monoclinic space group C2/m with a=12.725(7) Å, b=5.698(3) Å, c=7.344(4) Å, β=116.277(6)°. The electronic band structure and density of states of Pb2O[BO2(OH)] have been calculated via the density functional theory (DFT). Electron density difference calculation indicates that lone-pair electrons of Pb2+ cation should be stereoactive.

  16. Refined energetic ordering for sulphate-water (n = 3-6) clusters using high-level electronic structure calculations

    NASA Astrophysics Data System (ADS)

    Lambrecht, Daniel S.; McCaslin, Laura; Xantheas, Sotiris S.; Epifanovsky, Evgeny; Head-Gordon, Martin

    2012-10-01

    This work reports refinements of the energetic ordering of the known low-energy structures of sulphate-water clusters ? (n = 3-6) using high-level electronic structure methods. Coupled cluster singles and doubles with perturbative triples (CCSD(T)) is used in combination with an estimate of basis set effects up to the complete basis set limit using second-order Møller-Plesset theory. Harmonic zero-point energy (ZPE), included at the B3LYP/6-311 + + G(3df,3pd) level, was found to have a significant effect on the energetic ordering. In fact, we show that the energetic ordering is a result of a delicate balance between the electronic and vibrational energies. Limitations of the ZPE calculations, both due to electronic structure errors, and use of the harmonic approximation, probably constitute the largest remaining errors. Due to the often small energy differences between cluster isomers, and the significant role of ZPE, deuteration can alter the relative energies of low-lying structures, and, when it is applied in conjunction with calculated harmonic ZPEs, even alters the global minimum for n = 5. Experiments on deuterated clusters, as well as more sophisticated vibrational calculations, may therefore be quite interesting.

  17. 57Fe Mössbauer spectroscopy, X-ray single-crystal diffractometry, and electronic structure calculations on natural alexandrite

    NASA Astrophysics Data System (ADS)

    Weber, Sven-Ulf; Grodzicki, Michael; Lottermoser, Werner; Redhammer, Günther J.; Tippelt, Gerold; Ponahlo, Johann; Amthauer, Georg

    2007-09-01

    Natural alexandrite Al2BeO4:Cr from Malyshevo near Terem Tschanka, Sverdlovsk, Ural, Russia, has been characterized by 57Fe Mössbauer spectroscopy, electron microprobe, X-ray single-crystal diffractometry and by electronic structure calculations in order to determine oxidation state and location of iron. The sample contains 0.3 wt% of total iron oxide. The 57Fe Mössbauer spectrum can be resolved into three doublets. Two of them with hyperfine parameters typical for octahedrally coordinated high-spin Fe3+ and Fe2+, respectively, are assigned to iron substituting for Al in the octahedral M2-site. The third doublet is attributed to Fe3+ in hematite. Electronic structure calculations in the local spin density approximation are in reasonable agreement with experimental data provided that expansion and/or distortion of the coordination octahedra are presumed upon iron substitution. The calculated hyperfine parameters of Fe3+ are almost identical for the M1 and M2 positions, but the calculated ligand-field splitting is by far too large for high-spin Fe3+ on M1.

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

    NASA Astrophysics Data System (ADS)

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

    2015-03-01

    Ab initio techniques have been applied to investigate the electronic structure of the LiYb molecule. The potential energy curves have been computed in the Born-Oppenheimer approximation for the ground and 29 low-lying doublet and quartet excited electronic states. Complete active space self-consistent field, multi-reference configuration interaction, and Rayleigh Schrödinger perturbation theory to second order calculations have been utilized to investigate these states. The spectroscopic constants, ωe, Re, Be, …, and the static dipole moment, μ, have been investigated by using the two different techniques of calculation with five different types of basis. The eigenvalues, Ev, the rotational constant, Bv, the centrifugal distortion constant, Dv, and the abscissas of the turning points, Rmin and Rmax, have been calculated by using the canonical functions approach. The comparison between the values of the present work, calculated by different techniques, and those available in the literature for several electronic states shows a very good agreement. Twenty-one new electronic states have been studied here for the first time.

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

    SciTech Connect

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

    2015-03-21

    Ab initio techniques have been applied to investigate the electronic structure of the LiYb molecule. The potential energy curves have been computed in the Born–Oppenheimer approximation for the ground and 29 low-lying doublet and quartet excited electronic states. Complete active space self-consistent field, multi-reference configuration interaction, and Rayleigh Schrödinger perturbation theory to second order calculations have been utilized to investigate these states. The spectroscopic constants, ω{sub e}, R{sub e}, B{sub e}, …, and the static dipole moment, μ, have been investigated by using the two different techniques of calculation with five different types of basis. The eigenvalues, E{sub v}, the rotational constant, B{sub v}, the centrifugal distortion constant, D{sub v}, and the abscissas of the turning points, R{sub min} and R{sub max}, have been calculated by using the canonical functions approach. The comparison between the values of the present work, calculated by different techniques, and those available in the literature for several electronic states shows a very good agreement. Twenty-one new electronic states have been studied here for the first time.

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

    PubMed

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

    2015-03-21

    Ab initio techniques have been applied to investigate the electronic structure of the LiYb molecule. The potential energy curves have been computed in the Born-Oppenheimer approximation for the ground and 29 low-lying doublet and quartet excited electronic states. Complete active space self-consistent field, multi-reference configuration interaction, and Rayleigh Schrödinger perturbation theory to second order calculations have been utilized to investigate these states. The spectroscopic constants, ωe, Re, Be, …, and the static dipole moment, μ, have been investigated by using the two different techniques of calculation with five different types of basis. The eigenvalues, Ev, the rotational constant, Bv, the centrifugal distortion constant, Dv, and the abscissas of the turning points, Rmin and Rmax, have been calculated by using the canonical functions approach. The comparison between the values of the present work, calculated by different techniques, and those available in the literature for several electronic states shows a very good agreement. Twenty-one new electronic states have been studied here for the first time. PMID:25796254

  1. ELECTRONIC STRUCTURE CALCULATIONS FOR PrFe4P12 FILLED SKUTTERUDITE USING EXTENDED HUCKEL TIGHT-BINDING METHOD

    NASA Astrophysics Data System (ADS)

    GALVAN, DONALD H.

    To gain insight into the electronic properties of PrFe4P12 filled skutterudite, band electronic structure calculations, total and projected density of states, crystal orbital overlap population and Mulliken population analysis were performed. The energy bands yield a semi-metallic behavior with a direct gap (at Γ) of 0.02 eV. Total and Projected Density of States provided information of the contribution from each orbital of each atom to the total Density of States. Moreover, the bonding strength between some atoms within the unit cell was obtained. Mulliken Population Analysis suggests ionic behavior for this filled skutterudite.

  2. Analysis of structural and electronic properties of Pr2NiO4 through first-principles calculations.

    PubMed

    Aspera, S M; Sakaue, M; Wungu, T D K; Alaydrus, M; Linh, T P T; Kasai, H; Nakanishi, M; Ishihara, T

    2012-10-10

    The structural and electronic properties of bulk Pr(2)NiO(4+δ) (δ = 0 and 0.031) were analyzed using first-principles calculations based on the density functional theory (DFT) for application to electrode materials in solid-oxide fuel cells (SOFCs). Two structures of Pr(2)NiO(4) were analyzed: one in space group I4/mmm associated with the high temperature tetragonal (HTT) structure, and the other in Bmab with the low temperature orthorhombic (LTO) structure. The main difference between the two structures is the pronounced tilting of the nickelate octahedra found in the Bmab structure. Here, we will show that the difference in the electronic properties between the two structures, i.e. half-metallic for the I4/mmm structure and metallic for the Bmab structure, is attributed to the tilting of the nickelate octahedra. Furthermore, we found that the presence of interstitial O atoms at the Pr(2)O(2) bilayers is responsible for the tilting of the octahedra and thus is a dominant factor in the transition from the I4/mmm structure to the Bmab structure. These results would be of great significance to materials design related to the enhancement of O diffusivity in this material.

  3. Prediction of new stable structure, promising electronic and thermodynamic properties of MoS3: Ab initio calculations

    NASA Astrophysics Data System (ADS)

    Pan, Yong; Guan, Weiming

    2016-09-01

    MoS3 has attracted considerable attention as potential hydrogen storage material due to the interaction between the hydrogen and unsaturated sulfur atoms. However, its structure and physical properties are unknown. By means of first-principles approach and Inorganic crystal structure Database (ISCD), we systematically investigated the structure, relevant physical and thermodynamic properties of MoS3. Phonon dispersion, electronic structure, band structure and heat capacity are calculated in detail. We predicted the orthorhombic B2ab (SrS3-type) and tetragonal P-421m (BaS3-type) structures of MoS3, which prefers to form the SrS3-type (Space group: B2ab, No.41) structure at the ground state. High pressure results in structural transition from SrS3-type structure to BaS3-type structure. This sulfide exhibits a degree of metallic behavior. The calculated heat capacity of MoS3 with SrS3-type structure is about of 39 J/(mol·K).

  4. Contribution of interlayer hybridization to the electronic structure in iron pnictides: a study of EELS and first-principles calculations.

    PubMed

    Ma, Chao; Yang, Huaixin; Tian, Huanfang; Shi, Honglong; Wang, Zhiwei; Li, Jianqi

    2013-03-20

    Using electron energy loss spectroscopy (EELS) measurements and first-principles electronic structure calculations, the significant interlayer hybridization between the insulating layers (ReO or Ba) and the conducting FeAs layers was investigated in the layered iron pnictides, which is quite different from the case in the cuprate superconductors. This interlayer hybridization would result in an increase in the bandwidth near the Fermi level and interorbital charge transfer in the Fe 3d orbitals, which subsequently leads to a decrease in the Fe local moment and the modification of the Fermi surface topology. Therefore, a three-dimensional character of the electronic structure due to the interlayer hybridization is expected, as observed in previous experiments. These findings indicate that reduced dimensionality is no longer a necessary condition in the search for high-T(c) superconductors in iron pnictides.

  5. Close-coupling calculations of fine-structure excitation of Ne II due to H and electron collisions

    NASA Astrophysics Data System (ADS)

    Stancil, Phillip C.; Cumbee, Renata; Wang, Qianxia; Loch, Stuart; Pindzola, Michael; Schultz, David R.; Buenker, Robert; McLaughlin, Brendan; Ballance, Connor

    2016-06-01

    Fine-structure transitions within the ground term of ions and neutral atoms dominate the cooling in a variety of molecular regions and also provide important density and temperature diagnostics. While fine-structure rates due to electron collisions have been studied for many systems, data are generally sparse for elements larger than oxygen, at low temperatures, and for collisions due to heavy particles. We provide rate coefficients for H collisions for the first time. The calculations were performed using the quantum molecular-orbital close-coupling approach and the elastic approximation. The heavy-particle collisions use new potential energies for the lowest-lying NeH+ states computed with the MRDCI method. The focus of the electron-impact calculations is to provide fine-structure excitation rate coefficients down to 10 K. We compare with previous calculations at higher temperatures (Griffin et al. 2001), and use a range of calculations to provide an estimate of the uncertainty on our recommended rate coefficients. A brief discussion of astrophysical applications is also provided.Griffin, D.C., et al., 2001, J. Phys. B, 34, 4401This work partially supported by NASA grant No. NNX15AE47G.

  6. Real-space electronic structure calculations with full-potential all-electron precision for transition metals

    NASA Astrophysics Data System (ADS)

    Ono, Tomoya; Heide, Marcus; Atodiresei, Nicolae; Baumeister, Paul; Tsukamoto, Shigeru; Blügel, Stefan

    2010-11-01

    We have developed an efficient computational scheme utilizing the real-space finite-difference formalism and the projector augmented-wave (PAW) method to perform precise first-principles electronic-structure simulations based on the density-functional theory for systems containing transition metals with a modest computational effort. By combining the advantages of the time-saving double-grid technique and the Fourier-filtering procedure for the projectors of pseudopotentials, we can overcome the egg box effect in the computations even for first-row elements and transition metals, which is a problem of the real-space finite-difference formalism. In order to demonstrate the potential power in terms of precision and applicability of the present scheme, we have carried out simulations to examine several bulk properties and structural energy differences between different bulk phases of transition metals and have obtained excellent agreement with the results of other precise first-principles methods such as a plane-wave-based PAW method and an all-electron full-potential linearized augmented plane-wave (FLAPW) method.

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

    SciTech Connect

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

    2001-03-15

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

  8. First-Principles Calculations of Structural, Electronic and Optical Properties of CaTiO3 Crystal

    NASA Astrophysics Data System (ADS)

    Medeiros, Subênia; Silva, Jusciane; Albuquerque, Eudenilson; Freire, Valder

    2013-03-01

    The structural, electronic, vibrational, and optical properties of perovskite CaTiO3 in the cubic, orthorhombic, and tetragonal phase are calculated in the framework of density functional theory (DFT) with different exchange-correlation potentials by CASTEP package. The calculated band structure shows an indirect band gap of 1.88 eV at the Γ-R points in the Brillouin zone to the cubic structure, a direct band gap of 2.41 eV at the Γ - Γ points to the orthorhombic structure, and an indirect band gap of 2.31 eV at the M' Γ points to the tetragonal phase. I have concluded that the bonding between Ca and TiO2 is mainly ionic and that the TiO2 entities bond covalently. Unlike some perovskites the CaTiO3 does not exhibit a ferroelectric phase transition down to 4.2 K. It is still known that the CaTiO3 has a static dielectric constant that extrapolates to a value greater than 300 at zero temperature. Our calculated lattice parameters, elastic constants, optical properties, and vibrational frequencies are found to be in good agreement with the available theoretical and experimental values. The results for the effective mass in the electron and hole carriers are also presented in this work.

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

    NASA Astrophysics Data System (ADS)

    Kong, Bo; Zhang, Yachao

    2016-07-01

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

  10. Calculation of the spin-polarized electronic structure of an interstitial iron impurity in silicon

    NASA Astrophysics Data System (ADS)

    Katayama-Yoshida, H.; Zunger, Alex

    1985-06-01

    We apply our self-consistent, all-electron, spin-polarized Green's-function method within an impurity-centered, dynamic basis set to study the interstitial iron impurity in silicon. We use two different formulations of the interelectron interactions: the local-spin-density (LSD) formalism and the self-interaction-corrected (SIC) local-spin-density (SIC-LSD) formalism. We find that the SIC-LSD approach is needed to obtain the correct high-spin ground state of Si:Fe+. We propose a quantitative explanation to the observed donor ionization energy and the high-spin ground states for Si:Fe+ within the SIC-LSD approach. For both Si:Fe0 and Si:Fe+, this approach leads to a hyperfine field, contact spin density, and ionization energy in better agreement with experiments than the simple LSD approach. The apparent dichotomy between the covalently delocalized nature of Si:Fe as suggested on the one hand by its reduced hyperfine field (relative to the free atom) and extended spin density and by the occurrence of two closely spaced, stable charge states (within 0.4 eV) and on the other hand by the atomically localized picture (suggested, for example, by the stability of a high-spin, ground-state configuration) is resolved. We find a large reduction in the hyperfine field and contact spin density due to the covalent hybridization between the impurity 3d orbitals and the tails of the delocalized sp3 hybrid orbitals of the surrounding silicon atoms. Using the calculated results, we discuss (i) the underlying mechanism for the stability and plurality of charged states, (ii) the covalent reduction in the hyperfine field, (iii) the remarkable constancy of the impurity Mössbauer isomer shift for different charged states, (iv) comparison with the multiple charged states in ionic crystals, and (v) some related speculation about the mechanism of (Fe2+/Fe3+) oxidation-reduction ionizations in heme proteins and electron-transporting biological systems.

  11. Python-based finite element code used as a universal and modular tool for electronic structure calculation

    NASA Astrophysics Data System (ADS)

    Cimrman, Robert; Tůma, Miroslav; Novák, Matyáš; Čertík, Ondřej; Plešek, Jiří; Vackář, Jiří

    2013-10-01

    Ab-initio calculations of electronic states within the density-functional framework has been performed by means of the open source finite element package SfePy (Simple Finite Elements in Python, http://sfepy.org). We describe a new robust ab-initio real-space code based on (i) density functional theory, (ii) finite element method and (iii) environment-reflecting pseudopotentials. This approach brings a new quality to solving Kohn-Sham equations, calculating electronic states, total energy, Hellmann-Feynman forces and material properties particularly for non-crystalline, non-periodic structures. The main asset of the above approach is an efficient combination of excellent convergence control of standard, universal basis used in industrially proved finite-element method, high precision of ab-initio environment-reflecting pseudopotentials, and applicability not restricted to electrically neutral periodic environment. We present also numerical examples illustrating the outputs of the method.

  12. The structural and electronic properties of cubic AgMO3 (M=Nb, Ta) by first principles calculations

    NASA Astrophysics Data System (ADS)

    Prasad, K. Ganga; Niranjan, Manish K.; Asthana, Saket

    2016-05-01

    We report the electronic structure of the AgMO3(M=Nb, Ta) within the frame work of density functional theory and calculations are performed within the generalized gradient approximation (GGA) by using ultrasoft pseudopotentials. The calculated equilibrium lattice parameters and volumes are extracted from fitting of Birch third order equation of state and which are reasonable agreement with the available experimental results. The density of states,band structure of Ag(Nb,Ta)O3 reveals that the valance bands mostly occupied with O-2p and O-2s states and whereas conduction band occupied with Nb (Ta) 4d(5d) states including less contribution from Ag 5s states.

  13. First-Principles Electronic Structure Calculations of N2H4 Adsorbed on Single-Wall Carbon Nanotubes

    NASA Astrophysics Data System (ADS)

    Yu, M.; Tian, W. Q.; Jayanthi, C. S.; Wu, S. Y.

    2008-03-01

    Recent experiments conducted by Desai et al. [1] reveal that single-wall carbon nanotube (SWCNT) networks exposed to N2H4 vapor at various pressures exhibit considerable drop in resistance with respect to the pristine sample. Experimental findings reveal: (i) n-type behavior for the adsorption of N2H4/SWCNT, and (ii) the binding of N2H4 on SWCNT as chemisorption. In the present work, we have performed first-principles electronic structure calculations [2] for the N2H4 adsorbed on the (14, 0) SWCNT, where several orientations for the N2H4 molecule were considered. Calculations for the combined system were performed using 3 unit cells with the DFT/GGA and ultra soft pseudo-potentials. Our calculations reveal: (i) the binding of N2H4 on SWCNT as physisorption, and (ii) the electronic structure of SWCNT to be practically unaltered by the adsorption of N2H4, suggesting that there will not be a dramatic drop in resistance for N2H4/SWCNT. This is in disagreement with the experimental findings. To further understand the experimental observations, we will discuss mechanisms that may alter the binding nature of N2H4 on SWCNT. [1] S. Desai, G. Sumanasekera, et al. (APS, March 2008). [2] G. Kresse and J. Furthmuller, Phys. Rev. B 54, 11169 (1996).

  14. Structures and Energetics of Protonated Clusters of Methylamine with Phenylalanine Analogs, Characterized by Infrared Multiple Photon Dissociation Spectroscopy and Electronic Structure Calculations.

    PubMed

    Kleisath, Elizabeth; Marta, Rick A; Martens, Sabrina; Martens, Jon; McMahon, Terry

    2015-06-25

    Gas-phase clusters of protonated methylamine and phenylalanine (Phe) derivatives have been studied using infrared multiple photon dissociation (IRMPD) spectroscopy in combination with electronic structure calculations at the MP2/aug-cc-pVTZ//B3LYP/6-311+G(d,p) level of theory. Experiments were performed on several Phe derivatives including 4-chloro-l-phenylalanine (4Chloro-Phe), 4-nitro-l-phenylalanine (4Nitro-Phe), 3-cyano-l-phenylalanine (3Cyano-Phe), and 3-trifluoromethyl-l-phenylalanine (3CF3-Phe). Through comparisons between experimental IRMPD spectra and stimulated spectra obtained by electronic structure calculations, charge-solvated structures were found to be prevalent in both 4Chloro-Phe and 4Nitro-Phe, whereas 3Cyano-Phe favored zwitterionic structures and 3-CF3-Phe likely have both zwitterionic and charge-solvated structures present.

  15. First Principle Calculations of the Electronic Structure, Phase Transition and Properties of ZrSiO4 Polymorphs

    SciTech Connect

    Du, Jincheng; Devanathan, Ram; Corrales, L Rene; Weber, William J

    2012-01-01

    First principle periodic density functional theory (DFT) calculations have been performed to understand the electronic structure, chemical bonding, phase transition, and physical properties of the zircon (in the chemical composition of ZrSiO4) and its high pressure phase reidite. Temperature effect on phase transition and thermal-mechanical properties such as heat capacity and bulk modulus have been studied by combining the equation of states obtained from DFT calculations with the quasi-harmonic Debye model to take into account the entropy contribution to free energy. Local density approximation (LDA) and generalized gradient approximation (GGA) DFT functionals have been systematically compared in predicting the structure and property of this material. It is found that the LDA functional provides a better description of the equilibrium structure and bulk modulus, while GGA predicts a transition pressure closer to experimental values. Both functionals correctly predict the relative stability of the two phases, with GGA giving slightly larger energy differences. The calculated band structures show that both zircon and reidite have indirect bandgaps and the reidite phase has a narrower bandgap than the zircon phase. The atomic charges determined using the Bader method show that bonding in reidite has a stronger covalent character.

  16. Analysis of electronic structure and optical properties of N-doped SiO2 based on DFT calculations

    NASA Astrophysics Data System (ADS)

    Zhang, Sui-Shuan; Zhao, Zong-Yan; Yang, Pei-Zhi

    2015-07-01

    The crystal structure, electronic structure and optical properties of N-doped SiO2 with different N impurity concentrations were calculated by density function theory within GGA+U method. The crystal distortion, impurity formation energy, band gap, band width and optical parameter of N-doped SiO2 are closely related with N impurity concentration. Based on the calculated results, there are three new impurity energy levels emerging in the band gap of N-doped SiO2, which determine the electronic structure and optical properties. The variations of optical properties induced by N doping are predominately determined by the unsaturated impurity states, which are more obvious at higher N impurity concentration. In addition, all the doping effects of N in both α-quartz SiO2 and β-quartz SiO2 are very similar. According to these findings, one could understand the relationship between nitrogen concentration and optical parameter of SiOxNy materials, and design new optoelectrionic Si-O-N compounds.

  17. First-principles calculations of the structural, electronic, optical and thermal properties of the BNxAs1-x alloys

    NASA Astrophysics Data System (ADS)

    Hamioud, L.; Boumaza, A.; Touam, S.; Meradji, H.; Ghemid, S.; El Haj Hassan, F.; Khenata, R.; Omran, S. Bin

    2016-06-01

    The present paper aims to study the structural, electronic, optical and thermal properties of the boron nitride (BN) and BAs bulk materials as well as the BNxAs1-x ternary alloys by employing the full-potential-linearised augmented plane wave method within the density functional theory. The structural properties are determined using the Wu-Cohen generalised gradient approximation that is based on the optimisation of the total energy. For band structure calculations, both the Wu-Cohen generalised gradient approximation and the modified Becke-Johnson of the exchange-correlation energy and potential, respectively, are used. We investigated the effect of composition on the lattice constants, bulk modulus and band gap. Deviations of the lattice constants and the bulk modulus from the Vegard's law and the linear concentration dependence, respectively, were observed for the alloys where this result allows us to explain some specific behaviours in the electronic properties of the alloys. For the optical properties, the calculated refractive indices and the optical dielectric constants were found to vary nonlinearly with the N composition. Finally, the thermal effect on some of the macroscopic properties was predicted using the quasi-harmonic Debye model in which the lattice vibrations are taken into account.

  18. Electronic structure of UO2.12 calculated in the coherent potential approximation taking into account strong electron correlations and spin-orbit coupling

    NASA Astrophysics Data System (ADS)

    Korotin, M. A.; Pchelkina, Z. V.; Skorikov, N. A.; Efremov, A. V.; Anisimov, V. I.

    2016-07-01

    Based on the coherent potential approximation, the method of calculating the electronic structure of nonstoichiometric and hyperstoichiometric compounds with strong electron correlations and spin-orbit coupling has been developed. This method can be used to study both substitutional and interstitial impurities, which is demonstrated based on the example of the hyperstoichiometric UO2.12 compound. The influence of the coherent potential on the electronic structure of compounds has been shown for the nonstoichiometric UO1.87 containing vacancies in the oxygen sublattice as substitutional impurities, for stoichiometric UO2 containing vacancies in the oxygen sublattice and oxygen as an interstitial impurity, and for hyperstoichiometric UO2.12 with excess oxygen also as interstitial impurity. In the model of the uniform distribution of impurities, which forms the basis of the coherent potential approximation, the energy spectrum of UO2.12 has a metal-like character.

  19. Electronic structure of quasi-one-dimensional superconductor K2Cr3As3 from first-principles calculations.

    PubMed

    Jiang, Hao; Cao, Guanghan; Cao, Chao

    2015-01-01

    The electronic structure of quasi-one-dimensional superconductor K2Cr3As3 is studied through systematic first-principles calculations. The ground state of K2Cr3As3 is paramagnetic. Close to the Fermi level, the Cr-3dz(2), dxy, and d(x(2)-y(2)) orbitals dominate the electronic states, and three bands cross EF to form one 3D Fermi surface sheet and two quasi-1D sheets. The electronic DOS at EF is less than 1/3 of the experimental value, indicating a large electron renormalization factor around EF. Despite of the relatively small atomic numbers, the antisymmetric spin-orbit coupling splitting is sizable (≈60 meV) on the 3D Fermi surface sheet as well as on one of the quasi-1D sheets. Finally, the imaginary part of bare electron susceptibility shows large peaks at Γ, suggesting the presence of large ferromagnetic spin fluctuation in the compound.

  20. Structural, elastic, electronic and optical properties of various mineral phases of TiO2 from first-principles calculations

    NASA Astrophysics Data System (ADS)

    Liu, Qi-Jun; Zhang, Ning-Chao; Liu, Fu-Sheng; Liu, Zheng-Tang

    2014-07-01

    Titanium dioxide is well known as a semiconductor material, which attracts a great deal of attention for promising applications in many fields due to its outstanding physical and chemical properties. To investigate the structural, elastic, mechanical, electronic and optical properties of various TiO2 phases systematically, we present the ultrasoft pseudopotential planewave method within local density approximation and generalized gradient approximation, as well as the norm-conserving pseudopotential within hybrid functional B3LYP by first-principles calculations on fluorite, pyrite, rutile, anatase, hollandite, brookite, columbite, cotunnite, bronze and baddeleyite TiO2 phases. The structural parameters of ten phases are calculated, which are shown to be consistent with previous theoretical and experimental data. We obtain the elastic constants of ten phases and then estimate the bulk, shear and Young’s moduli, Poisson’s coefficient and Lamé’s constants using the Voigt-Reuss-Hill approximation. The energy band structures, density of states and charge populations of ten phases were obtained and indicated there is covalency in TiO2. Moreover, the complex dielectric function, refractive index and extinction coefficient of the ten phases were calculated; this data can aid future experimental research.

  1. Magnetic, electrical, and thermodynamic properties of NpIr: Ambient and high-pressure measurements, and electronic structure calculations

    NASA Astrophysics Data System (ADS)

    Walker, H. C.; McEwen, K. A.; Griveau, J.-C.; Eloirdi, R.; Amador, P.; Maldonado, P.; Oppeneer, P. M.; Colineau, E.

    2015-05-01

    We present bulk property measurements of NpIr, a newly synthesized member of the Np-Ir binary phase diagram, which is isostructural to the noncentrosymmetric pressure-induced ferromagnetic superconductor UIr. Magnetic susceptibility, electronic transport properties at ambient and high pressure, and heat capacity measurements have been performed for temperatures T =0.55 -300 K in a range of magnetic fields up to 14 T and under pressure up to 17.3 GPa. These reveal that NpIr is a moderately heavy fermion Kondo system with strong antiferromagnetic interactions, but there is no evidence of any phase transition down to 0.55 K or at the highest pressure achieved. Experimental results are compared with ab initio calculations of the electronic band structure and lattice heat capacity. An extremely low lattice thermal conductivity is predicted for NpIr at temperatures above 300 K.

  2. Electronic structure of ReO3Me by variable photon energy photoelectron spectroscopy, absorption spectroscopy and density functional calculations.

    PubMed

    de Simone, Monica; Coreno, Marcello; Green, Jennifer C; McGrady, Sean; Pritchard, Helen

    2003-03-24

    Valence photoelectron (PE) spectra have been measured for ReO(3)Me using a synchrotron source for photon energies ranging between 20 and 110 eV. Derived branching ratios (BR) and relative partial photoionization cross sections (RPPICS) are interpreted in the context of a bonding model calculated using density functional theory (DFT). Agreement between calculated and observed ionization energies (IE) is excellent. The 5d character of the orbitals correlates with the 5p --> 5d resonances of the associated RPPICS; these resonances commence around 47 eV. Bands with 5d character also show a RPPICS maximum at 35 eV. The RPPICS associated with the totally symmetric 4a(1) orbital, which has s-like character, shows an additional shape resonance with an onset of 43 eV. The PE spectrum of the inner valence and core region measured with photon energies of 108 and 210 eV shows ionization associated with C 2s, O 2s, and Re 4f and 5p electrons. Absorption spectra measured in the region of the O1s edge showed structure assignable to excitation to the low lying empty "d" orbitals of this d(0) molecule. The separation of the absorption bands corresponded with the calculated orbital splitting and their intensity with the calculated O 2p character. Broad bands associated with Re 4d absorption were assigned to (2)D(5/2) and (2)D(3/2) hole states. Structure was observed associated with the C1s edge but instrumental factors prevented firm assignment. At the Re 5p edge, structure was observed on the (2)P(3/2) absorption band resulting from excitation to the empty "d" levels. The intensity ratios differed from that of the O 1s edge structure but were in good agreement with the calculated 5d character of these orbitals. An absorption was observed at 45 eV, which, in the light of the resonance in the 4a(1) RPPICS, is assigned to a 4a(1) --> ne, na(2) transition. The electronic structure established for ReO(3)Me differs substantially from that of TiCl(3)Me and accounts for the difference in

  3. A Detailed Derivation of Gaussian Orbital-Based Matrix Elements in Electron Structure Calculations

    ERIC Educational Resources Information Center

    Petersson, T.; Hellsing, B.

    2010-01-01

    A detailed derivation of analytic solutions is presented for overlap, kinetic, nuclear attraction and electron repulsion integrals involving Cartesian Gaussian-type orbitals. It is demonstrated how s-type orbitals can be used to evaluate integrals with higher angular momentum via the properties of Hermite polynomials and differentiation with…

  4. Structural, electronic, and optical properties of ZnO1-xSex alloys using first-principles calculations

    NASA Astrophysics Data System (ADS)

    Muhammad, Rashid; Fayyaz, Hussain; Muhammad, Imran; S, A. Ahmad; N, A. Noor; M, U. Sohaib; S, M. Alay-e.-Abbas

    2013-08-01

    The structural, electronic, and optical properties of binary ZnO, ZnSe compounds, and their ternary ZnO1-xSex alloys are computed using the accurate full potential linearized augmented plane wave plus local orbital (FP-LAPW + lo) method in the rocksalt (B1) and zincblende (B3) crystallographic phases. The electronic band structures, fundamental energy band gaps, and densities of states for ZnO1-xSex are evaluated in the range 0 <= x <= 1 using Wu—Cohen (WC) generalized gradient approximation (GGA) for the exchange—correlation potential. Our calculated results of lattice parameters and bulk modulus reveal a nonlinear variation for pseudo-binary and their ternary alloys in both phases and show a considerable deviation from Vegard's law. It is observed that the predicted lattice parameter and bulk modulus are in good agreement with the available experimental and theoretical data. We establish that the composition dependence of band gap is semi-metallic in B1 phase, while a direct band gap is observed in B3 phase. The calculated density of states is described by taking into account the contribution of Zn 3d, O 2p, and Se 4s, and the optical properties are studied in terms of dielectric functions, refractive index, reflectivity, and energy loss function for the B3 phase and are compared with the available experimental data.

  5. The potential, limitations, and challenges of divide and conquer quantum electronic structure calculations on energetic materials.

    SciTech Connect

    Tucker, Jon R.; Magyar, Rudolph J.

    2012-02-01

    High explosives are an important class of energetic materials used in many weapons applications. Even with modern computers, the simulation of the dynamic chemical reactions and energy release is exceedingly challenging. While the scale of the detonation process may be macroscopic, the dynamic bond breaking responsible for the explosive release of energy is fundamentally quantum mechanical. Thus, any method that does not adequately describe bonding is destined to lack predictive capability on some level. Performing quantum mechanics calculations on systems with more than dozens of atoms is a gargantuan task, and severe approximation schemes must be employed in practical calculations. We have developed and tested a divide and conquer (DnC) scheme to obtain total energies, forces, and harmonic frequencies within semi-empirical quantum mechanics. The method is intended as an approximate but faster solution to the full problem and is possible due to the sparsity of the density matrix in many applications. The resulting total energy calculation scales linearly as the number of subsystems, and the method provides a path-forward to quantum mechanical simulations of millions of atoms.

  6. Interactions of biopolymers with silica surfaces: Force measurements and electronic structure calculation studies

    NASA Astrophysics Data System (ADS)

    Kwon, Kideok D.; Vadillo-Rodriguez, Virginia; Logan, Bruce E.; Kubicki, James D.

    2006-08-01

    Pull-off forces were measured between a silica colloid attached to an atomic force microscope (AFM) cantilever and three homopolymer surfaces representing constituents of extracellular polymeric substances (EPS). The pull-off forces were -0.84 (±0.16), -0.68 (±0.15), and -2.37 (±0.31) nN as measured in water for dextran, phosphorylated dextran, and poly- L-lysine, respectively. Molecular orbital and density functional theory methods (DFT) were applied to analyze the measured pull-off forces using dimer clusters representing interactions between the three polymers and silica surfaces. Binding energies for each dimer were calculated with basis set superposition error (BSSE) and interpolated using corrections for silica surface hydroxyl density and silica charge density. The binding energies were compared with the normalized pull-off forces with the effective silica surface area contacting the polymer surfaces. The predicted binding energies at a -0.064 C/m 2 silica surface charge density corresponding to circum-neutral pH were -0.055, -0.029, and -0.338 × 10 -18 J/nm 2 for the dimers corresponding to the silica surface with dextran, phosphorylated dextran, and poly- L-lysine, respectively. Polarizable continuum model (PCM) calculations with different solvents, silanol vibrational frequency calculations, and orbital interaction analysis based on natural bonding orbital (NBO) showed that phosphate groups formed stronger H-bonds with neutral silanols than hydroxyl and amino functional groups of polymers, implying that phosphate containing polymers would play important roles in EPS binding to silica surfaces.

  7. Electronic structure and physical properties of the spinel-type phase of BeP{sub 2}N{sub 4} from all-electron density functional calculations

    SciTech Connect

    Ching, W. Y.; Aryal, Sitram; Rulis, Paul; Schnick, Wolfgang

    2011-04-15

    Using density-functional-theory-based ab initio methods, the electronic structure and physical properties of the newly synthesized nitride BeP{sub 2}N{sub 4} with a phenakite-type structure and the predicted high-pressure spinel phase of BeP{sub 2}N{sub 4} are studied in detail. It is shown that both polymorphs are wide band-gap semiconductors with relatively small electron effective masses at the conduction-band minima. The spinel-type phase is more covalently bonded due to the increased number of P-N bonds for P at the octahedral sites. Calculations of mechanical properties indicate that the spinel-type polymorph is a promising superhard material with notably large bulk, shear, and Young's moduli. Also calculated are the Be K, P K, P L{sub 3}, and N K edges of the electron energy-loss near-edge structure for both phases. They show marked differences because of the different local environments of the atoms in the two crystalline polymorphs. These differences will be very useful for the experimental identification of the products of high-pressure syntheses targeting the predicted spinel-type phase of BeP{sub 2}N{sub 4}.

  8. Bis(alpha-diimine)iron complexes: electronic structure determination by spectroscopy and broken symmetry density functional theoretical calculations.

    PubMed

    Muresan, Nicoleta; Lu, Connie C; Ghosh, Meenakshi; Peters, Jonas C; Abe, Megumi; Henling, Lawrence M; Weyhermöller, Thomas; Bill, Eckhard; Wieghardt, Karl

    2008-06-01

    The electronic structure of a family comprising tetrahedral (alpha-diimine)iron dichloride, and tetrahedral bis(alpha-diimine)iron compounds has been investigated by Mossbauer spectroscopy, magnetic susceptibility measurements, and X-ray crystallography. In addition, broken-symmetry density functional theoretical (B3LYP) calculations have been performed. A detailed understanding of the electronic structure of these complexes has been obtained. A paramagnetic (St=2), tetrahedral complex [FeII(4L)2], where (4L)1- represents the diamagnetic monoanion N-tert-butylquinolinylamide, has been synthesized and characterized to serve as a benchmark for a Werner-type complex containing a tetrahedral FeIIN4 geometry and a single high-spin ferrous ion. In contrast to the most commonly used description of the electronic structure of bis(alpha-diimine)iron(0) complexes as low-valent iron(0) species with two neutral alpha-diimine ligands, it is established here that they are, in fact, complexes containing two (alpha-diiminato)1-* pi radical monoanions and a high-spin ferrous ion (in tetrahedral N4 geometry) (SFe=2). Intramolecular antiferromagnetic coupling between the pi radical ligands (Srad=1/2) and the ferrous ion (SFe=2) yields the observed St=1 ground state. The study confirms that alpha-diimines are redox noninnocent ligands with an energetically low-lying antibonding pi* lowest unoccupied molecular orbital which can accept one or two electrons from a transition metal ion. The (alpha-diimine)FeCl2 complexes (St=2) are shown to contain a neutral alpha-diimine ligand, a high spin ferrous ion, and two chloride ligands. PMID:18442239

  9. Electronic structure of interstitial hydrogen in lutetium oxide from DFT+U calculations and comparison study with μ SR spectroscopy

    NASA Astrophysics Data System (ADS)

    da Silva, E. Lora; Marinopoulos, A. G.; Vieira, R. B. L.; Vilão, R. C.; Alberto, H. V.; Gil, J. M.; Lichti, R. L.; Mengyan, P. W.; Baker, B. B.

    2016-07-01

    The electronic structure of hydrogen impurity in Lu2O3 was studied by first-principles calculations and muonium spectroscopy. The computational scheme was based on two methods which are well suited to treat defect calculations in f -electron systems: first, a semilocal functional of conventional density-functional theory (DFT) and secondly a DFT+U approach which accounts for the on-site correlation of the 4 f electrons via an effective Hubbard-type interaction. Three different types of stable configurations were found for hydrogen depending upon its charge state. In its negatively charged and neutral states, hydrogen favors interstitial configurations residing either at the unoccupied sites of the oxygen sublattice or at the empty cube centers surrounded by the lanthanide ions. In contrast, the positively charged state stabilized only as a bond configuration, where hydrogen binds to oxygen ions. Overall, the results between the two methods agree in the ordering of the formation energies of the different impurity configurations, though within DFT+U the charge-transition (electrical) levels are found at Fermi-level positions with higher energies. Both methods predict that hydrogen is an amphoteric defect in Lu2O3 if the lowest-energy configurations are used to obtain the charge-transition, thermodynamic levels. The calculations of hyperfine constants for the neutral interstitial configurations show a predominantly isotropic hyperfine interaction with two distinct values of 926 MHz and 1061 MHz for the Fermi-contact term originating from the two corresponding interstitial positions of hydrogen in the lattice. These high values are consistent with the muonium spectroscopy measurements which also reveal a strongly isotropic hyperfine signature for the neutral muonium fraction with a magnitude slightly larger (1130 MHz) from the ab initio results (after scaling with the magnetic moments of the respective nuclei).

  10. Electronic structures in coupled two quantum dots by 3D-mesh Hartree-Fock-Kohn-Sham calculation

    NASA Astrophysics Data System (ADS)

    Matsuse, T.; Hama, T.; Kaihatsu, H.; Toyoda, N.; Takizawa, T.

    To study the electronic structures of quantum dots in the framework of self-interaction-free including three dimensional effects, we adopt the theory of nonlocal effective potential introduced by Kohn and Sham [#!ks65!#]. For utilizing the advantageous point of the real space (3D) mesh method to solve the original nonlinear and nonlocal Hartree-Fock-Kohn-Sham (HFKS)-equation, we introduce a linearization of the equation in the local form by introducing the local Coulomb potentials which depend on explicitly the two single particle states. In practice, for solving the local form HFKS-equation, we use the Car-Parrinello-like relaxation method and the Coulomb potentials are obtained by solving the Poisson equation under proper boundary conditions. Firstly the observed energy gap between triplet- and singlet-states of N = 4 in DBS [#!tarucha96!#] is discussed to reproduce the addition energies and chemical potentials depending the magnetic field. Next the coupling between two-quantum dots in TBS [#!aht97!#] is studied by adding the square barrier between two dots. The spin-degeneracy [#!aht97!#] measured in gate-voltage depending on magnetic field is well reproduced in the limit of small mismatch. Finally, the electronic states in the ring structure are calculated and discussed how the ring size and magnetic field affect to the structures.

  11. Fermi-orbitals for improved electronic structure calculations on coordination complexes

    NASA Astrophysics Data System (ADS)

    Kao, Der-You; Pederson, Mark R.; Lee, James D.

    An improved density-functional formalism proceeds by adopting the Perdew-Zunger expression for a self-interaction-corrected (SIC) density-functional energy but evaluates the total energy based on Fermi Orbitals (FOs). Each localized electron is represented by an FO, determined from the occupied Kohn-Sham orbitals and a semi-classical FO descriptor. The SIC energy is then minimized through the gradients of the energy with respect to these descriptors. In addition to providing a review of the methodology, work here identifies the need for an algorithm which thoroughly searches over initial configurations. The strategy for sampling and prioritizing initial configurations is described. Applications on coordination complexes are presented. The FO descriptors and FOs for semi-classical and quantum-mechanical understanding of bondingis discussed. Cohesive energies are improved andthe eigenvalues are shifted downward relative to the standard DFT results.Spin-dependent vibrational spectra, as a possible means for spectroscopic determination of the transition-metal moment, are also presented. DK acknowledges her fellowship from The George Washington University Institude of Nanotechnology.

  12. Kinetic Formulation of the Kohn-Sham Equations for ab initio Electronic Structure Calculations

    NASA Astrophysics Data System (ADS)

    Mendoza, M.; Succi, S.; Herrmann, H. J.

    2014-08-01

    We introduce a new connection between density functional theory and kinetic theory. In particular, we show that the Kohn-Sham equations can be reformulated as a macroscopic limit of the steady-state solution of a suitable single-particle kinetic equation. We derive a Boltzmann-like equation for a gas of quasiparticles, where the potential plays the role of an external source that generates and destroys particles, so as to drive the system towards its ground state. The ions are treated as classical particles by using either the Born-Oppenheimer dynamics or by imposing concurrent evolution with the electronic orbitals. In order to provide quantitative support to our approach, we implement a discrete (lattice) kinetic model and compute the exchange and correlation energies of simple atoms and the geometrical configuration of the methane molecule. Moreover, we also compute the first vibrational mode of the hydrogen molecule, with both Born-Oppenheimer and concurrent dynamics. Excellent agreement with values in the literature is found in all cases.

  13. Kinetic formulation of the Kohn-Sham Equations for ab initio electronic structure calculations.

    PubMed

    Mendoza, M; Succi, S; Herrmann, H J

    2014-08-29

    We introduce a new connection between density functional theory and kinetic theory. In particular, we show that the Kohn-Sham equations can be reformulated as a macroscopic limit of the steady-state solution of a suitable single-particle kinetic equation. We derive a Boltzmann-like equation for a gas of quasiparticles, where the potential plays the role of an external source that generates and destroys particles, so as to drive the system towards its ground state. The ions are treated as classical particles by using either the Born-Oppenheimer dynamics or by imposing concurrent evolution with the electronic orbitals. In order to provide quantitative support to our approach, we implement a discrete (lattice) kinetic model and compute the exchange and correlation energies of simple atoms and the geometrical configuration of the methane molecule. Moreover, we also compute the first vibrational mode of the hydrogen molecule, with both Born-Oppenheimer and concurrent dynamics. Excellent agreement with values in the literature is found in all cases.

  14. Efficient and accurate linear algebraic methods for large-scale electronic structure calculations with nonorthogonal atomic orbitals

    NASA Astrophysics Data System (ADS)

    Teng, H.; Fujiwara, T.; Hoshi, T.; Sogabe, T.; Zhang, S.-L.; Yamamoto, S.

    2011-04-01

    The need for large-scale electronic structure calculations arises recently in the field of material physics, and efficient and accurate algebraic methods for large simultaneous linear equations become greatly important. We investigate the generalized shifted conjugate orthogonal conjugate gradient method, the generalized Lanczos method, and the generalized Arnoldi method. They are the solver methods of large simultaneous linear equations of the one-electron Schrödinger equation and map the whole Hilbert space to a small subspace called the Krylov subspace. These methods are applied to systems of fcc Au with the NRL tight-binding Hamiltonian [F. Kirchhoff , Phys. Rev. BJCOMEL1098-012110.1103/PhysRevB.63.195101 63, 195101 (2001)]. We compare results by these methods and the exact calculation and show them to be equally accurate. The system size dependence of the CPU time is also discussed. The generalized Lanczos method and the generalized Arnoldi method are the most suitable for the large-scale molecular dynamics simulations from the viewpoint of CPU time and memory size.

  15. Ionization of cytosine monomer and dimer studied by VUV photoionization and electronic structure calculations

    SciTech Connect

    Kostko, Oleg; Bravaya, Ksenia; Krylov, Anna; Ahmed, Musahid

    2009-12-14

    We report a combined theoretical and experimental study of ionization of cytosine monomers and dimers. Gas-phase molecules are generated by thermal vaporization of cytosine followed by expansion of the vapor in a continuous supersonic jet seeded in Ar. The resulting species are investigated by single photon ionization with tunable vacuum-ultraviolet (VUV) synchrotron radiation and mass analyzed using reflectron mass spectrometry. Energy onsets for the measured photoionization efficiency (PIE) spectra are 8.60+-0.05 eV and 7.6+-0.1 eV for the monomer and the dimer, respectively, and provide an estimate for the adiabatic ionization energies (AIE). The first AIE and the ten lowest vertical ionization energies (VIEs) for selected isomers of cytosine dimer computed using equation-of-motion coupled-cluster (EOM-IP-CCSD) method are reported. The comparison of the computed VIEs with the derivative of the PIE spectra, suggests that multiple isomers of the cytosine dimer are present in the molecular beam. The calculations reveal that the large red shift (0.7 eV) of the first IE of the lowest-energy cytosine dimer is due to strong inter-fragment electrostatic interactions, i.e., the hole localized on one of the fragments is stabilized by the dipole moment of the other. A sharp rise in the CH+ signal at 9.20+-0.05 eV is ascribed to the formation of protonated cytosine by dissociation of the ionized dimers. The dominant role of this channel is supported by the computed energy thresholds for the CH+ appearance and the barrierless or nearly barrierless ionization-induced proton transfer observed for five isomers of the dimer.

  16. Ionization of cytosine monomer and dimer studied by VUV photoionization and electronic structure calculations.

    PubMed

    Kostko, Oleg; Bravaya, Ksenia; Krylov, Anna; Ahmed, Musahid

    2010-03-28

    We report a combined theoretical and experimental study of ionization of cytosine monomers and dimers. Gas-phase molecules are generated by thermal vaporization of cytosine followed by expansion of the vapor in a continuous supersonic jet seeded in Ar. The resulting species are investigated by single photon ionization with tunable vacuum-ultraviolet (VUV) synchrotron radiation and mass analyzed using reflectron mass spectrometry. Energy onsets for the measured photoionization efficiency (PIE) spectra are 8.60 +/- 0.05 eV and 7.6 +/- 0.1 eV for the monomer and the dimer, respectively, and provide an estimate for the adiabatic ionization energies (AIE). The first AIE and the ten lowest vertical ionization energies (VIEs) for selected isomers of cytosine dimer computed using equation-of-motion coupled-cluster (EOM-IP-CCSD) method are reported. The comparison of the computed VIEs with the derivative of the PIE spectra suggests that multiple isomers of the cytosine dimer are present in the molecular beam. The calculations reveal that the large red shift (0.7 eV) of the first IE of the lowest-energy cytosine dimer is due to strong inter-fragment electrostatic interactions, i.e., the hole localized on one of the fragments is stabilized by the dipole moment of the other. A sharp rise in the protonated cytosine ion (CH(+)) signal at 9.20 +/- 0.05 eV is ascribed to the formation of protonated cytosine by dissociation of the ionized dimers. The dominant role of this channel is supported by the computed energy thresholds for the CH(+) appearance and the barrierless or nearly barrierless ionization-induced proton transfer observed for five isomers of the dimer.

  17. Comparative study between LMTO and FPLAPW into the calculation of the electronic structure of carbide Cr 23C 6

    NASA Astrophysics Data System (ADS)

    dos Santos, A. V.

    2007-01-01

    Considering the actual state of the art in Materials Science, it is necessary to do a theoretical analysis of the compounds obtained through experimenting, with the objective of understanding them better, by foreseeing their behaviour and possible new compounds. For this, in this work, we calculate electronic structures of Cr 23C 6 chromium carbide, which are present in fast steels, using two methods of calculating the band structure of first principles, the method of linear muffin-tin orbital (LMTO) with the Andersen's atomic sphere approximation (ASA) and the method of linear plain and expanded waves (LAPW) with generalized gradient approximation (GGA). Through calculations of formation energy in relation to its volume we obtain the equilibrium volume of 379.16 u.a. using the LMTO, and 375.13 u.a, using the LAPW. In the equilibrium volume we calculated some fundamental state properties. We observed an extremely low magnetization in both methods; nevertheless, in LAPW we verified a little magnetic moment in the Crl site that is 0.2512μB. The method LAPW affirms the existence of an interstitial region motivating the charge transference to this region. As the LMTO does not have the interstitial region, we do not see the charge transference to this region; in this case the charges come out of the C and Crl sites to take place in the Crll site. The density of states (DOS) shows that there is an interaction between the “s” states of C with the other sites and in a more intense way with the Crll site. When we compared the DOS, in relation to the methods used, we saw that in case of the LMTO, these are slightly placed in regions where energy is lower as well as its Fermi energy.

  18. Dose calculation for electron therapy

    NASA Astrophysics Data System (ADS)

    Gebreamlak, Wondesen T.

    The dose delivered by electron beams has a complex dependence on the shape of the field; any field shaping shields, design of collimator systems, and energy of the beam. This complicated dependence is due to multiple scattering of the electron beam as the beam travels from the accelerator head to the patient. The dosimetry of only regular field shapes (circular, square, or rectangular) is well developed. However, most tumors have irregular shapes and their dosimetry is calculated by direct measurement. This is laborious and time consuming. In addition, error can be introduced during measurements. The lateral build up ratio method (LBR), which is based on the Fermi-Eyges multiple scattering theory, calculates the dosimetry of irregular electron beam shapes. The accuracy of this method depends on the function sigma r(r,E) (the mean square radial displacement of the electron beam in the medium) used in the calculation. This research focuses on improving the accuracy of electron dose calculations using lateral build up ratio method by investigating the properties of sigmar(r,E). The percentage depth dose curves of different circular cutouts were measured using four electron beam energies (6, 9, 12, and 15 MeV), four electron applicator sizes (6x6, 10x10, 14x14, and 20x20 cm), three source-surface distance values (100, 105, 110 cm). The measured percentage depth dose curves were normalized at a depth of 0.05 cm. Using the normalized depth dose, the lateral build up ratio curves were determined. Using the cutout radius and the lateral build up ratio values, sigmar(z,E) were determined. It is shown that the sigma value increases linearly with cutout size until the cutout radius reaches the equilibrium range of the electron beam. The sigma value of an arbitrary circular cutout was determined from the interpolation of sigma versus cutout curve. The corresponding LBR value of the circular cutout was determined using its radius and sigma values. The depth dose distribution of

  19. SaX: An open source package for electronic-structure and optical-properties calculations in the GW approximation

    NASA Astrophysics Data System (ADS)

    Martin-Samos, Layla; Bussi, Giovanni

    2009-08-01

    We present here SaX (Self-energies and eXcitations), a plane-waves package aimed at electronic-structure and optical-properties calculations in the GW framework, namely using the GW approximation for quasi-particle properties and the Bethe-Salpeter equation for the excitonic effects. The code is mostly written in FORTRAN90 in a modern style, with extensive use of data abstraction (i.e. objects). SaX employs state of the art techniques and can treat large systems. The package is released with an open source license and can be also download from http://www.sax-project.org/. Program summaryProgram title: SaX (Self-energies and eXcitations) Catalogue identifier: AEDF_v1_0 Program summary URL:http://cpc.cs.qub.ac.uk/summaries/AEDF_v1_0.html Program obtainable from: CPC Program Library, Queen's University, Belfast, N. Ireland Licensing provisions: GNU General Public License No. of lines in distributed program, including test data, etc.: 779 771 No. of bytes in distributed program, including test data, etc.: 4 894 755 Distribution format: tar.gz Programming language: FORTRAN, plus some C utilities Computer: Linux PC, Linux clusters, IBM-SP5 Operating system: Linux, Aix Has the code been vectorised or parallelized?: Yes RAM: depending on the system complexity Classification: 7.3 External routines: Message-Passing Interface (MPI) to perform parallel computations. ESPRESSO ( http://www.quantum-espresso.org) Nature of problem: SaX is designed to calculate the electronic band-structure of semiconductors, including quasi-particle effects and optical properties including excitonic effects. Solution method: The electronic band-structure is calculated using the GW approximation for the self-energy operator. The optical properties are calculated solving the Bethe-Salpeter equation in the GW approximation. The wavefunctions are expanded on a plane-waves basis set, using norm-conserving pseudopotentials. Restrictions: Many objects are non-local matrix represented in plane wave basis

  20. Ab initio calculations of structural, electronic, optical and thermodynamic properties of alkaline earth tellurides BaxSr1-XTe

    NASA Astrophysics Data System (ADS)

    Bahloul, B.; Bentabet, A.; Amirouche, L.; Bouhadda, Y.; Bounab, S.; Deghfel, B.; Fenineche, N.

    2014-03-01

    Structural, electronic and thermodynamic properties of SrTe and BaTe compounds and their ternary mixed crystals BaxSr1-xTe in the rock-salt structure have been studied with density functional theory (DFT), whereas the optical properties have been obtained by using empirical methods such as the modified Moss relation. The exchange-correlation potential was calculated using the generalized gradient approximation (GGA) of Perdew-Burke-Ernzerhof (PBE) and the local density approximation (LDA) of Teter-Pade (TP). In the present work, we used the virtual-crystal approximation (VCA) to study the effect of composition (x). The calculated lattice parameters at equilibrium volume and the bulk modulus for x=0 and x=1 are in good agreement with the literature data. Furthermore, the BaxSr1-xTe alloys are found to be an indirect band gap semiconductor. In addition, we have also predicted the heat capacities (CV), the entropy(S), the internal energy (U) and the Helmholtz free energy (F) of the parent compounds SrTe and BaTe.

  1. Internal conversion and intersystem crossing in α,β-enones: a combination of electronic structure calculations and dynamics simulations.

    PubMed

    Cao, Jun; Xie, Zhi-Zhong

    2016-03-01

    The ab initio electronic structure calculations and CASSCF-based nonadiabatic dynamics simulations have been used to investigate the internal conversion and intersystem crossing process of both trans-acrolein and 2-cyclopentenone in the gas phase. Our calculation results show that relaxation from the Franck-Condon region to an S1 minimum is ultrafast and that the S1 state will dominantly undergo intersystem crossing to triplet states due to the existence of significant barriers to access the S1/S0 intersection points and of energetically close-lying triplet states. The S1/T2/T1 three-state intersection is observed in our dynamics simulations to play an important role in the population of the lowest triplet state, which is consistent with previous suggestions. Although the evolution into triplet states involves a similar path and gives rise to a similar triplet quantum yield for these two molecules, the intersystem crossing rate of 2-cyclopentenone is lower owing to the ring constraint that results in a smaller spin-orbital coupling in the singlet-triplet crossing region. The present theoretical study reproduces the experimental results and gives an explanation about the structural factors that govern the excited-state decay of some types of α,β-enones.

  2. Electronic structure calculations with GPAW: a real-space implementation of the projector augmented-wave method

    NASA Astrophysics Data System (ADS)

    Enkovaara, J.; Rostgaard, C.; Mortensen, J. J.; Chen, J.; Dułak, M.; Ferrighi, L.; Gavnholt, J.; Glinsvad, C.; Haikola, V.; Hansen, H. A.; Kristoffersen, H. H.; Kuisma, M.; Larsen, A. H.; Lehtovaara, L.; Ljungberg, M.; Lopez-Acevedo, O.; Moses, P. G.; Ojanen, J.; Olsen, T.; Petzold, V.; Romero, N. A.; Stausholm-Møller, J.; Strange, M.; Tritsaris, G. A.; Vanin, M.; Walter, M.; Hammer, B.; Häkkinen, H.; Madsen, G. K. H.; Nieminen, R. M.; Nørskov, J. K.; Puska, M.; Rantala, T. T.; Schiøtz, J.; Thygesen, K. S.; Jacobsen, K. W.

    2010-06-01

    Electronic structure calculations have become an indispensable tool in many areas of materials science and quantum chemistry. Even though the Kohn-Sham formulation of the density-functional theory (DFT) simplifies the many-body problem significantly, one is still confronted with several numerical challenges. In this article we present the projector augmented-wave (PAW) method as implemented in the GPAW program package (https://wiki.fysik.dtu.dk/gpaw) using a uniform real-space grid representation of the electronic wavefunctions. Compared to more traditional plane wave or localized basis set approaches, real-space grids offer several advantages, most notably good computational scalability and systematic convergence properties. However, as a unique feature GPAW also facilitates a localized atomic-orbital basis set in addition to the grid. The efficient atomic basis set is complementary to the more accurate grid, and the possibility to seamlessly switch between the two representations provides great flexibility. While DFT allows one to study ground state properties, time-dependent density-functional theory (TDDFT) provides access to the excited states. We have implemented the two common formulations of TDDFT, namely the linear-response and the time propagation schemes. Electron transport calculations under finite-bias conditions can be performed with GPAW using non-equilibrium Green functions and the localized basis set. In addition to the basic features of the real-space PAW method, we also describe the implementation of selected exchange-correlation functionals, parallelization schemes, ΔSCF-method, x-ray absorption spectra, and maximally localized Wannier orbitals.

  3. Structural determination of carvone, a component of spearmint, by means of gas electron diffraction augmented by theoretical calculations

    NASA Astrophysics Data System (ADS)

    Egawa, Toru; Kachi, Yukari; Takeshima, Tsuguhide; Takeuchi, Hiroshi; Konaka, Shigehiro

    2003-10-01

    The molecular structure and conformation of carvone, a compound with a minty odor, were investigated by means of gas electron diffraction supported by theoretical calculations. Electron diffraction patterns were recorded by heating the nozzle up to 128 °C to obtain enough scattering intensity. The infrared spectrum was also measured by using an absorption cell with a path length of 10 m. The obtained molecular scattering intensities were analyzed with the aid of theoretical calculations and infrared spectroscopy. It was revealed that the experimental data are well reproduced by assuming that carvone consists of a mixture of three conformers that have the isopropenyl group in the equatorial position and mutually differ in the torsional angle around the single bond connecting the ring and the isopropenyl group. It was also found that the puckering amplitude of the ring of carvone is close to those of menthol and isomenthol, a minty compound and its nonminty isomer. The determined structural parameters ( rg and ∠ α) of the most abundant conformer of carvone are as follows: < r(C-C)>=1.520(3) Å; < r(CC)>=1.360(5) Å; r(CO)=1.225(5) Å; < r(C-H)>=1.104(4)Å; <∠CC-C>=121.1(5)°; <∠C-C-C>=110.4(5)°; ∠C-CO-C=117.1(14)°; <∠C-C-H>=111.1(13)°. Angle brackets denote average values and parenthesized values are the estimated limits of error (3 σ) referring to the last significant digit.

  4. Chebyshev polynomial filtered subspace iteration in the discontinuous Galerkin method for large-scale electronic structure calculations

    NASA Astrophysics Data System (ADS)

    Banerjee, Amartya S.; Lin, Lin; Hu, Wei; Yang, Chao; Pask, John E.

    2016-10-01

    The Discontinuous Galerkin (DG) electronic structure method employs an adaptive local basis (ALB) set to solve the Kohn-Sham equations of density functional theory in a discontinuous Galerkin framework. The adaptive local basis is generated on-the-fly to capture the local material physics and can systematically attain chemical accuracy with only a few tens of degrees of freedom per atom. A central issue for large-scale calculations, however, is the computation of the electron density (and subsequently, ground state properties) from the discretized Hamiltonian in an efficient and scalable manner. We show in this work how Chebyshev polynomial filtered subspace iteration (CheFSI) can be used to address this issue and push the envelope in large-scale materials' simulations in a discontinuous Galerkin framework. We describe how the subspace filtering steps can be performed in an efficient and scalable manner using a two-dimensional parallelization scheme, thanks to the orthogonality of the DG basis set and block-sparse structure of the DG Hamiltonian matrix. The on-the-fly nature of the ALB functions requires additional care in carrying out the subspace iterations. We demonstrate the parallel scalability of the DG-CheFSI approach in calculations of large-scale two-dimensional graphene sheets and bulk three-dimensional lithium-ion electrolyte systems. Employing 55 296 computational cores, the time per self-consistent field iteration for a sample of the bulk 3D electrolyte containing 8586 atoms is 90 s, and the time for a graphene sheet containing 11 520 atoms is 75 s.

  5. Structural, electronic, and magnetic properties of tetragonal Mn{sub 3-x}Ga: Experiments and first-principles calculations

    SciTech Connect

    Winterlik, Juergen; Balke, Benjamin; Fecher, Gerhard H.; Felser, Claudia; Alves, Maria C. M.; Bernardi, Fabiano; Morais, Jonder

    2008-02-01

    This work reports on the electronic, magnetic, and structural properties of the binary intermetallic compounds Mn{sub 3-x}Ga. The tetragonal DO{sub 22} phase of the Mn{sub 3-x}Ga series, with x varying from 0 to 1.0 in steps of x=0.1, was successfully synthesized and investigated. It was found that all these materials are hard magnetic, with energy products ranging from 10.1 kJ m{sup -3} for low Mn content (x{yields}1) to 61.6 kJ m{sup -3} for high Mn content (x{yields}0). With decreasing Mn content, the average saturation magnetization per atom increases from 0.26{mu}{sub B} for Mn{sub 3}Ga to 0.47{mu}{sub B} for Mn{sub 2}Ga. The increase in the saturation magnetization as the Mn content is reduced indicates a ferrimagnetic order with partially compensating moments of the two different Mn atoms on the two crystallographically different sites of the DO{sub 22} structure. This type of magnetic order is supported by ab initio calculations of the electronic structure that predict a nearly half-metallic ferrimagnet with the highest spin polarization of 88% at the Fermi energy for Mn{sub 3}Ga. The Curie temperature of the compounds is restricted to approximately 770 K because of a structural phase transition to the hexagonal DO{sub 19} phase. Thermal irreversibilities between zero-field-cooled and field-cooled measurements suggest that the Mn{sub 3-x}Ga series belongs to the class of magnetically frustrated ferrimagnets. The most pronounced magnetic anomaly is found for Mn{sub 3}Ga.

  6. Novel Linear Algebraic Theory and One-Hundred-Million-Atom Electronic Structure Calculation on The K Computer

    NASA Astrophysics Data System (ADS)

    Hoshi, Takeo; Yamazaki, Keita; Akiyama, Yohei

    A novel linear-algebraic algorithm, multiple Arnoldi method, was developed in an interdisciplinary study between physics and applied mathematics and realized one-hundred-million-atom (100-nm-scale) electronic state calculations on the K computer. The algorithms are Krylov-subspace solvers for generalized shifted linear equations and were implemented in our order-N calculation code ELSES (http://www.elses.jp/). Moreover, a method for calculating eigen states is presented as a theoretical extension.

  7. First-principles calculations for the structural and electronic properties of GaAs1-xPx nanowires

    NASA Astrophysics Data System (ADS)

    Mohammad, Rezek; Katırcıoğlu, Şenay

    2016-09-01

    Structural stability and electronic properties of GaAs1-xPx (0.0≤x≤1.0) nanowires (NWs) in zinc-blende (ZB) (˜5≤ diameter ≤˜21Å) and wurtzite (WZ) (˜5≤diameter≤˜29Å) phases are investigated by first-principles calculations based on density functional theory (DFT). GaAs (x=0.0) and GaP (x=1.0) compound NWs in WZ phase are found energetically more stable than in ZB structural ones. In the case of GaAs1-xPx alloy NWs, the energetically favorable phase is found size and composition dependent. All the presented NWs have semiconductor characteristics. The quantum size effect is clearly demonstrated for all GaAs1-xPx (0.0≤x≤1.0) NWs. The band gaps of ZB and WZ structural GaAs compound NWs with ˜10≤ diameter ≤˜21Å and ˜5≤diameter≤˜29Å, respectively are enlarged by the addition of concentrations of phosphorus for obtaining GaAs1-xPx NWs proportional to the x values around 0.25, 0.50 and 0.75.

  8. Molecular structures of benzoic acid and 2-hydroxybenzoic acid, obtained by gas-phase electron diffraction and theoretical calculations.

    PubMed

    Aarset, Kirsten; Page, Elizabeth M; Rice, David A

    2006-07-20

    The structures of benzoic acid (C6H5COOH) and 2-hydroxybenzoic acid (C6H4OHCOOH) have been determined in the gas phase by electron diffraction using results from quantum chemical calculations to inform restraints used on the structural parameters. Theoretical methods (HF and MP2/6-311+G(d,p)) predict two conformers for benzoic acid, one which is 25.0 kJ mol(-1) (MP2) lower in energy than the other. In the low-energy form, the carboxyl group is coplanar with the phenyl ring and the O-H group eclipses the C=O bond. Theoretical calculations (HF and MP2/6-311+G(d,p)) carried out for 2-hydroxybenzoic acid gave evidence for seven stable conformers but one low-energy form (11.7 kJ mol(-1) lower in energy (MP2)) which again has the carboxyl group coplanar with the phenyl ring, the O-H of the carboxyl group eclipsing the C=O bond and the C=O of the carboxyl group oriented toward the O-H group of the phenyl ring. The effects of internal hydrogen bonding in 2-hydroxybenzoic acid can be clearly observed by comparison of pertinent structural parameters between the two compounds. These differences for 2-hydroxybenzoic acid include a shorter exocyclic C-C bond, a lengthening of the ring C-C bond between the substituents, and a shortening of the carboxylic single C-O bond. PMID:16836466

  9. Study of molecular structure, vibrational, electronic and NMR spectra of oncocalyxone A using DFT and quantum chemical calculations

    NASA Astrophysics Data System (ADS)

    Joshi, Bhawani Datt; Srivastava, Anubha; Honorato, Sara Braga; Tandon, Poonam; Pessoa, Otília Deusdênia Loiola; Fechine, Pierre Basílio Almeida; Ayala, Alejandro Pedro

    2013-09-01

    Oncocalyxone A (C17H18O5) is the major secondary metabolite isolated from ethanol extract from the heartwood of Auxemma oncocalyx Taub popularly known as “pau branco”. Oncocalyxone A (Onco A) has many pharmaceutical uses such as: antitumor, analgesic, antioxidant and causative of inhibition of platelet activation. We have performed the optimized geometry, total energy, conformational study, molecular electrostatic potential mapping, frontier orbital energy gap and vibrational frequencies of Onco A employing ab initio Hartree-Fock (HF) and density functional theory (DFT/B3LYP) method with 6-311++G(d, p) basis set. Stability of the molecule arising from hyperconjugative interactions and/or charge delocalization has been analyzed using natural bond orbital (NBO) analysis. UV-vis spectrum of the compound was recorded in DMSO and MeOH solvent. The TD-DFT calculations have been performed to explore the influence of electronic absorption spectra in the gas phase, as well as in solution environment using IEF-PCM and 6-31G basis set. The 13C NMR chemical shifts have been calculated with the B3LYP/6-311++G(d, p) basis set and compared with the experimental values. These methods have been used as tools for structural characterization of Onco A.

  10. Nonlocal Pseudopotentials and Long-Range Interactions in Ab Initio Finite-Element Electronic-Structure Calculations

    NASA Astrophysics Data System (ADS)

    Pask, J. E.; Sterne, P. A.

    2004-03-01

    The finite-element (FE) method is a general approach for the solution of partial differential equations. Like the planewave (PW) method, the FE method is a systematically improvable expansion approach. Unlike the PW method, however, its basis functions are strictly local in real space, which allows for variable resolution in real space and facilitates massively parallel implementation. We discuss the application of the FE method to ab initio electronic-structure calculations.(J.E. Pask, B.M. Klein, C.Y. Fong, and P.A. Sterne, Phys. Rev. B 59), 12352 (1999). In particular, we discuss the use of nonlocal pseudopotentials in bulk calculations, and the handling of long-range interactions in the construction of the Kohn-Sham effective potential and total energy. We show that the total energy converges variationally, and at the optimal theoretical rate consistent with the cubic completeness of the basis. This work was performed under the auspices of the U.S. Department of Energy by University of California, Lawrence Livermore National Laboratory under Contract W-7405-Eng-48.

  11. First-principles calculation of the electronic structure, chemical bonding, and thermodynamic properties of β-US2

    NASA Astrophysics Data System (ADS)

    Li, Shi-Chang; Zheng, Yuan-Lei; Ma, Sheng-Gui; Gao, Tao; Ao, Bing-Yun

    2015-12-01

    The electronic structure, magnetic states, chemical bonding, and thermodynamic properties of β-US2 are investigated by using first-principles calculation through the density functional theory (DFT) +U approach. The obtained band structure exhibits a direct band gap semiconductor at Γ point with a band gap of 0.9 eV for β-US2, which is in good agreement with the recent experimental data. The charge-density differences, the Bader charge analysis, and the Born effective charges suggest that the U-S bonds of the β-US2 have a mixture of covalent and ionic characters, but the ionic character is stronger than covalent character. The Raman-active, infrared-active, and silent modes at the Γ point are further assigned and discussed. The obtained optical-mode frequencies indicate that the three apparent LO-TO (longitudinal optical-transverse optical) splittings occur in B1u, B2u, and B3u modes, respectively. Furthermore, the Helmholtz free energy ΔF, the specific heat ΔE, vibrational entropy S, and constant volume CV are studied over a range from 0 K˜100 K. We expect that our work can provide some valuable information for further experimental investigation of the dielectric properties and the infrared reflectivity spectrum of uranium chalcogenide. Project supported by the National Natural Science Foundation of China (Grant Nos. 21371160 and 21401173).

  12. Electronic Structure calculations in a 2D SixGe1-x alloy under an applied electric field

    NASA Astrophysics Data System (ADS)

    Padilha, José. Eduardo; Pontes, Renato B.; Seixas, Leandro; da Silva, António J. R.; Fazzio, Adalberto

    2013-03-01

    The recent advances and promises in nanoscience and nanotechnology have been focused on hexagonal materials, mainly on carbon-based nanostructures. Recently, new candidates have been raised, where the greatest efforts are devoted to a new hexagonal and buckled material made of silicon, named Silicene. This new material presents an energy gap due to spin-orbit interaction of approximately 1.5 meV, where the measurement of quantum spin Hall effect(QSHE) can be made experimentally. Some investigations also show that the QSHE in 2D low-buckled hexagonal structures of germanium is present. Since the similarities, and at the same time the differences, between Si and Ge, over the years, have motivated a lot of investigations in these materials. In this work we performed systematic investigations on the electronic structure and band topology in both ordered and disordered SixGe1-x alloys monolayer with 2D honeycomb geometry by first-principles calculations. We show that an applied electric field can tune the gap size for both alloys. However, as a function of electric field, the disordered alloy presents a W-shaped behavior, similarly to the pure Si or Ge, whereas for the ordered alloy a V-shaped behavior is observed. This work is supported by CAPES, CNPq and FAPESP.

  13. First Principles Calculations of Structural, Electronic, Thermodynamic and Thermal Properties of BaxSr1-xTe Ternary Alloys

    NASA Astrophysics Data System (ADS)

    Chelli, S.; Meradji, H.; Amara Korba, S.; Ghemid, S.; El Haj Hassan, F.

    2014-12-01

    The structural, electronic thermodynamic and thermal properties of BaxSr1-xTe ternary mixed crystals have been studied using the ab initio full-potential linearized augmented plane wave (FP-LAPW) method within density functional theory (DFT). In this approach, the Perdew-Burke-Ernzerhof-generalized gradient approximation (PBE-GGA) was used for the exchange-correlation potential. Moreover, the recently proposed modified Becke Johnson (mBJ) potential approximation, which successfully corrects the band-gap problem was also used for band structure calculations. The ground-state properties are determined for the cubic bulk materials BaTe, SrTe and their mixed crystals at various concentrations (x = 0.25, 0.5 and 0.75). The effect of composition on lattice constant, bulk modulus and band gap was analyzed. Deviation of the lattice constant from Vegard's law and the bulk modulus from linear concentration dependence (LCD) were observed for the ternary BaxSr1-xTe alloys. The microscopic origins of the gap bowing were explained by using the approach of Zunger and co-workers. On the other hand, the thermodynamic stability of these alloys was investigated by calculating the excess enthalpy of mixing, ΔHm as well as the phase diagram. It was shown that these alloys are stable at high temperature. Thermal effects on some macroscopic properties of BaxSr1-xTe alloys were investigated using the quasi-harmonic Debye model, in which the phononic effects are considered.

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

    NASA Astrophysics Data System (ADS)

    Aryal, Sita Ram

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

  15. X-ray absorption near edge structure/electron energy loss near edge structure calculation using the supercell orthogonalized linear combination of atomic orbitals method

    NASA Astrophysics Data System (ADS)

    Ching, Wai-Yim; Rulis, Paul

    2009-03-01

    Over the last eight years, a large number of x-ray absorption near edge structure (XANES) and/or electron energy loss near edge structure (ELNES) spectroscopic calculations for complex oxides and nitrides have been performed using the supercell-OLCAO (orthogonalized linear combination of atomic orbitals) method, obtaining results in very good agreement with experiments. The method takes into account the core-hole effect and includes the dipole matrix elements calculated from ab initio wavefunctions. In this paper, we describe the method in considerable detail, emphasizing the special advantages of this method for large complex systems. Selected results are reviewed and several hitherto unpublished results are also presented. These include the Y K edge of Y ions segregated to the core of a Σ31 grain boundary in alumina, O K edges of water molecules, C K edges in different types of single walled carbon nanotubes, and the Co K edge in the cyanocobalamin (vitamin B12) molecule. On the basis of these results, it is argued that the interpretation of specific features of the calculated XANES/ELNES edges is not simple for complex material systems because of the delocalized nature of the conduction band states. The long-standing notion of the 'fingerprinting' technique for spectral interpretation of experimental data is not tenable. A better approach is to fully characterize the structure under study, using either crystalline data or accurate ab initio modeling. Comparison between calculated XANES/ELNES spectra and available measurements enables us to ascertain the validity of the modeled structure. For complex crystals or structures, it is necessary to use the weighted sum of the spectra from structurally nonequivalent sites for comparison with the measured data. Future application of the supercell-OLCAO method to complex biomolecular systems is also discussed.

  16. First principles many-body calculations of electronic structure and optical properties of SiC nanoribbons

    NASA Astrophysics Data System (ADS)

    Alaal, Naresh; Loganathan, Vaideesh; Medhekar, Nikhil; Shukla, Alok

    2016-03-01

    A first principles many-body approach is employed to calculate the band structure and optical response of nanometer-sized ribbons of SiC. Many-body effects are incorporated using the GW approximation, and excitonic effects are included using the Bethe-Salpeter equation. Both unpassivated and hydrogen-passivated armchair SiC nanoribbons are studied. As a consequence of low dimensionality, large quasiparticle corrections are seen to the Kohn-Sham energy gaps. In both cases quasiparticle band gaps are increased by up to 2 eV, as compared to their Kohn-Sham energy values. Inclusion of electron-hole interactions modifies the absorption spectra significantly, giving rise to strongly bound excitonic peaks in these systems. The results suggest that hydrogen passivated armchair SiC nanoribbons have the potential to be used in optoelectronic devices operating in the UV-Vis region of the spectrum. We also compute the formation energies of these nanoribbons as a function of their widths, and conclude that hydrogen-saturated ribbons will be much more stable as compared to bare ones.

  17. Infrared spectra and electronic structure calculations for NN complexes with U, UN, and NUN in solid argon, neon, and nitrogen.

    PubMed

    Andrews, Lester; Wang, Xuefeng; Gong, Yu; Kushto, Gary P; Vlaisavljevich, Bess; Gagliardi, Laura

    2014-07-17

    Reactions of laser-ablated U atoms with N2 molecules upon codeposition in excess argon or neon at 4 K gave intense NUN and weak UN absorptions. Annealing produced progressions of new absorptions for the UN2(N2)1,2,3,4,5 and UN(N2)1,2,3,4,5,6 complexes. The neon-to-argon matrix shift decreases with increasing NN ligation and therefore the number of noble gas atoms left in the primary coordination sphere around the NUN molecule. Small matrix shifts are observed when the secondary coordination layers around the primary UN2(N2)1,2,3,4,5 and UN(N2)1,2,3,4,5,6 complexes are changed from neon-to-argon to nitrogen. Electronic structure, energy, and frequency calculations provide support for the identification of these complexes and the characterization of the N≡U≡N and U≡N core molecules as terminal uranium nitrides. Codeposition of U with pure nitrogen produced the saturated U(NN)7 complex, which UV irradiation converted to the NUN(NN)5 complex with slightly lower frequencies than found in solid argon.

  18. Theoretical calculations of structural, electronic, and elastic properties of CdSe1‑x Te x : A first principles study

    NASA Astrophysics Data System (ADS)

    M, Shakil; Muhammad, Zafar; Shabbir, Ahmed; Muhammad Raza-ur-rehman, Hashmi; M, A. Choudhary; T, Iqbal

    2016-07-01

    The plane wave pseudo-potential method was used to investigate the structural, electronic, and elastic properties of CdSe1‑x Te x in the zinc blende phase. It is observed that the electronic properties are improved considerably by using LDA+U as compared to the LDA approach. The calculated lattice constants and bulk moduli are also comparable to the experimental results. The cohesive energies for pure CdSe and CdTe binary and their mixed alloys are calculated. The second-order elastic constants are also calculated by the Lagrangian theory of elasticity. The elastic properties show that the studied material has a ductile nature.

  19. Noncollinear Fe spin structure in (Sm-Co)/Fe exchange-spring bilayers: layer-resolved {sup 57}Fe Mssbauer spectroscopy and electronic structure calculations.

    SciTech Connect

    Uzdin, V. M.; Vega, A.; Khrenov, A.; Keune, W.; Kuncser, V. E.; Jiang, J. S.; Bader, S. D.

    2012-01-01

    Magnetization reversal in nanoscale (Sm-Co)/Fe (hard/soft) bilayer exchange-spring magnets with in-plane uniaxial magnetic anisotropy was investigated by magnetometry, conversion-electron Moessbauer spectroscopy (CEMS) and atomistic Fe spin-structure calculations. Magnetization loops along the easy direction exhibit signatures typical of exchange-spring magnets. In-field CEMS at inclined {gamma}-ray incidence onto thin (2 nm) {sup 57}Fe probe layers embedded at various depths in the 20-nm-thick natural (soft) Fe layer provides depth-dependent information (via the line-intensity ratio R{sub 23} as a function of the applied field H) about the in-plane rotation of Fe spins. A minimum in the R{sub 23}-vs-H dependence at (H{sub min}, R{sub min}) determines the field where Fe magnetic moments roughly adopt an average perpendicular orientation during their reversal from positive to negative easy-axis orientation. A monotonic decrease of H{sub min} with distance from the hard/soft interface is observed. Rotation of Fe spins takes place even in the interface region in applied fields far below the field of irreversible switching, H{sub irr}, of the hard phase. Formation of an Fe-Co alloy is detected in the interface region. For comparison, the noncollinear Fe spin structure during reversal and the resulting R{sub 23} ratio were obtained by electronic-structure calculations based on a quantum-mechanical Hamiltonian for itinerant electrons. The coupling at the hard/soft interface is described by the uniaxial exchange-anisotropy field, hint, as a parameter. Our calculated R{sub 23} ratios as a function of the (reduced) applied field h exhibit similar features as observed in the experiment, in particular a minimum at (h{sub min}, R{sub min}). R{sub min} is found to increase with hint, thus providing a measure of the interface coupling. Evidence is provided for the existence of fluctuations of the interface coupling. The calculations also show that the Fe spin spiral formed

  20. Electronic structures and optical properties of rutile TiO2 with different point defects from DFT + U calculations

    NASA Astrophysics Data System (ADS)

    Zhu, H. X.; Zhou, P. X.; Li, X.; Liu, J.-M.

    2014-07-01

    The electronic states and formation energies of four types of lattice point defects in rutile TiO2 are studied using the first-principles calculations. The existence of oxygen vacancy leads to a deep donor defect level in the forbidden band, while the Ti interstitial forms two local states. It is predicted that oxygen vacancy prefers to combine with Ti-interstitial to form VO-Tii dimer by a partial 3d electron transfer from the Tii to its neighboring VO. The charge distribution between a Ti interstitial and its neighboring Ti ions partially shields the Coulomb interactions. Lastly, optical properties of these defective lattices are discussed.

  1. Electronic structure and rovibrational calculation of the low-lying states of the RbYb molecule

    NASA Astrophysics Data System (ADS)

    Tohme, S. N.; Korek, M.

    2013-01-01

    Complete Active Space Self Consistent Field (CASSCF) method with Multi Reference Configuration Interaction (MRCI) calculations is used to investigate the potential energy curves of the low-lying 29 electronic states in the representation 2s+1Λ(+/-) of the RbYb molecule (single and double excitations with Davidson corrections). The harmonic frequency ωe, the internuclear distance Re and the electronic energy with respect to the ground state Te have been calculated. The eigenvalues Ev, the rotational constant Bv, and the abscissas of the turning points Rmin and Rmax have been investigated using the canonical functions approach. The comparison between the values of the present work and those available in the literature for several states shows a very good agreement. Twenty-six new states have been studied here for the first time.

  2. Electron Structure of Francium

    NASA Astrophysics Data System (ADS)

    Koufos, Alexander

    2012-02-01

    This talk presents the first calculations of the electronic structure of francium for the bcc, fcc and hcp structures, using the Augmented Plane Wave (APW) method in its muffin-tin and linearized general potential forms. Both the Local Density Approximation (LDA) and Generalized Gradient Approximation (GGA), were used to calculate the electronic structure and total energy of francium (Fr). The GGA and LDA both found the total energy of the hcp structure slightly below that of the fcc and bcc structure, respectively. This is in agreement with similar results for the other alkali metals using the same methodology. The equilibrium lattice constant, bulk modulus and superconductivity parameters were calculated. We found that under pressures, in the range of 1-5 GPa, Fr could be a superconductor at a critical temperature of about 4K.

  3. Hybrid functional calculated optical and electronic structures of thin anatase TiO2 nanowires with organic dye adsorbates

    NASA Astrophysics Data System (ADS)

    Ünal, Hatice; Gunceler, Deniz; Gülseren, Oğuz; Ellialtıoğlu, Şinasi; Mete, Ersen

    2015-11-01

    The electronic and optical properties of thin anatase TiO2 (1 0 1) and (0 0 1) nanowires have been investigated using the screened Coulomb hybrid density functional calculations. For the bare nanowires with sub-nanometer diameters, the calculated band gaps are larger relative to the bulk values due to size effects. The role of organic light harvesting sensitizers on the absorption characteristics of the anatase nanowires has been examined using the hybrid density functional method incorporating partial exact exchange with range separation. For the lowest lying excitations, directional charge redistribution of tetrahydroquinoline (C2-1) dye shows a remarkably different profile in comparison to a simple molecule which is chosen as the coumarin skeleton. The binding modes and the adsorption energies of C2-1 dye and coumarin core on the anatase nanowires have been studied including non-linear solvation effetcs. The calculated optical and electronic properties of the nanowires with these two different types of sensitizers have been interpreted in terms of their electron-hole generation, charge carrier injection and recombination characteristics.

  4. X-ray diffraction-based electronic structure calculations and experimental x-ray analysis for medical and materials applications

    NASA Astrophysics Data System (ADS)

    Mahato, Dip Narayan

    This thesis includes x-ray experiments for medical and materials applications and the use of x-ray diffraction data in a first-principles study of electronic structures and hyperfine properties of chemical and biological systems. Polycapillary focusing lenses were used to collect divergent x rays emitted from conventional x-ray tubes and redirect them to form an intense focused beam. These lenses are routinely used in microbeam x-ray fluorescence analysis. In this thesis, their potential application to powder diffraction and focused beam orthovoltage cancer therapy has been investigated. In conventional x-ray therapy, very high energy (˜ MeV) beams are used, partly to reduce the skin dose. For any divergent beam, the dose is necessarily highest at the entry point, and decays exponentially into the tissue. To reduce the skin dose, high energy beams, which have long absorption lengths, are employed, and rotated about the patient to enter from different angles. This necessitates large expensive specialized equipment. A focused beam could concentrate the dose within the patient. Since this is inherently skin dose sparing, lower energy photons could be employed. A primary concern in applying focused beams to therapy is whether the focus would be maintained despite Compton scattering within the tissue. To investigate this, transmission and focal spot sizes as a function of photon energy of two polycapillary focusing lenses were measured. The effects of tissue-equivalent phantoms of different thicknesses on the focal spot size were studied. Scatter fraction and depth dose were calculated. For powder diffraction, the polycapillary optics provide clean Gaussian peaks, which result in angular resolution that is much smaller than the peak width due to the beam convergence. Powder diffraction (also called coherent scatter) without optics can also be used to distinguish between tissue types that, because they have different nanoscale structures, scatter at different angles

  5. Calculation of the Energy-Band Structure of the Kronig-Penney Model Using the Nearly-Free and Tightly-Bound-Electron Approximations

    ERIC Educational Resources Information Center

    Wetsel, Grover C., Jr.

    1978-01-01

    Calculates the energy-band structure of noninteracting electrons in a one-dimensional crystal using exact and approximate methods for a rectangular-well atomic potential. A comparison of the two solutions as a function of potential-well depth and ratio of lattice spacing to well width is presented. (Author/GA)

  6. Using a Hand-Held Electronic Calculator

    ERIC Educational Resources Information Center

    North, Roger

    1975-01-01

    The arithmetic needed for complex calculation using an electronic calculator is explained and exemplified. Problems involving square roots, number theory, Fibonacci numbers, and electrical resistances are solved. (SD)

  7. Comparison of Conjugate Gradient Density Matrix Search and Chebyshev Expansion Methods for Avoiding Diagonalization in Large-Scale Electronic Structure Calculations

    NASA Technical Reports Server (NTRS)

    Bates, Kevin R.; Daniels, Andrew D.; Scuseria, Gustavo E.

    1998-01-01

    We report a comparison of two linear-scaling methods which avoid the diagonalization bottleneck of traditional electronic structure algorithms. The Chebyshev expansion method (CEM) is implemented for carbon tight-binding calculations of large systems and its memory and timing requirements compared to those of our previously implemented conjugate gradient density matrix search (CG-DMS). Benchmark calculations are carried out on icosahedral fullerenes from C60 to C8640 and the linear scaling memory and CPU requirements of the CEM demonstrated. We show that the CPU requisites of the CEM and CG-DMS are similar for calculations with comparable accuracy.

  8. Electronic structures and ferromagnetism of SnO2 (rutile) doped with double-impurities: First-principles calculations

    NASA Astrophysics Data System (ADS)

    Fakhim Lamrani, A.; Belaiche, M.; Benyoussef, A.; Kenz, El

    2014-01-01

    The electronic and magnetic properties of double-impurities-doped SnO2 (rutile) are explored using first-principles calculations within the generalized gradient approximation to examine their potential use as spintronic system. Calculations are performed for double impurities (M1 and M2) from M1 = Cr, and M2 = Mn, and Re. The origins of ferromagnetism are shown to be different in the two cases. For Sn1-2xCrxMnxO2, the hybridization between Cr-3d and O-2p results in Cr becoming ferromagnetic with a magnetic moment of about 5.0 μB per supercell. The Cr-and Mn-doped SnO2 system exhibits half-metallic ferromagnetism. The strong ferromagnetic couplings between local magnetic moments can be attributed to p-d hybridization. In contrast, in (Cr, Re) codoped TiO2, the local magnetic moments of the impurities and their oxidation states agree with the charge transfer between Cr and Re, which would lead to the ferromagnetic through the double-exchange mechanism in transition metal oxides. Since there are two possible couplings between the impurities, we studied both configurations (ferromagnetic and antiferromagnetic (AF)) for double-impurities-doped SnO2. Our calculations show that a ferromagnetic alignment of the spins is energetically always more stable than simple AF arrangements, which makes these materials possible candidates for spin injection in spintronic devices.

  9. Ab-initio calculation of electronic structure and optical properties of AB-stacked bilayer α-graphyne

    NASA Astrophysics Data System (ADS)

    Behzad, Somayeh

    2016-09-01

    Monolayer α-graphyne is a new two-dimensional carbon allotrope with many special features. In this work the electronic properties of AA- and AB-stacked bilayers of this material and then the optical properties are studied, using first principle plane wave method. The electronic spectrum has two Dirac cones for AA stacked bilayer α-graphyne. For AB-stacked bilayer, the interlayer interaction changes the linear bands into parabolic bands. The optical spectra of the most stable AB-stacked bilayer closely resemble to that of the monolayer, except for small shifts of peak positions and increasing of their intensity. For AB-stacked bilayer, a pronounced peak has been found at low energies under the perpendicular polarization. This peak can be clearly ascribed to the transitions at the Dirac point as a result of the small degeneracy lift in the band structure.

  10. Electronic structure of lithium borocarbide as a cathode material for a rechargeable Li-ion battery: First-principles calculation

    NASA Astrophysics Data System (ADS)

    Xu, Qiang; Ban, Chunmei; Dillon, Anne; Wei, Suhuai; Zhao, Yufeng

    2011-03-01

    Traditional cathode materials, such as transition-metal oxides, are heavy, expensive, and often not benign. Therefore, alternative materials without transition metal elements are highly desirable in order to design high-capacity Li-ion batteries of light weight and low price. Here we report on potential application of the LiBC compound as cathode materials, in which graphene-like BC sheets are intercalated by Li ions. The crystal structure and properties of LiBC were firstly reported by Wörle et al. in 1995. Importantly, it was found that the 75% Li ions can be retrieved out of the compound without changing the layered structure. We have performed first-principles calculations based on density functional theory, as implemented in the Vienna Ab-initio Simulation Package. According to our calculation, the layered Li x BC structure can be well preserved at x > 0.5 . Thereversibleelectrochemicalreaction , LiBC <--> Li 0.5 , gives an energy capacity of 609mAh/g and an open-circuit voltage of 2.42V. The volume change is only about 5% during the charging and discharging process. All these results point to a potentially promising application of LiBC as a novel cathode material for high-capacity Li-ion batteries in replacement of the transition metal oxides.

  11. First-principles calculation of structural and electronic properties of memantine (Alzheimer's disease) and adamantane (anti-flu) drugs

    NASA Astrophysics Data System (ADS)

    Middleton, Kirsten; Zhang, Guoping; George, Thomas F.

    2012-02-01

    Memantine is currently used as a treatment for mild to severe Alzheimer's disease, although its functionality is complicated. Using various density functional theory calculations and basis sets, we first examine memantine alone and then add ions which are present in the human body. This provides clues as to how the compound may react in the calcium ion channel, where it is believed to treat the disease. In order to understand the difference between calcium and magnesium ions interacting with memantine, we compute the electron affinity of each complex. We find that memantine is more strongly attracted to magnesium ions than calcium ions within the channel. By observing the HOMO-LUMO gap within memantine in comparison to adamantane, we find that memantine is more excitable than the anti-flu drug. We believe these factors to affect the efficiency of memantine as a treatment of Alzheimer's disease.

  12. Electronic structure of CeRhIn5: de Haas-van Alphen and energy band calculations

    NASA Astrophysics Data System (ADS)

    Hall, Donavan; Palm, E. C.; Murphy, T. P.; Tozer, S. W.; Petrovic, C.; Miller-Ricci, Eliza; Peabody, Lydia; Li, Charis Quay Huei; Alver, U.; Goodrich, R. G.; Sarrao, J. L.; Pagliuso, P. G.; Wills, J. M.; Fisk, Z.

    2001-08-01

    The de Haas-van Alphen effect and energy-band calculations are used to study angular-dependent extremal areas and effective masses of the Fermi surface of the highly correlated antiferromagnetic material CeRhIn5. The agreement between experiment and theory is reasonable for the areas measured with the field applied along the (100) axis of the tetragonal structure, but there is disagreement in size for the areas observed with the field applied along the (001) axis where the antiferromagnetic spin alignment is occurring. Detailed comparisons between experiment and theory are given.

  13. Fluorescence excitation and ultraviolet absorption spectra and theoretical calculations for benzocyclobutane: Vibrations and structure of its excited S{sub 1}(π,π{sup *}) electronic state

    SciTech Connect

    Shin, Hee Won; Ocola, Esther J.; Laane, Jaan; Kim, Sunghwan

    2014-01-21

    The fluorescence excitation spectra of jet-cooled benzocyclobutane have been recorded and together with its ultraviolet absorption spectra have been used to assign the vibrational frequencies for this molecule in its S{sub 1}(π,π{sup *}) electronic excited state. Theoretical calculations at the CASSCF(6,6)/aug-cc-pVTZ level of theory were carried out to compute the structure of the molecule in its excited state. The calculated structure was compared to that of the molecule in its electronic ground state as well as to the structures of related molecules in their S{sub 0} and S{sub 1}(π,π{sup *}) electronic states. In each case the decreased π bonding in the electronic excited states results in longer carbon-carbon bonds in the benzene ring. The skeletal vibrational frequencies in the electronic excited state were readily assigned and these were compared to the ground state and to the frequencies of five similar molecules. The vibrational levels in both S{sub 0} and S{sub 1}(π,π{sup *}) states were remarkably harmonic in contrast to the other bicyclic molecules. The decreases in the frequencies of the out-of-plane skeletal modes reflect the increased floppiness of these bicyclic molecules in their S{sub 1}(π,π{sup *}) excited state.

  14. Electronic structures and formation energies of pentavalent-ion-doped SnO2: First-principles hybrid functional calculations

    NASA Astrophysics Data System (ADS)

    Behtash, Maziar; Joo, Paul H.; Nazir, Safdar; Yang, Kesong

    2015-05-01

    We studied the electronic properties and relative thermodynamic stability of several pentavalent-ion (Ta, Nb, P, Sb, and I) doped SnO2 systems using first-principles hybrid density functional theory calculations, in order to evaluate their potential as transparent conducting oxides (TCOs). I-doped SnO2, though conductive, shows a narrowed optical band gap with respect to the undoped system due to the formation of gap states above the valence band. Nb-doped SnO2 forms localized impurity states below the conduction band bottom, suggesting that the Nb dopant exists as an Nb4+-like cation, which is consistent with the recent experimental finding of the formation of the impurity level below the conduction band bottom [Appl. Phys. Express 5, 061201 (2012)]. Ta- and Sb-doped SnO2 display n-type conductivity, high charge carrier density, and widened optical band gap. P-doped SnO2 shows similar n-type electronic properties with that of Sb- and Ta-doped systems, and thus P-doped SnO2 is proposed as a promising candidate TCO for further experimental validation.

  15. Accuracy of Lagrange-sinc functions as a basis set for electronic structure calculations of atoms and molecules

    SciTech Connect

    Choi, Sunghwan; Hong, Kwangwoo; Kim, Jaewook; Kim, Woo Youn

    2015-03-07

    We developed a self-consistent field program based on Kohn-Sham density functional theory using Lagrange-sinc functions as a basis set and examined its numerical accuracy for atoms and molecules through comparison with the results of Gaussian basis sets. The result of the Kohn-Sham inversion formula from the Lagrange-sinc basis set manifests that the pseudopotential method is essential for cost-effective calculations. The Lagrange-sinc basis set shows faster convergence of the kinetic and correlation energies of benzene as its size increases than the finite difference method does, though both share the same uniform grid. Using a scaling factor smaller than or equal to 0.226 bohr and pseudopotentials with nonlinear core correction, its accuracy for the atomization energies of the G2-1 set is comparable to all-electron complete basis set limits (mean absolute deviation ≤1 kcal/mol). The same basis set also shows small mean absolute deviations in the ionization energies, electron affinities, and static polarizabilities of atoms in the G2-1 set. In particular, the Lagrange-sinc basis set shows high accuracy with rapid convergence in describing density or orbital changes by an external electric field. Moreover, the Lagrange-sinc basis set can readily improve its accuracy toward a complete basis set limit by simply decreasing the scaling factor regardless of systems.

  16. Accuracy of Lagrange-sinc functions as a basis set for electronic structure calculations of atoms and molecules.

    PubMed

    Choi, Sunghwan; Hong, Kwangwoo; Kim, Jaewook; Kim, Woo Youn

    2015-03-01

    We developed a self-consistent field program based on Kohn-Sham density functional theory using Lagrange-sinc functions as a basis set and examined its numerical accuracy for atoms and molecules through comparison with the results of Gaussian basis sets. The result of the Kohn-Sham inversion formula from the Lagrange-sinc basis set manifests that the pseudopotential method is essential for cost-effective calculations. The Lagrange-sinc basis set shows faster convergence of the kinetic and correlation energies of benzene as its size increases than the finite difference method does, though both share the same uniform grid. Using a scaling factor smaller than or equal to 0.226 bohr and pseudopotentials with nonlinear core correction, its accuracy for the atomization energies of the G2-1 set is comparable to all-electron complete basis set limits (mean absolute deviation ≤1 kcal/mol). The same basis set also shows small mean absolute deviations in the ionization energies, electron affinities, and static polarizabilities of atoms in the G2-1 set. In particular, the Lagrange-sinc basis set shows high accuracy with rapid convergence in describing density or orbital changes by an external electric field. Moreover, the Lagrange-sinc basis set can readily improve its accuracy toward a complete basis set limit by simply decreasing the scaling factor regardless of systems.

  17. The First Principles Calculation of Structural, Electronic and Magnetic Properties of MnXY (x = Ru, rh and Y = Ga, Ge, Sb) Alloys

    NASA Astrophysics Data System (ADS)

    Moniri, S. M.; Nourbakhsh, Z.; Mostajabodaavati, M.

    The structural, electronic and magnetic properties of MnXY (X = Ru, Rh and Y = Ga, Ge, Sb) Heusler alloys are studied using density functional theory by the WIEN2k package. These materials are ferromagnetic. Also they have some interesting half-metallic properties. The electron density of states, total and local magnetic moment of these alloys are calculated. We have calculated the effective Coulomb interaction Ueff using the ab initio method. We have compared the magnetic moments of these alloys in GGA and LDA+U with the Slater-Pauling rule. Furthermore the effect of hydrostatic pressure on the magnetic moment of these alloys is studied. The calculated results are fitted with a second order polynomial.

  18. Electronic structures and ferromagnetism of SnO{sub 2} (rutile) doped with double-impurities: First-principles calculations

    SciTech Connect

    Fakhim Lamrani, A.; Belaiche, M.; Benyoussef, A.; and others

    2014-01-07

    The electronic and magnetic properties of double-impurities-doped SnO{sub 2} (rutile) are explored using first-principles calculations within the generalized gradient approximation to examine their potential use as spintronic system. Calculations are performed for double impurities (M1 and M2) from M1 = Cr, and M2 = Mn, and Re. The origins of ferromagnetism are shown to be different in the two cases. For Sn{sub 1-2x}Cr{sub x}Mn{sub x}O2, the hybridization between Cr-3d and O-2p results in Cr becoming ferromagnetic with a magnetic moment of about 5.0 μ{sub B} per supercell. The Cr-and Mn-doped SnO{sub 2} system exhibits half-metallic ferromagnetism. The strong ferromagnetic couplings between local magnetic moments can be attributed to p-d hybridization. In contrast, in (Cr, Re) codoped TiO{sub 2}, the local magnetic moments of the impurities and their oxidation states agree with the charge transfer between Cr and Re, which would lead to the ferromagnetic through the double-exchange mechanism in transition metal oxides. Since there are two possible couplings between the impurities, we studied both configurations (ferromagnetic and antiferromagnetic (AF)) for double-impurities-doped SnO{sub 2}. Our calculations show that a ferromagnetic alignment of the spins is energetically always more stable than simple AF arrangements, which makes these materials possible candidates for spin injection in spintronic devices.

  19. Linear augmented-Slater-type-orbital method for electronic-structure calculations. IV. 5d-5d alloys

    SciTech Connect

    Watson, R.E.; Davenport, J.W.; Weinert, M.

    1986-12-15

    We have used local-density calculations to study a series of transition-metal compounds which are isoelectronic with rhenium: WOs, TaIr, and HfPt. The calculations were carried out for two different crystal structures, CsCl and CuAuI. We find that the heats of formation are in reasonable accord with experiment and increase with the difference in atomic number. We also find a crossover in crystal structure from CuAuI for OsW and TaIr to CsCl for HfPt, which is consistent with experiment. Charge transfer in the series was investigated by Mulliken populations and by Wigner-Seitz sphere counts. These were compared with the shifts in contact density and core-level binding energy. We find that the change in contact density is consistent with electronegativity arguments and involves both changes in s count and d (or at least non-s) screening contributions. The changes in (initial-state) core-level binding energy do not follow the same trend--in fact, for two of the compounds, the change in binding energy relative to the Fermi energy has the same sign for the two constituents.

  20. Structural, mechanical, and electronic properties of Rh2B and RhB2: first-principles calculations

    PubMed Central

    Chu, Binhua; Li, Da; Tian, Fubo; Duan, Defang; Sha, Xiaojing; Lv, Yunzhou; Zhang, Huadi; Liu, Bingbing; Cui, Tian

    2015-01-01

    The crystal structures of Rh2B and RhB2 at ambient pressure were explored by using the evolutionary methodology. A monoclinic P21/m structure of Rh2B was predicted and donated as Rh2B-I, which is energetically much superior to the previously experimentally proposed Pnma structure. At the pressure of about 39 GPa, the P21/m phase of Rh2B transforms to the C2/m phases. For RhB2, a new monoclinic P21/m phase was predicted, named as RhB2-II, it has the same structure type with Rh2B. Rh2B-I and RhB2-II are both mechanically and dynamically stable. They are potential low compressible materials. The analysis of electronic density of states and chemical bonding indicates that the formation of strong and directional covalent B-B and Rh-B bonds in these compounds contribute greatly to their stabilities and high incompressibility. PMID:26123399

  1. Illustration of high-active Ag2CrO4 photocatalyst from the first-principle calculation of electronic structures and carrier effective mass

    NASA Astrophysics Data System (ADS)

    Zhang, Jinfeng; Yu, Weilai; Liu, Jianjun; Liu, Baoshun

    2015-12-01

    Although Ag2CrO4 has been frequently studied as a highly active photocatalytic material under visible light irradiation in recent years, we are still less-known on its detailed mechanism. Also, it is difficult to illustrate this issue just from the experimental discussion. Contrarily, theoretical investigation can deepen our understanding on its photocatalytic mechanism from the electronic level. In this work, the crystal structures, band structures, density of states, and chemical bonding for Ag2CrO4 were studied by the first-principles calculation based on the density functional theory. The calculation results indicate that Ag2CrO4 has an indirect band gap of ca. 1.42 eV, a deep position of valence band edge and a strong optical absorption coefficient, implying that Ag2CrO4 has strong oxidation ability and high photocatalytic activity for decomposing organic pollutant under visible light irradiation. Moreover, our calculation also indicates that Ag2CrO4 has small effective mass of electrons and holes, and great effective mass difference between hole and electron, which can respectively facilitate the migration and separation of electrons and holes, and finally improve the photocatalytic performance.

  2. Investigation of the electron structure of ZnO by the GGA and mBJ calculations associated with the characterization techniques AES and EELS

    NASA Astrophysics Data System (ADS)

    Mokadem, A.; Bouslama, M.; Benhelal, O.; Assali, A.; Ghaffour, M.; Chelahi Chikr, Z.; Boulenouar, K.; Boubaia, A.

    2014-03-01

    The semiconductor ZnO of large gap of 3,4 eV is of great interest for the technological applications as chemical sensors, UV light emission, optical memories, laser emission, solar cells, etc. These applications depend on the electron structure of material. We adopt the density functional theory (DFT) calculation by using the program Wien2K, within the Generalized Gradient Approximation (GGA) and modified Becke-Johnson (mBJ) for studying the electron behavior of ZnO. The features of the valence band derived from the hybridization of Zn-3d and O-2p states. The electron charge density calculated by these simulation methods indicates a charge transfer between zinc and oxygen inducing a difference in electronegativity between both species (Zn and O), responsible to ionic character of bonding in ZnO. The predictions based on the GGA and mBJ calculations are confirmed by the results of the experimental spectroscopic analysis Auger Electron Spectroscopy (AES) and Electron Energy Loss Spectroscopy (EELS).

  3. Structural, electronic, elastic, thermoelectric and thermodynamic properties of the NbMSb half heusler (M=Fe, Ru, Os) compounds with first principle calculations

    NASA Astrophysics Data System (ADS)

    Abid, O. Miloud; Menouer, S.; Yakoubi, A.; Khachai, H.; Omran, S. Bin; Murtaza, G.; Prakash, Deo; Khenata, R.; Verma, K. D.

    2016-05-01

    The structural, electronic, elastic, thermoelectric and thermodynamic properties of NbMSb (M = Fe, Ru, Os) half heusler compounds are reported. The full-potential linearized augmented plane wave (FP-LAPW) plus local orbital (lo) method, based on the density functional theory (DFT) was employed for the present study. The equilibrium lattice parameter results are in good compliance with the available experimental measurements. The electronic band structure and Boltzmann transport calculations indicated a narrow indirect energy band gap for the compound having electronic structure favorable for thermoelectric performance as well as with substantial thermopowers at temperature ranges from 300 K to 800 K. Furthermore, good potential for thermoelectric performance (thermopower S ≥ 500 μeV) was found at higher temperature. In addition, the analysis of the charge density, partial and total densities of states (DOS) of three compounds demonstrate their semiconducting, ionic and covalent characters. Conversely, the calculated values of the Poisson's ratio and the B/G ratio indicate their ductile makeup. The thermal properties of the compounds were calculated by quasi-harmonic Debye model as implemented in the GIBBS code.

  4. Demystifying fluorine chemical shifts: electronic structure calculations address origins of seemingly anomalous (19)F-NMR spectra of fluorohistidine isomers and analogues.

    PubMed

    Kasireddy, Chandana; Bann, James G; Mitchell-Koch, Katie R

    2015-11-11

    Fluorine NMR spectroscopy is a powerful tool for studying biomolecular structure, dynamics, and ligand binding, yet the origins of (19)F chemical shifts are not well understood. Herein, we use electronic structure calculations to describe the changes in (19)F chemical shifts of 2F- and 4F-histidine/(5-methyl)-imidazole upon acid titration. While the protonation of the 2F species results in a deshielded chemical shift, protonation of the 4F isomer results in an opposite, shielded chemical shift. The deshielding of 2F-histidine/(5-methyl)-imidazole upon protonation can be rationalized by concomitant decreases in charge density on fluorine and a reduced dipole moment. These correlations do not hold for 4F-histidine/(5-methyl)-imidazole, however. Molecular orbital calculations reveal that for the 4F species, there are no lone pair electrons on the fluorine until protonation. Analysis of a series of 4F-imidazole analogues, all with delocalized fluorine electron density, indicates that the deshielding of (19)F chemical shifts through substituent effects correlates with increased C-F bond polarity. In summary, the delocalization of fluorine electrons in the neutral 4F species, with gain of a lone pair upon protonation may help explain the difficulty in developing a predictive framework for fluorine chemical shifts. Ideas debated by chemists over 40 years ago, regarding fluorine's complex electronic effects, are shown to have relevance for understanding and predicting fluorine NMR spectra.

  5. Possibility of transforming the electronic structure of one species of graphene adatoms into that of another by application of gate voltage: First-principles calculations

    NASA Astrophysics Data System (ADS)

    Chan, Kevin T.; Lee, Hoonkyung; Cohen, Marvin L.

    2011-10-01

    Graphene provides many advantages for controlling the electronic structure of adatoms and other adsorbates via gating. Using the projected density of states and charge density obtained from first-principles density-functional periodic supercell calculations, we investigate the possibility of performing “alchemy” of adatoms on graphene, i.e., transforming the electronic structure of one species of adatom into that of another species by application of a gate voltage. Gating is modeled as a change in the number of electrons in the unit cell, with the inclusion of a compensating uniform background charge. Within this model and the generalized gradient approximation to the exchange-correlation functional, we find that such transformations are possible for K, Ca, and several transition-metal adatoms. Gate control of the occupation of the p states of In on graphene is also investigated. The validity of the supercell approximation with uniform compensating charge and the model for exchange and correlation is also discussed.

  6. Investigation of intravalence, core-valence and core-core electron correlation effects in polonium atomic structure calculations

    NASA Astrophysics Data System (ADS)

    Quinet, Pascal

    2014-09-01

    A detailed investigation of the atomic structure and radiative parameters involving the lowest states within the 6p4, 6p36d, 6p37s, 6p37p and 6p37d configurations of neutral polonium is reported in the present paper. Using different physical models based on the pseudo-relativistic Hartree-Fock approach, the influence of intravalence, core-valence and core-core electron correlation on the atomic parameters is discussed in detail. This work allowed us to fix the spectroscopic designation of some experimental level energy values and to provide for the first time a set of reliable oscillator strengths corresponding to 31 Po I spectral lines in the wavelength region from 175 to 987 nm.

  7. Structural, magnetic, and electronic properties of the Co-Fe-Al oxide spinel system: Density-functional theory calculations

    SciTech Connect

    Walsh, Aron; Wei, S.-H.; Yan Yanfa; Al-Jassim, M. M.; Turner, John A.; Woodhouse, Michael; Parkinson, B. A.

    2007-10-15

    A systematic study of nine binary and ternary spinel oxides formed from Co, Al, and Fe is presented by means of density functional theory. Analysis of the structural, magnetic, and electronic properties through the series of materials is carried out. Preference for the octahedral spinel sites are found in the order Feelectronic band gaps of Co{sub 3}O{sub 4} and Fe{sub 3}O{sub 4} are shown to remain largely unchanged as Al is substituted into the lattice forming M{sub 2}AlO{sub 4} (M=Fe,Co), but increase greater than 1 eV for MAl{sub 2}O{sub 4} as the octahedral M metal sites are lost. However, for stoichiometric FeAl{sub 2}O{sub 4}, the unsatisfied valence state of Fe results in partial occupation of the conduction band. The results and chemical trends are discussed in terms of atomic site and orbital energies, and in relation to potential photoelectrolysis activity for the splitting of water as a renewable means of hydrogen production.

  8. Spectroscopic and electronic structure calculation of a potential antibacterial agent incorporating pyrido-dipyrimidine-dione moiety using first principles

    NASA Astrophysics Data System (ADS)

    Fatma, Shaheen; Bishnoi, Abha; Singh, Vineeta; Al-Omary, Fatmah A. M.; El-Emam, Ali A.; Pathak, Shilendra; Srivastava, Ruchi; Prasad, Onkar; Sinha, Leena

    2016-04-01

    Quantum chemical calculations of geometrical structure, energy and vibrational wavenumbers of a novel functionalized pyrido-pyrimidine compound (a prospective antibacterial agent), chemically known as 6-Methyl,13,14,15-Trihydro-14-(4-Nitrophenyl)pyrido[1,2-a:1‧,2‧-a‧] pyrido[2″,3″-d:6″,5″-d‧]dipyrimidine-13,15-dione (C24H16N6O4), were carried out, using B3LYP/6311++G(d,p) method. Comprehensive interpretation of the infrared and Raman spectra of the compound under study is based on potential energy distribution. A good coherence between experimental and theoretical wavenumbers shows the preciseness of the assignments. NLO properties like the dipole moment, polarizability, first static hyperpolarizability and molecular electrostatic potential surface have been calculated to get a better cognizance of the properties of the title compound. Molecular docking results reveal that the title compound exhibit inhibitory activity against Staphylococcus aureus.

  9. Electronic structure and mechanical properties of ternary ZrTaN alloys studied by ab initio calculations and thin-film growth experiments

    NASA Astrophysics Data System (ADS)

    Abadias, G.; Kanoun, M. B.; Goumri-Said, S.; Koutsokeras, L.; Dub, S. N.; Djemia, Ph.

    2014-10-01

    The structure, phase stability, and mechanical properties of ternary alloys of the Zr-Ta-N system are investigated by combining thin-film growth and ab initio calculations. Zr1-xTaxN films with 0≤x≤1 were deposited by reactive magnetron cosputtering in Ar +N2 plasma discharge and their structural properties characterized by x-ray diffraction. We considered both ordered and disordered alloys, using supercells and special quasirandom structure approaches, to account for different possible metal atom distributions on the cation sublattice. Density functional theory within the generalized gradient approximation was employed to calculate the electronic structure as well as predict the evolution of the lattice parameter and key mechanical properties, including single-crystal elastic constants and polycrystalline elastic moduli, of ternary Zr1-xTaxN compounds with cubic rocksalt structure. These calculated values are compared with experimental data from thin-film measurements using Brillouin light scattering and nanoindentation tests. We also study the validity of Vegard's empirical rule and the effect of growth-dependent stresses on the lattice parameter. The thermal stability of these Zr1-xTaxN films is also studied, based on their structural and mechanical response upon vacuum annealing at 850 °C for 3 h. Our findings demonstrate that Zr1-xTaxN alloys with Ta fraction 0.51⩽x⩽0.78 exhibit enhanced toughness, while retaining high hardness ˜30 GPa, as a result of increased valence electron concentration and phase stability tuning. Calculations performed for disordered or ordered structures both lead to the same conclusion regarding the mechanical behavior of these nitride alloys, in agreement with recent literature findings [H. Kindlund, D. G. Sangiovanni, L. Martinez-de-Olcoz, J. Lu, J. Jensen, J. Birch, I. Petrov, J. E. Greene, V. Chirita, and L. Hultman, APL Materials 1, 042104 (2013), 10.1063/1.4822440].

  10. Comparative Study Between GGA and LDA Approximation Using First- Principles Calculations of Structural, Electronic, Optical and Vibrational Properties of CaTiO3 Crystal

    NASA Astrophysics Data System (ADS)

    Medeiros, Subenia; Araujo, Maeva

    2015-03-01

    The structural, electronic, vibrational, and optical properties of perovskite CaTiO3 in the cubic, orthorhombic, and tetragonal phase are calculated in the framework of density functional theory (DFT) with different exchange-correlation potentials by CASTEP package. The calculated band structure shows an indirect band gap of 1.88 eV at the Γ-R points in the Brillouin zone to the cubic structure, a direct band gap of 2.41 eV at the Γ- Γ points to the orthorhombic structure, and an indirect band gap of 2.31 eV at theM - Γ points to the tetragonal phase. It is still known that the CaTiO3 has a static dielectric constant that extrapolates to a value greater than 300 at zero temperature, and the dielectric response is dominated by low frequency (ν ~ 90cm-1) polar optical modes in which cation motion opposes oxygen motion. Our calculated lattice parameters, elastic constants, optical properties, and vibrational frequencies are found to be in good agreement with the available theoretical and experimental values. The results for the effective mass in the electron and hole carriers are also presented in this work.

  11. Electronic structure and optical properties of F-doped β-Ga2O3 from first principles calculations

    NASA Astrophysics Data System (ADS)

    Jinliang, Yan; Chong, Qu

    2016-04-01

    The effects of F-doping concentration on geometric structure, electronic structure and optical property of β-Ga2O3 were investigated. All F-doped β-Ga2O3 with different concentrations are easy to be formed under Ga-rich conditions, the stability and lattice parameters increase with the F-doping concentration. F-doped β-Ga2O3 materials display characteristics of the n-type semiconductor, occupied states contributed from Ga 4s, Ga 4p and O 2p states in the conduction band increase with an increase in F-doping concentration. The increase of F concentration leads to the narrowing of the band gap and the broadening of the occupied states. F-doped β-Ga2O3 exhibits the sharp band edge absorption and a broad absorption band. Absorption edges are blue-shifted, and the intensity of broad band absorption has been enhanced with respect to the fluorine content. The broad band absorption is ascribed to the intra-band transitions from occupied states to empty states in the conduction band. Project supported by the Innovation Project of Shandong Graduate Education, China (No. SDYY13093) and the National Natural Science Foundation of China (No. 10974077).

  12. Two ferromagnetic azido-bridged copper(ll) complexes studied by first-principle electronic-structure calculation.

    PubMed

    Zhang, Y S; Yao, K L; Liu, Z L

    2005-09-22

    The electronic structures of two ferromagnetic polynuclear copper(II) complexes, derived from end-to-end azido ligand and tridentate (NNN donor) Schiff base ligand, have been studied using the full-potential linearized augmented plane-wave method based on the density-functional theory. They are [Cu(L1)(micro-1,3-N3)]n(ClO4)n (1) and [Cu(L2)(micro-1,3-N3)]n(ClO4)n (2). The result shows that the spin populations in these two complexes are mainly distributed on the equatorial planes of a square pyramidal that surround the copper(II) ions. There are large and positive spin populations on copper(II) ions, small and positive spin populations on the three nitrogen atoms of tridentate Schiff base ligand, and the two terminal nitrogen atoms of asymmetrical end-to-end azido ligand, while weak and negative spin populations on the central nitrogen atoms of asymmetrical end-to-end azido ligand. Ferromagnetic coupling through the asymmetrical azido ligand in these two complexes has been mainly attributed to the spin delocalization, also with weak spin-polarization effect. PMID:16392483

  13. Two ferromagnetic azido-bridged copper(II) complexes studied by first-principle electronic-structure calculation

    NASA Astrophysics Data System (ADS)

    Zhang, Y. S.; Yao, K. L.; Liu, Z. L.

    2005-09-01

    The electronic structures of two ferromagnetic polynuclear copper(II) complexes, derived from end-to-end azido ligand and tridentate (NNN donor) Schiff base ligand, have been studied using the full-potential linearized augmented plane-wave method based on the density-functional theory. They are [Cu(L1)(μ-1,3-N3)]n(ClO4)n (1) and [Cu(L2)(μ-1,3-N3)]n(ClO4)n (2). The result shows that the spin populations in these two complexes are mainly distributed on the equatorial planes of a square pyramidal that surround the copper(II) ions. There are large and positive spin populations on copper(II) ions, small and positive spin populations on the three nitrogen atoms of tridentate Schiff base ligand, and the two terminal nitrogen atoms of asymmetrical end-to-end azido ligand, while weak and negative spin populations on the central nitrogen atoms of asymmetrical end-to-end azido ligand. Ferromagnetic coupling through the asymmetrical azido ligand in these two complexes has been mainly attributed to the spin delocalization, also with weak spin-polarization effect.

  14. Molecular structure and electronic properties of pyridylindolizine derivative containing phenyl and phenacyl groups: Comparison between semi-empirical calculations and experimental studies

    NASA Astrophysics Data System (ADS)

    Cojocaru, Corneliu; Rotaru, Alexandru; Harabagiu, Valeria; Sacarescu, Liviu

    2013-02-01

    This work deals with theoretical investigations of a pyridylindolizine derivative containing phenyl and phenacyl groups, namely [1-benzoyl-2-phenyl-7-(pyridin-4-yl)indolizin-3-yl](4-methoxyphenyl)methanone (C34H24N2O3), and comparison of modeling results with available experimental data (e.g. X-ray-structure analysis). The molecular modeling has been performed by means of AM1, MNDO, PM3 and RM1 semi-empirical methods. The deviation between experimental and calculated parameters has been ascertained in terms of average relative error, ARE (%). The calculated geometries, after comparisons with corresponding X-ray structure, have pointed out that RM1 and PM3 predict better the bond lengths than other semi-empirical methods, exhibiting the average relative errors of 4.529% and 4.680%, respectively. The best model for the prediction of interatomic angles is AM1 method, revealing a deviation error of 1.067% from the observed angles determined by X-ray structure analysis. Likewise, the theoretical vibrational and electronic spectra have been calculated and reported. In addition, the optimized structures, binding energies, atomic charges, molecular orbital energy spectra, the electrostatic potential as well as the quantitative structure activity relationship (QSAR) properties of the molecule have been computed and discussed.

  15. Research of the structural and electronic properties of VN/AlN/VN and AlN/VN/AlN based on DFT calculation

    NASA Astrophysics Data System (ADS)

    Díaz F, J. H.; Espitia R, M. J.; Rodriguez Martínez, J. A.

    2016-08-01

    We investigated the structural, electronic, and magnetic properties of AlN/VN/AlN and VN/AlN/VN interlayers in the wurtzite structure, via first-principles calculations using the psuedopotential method within density functional theory (DFT) as implemented in the Quantum ESPRESSO code. The total energy calculation showed that the VN/AlN/VN interlayer is energetically more favorable than the AlN/VN/AlN one. Analysis of the density of states showed that the interlayers exhibit a metallic behavior that essentially comes from the hybridization and polarization of states V-d and N-p across the Fermi level. The interlayers exhibit magnetic properties, with a magnetic moment of 4μβ/cell. Due to these properties, the superlattices can potentially be used in the field of spintronics.

  16. Probing the limits of accuracy in electronic structure calculations: is theory capable of results uniformly better than "chemical accuracy"?

    PubMed

    Feller, David; Peterson, Kirk A

    2007-03-21

    Current limitations in electronic structure methods are discussed from the perspective of their potential to contribute to inherent uncertainties in predictions of molecular properties, with an emphasis on atomization energies (or heats of formation). The practical difficulties arising from attempts to achieve high accuracy are illustrated via two case studies: the carbon dimer (C2) and the hydroperoxyl radical (HO2). While the HO2 wave function is dominated by a single configuration, the carbon dimer involves considerable multiconfigurational character. In addition to these two molecules, statistical results will be presented for a much larger sample of molecules drawn from the Computational Results Database. The goal of this analysis will be to determine if a combination of coupled cluster theory with large 1-particle basis sets and careful incorporation of several computationally expensive smaller corrections can yield uniform agreement with experiment to better than "chemical accuracy" (+/-1 kcal/mol). In the case of HO2, the best current theoretical estimate of the zero-point-inclusive, spin-orbit corrected atomization energy (SigmaD0=166.0+/-0.3 kcal/mol) and the most recent Active Thermochemical Table (ATcT) value (165.97+/-0.06 kcal/mol) are in excellent agreement. For C2 the agreement is only slightly poorer, with theory (D0=143.7+/-0.3 kcal/mol) almost encompassing the most recent ATcT value (144.03+/-0.13 kcal/mol). For a larger collection of 68 molecules, a mean absolute deviation of 0.3 kcal/mol was found. The same high level of theory that produces good agreement for atomization energies also appears capable of predicting bond lengths to an accuracy of +/-0.001 A. PMID:17381194

  17. Probing the limits of accuracy in electronic structure calculations: Is theory capable of results uniformly better than ``chemical accuracy''?

    NASA Astrophysics Data System (ADS)

    Feller, David; Peterson, Kirk A.

    2007-03-01

    Current limitations in electronic structure methods are discussed from the perspective of their potential to contribute to inherent uncertainties in predictions of molecular properties, with an emphasis on atomization energies (or heats of formation). The practical difficulties arising from attempts to achieve high accuracy are illustrated via two case studies: the carbon dimer (C2) and the hydroperoxyl radical (HO2). While the HO2 wave function is dominated by a single configuration, the carbon dimer involves considerable multiconfigurational character. In addition to these two molecules, statistical results will be presented for a much larger sample of molecules drawn from the Computational Results Database. The goal of this analysis will be to determine if a combination of coupled cluster theory with large 1-particle basis sets and careful incorporation of several computationally expensive smaller corrections can yield uniform agreement with experiment to better than "chemical accuracy" (±1kcal /mol). In the case of HO2, the best current theoretical estimate of the zero-point-inclusive, spin-orbit corrected atomization energy (ΣD0=166.0±0.3kcal /mol) and the most recent Active Thermochemical Table (ATcT) value (165.97±0.06kcal/mol) are in excellent agreement. For C2 the agreement is only slightly poorer, with theory (D0=143.7±0.3kcal/mol) almost encompassing the most recent ATcT value (144.03±0.13kcal/mol). For a larger collection of 68molecules, a mean absolute deviation of 0.3kcal/mol was found. The same high level of theory that produces good agreement for atomization energies also appears capable of predicting bond lengths to an accuracy of ±0.001Å.

  18. First-principles calculation of the structural, electronic, elastic, and optical properties of sulfur-doping ε-GaSe crystal

    NASA Astrophysics Data System (ADS)

    Huang, Chang-Bao; Wu, Hai-Xin; Ni, You-Bao; Wang, Zhen-You; Qi, Ming; Zhang, Chun-Li

    2016-08-01

    The structural, electronic, mechanical properties, and frequency-dependent refractive indexes of GaSe1–x S x (x = 0, 0.25, and 1) are studied by using the first-principles pseudopotential method within density functional theory. The calculated results demonstrate the relationships between intralayer structure and elastic modulus in GaSe1–x S x (x = 0, 0.25, and 1). Doping of ε-GaSe with S strengthens the Ga–X bonds and increases its elastic moduli of C 11 and C 66. Born effective charge analysis provides an explanation for the modification of cleavage properties about the doping of ε-GaSe with S. The calculated results of band gaps suggest that the distance between intralayer atom and substitution of SSe, rather than interlayer force, is a key factor influencing the electronic exciton energy of the layer semiconductor. The calculated refractive indexes indicate that the doping of ε-GaSe with S reduces its refractive index and increases its birefringence. Project supported by the National Natural Science Foundation of China (Grant No. 51202250).

  19. First-principles calculation of the structural, electronic, elastic, and optical properties of sulfur-doping ɛ-GaSe crystal

    NASA Astrophysics Data System (ADS)

    Huang, Chang-Bao; Wu, Hai-Xin; Ni, You-Bao; Wang, Zhen-You; Qi, Ming; Zhang, Chun-Li

    2016-08-01

    The structural, electronic, mechanical properties, and frequency-dependent refractive indexes of GaSe1-x S x (x = 0, 0.25, and 1) are studied by using the first-principles pseudopotential method within density functional theory. The calculated results demonstrate the relationships between intralayer structure and elastic modulus in GaSe1-x S x (x = 0, 0.25, and 1). Doping of ɛ-GaSe with S strengthens the Ga-X bonds and increases its elastic moduli of C 11 and C 66. Born effective charge analysis provides an explanation for the modification of cleavage properties about the doping of ɛ-GaSe with S. The calculated results of band gaps suggest that the distance between intralayer atom and substitution of SSe, rather than interlayer force, is a key factor influencing the electronic exciton energy of the layer semiconductor. The calculated refractive indexes indicate that the doping of ɛ-GaSe with S reduces its refractive index and increases its birefringence. Project supported by the National Natural Science Foundation of China (Grant No. 51202250).

  20. Comparison of the electronic band structures of LiCaAlF6 and LiSrAlF6 ultraviolet laser host media from ab initio calculations

    NASA Astrophysics Data System (ADS)

    Viet Luong, Mui; Cadatal-Raduban, Marilou; Empizo, Melvin John F.; Arita, Ren; Minami, Yuki; Shimizu, Toshihiko; Sarukura, Nobuhiko; Azechi, Hiroshi; Pham, Minh Hong; Nguyen, Hung Dai; Kawazoe, Yoshiyuki

    2015-12-01

    We report the electronic structures and density of states (DOS) of perfect LiCAF and LiSAF crystals calculated from density functional theory (DFT) with local density approximation (LDA) using optimized lattice constants. DOS calculations reveal that the valence band is mainly derived from F 2p, thereby resulting to a very narrow valence band manifold. Meanwhile, the conduction band is mainly derived from Ca 4s or Sr 5s resulting to Sr having a broader band dispersion compared to Ca. Both fluoride compounds have indirect band gaps with LiCAF having a band gap of 8.02 eV and LiSAF a band gap of 7.92 eV. This is, to the best of our knowledge, the first report on the electronic structure of LiSAF calculated using DFT with LDA. Our results suggest that when doped with Ce3+, the shorter 5d-conduction band distance in Ce:LiSAF combined with the difficulty of growing high-purity crystals lead to the more pronounced excited state absorption (ESA) and solarization effect experimentally observed in Ce:LiSAF, limiting its potential as a laser material compared with Ce:LiCAF.

  1. First principles phase transition, elastic properties and electronic structure calculations for cadmium telluride under induced pressure: density functional theory, LDA, GGA and modified Becke-Johnson potential

    NASA Astrophysics Data System (ADS)

    Kabita, Kh; Maibam, Jameson; Indrajit Sharma, B.; Brojen Singh, R. K.; Thapa, R. K.

    2016-01-01

    We report first principles phase transition, elastic properties and electronic structure for cadmium telluride (CdTe) under induced pressure in the light of density functional theory using the local density approximation (LDA), generalised gradient approximation (GGA) and modified Becke-Johnson (mBJ) potential. The structural phase transition of CdTe from a zinc blende (ZB) to a rock salt (RS) structure within the LDA calculation is 2.2 GPa while that within GGA is found to be at 4 GPa pressure with a volume collapse of 20.9%. The elastic constants and parameters (Zener anisotropy factor, Shear modulus, Poisson’s ratio, Young’s modulus, Kleinmann parameter and Debye’s temperature) of CdTe at different pressures of both the phases have been calculated. The band diagram of the CdTe ZB structure shows a direct band gap of 1.46 eV as predicted by mBJ calculation which gives better results in close agreement with experimental results as compared to LDA and GGA. An increase in the band gap of the CdTe ZB phase is predicted under induced pressure while the metallic nature is retained in the CdTe RS phase.

  2. First-principles calculation of the effect of atomic disorder on the electronic structure of the half-metallic ferromagnet NiMnSb

    SciTech Connect

    Orgassa, D.; Fujiwara, H.; Schulthess, T.C.; Butler, W.H.

    1999-11-01

    The electronic structure of the half-metallic ferromagnet NiMnSb with three different types of atomic disorder is calculated using the layer Korringa-Kohn-Rostoker method in conjunction with the coherent potential approximation. Results indicate the presence of minority-spin states at the Fermi energy for degrees of disorder as low as a few percent. The resulting spin polarization below 100{percent} is discussed in the light of experimental difficulties confirming the half-metallic property of NiMnSb thin films directly. {copyright} {ital 1999} {ital The American Physical Society}

  3. First-Principles Calculation of structural, electronic and magnetic properties of half-Heusler LiCaC and NaCaC compounds

    NASA Astrophysics Data System (ADS)

    Umamaheswari, R.; Vijayalakshmi, D.; Kalpana, G.

    2014-09-01

    The structural, electronic and magnetic properties of LiCaC and NaCaC compounds in half-Heusler structure have been studied using local density approximation (LDA) based on density functional theory (DFT). From the total energy calculation, it is found that the compounds LiCaC and NaCaC are stable in ferromagnetic phase. The spin-polarized electronic band structure and density of states of these compounds show that the minority spin channel has metallic nature and the majority spin channel has a semiconducting gap of 2.27 and 2.0 eV for LiCaC and NaCaC respectively, resulting in a stable half-metallic ferromagnetic (HMF) behavior with magnetic moment of 1 μB per formula unit. Analysis of density of states of these compounds indicates that the magnetic moment mainly originates from the strong spin-polarization of 2p like states of C and the hybridization between the C-2p like states and the Ca-3d like states. The robustness of half-metallicity against the lattice constant is also calculated. Presence of HMF in LiCaC and NaCaC compounds without any transition metal makes these compounds promising materials for spintronic applications.

  4. The effects of surface bond relaxation on electronic structure of Sb{sub 2}Te{sub 3} nano-films by first-principles calculation

    SciTech Connect

    Li, C. Zhao, Y. F.; Fu, C. X.; Gong, Y. Y.; Chi, B. Q.; Sun, C. Q.

    2014-10-15

    The effects of vertical compressive stress on Sb{sub 2}Te{sub 3} nano-films have been investigated by the first principles calculation, including stability, electronic structure, crystal structure, and bond order. It is found that the band gap of nano-film is sensitive to the stress in Sb{sub 2}Te{sub 3} nano-film and the critical thickness increases under compressive stress. The band gap and band order of Sb{sub 2}Te{sub 3} film has been affected collectively by the surface and internal crystal structures, the contraction ratio between surface bond length of nano-film and the corresponding bond length of bulk decides the band order of Sb{sub 2}Te{sub 3} film.

  5. First principles calculations on electronic structure and magnetism of (CrAs)1(GaAs)x (x = 1, 3, and 5) superlattices

    NASA Astrophysics Data System (ADS)

    Cha, Gi-Beom; Cho, Sunglae; Hong, Soon C.

    2004-06-01

    Recently CrAs, which has a NiAs structure in nature, was grown epitaxially in a zinc-blende structure on a GaAs substrate and was proved to be a ferromagnetic half-metal with Curie temperature over 400 K. In this study, we investigated zinc-blende bulk CrAs and (CrAs)1(GaAs)x (x = 1, 3, and 5) superlattices, using the full-potential linearized augmented plane-wave method based on local spin density approximation. Their ferromagnetic states were found to be energetically more stable, compared to their antiferromagnetic states. The magnetism and electronic structure of CrAs in the superlattices were not modified significantly from those of the bulk zinc-blende CrAs. The calculated total magnetic moments per Cr are 3.0 B for all the systems, and As atoms are coupled antiferromagnetically to the Cr atoms.

  6. Structural and electronic properties of ZrX2)and HfX2 (X=S and Se) from first principles calculations.

    PubMed

    Jiang, Hong

    2011-05-28

    Early transition metal dichalcogenides (TMDC), characterized by their quasi-two-dimensional layered structure, have attracted intensive interest due to their versatile chemical and physical properties, but a comprehensive understanding of their structural and electronic properties from a first-principles point of view is still lacking. In this work, four simple TMDC materials, MX(2) (M = Zr and Hf, X = S and Se), are investigated by the Kohn-Sham density functional theory (KS-DFT) with different local or semilocal exchange-correlation (xc) functionals and many-body perturbation theory in the GW approximation. Although the widely used Perdew-Burke-Ernzelhof (PBE) generalized gradient approximation (GGA) xc functional overestimates the interlayer distance dramatically, two newly developed GGA functionals, PBE-for-solids (PBEsol) and Wu-Cohen 2006 (WC06), can reproduce experimental crystal structures of these TMDC materials very well. The GW method, currently the most accurate first-principles approach for electronic band structures of extended systems, gives the fundamental band gaps of all these materials in good agreement with the experimental values obtained from optical absorption. The minimal direct gaps from GW are systematically larger than those measured from thermoreflectance by about 0.1-0.3 eV, implying that excitonic effects may be stronger than previously estimated. The calculated density of states from GW quasi-particle band energies agrees very well with photo-emission spectroscopy data. Ionization potentials of these materials are also computed by combining PBE calculations based on the slab model and GW quasi-particle corrections. The calculated absolute band energies with respect to the vacuum level indicate that that ZrS(2) and HfS(2), although having suitable band gaps for visible light absorption, cannot be used for overall water splitting as a result of mismatch of the conduction band minimum with the redox potential of H(+)/H(2).

  7. Crystal and electronic structures of pentacene thin films from grazing-incidence x-ray diffraction and first-principles calculations

    SciTech Connect

    Nabok, Dmitrii; Puschnig, Peter; Ambrosch-Draxl, Claudia; Werzer, Oliver; Resel, Roland; Smilgies, Detlef-M.

    2007-12-15

    Combined experimental and theoretical investigations on thin films of pentacene are performed in order to determine the structure of the pentacene thin film phase. Grazing incidence x-ray diffraction is used for studying a pentacene thin film with a nominal thickness of 180 nm. The crystal structure is found to exhibit the lattice parameters a=0.592 nm, b=0.754 nm, c=1.563 nm, {alpha}=81.5 deg. , {beta}=87.2 deg. , and {gamma}=89.9 deg. . These crystallographic unit cell dimensions are used as the only input parameters for ab initio total-energy calculations within the framework of density functional theory revealing the molecular packing within the crystal structure. Moreover, we calculate the electronic band structure of the thin film phase and compare it to that of the bulk phase. We find the intermolecular bandwidths of the thin film phase to be significantly larger compared to the bulk structure, e.g., the valence bandwidth is twice as large. This remarkable effect is traced back to an enhanced intermolecular {pi}-{pi} overlap due to the upright standing molecules in the thin film phase.

  8. Electronic structure and relative stability of 1:1 Cu-O2 adducts from difference-dedicated configuration interaction calculations.

    PubMed

    Zapata-Rivera, Jhon; Caballol, Rosa; Calzado, Carmen J

    2011-04-30

    A computational strategy to analyze Cu-O(2) adducts based on the use of difference-dedicated configuration interaction (DDCI) calculations is presented. The electronic structure, vertical gaps and nature of the metal-O(2) interaction, and the extension of the charge transfer between both fragments have been investigated. Relative stabilities between isomers are determined from triplet states CCSD(T) calculations. The key point of the here proposed strategy rests on the use of a rationally designed active space, containing only those orbitals, which optimize the interaction pathways between LCu and O(2) fragments. The procedure has been tested on a broad set of model and synthetic biomimetic systems, the results compared with previous theoretical evaluations and/or available experimental data. Our study indicates that this strategy can be considered as an alternative approach to multireference second-order perturbation theory methods to deal with this type of systems with remarkable biradical nature.

  9. Electronic structure and optical properties of the nonlinear optical crystal Pb{sub 4}O(BO{sub 3}){sub 2} by first-principles calculations

    SciTech Connect

    Yang, Zhihua; Pan, Shilie; Yu, Hongwei; Lee, Ming-Hsien

    2013-02-15

    Pb{sub 4}O(BO{sub 3}){sub 2} has a layered-type arrangement with optimally aligned BO{sub 3} triangles. The optical band gap is 3.317 eV obtained via the extrapolation method from the UV-vis-IR optical diffuse reflectance spectrum, consequently the absorption edge is about 374 nm. Density functional calculations using a generalized gradient approximation were utilized to investigate the electronic structures and optical properties of Pb{sub 4}O(BO{sub 3}){sub 2}. The calculated band structures show a direct gap of 2.608 eV, which is in agreement with the experimental optical band gap. A delocalized {pi} bonding of BO{sub 3} triangles and the stereo-effect of the lone pair 6s{sup 2} of lead cations are studied in electron densities. The birefringence is about 0.039-0.061 with the wavelength larger than about 375 nm. The calculated second-order susceptibility d{sub 24}=3.5 d{sub 36} (KDP) which is well consistent with the powder SHG intensity. - Graphical abstract: The density of state (DOS) show that the bottom of the valence bands is mainly derived from of the lone pair 6s{sup 2} of Pb{sup 2+}, and the top of the valence band is attributed to the hybridization orbitals from B-O groups. Calculated electronic structures indicate that the BO{sub 3} group with typical delocalization {pi} orbitals and strongly distorted lead oxygen polyhedra with highly asymmetric lobes on lead cations make a large SHG effect in Pb{sub 4}O(BO{sub 3}){sub 2}. Highlights: Black-Right-Pointing-Pointer Lone pair effect on Pb{sup 2+} and delocalization {pi} orbital in BO{sub 3} group is studied. Black-Right-Pointing-Pointer The combination of PbO{sub n} (n=3,4,5) and BO{sub 3} group makes Pb{sub 4}O(BO{sub 3}){sub 2} a large SHG effect. Black-Right-Pointing-Pointer Pb{sub 4}O(BO{sub 3}){sub 2} is a direct gap material with the gap 2.608 eV by the ab initio method. Black-Right-Pointing-Pointer The calculated birefringence is about 0.039-0.061 with the wavelength of about 375 nm. Black

  10. Electronic structure and optical properties of Cs2HgCl4: DFT calculations and X-ray photoelectron spectroscopy measurements

    NASA Astrophysics Data System (ADS)

    Lavrentyev, A. A.; Gabrelian, B. V.; Vu, V. T.; Parasyuk, O. V.; Fedorchuk, A. O.; Khyzhun, O. Y.

    2016-10-01

    A high-quality single crystal of cesium mercury tetrabromide, Cs2HgCl4, was synthesized by using the vertical Bridgman-Stockbarger method and its electronic structure was studied from both experimental and theoretical viewpoints. In particular, X-ray photoelectron spectra were measured for both pristine and Ar+ ion-bombarded Cs2HgCl4 single crystal surfaces. The present XPS measurements indicate that the Cs2HgCl4 single crystal surface is sensitive with respect to Ar+ ion-bombardment: such a treatment changes substantially its elemental stoichiometry. With the aim of exploring total and partial densities of states within the valence band and conduction band regions of the Cs2HgCl4 compound, band-structure calculations based on density functional theory (DFT) using the augmented plane wave + local orbitals (APW + lo) method as incorporated within the WIEN2k package are performed. The calculations indicate that the Cl 3p states are the principal contributors in the upper portion of the valence band, while the Hg 5d and Cs 5p states dominate in its lower portion. In addition, the calculations allow for concluding that the unoccupied Cl p and Hg s states are the main contributors to the bottom of the conduction band. Furthermore, main optical characteristics of Cs2HgCl4, namely dispersion of the absorption coefficient, real and imaginary parts of dielectric function, electron energy-loss spectrum, refractive index, extinction coefficient and optical reflectivity, are elucidated based on the DFT calculations.

  11. Properties of ThF(x) from infrared spectra in solid argon and neon with supporting electronic structure and thermochemical calculations.

    PubMed

    Thanthiriwatte, K Sahan; Wang, Xuefeng; Andrews, Lester; Dixon, David A; Metzger, Jens; Vent-Schmidt, Thomas; Riedel, Sebastian

    2014-03-20

    Laser-ablated Th atoms react with F2 in condensing noble gases to give ThF4 as the major product. Weaker higher frequency infrared absorptions at 567.2, 564.8 (576.1, 573.8) cm(-1), 575.1 (582.7) cm(-1) and 531.0, (537.4) cm(-1) in solid argon (neon) are assigned to the ThF, ThF2 and ThF3 molecules based on annealing and photolysis behavior and agreement with CCSD(T)/aug-cc-pVTZ vibrational frequency calculations. Bands at 528.4 cm(-1) and 460 cm(-1) with higher fluorine concentrations are assigned to the penta-coordinated species (ThF3)(F2) and ThF5(-). These bands shift to 544.2 and 464 cm(-1) in solid neon. The ThF5 molecule has the (ThF3)(F2) Cs structure and is essentially the unique [ThF3(+)][F2(-)] ion pair based on charge and spin density calculations. Electron capture by (ThF3)(F2) forms the trigonal bipyramidal ThF5(-) anion in a highly exothermic process. Extensive structure and frequency calculations were also done for thorium oxyfluorides and Th2F4,6,8 dimer species. The calculations provide the ionization potentials, electron affinities, fluoride affinities, Th-F bond dissociation energies, and the energies to bind F2 and F2(-) to a cluster as well as dimerization energies.

  12. Electronic structure calculations and physicochemical experiments quantify the competitive liquid ion association and probe stabilisation effects for nitrobenzospiropyran in phosphonium-based ionic liquids.

    PubMed

    Thompson, Damien; Coleman, Simon; Diamond, Dermot; Byrne, Robert

    2011-04-01

    Liquid ion association in ionic liquids (ILs) has been examined using a comprehensive series of electronic structure calculations that measure the relative extents of ion association and probe stabilisation for the photochromic dye nitrobenzospiropyran (BSP) in a range of ILs featuring both long-tailed phosphonium cations and short-tailed imidazolium cations, paired with both chloride and NTf(2) anions. New physicochemical experiments measured the photochromic properties of BSP in the phosphonium-based room temperature ILs. Taken together, the computed complexation energies and measured spectroscopic properties support recent Walden plots of unusual conductivity-viscosity behaviour obtained for the same ILs and reveal some new features in the atom-scale structure and energetics of local, ion-ion and ion-molecule interactions. Calculations show inter-ion interactions strengthened by between 0.4 and 0.7 eV as stronger constituent ions are used, which contributes to the longer range rigidity of the Cl-based IL structure as reflected in the doubled |zwitterion → closed| probe relaxation time measured for Cl(-)vs. NTf(2)(-) in phosphonium-based ILs. Calculations further reveal a similar, approximately 0.6-0.7 eV maximum "residual" IL headgroup-mediated probe stabilisation potentially available for the anion-probe-cation complexes via the stabilising interaction that remains following the "quenching" interaction between the IL anion and cation. This potential stabilisation, however, is offset by both longer-range charge networks, beyond the scope of the current purely quantum mechanical simulations, and also energetic penalties for disruption of the highly-interdigitated alkyl tail networks in the phosphonium-based ILs which may be estimated from known diffusion data. Overall the electronic calculations of local, individual ion-ion and ion-molecule interactions serve to clarify some of the measured physicochemical properties and provide new data for the development of

  13. Electronic Structure and Optical Properties of Cu2ZnGeSe4 : First-Principles Calculations and Vacuum-Ultraviolet Spectroscopic Ellipsometric Studies

    NASA Astrophysics Data System (ADS)

    Choi, S. G.; Park, J.-S.; Donohue, A. L.; Christensen, S. T.; To, B.; Beall, C.; Wei, S.-H.; Repins, I. L.

    2015-11-01

    Cu2ZnGeSe4 is of interest for the development of next-generation thin-film photovoltaic technologies. To understand its electronic structure and related fundamental optical properties, we perform first-principles calculations for three structural variations: kesterite, stannite, and primitive-mixed CuAu phases. The calculated data are compared with the room-temperature dielectric function ɛ =ɛ1+i ɛ2 spectrum of polycrystalline Cu2ZnGeSe4 determined by vacuum-ultraviolet spectroscopic ellipsometry in the photon-energy range of 0.7 to 9.0 eV. Ellipsometric data are modeled with the sum of eight Tauc-Lorentz oscillators, and the best-fit model yields the band-gap and Tauc-gap energies of 1.25 and 1.19 eV, respectively. A comparison of overall peak shapes and relative intensities between experimental spectra and the calculated ɛ data for three structural variations suggests that the sample may not have a pure (ordered) kesterite phase. The complex refractive index N =n +i k , normal-incidence reflectivity R , and absorption coefficients α are calculated from the modeled ɛ spectrum, which are also compared with those of Cu2ZnSnSe4 . The spectral features for Cu2ZnGeSe4 appear to be weaker and broader than those for Cu2ZnSnSe4 , which is possibly due to more structural imperfections presented in Cu2ZnGeSe4 than Cu2ZnSnSe4 .

  14. Insight into structural, mechanical, electronic and thermodynamic properties of intermetallic phases in Zr-Sn system from first-principles calculations

    NASA Astrophysics Data System (ADS)

    Liu, Shuai; Zhan, Yongzhong; Wu, Junyan; Wei, Xuanchen

    2015-11-01

    The structural, phase stabilities, mechanical, electronic and thermodynamic properties of intermetallic phases in Zr-Sn system are investigated by using first-principles method. The equilibrium lattice constants, enthalpy of formation (ΔHform) and elastic constants are obtained and compared with available experimental and theoretical data. The configuration of Zr4Sn is measured with reasonable precision. The ΔHform of five hypothetical structures are obtained in order to find possible metastable phase for Zr-Sn system. The mechanical properties, including bulk modulus, shear modulus, Young's modulus and Poisson's ratio, are calculated by Voigt-Reuss-Hill approximation and the Zr5Sn4 and Zr5Sn3 show excellent mechanical properties. The electronic density of states for Zr5Sn4, Zr5Sn3 and cP8-Zr3Sn are calculated to further investigate the stability of intermetallic compounds. Through the quasi-harmonic Debye model, the Debye temperature, heat capacity and thermal expansion coefficient under temperature of 0-300 K and pressure of 0-50 GPa for Zr5Sn3 and Zr5Sn4 are deeply investigated.

  15. Electronic and magnetic structure of 3d-transition-metal point defects in silicon calculated from first principles

    NASA Astrophysics Data System (ADS)

    Beeler, F.; Andersen, O. K.; Scheffler, M.

    1990-01-01

    We describe spin-unrestricted self-consistent linear muffin-tin-orbital (LMTO) Green-function calculations for Sc, Ti, V, Cr, Mn, Fe, Co, Ni, and Cu transition-metal impurities in crystalline silicon. Both defect sites of tetrahedral symmetry are considered. All possible charge states with their spin multiplicities, magnetization densities, and energy levels are discussed and explained with a simple physical picture. The early transition-metal interstitial and late transition-metal substitutional 3d ions are found to have low spin. This is in conflict with the generally accepted crystal-field model of Ludwig and Woodbury, but not with available experimental data. For the interstitial 3d ions, the calculated deep donor and acceptor levels reproduce all experimentally observed transitions. For substitutional 3d ions, a large number of predictions is offered to be tested by future experimental studies.

  16. Detection of Structural Changes upon One-Electron Oxidation and Reduction of Stilbene Derivatives by Time-Resolved Resonance Raman Spectroscopy during Pulse Radiolysis and Theoretical Calculations.

    PubMed

    Fujitsuka, Mamoru; Cho, Dae Won; Choi, Jungkweon; Tojo, Sachiko; Majima, Tetsuro

    2015-07-01

    Stilbene (St) derivatives have been investigated for many years because of their interesting photochemical reactions such as cis-trans isomerization in the excited states and charged states and their relation to poly(p-phenylenevinylene)s. To clarify their charged state properties, structural information is indispensable. In the present study, radical cations and radical anions of St derivatives were investigated by radiation chemical methods. Absorption spectra of radical ion states were obtained by transient absorption measurements during pulse radiolysis; theoretical calculations that included the solvent effect afforded reasonable assignments. The variation in the peak position was explained by using HOMO and LUMO energy levels. Structural changes upon one-electron oxidation and reduction were detected by time-resolved resonance Raman measurements during pulse radiolysis. Significant downshifts were observed with the CC stretching mode of the ethylenic groups, indicative of the decrease in the bonding order. It was confirmed that the downshifts observed with reduction were larger than those with oxidation. On the other hand, the downshift caused by oxidation depends significantly on the electron-donating or electron-withdrawing nature of the substituents.

  17. Detection of Structural Changes upon One-Electron Oxidation and Reduction of Stilbene Derivatives by Time-Resolved Resonance Raman Spectroscopy during Pulse Radiolysis and Theoretical Calculations.

    PubMed

    Fujitsuka, Mamoru; Cho, Dae Won; Choi, Jungkweon; Tojo, Sachiko; Majima, Tetsuro

    2015-07-01

    Stilbene (St) derivatives have been investigated for many years because of their interesting photochemical reactions such as cis-trans isomerization in the excited states and charged states and their relation to poly(p-phenylenevinylene)s. To clarify their charged state properties, structural information is indispensable. In the present study, radical cations and radical anions of St derivatives were investigated by radiation chemical methods. Absorption spectra of radical ion states were obtained by transient absorption measurements during pulse radiolysis; theoretical calculations that included the solvent effect afforded reasonable assignments. The variation in the peak position was explained by using HOMO and LUMO energy levels. Structural changes upon one-electron oxidation and reduction were detected by time-resolved resonance Raman measurements during pulse radiolysis. Significant downshifts were observed with the CC stretching mode of the ethylenic groups, indicative of the decrease in the bonding order. It was confirmed that the downshifts observed with reduction were larger than those with oxidation. On the other hand, the downshift caused by oxidation depends significantly on the electron-donating or electron-withdrawing nature of the substituents. PMID:26052901

  18. Quantum fluid dynamics approach for electronic structure calculation: application to the study of ground-state properties of rare gas atoms

    NASA Astrophysics Data System (ADS)

    Roy, Amlan K.; Chu, Shih-I.

    2002-05-01

    We explore the usefulness of a quantum fluid dynamics (QFD) approach for quantitative electronic structure calculations of many-electron systems. By combining QFD and density functional theory, a single time-dependent nonlinear QFD equation can be derived. The equation is further transformed into a diffusion-type form by an imaginary-time evolution method, whose asymptotic solution reaches a global minimum and the many-body ground-state wavefunction. The time-dependent generalized pseudospectral method is extended to solve the diffusion equation in spherical coordinates, allowing optimal and nonuniform spatial discretization and accurate and efficient solution of the diffusion function in space and time. The procedure is applied to the study of electronic energies, densities and other ground-state properties of noble gas atoms (He, Ne, Ar, Kr, Xe). The results are in good agreement with other best available values. The method offers a conceptually appealing and computationally practical procedure for the treatment of many-electron systems beyond the Hartree-Fock level.

  19. The structure, energetics, and nature of the chemical bonding of phenylthiol adsorbed on the Au(111) surface: implications for density-functional calculations of molecular-electronic conduction.

    PubMed

    Bilić, Ante; Reimers, Jeffrey R; Hush, Noel S

    2005-03-01

    The adsorption of phenylthiol on the Au(111) surface is modeled using Perdew and Wang density-functional calculations. Both direct molecular physisorption and dissociative chemisorption via S-H bond cleavage are considered as well as dimerization to form disulfides. For the major observed product, the chemisorbed thiol, an extensive potential-energy surface is produced as a function of both the azimuthal orientation of the adsorbate and the linear translation of the adsorbate through the key fcc, hcp, bridge, and top binding sites. Key structures are characterized, the lowest-energy one being a broad minimum of tilted orientation ranging from the bridge structure halfway towards the fcc one. The vertically oriented threefold binding sites, often assumed to dominate molecular electronics measurements, are identified as transition states at low coverage but become favored in dense monolayers. A similar surface is also produced for chemisorption of phenylthiol on Ag(111); this displays significant qualitative differences, consistent with the qualitatively different observed structures for thiol chemisorption on Ag and Au. Full contours of the minimum potential energy as a function of sulfur translation over the crystal face are described, from which the barrier to diffusion is deduced to be 5.8 kcal mol(-1), indicating that the potential-energy surface has low corrugation. The calculated bond lengths, adsorbate charge and spin density, and the density of electronic states all indicate that, at all sulfur locations, the adsorbate can be regarded as a thiyl species that forms a net single covalent bond to the surface of strength 31 kcal mol(-1). No detectable thiolate character is predicted, however, contrary to experimental results for alkyl thiols that indicate up to 20%-30% thiolate involvement. This effect is attributed to the asymptotic-potential error of all modern density functionals that becomes manifest through a 3-4 eV error in the lineup of the adsorbate and

  20. Electronic structure of NaFeAs superconductor: LDA+DMFT calculations compared to the ARPES experiment

    NASA Astrophysics Data System (ADS)

    Nekrasov, I. A.; Pavlov, N. S.; Sadovskii, M. V.

    2015-07-01

    We present the results of extended theoretical LDA+DMFT calculations for a new iron-pnictide high temperature superconductor NaFeAs compared with the recent high quality angle-resolved photoemission (ARPES) experiments on this system (see arXiv:1409.1537). The universal manifestation of correlation effects in iron-pnictides is narrowing of conducting bands near the Fermi level. Our calculations demonstrate that for NaFeAs the effective mass is renormalized on average by a factor of the order of 3, in good agreement with ARPES data. This is essentially due to correlation effects on Fe-3 d orbitals only and no additional interactions with any kind of Boson modes, as suggested in the work mentioned, are necessary to describe the experiment. In addition, we show that ARPES data taken at about 160 eV beam energy most probably corresponds to k z = π Brillouin zone boundary, while ARPES data measured at about 80 eV beam energy rather represents k z = 0. Contributions of different Fe-3 d orbitals into spectral function map are also discussed.

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

    NASA Technical Reports Server (NTRS)

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

    1994-01-01

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

  2. Intrinsic acidity of aluminum, chromium (III) and iron (III) μ 3-hydroxo functional groups from ab initio electronic structure calculations

    NASA Astrophysics Data System (ADS)

    Rustad, James R.; Dixon, David A.; Felmy, Andrew R.

    2000-05-01

    Density functional calculations are performed on M 3(OH) 7(H 2O) 62+ and M 3O(OH) 6(H 2O) 6+ clusters for MAl, Cr(III), and Fe(III), allowing determination of the relative acidities of the μ 3-hydroxo and aquo functional groups. Contrary to previous predictions and rationalizations, Fe 3OH and Al 3OH groups have nearly the same intrinsic acidity, while Cr 3OH groups are significantly more acidic. The gas-phase acidity of the Fe 3OH site is in good agreement with the value predicted by the molecular mechanics model previously used to estimate the relative acidities of surface sites on iron oxides. [ J. R. Rustad et al. (1996)Geochim. Cosmochim. Acta 60, 1563]. Acidities of aquo functional groups were also computed for Al and Cr. The AlOH 2 site is more acidic than the Al 3OH site, whereas the Cr 3OH site is more acidic than the CrOH 2 site. These findings predict that the surface charging behavior of chromium oxides/oxyhydroxides should be distinguishable from their Fe, Al counterparts. The calculations also provide insight into why the lepidocrocite/boehmite polymorph is not observed for CrOOH.

  3. Calculations of structural, elastic, electronic, magnetic and phonon properties of FeNiMnAl by the first principles

    SciTech Connect

    Uğur, Şule; İyigör, Ahmet

    2014-10-06

    The electronic, elastic and dynamical properties of the quaternary alloy FeNiMnAl have been investigated using a pseudopotential plane wave method within the generalized gradient approximation (GGA). We determined the lattice parameters and the bulk modulus B. In addition, the elastic properties such as elastic constans (C{sub 11}, C{sub 12} and C{sub 44}), the shear modulus G, the young modulus E, the poisson's ratio σ and the B/G ratio are also given. The FeNiMnAl Heusler alloy exhibit a ferromagnetic half-metallic behavior with the total magnetic moment of 4.02 μ{sub B}. The phonon dispersion of FeNiMnAl has been performed using the density functional theory and the direct method with 2×2×2 supercell.

  4. Competitive fragmentation pathways of acetic acid dimer explored by synchrotron VUV photoionization mass spectrometry and electronic structure calculations

    SciTech Connect

    Guan Jiwen; Hu Yongjun; Zou Hao; Cao Lanlan; Liu Fuyi; Shan Xiaobin; Sheng Liusi

    2012-09-28

    In present study, photoionization and dissociation of acetic acid dimers have been studied with the synchrotron vacuum ultraviolet photoionization mass spectrometry and theoretical calculations. Besides the intense signal corresponding to protonated cluster ions (CH{sub 3}COOH){sub n}{center_dot}H{sup +}, the feature related to the fragment ions (CH{sub 3}COOH)H{sup +}{center_dot}COO (105 amu) via {beta}-carbon-carbon bond cleavage is observed. By scanning photoionization efficiency spectra, appearance energies of the fragments (CH{sub 3}COOH){center_dot}H{sup +} and (CH{sub 3}COOH)H{sup +}{center_dot}COO are obtained. With the aid of theoretical calculations, seven fragmentation channels of acetic acid dimer cations were discussed, where five cation isomers of acetic acid dimer are involved. While four of them are found to generate the protonated species, only one of them can dissociate into a C-C bond cleavage product (CH{sub 3}COOH)H{sup +}{center_dot}COO. After surmounting the methyl hydrogen-transfer barrier 10.84 {+-} 0.05 eV, the opening of dissociative channel to produce ions (CH{sub 3}COOH){sup +} becomes the most competitive path. When photon energy increases to 12.4 eV, we also found dimer cations can be fragmented and generate new cations (CH{sub 3}COOH){center_dot}CH{sub 3}CO{sup +}. Kinetics, thermodynamics, and entropy factors for these competitive dissociation pathways are discussed. The present report provides a clear picture of the photoionization and dissociation processes of the acetic acid dimer in the range of the photon energy 9-15 eV.

  5. CONDENSED MATTER: STRUCTURAL, MECHANICAL, AND THERMAL PROPERTIES: First-Principles Calculations of Atomic and Electronic Properties of Tl and In on Si(111)

    NASA Astrophysics Data System (ADS)

    Dai, Xian-Qi; Zhao, Jian-Hua; Sun, Yong-Can; Wei, Shu-Yi; Wei, Guo-Hong

    2010-09-01

    The atomic and electronic structures of Tl and In on Si(111) surfaces are investigated using the first-principles total energy calculations. Total energy optimizations show that the energetically favored structure is 1/3 ML Tl adsorbed at the T4 sites on Si(111) surfaces. The adsorption energy difference of one Tl adatom between (√3 × √3) and (1 × 1) is less than that of each In adatom. The DOS indicates that Tl 6p and Si 3p electrons play a very important role in the formation of the surface states. It is concluded that the bonding of Tl adatoms on Si(111) surfaces is mainly polar covalent, which is weaker than that of In on Si(111). So Tl atom is more easy to be migrated than In atom in the same external electric field and the structures of Tl on Si(111) is prone to switch between (√3 × √3) and (1 × 1).

  6. Low-lying electronic structure of EuH, EuOH, and EuO neutrals and anions determined by anion photoelectron spectroscopy and DFT calculations

    SciTech Connect

    Kafader, Jared O.; Ray, Manisha; Jarrold, Caroline Chick

    2015-07-21

    The anion photoelectron (PE) spectra of EuH{sup −} and the PE spectrum of overlapping EuOH{sup −} and EuO{sup −} anions are presented and analyzed with supporting results from density functional theory calculations on the various anions and neutrals. Results point to ionically bound, high-spin species. EuH and EuOH anions and neutrals exhibit analogous electronic structures: Transitions from {sup 8}Σ{sup −} anion ground states arising from the 4f{sup 7}σ{sub 6s}{sup 2} superconfiguration to the close-lying neutral {sup 9}Σ{sup −} and {sup 7}Σ{sup −} states arising from the 4f{sup 7}σ{sub 6s} superconfiguration are observed spaced by an energy interval similar to the free Eu{sup +} [4f{sup 7}6s] {sup 9}S - {sup 7}S splitting. The electron affinities (EAs) of EuH and EuOH are determined to be 0.771 ± 0.009 eV and 0.700 ± 0.011 eV, respectively. Analysis of spectroscopic features attributed to EuO{sup −} photodetachment is complicated by the likely presence of two energetically competitive electronic states of EuO{sup −} populating the ion beam. However, based on the calculated relative energies of the close-lying anion states arising from the 4f{sup 7}σ{sub 6s} and 4f{sup 6}σ{sub 6s}{sup 2} configurations and the relative energies of the one-electron accessible 4f{sup 7} and 4f{sup 6}σ{sub 6s} neutral states based on ligand-field theory [M. Dulick, E. Murad, and R. F. Barrow, J. Chem. Phys. 85, 385 (1986)], the remaining features are consistent with the 4f{sup 6}σ{sub 6s}{sup 2}  {sup 7}Σ{sup −} and 4f{sup 7}σ{sub 6s}{sup 7}Σ{sup −} anion states lying very close in energy (the former was calculated to be 0.15 eV lower in energy than the latter), though the true anion ground state and neutral EA could not be established unambiguously. Calculations on the various EuO anion and neutral states suggest 4f-orbital overlap with 2p orbitals in species with 4f{sup 6} occupancy.

  7. The n-particle picture and the calculation of the electronic structure of atoms, molecules, and solids

    SciTech Connect

    Gonis, A.; Turchi, P.E.A.; Schulthess, T.C.; Ek, J. van

    1997-08-01

    The works referred to above indicate the usefulness of viewing an N-particle system from a higher-dimensional perspective. In doing so, one should attempt to strike a balance between conceptual clarity and computational efficiency, which mitigates against considering calculations in 3n-dimensional space except for rather small values of n. It appears that such a procedure may be profitably employed if a system of N particles were to be considered as consisting of a collection of units or sets, (I{sub k}), each containing n{sub k} particles so that {Sigma}{sub k} n{sub k} = N. The resulting problem associated with these sets of particles that interact with one another is obviously formally identical to the original one. However, it possesses the formal advantage of allowing, in principle, the systematic approach to an exact solution by treating the entire system as a single unit. The operative words here are in principle, as practical applications do not seem to be possible but for the smallest number of particles in a unit, say n = 2 or n = 3. However, in such an implementation, the interparticle correlation is treated directly and explicitly within a unit, resulting in a more accurate treatment of the system the larger the number of particle in a unit.

  8. First-principles calculations of surface energy and electronic structure of LiF, NaCl and MgO (100) surfaces

    SciTech Connect

    Guo, J.

    1993-06-01

    Surface energy and electronic structure of LiF, NaCl and MgO (100) surfaces were calculated using the self-consistent-field Discrete Variational (DV) embedded cluster method in the local density approximation (LDA). Clusters of 100--164 atoms embedded in the semi-infinite host lattices were used to achieve the desired convergence. The (100) surface energies of 0.75J/m{sup 2}, 0.47J/m{sup 2} and 1.53J/m{sup 2} calculated for LiF, NaCl, and MgO, respectively, were compared with experimental data and other theoretical values. The surface atoms of LiF and NaCl were found to maintain their bulk ionic characters. The effective charges of MgO surface atoms were found to differ from the bulk atoms. The surface charge density contours were plotted and their corrugation amplitudes were compared with the He-atom diffraction results. The surface partial density of states were compared with optical, photoemission, and electron energy loss spectroscopic results.

  9. First-principle calculation of the elastic, band structure, electronic states, and optical properties of Cu-doped ZnS nanolayers

    NASA Astrophysics Data System (ADS)

    Lahiji, Mohammadreza Askaripour; Ziabari, Ali Abdolahzadeh

    2016-11-01

    The structural, elastic, electronic, and optical properties of undoped and Cu-doped ZnS nanostructured layers have been studied in the zincblende (ZB) phase, by first-principle approach. Density functional theory (DFT) has been employed to calculate the fundamental properties of the layers using full-potential linearized augmented plane-wave (FPLAPW) method. Mechanical analysis revealed that the bulk modulus increases with the increase of Cu content. Cu doping was found to reduce the band gap value of the material. In addition, DOS effective mass of the electrons and heavy holes was evaluated. Adding Cu caused the decrement/increment of transmission/reflectance of nanolayers in the UV-vis region. The substitution by Cu increased the intensity of the peaks, and a slight red shift was observed in the absorption peak. Moreover, the static dielectric constant, and static refractive index increased with Cu content. The optical conductivity also followed a similar trend to that of the dielectric constants. Energy loss function of the modeled compounds was also evaluated. All calculated parameters were compared with the available experimental and other theoretical results.

  10. The impact of +U term on the electronic structure of Mn and Fe ions and of the gallium vacancy in GaN: GGA+U calculations

    NASA Astrophysics Data System (ADS)

    Boguslawski, Piotr; Volnianska, Oksana; Zakrzewski, Tomasz

    2014-03-01

    Band structure of solids is commonly calculated in the Local Density Approximation or the Generalized Gradient Approximation to the Density Functional Theory. Their known failure is the underestimation of the band gap. Within LDA or GGA, the approach of semi-empirical character that leads to correct band gaps consists in adding the +U term for particular atomic orbitals. While the impact of the +U term on bands of an ideal crystal was extensively discussed, its impact on the electronic structure of defects is less understood. Here, we systematically analysed how the +U term affects the properties of the gallium vacancy V:Ga, and of the Mn and Fe transition metal (TM) ions in GaN. The +U term was treated as a free parameter, and it was applied to p(N) and d(TM) orbitals. The results of GGA+U calculations were compared to available experimental data. U(N)=4 eV reproduces well the gap of GaN. We find that the +U terms strongly affect the electronic structure of Mn, Fe, and V:Ga. Surprisingly, however, for U=0, the energies of the gap levels induced by these centers, and of the intra-center optical transitions, agree well with experiment. In contrast, for U(N)=U(TM)=4 eV, these energies are in substantial disagreement with experimental values by about 1-2 eV. Supported by grants POMOST/2012-5/10 and NCN 2012/05/B/ST3/03095.

  11. Specific features of the electronic structure and optical properties of KPb2Br5: DFT calculations and X-ray spectroscopy measurements

    NASA Astrophysics Data System (ADS)

    Lavrentyev, A. A.; Gabrelian, B. V.; Vu, V. T.; Denysyuk, N. M.; Shkumat, P. N.; Tarasova, A. Y.; Isaenko, L. I.; Khyzhun, O. Y.

    2016-03-01

    Density functional theory (DFT) calculations are made in order to explore the total and partial densities of states of potassium dilead pentabromide, KPb2Br5, by using the augmented plane wave + local orbitals (APW + lo) method as incorporated in the WIEN2k package. The present calculations reveal that the principle contributors to the valence band of KPb2Br5 are the Pb 6s and Br 4p states contributing predominantly at the bottom and at the top of the band, respectively, while the bottom of the conduction band is formed mainly from contributions of the unoccupied Pb 6p states. The curves of total density of states derived by the present DFT calculations of KPb2Br5 are found to be in agreement with the experimental X-ray photoelectron valence-band spectrum of the compound studied. Comparison on a common energy scale of the X-ray emission bands representing the energy distribution of the valence Br p and K s states and the X-ray photoelectron valence-band spectrum of the KPb2Br5 single crystal indicate that the Br 4p and K 4s states contribute mainly at the top and in the upper portion of the valence band, respectively, being in agreement with data of the present DFT band-structure calculations of this compound. Principal optical characteristics of KPb2Br5, namely dispersion of the absorption coefficient, real and imaginary parts of dielectric function, electron energy-loss spectrum, refractive index, extinction coefficient and optical reflectivity are also studied by the DFT calculations.

  12. Sulfur K-edge XAS and DFT calculations on nitrile hydratase: geometric and electronic structure of the non-heme iron active site.

    PubMed

    Dey, Abhishek; Chow, Marina; Taniguchi, Kayoko; Lugo-Mas, Priscilla; Davin, Steven; Maeda, Mizuo; Kovacs, Julie A; Odaka, Masafumi; Hodgson, Keith O; Hedman, Britt; Solomon, Edward I

    2006-01-18

    The geometric and electronic structure of the active site of the non-heme iron enzyme nitrile hydratase (NHase) is studied using sulfur K-edge XAS and DFT calculations. Using thiolate (RS(-))-, sulfenate (RSO(-))-, and sulfinate (RSO(2)(-))-ligated model complexes to provide benchmark spectral parameters, the results show that the S K-edge XAS is sensitive to the oxidation state of S-containing ligands and that the spectrum of the RSO(-) species changes upon protonation as the S-O bond is elongated (by approximately 0.1 A). These signature features are used to identify the three cysteine residues coordinated to the low-spin Fe(III) in the active site of NHase as CysS(-), CysSOH, and CysSO(2)(-) both in the NO-bound inactive form and in the photolyzed active form. These results are correlated to geometry-optimized DFT calculations. The pre-edge region of the X-ray absorption spectrum is sensitive to the Z(eff) of the Fe and reveals that the Fe in [FeNO](6) NHase species has a Z(eff) very similar to that of its photolyzed Fe(III) counterpart. DFT calculations reveal that this results from the strong pi back-bonding into the pi antibonding orbital of NO, which shifts significant charge from the formally t(2)(6) low-spin metal to the coordinated NO. PMID:16402841

  13. Electronic structure calculations of mercury mobilization from mineral phases and photocatalytic removal from water and the atmosphere.

    PubMed

    Da Pieve, Fabiana; Stankowski, Martin; Hogan, Conor

    2014-09-15

    Mercury is a hazardous environmental pollutant mobilized from natural sources, and anthropogenically contaminated and disturbed areas. Current methods to assess mobility and environmental impact are mainly based on field measurements, soil monitoring, and kinetic modelling. In order to understand in detail the extent to which different mineral sources can give rise to mercury release it is necessary to investigate the complexity at the microscopic level and the possible degradation/dissolution processes. In this work, we investigated the potential for mobilization of mercury structurally trapped in three relevant minerals occurring in hot spring environments and mining areas, namely, cinnabar (α-HgS), corderoite (α-Hg3S2Cl2), and mercuric chloride (HgCl2). Quantum chemical methods based on density functional theory as well as more sophisticated approaches are used to assess the possibility of a) direct photoreduction and formation of elemental Hg at the surface of the minerals, providing a path for ready release in the environment; and b) reductive dissolution of the minerals in the presence of solutions containing halogens. Furthermore, we study the use of TiO2 as a potential photocatalyst for decontamination of polluted waters (mainly Hg(2+)-containing species) and air (atmospheric Hg(0)). Our results partially explain the observed pathways of Hg mobilization from relevant minerals and the microscopic mechanisms behind photocatalytic removal of Hg-based pollutants. Possible sources of disagreement with observations are discussed and further improvements to our approach are suggested.

  14. Electric field gradients of CeMIn5 (M= Co, Rh, Ir) heavy-fermion systems studied by perturbed angular correlations and ab initio electronic structure calculations

    NASA Astrophysics Data System (ADS)

    Forker, M.; Silva, P. R. J.; Cavalcante, J. T. P. D.; Cavalcante, F. H. M.; Ramos, S. M.; Saitovitch, H.; Baggio-Saitovitch, E.; Alonso, R.; Taylor, M.; Errico, L. A.

    2013-04-01

    The electric field gradient (EFG) at the highly dilute nuclear probe 111Cd in the heavy fermion systems CeMIn5, M= Co, Rh, and Ir and YCoIn5 has been investigated by perturbed angular correlation (PAC) measurements of the nuclear electric quadrupole interaction (QI) of 111Cd on In sites. Pure and Sn-doped single crystals prepared by In-flux synthesis and polycrystalline samples prepared by arc melting have been studied. The samples were doped with the PAC probe 111Cd by diffusion of the mother isotope 111In. In all samples, several fractions of 111Cd probe nuclei subject to different QI's have been observed, among them a large fraction of 111Cd in unreacted In metal. Detailed calculations of the EFG at In nuclei and at Cd probes on In sites of pure and Sn-doped CeMIn5 were preformed, using the full-potential augmented plane wave+local orbital (APW+lo) formalism and taking into account different variables such as the electronic structure of the hyperfine probes, probe induced structural distortions, and impurity doping. The excellent agreement between the predicted EFG's and the experimental results allows us to assign two of the observed EFG components to the lattice sites 1c and 4i of the CeMIn5 compounds and to explain the pronounced difference of the EFG at In and Cd probes on the same lattice position. Structural distortions induced by the Cd probe and Sn-doping were found to have little effect on the EFG at the Cd probes. We also show that the local spin density approximation (LSDA) and LDA+U calculations predict very similar equilibrium structures and EFG's at the In/Cd sites. The extension of the experiments and the calculations from CeMIn5 to YCoIn5 and LaCoIn5 have established that the influence of the 4f electrons on the EFG's at impurity sites is negligibly small.

  15. Electronic structure and defect properties of B6O from hybrid functional and many-body perturbation theory calculations: A possible ambipolar transparent conductor

    NASA Astrophysics Data System (ADS)

    Varley, J. B.; Lordi, V.; Miglio, A.; Hautier, G.

    2014-07-01

    B6O is a member of icosahedral boron-rich solids known for their physical hardness and stability under irradiation bombardment, but it has also recently emerged as a promising high mobility p -type transparent conducting oxide. Using a combination of hybrid functional and many-body perturbation theory calculations, we report on the electronic structure and defect properties of this material. Our calculations identify B6O has a direct band gap in excess of 3.0 eV and possesses largely isotropic and low effective masses for both holes and electrons. Of the native defects, we identify no intrinsic origin to the reported p -type conductivity and confirm that p-type doping is not prevented by intrinsic defects such as oxygen vacancies, which we find act exclusively as neutral defects rather than hole-killing donors. We also investigate a number of common impurities and plausible dopants, finding that isolated acceptor candidates tend to yield deep states within the band gap or act instead as donors, and cannot account for p-type conductivity. Our calculations identify the only shallow acceptor candidate to be a complex consisting of interstitial H bonded to C substituting on the O site (CH)O. We therefore attribute the origins of p-type conductivity to these complexes formed during growth or more likely via isolated CO which later binds with H within the crystal. Lastly, we identify Si as a plausible n -type dopant, as it favorably acts as a shallow donor and does not suffer from self-compensation as may the C-related defects. Thus, in addition to the observed p-type conductivity, B6O exhibits promise of n -type dopability if the stoichiometry and both native and extrinsic sources of compensation can be sufficiently controlled.

  16. Studies of the electronic structure and biological activity of chosen 1,4-benzodiazepines by 35Cl NQR spectroscopy and DFT calculations

    NASA Astrophysics Data System (ADS)

    Bronisz, K.; Ostafin, M.; Poleshchuk, O. Kh.; Mielcarek, J.; Nogaj, B.

    2006-11-01

    Selected derivatives of 1,4-benzodiazepine: lorazepam, lormetazepam, oxazepam and temazepam, used as active substances in anxiolytic drugs, have been studied by 35Cl NQR method in order to find the correlation between electronic structure and biological activity. The 35Cl NQR resonance frequencies ( νQ) measured at 77 K have been correlated with the following parameters characterising their biological activity: biological half-life period ( t0.5), affinity to benzodiazepine receptor (IC 50) and mean dose equivalent. The results of experimental study of some benzodiazepine derivatives by nuclear quadrupole resonance of 35Cl nuclei are compared with theoretical results based on DFT calculations which were carried out by means of Gaussian'98 W software.

  17. Electronic structure and magnetic properties of (Cu, N)-codoped 3C-SiC studied by first-principles calculations

    NASA Astrophysics Data System (ADS)

    Pan, Feng-chun; Chen, Zhi-peng; Lin, Xue-ling; Zheng, Fu; Wang, Xu-ming; Chen, Huan-ming

    2016-09-01

    The electronic structures and magnetic properties of the Cu and N codoped 3C-SiC system have been investigated by the first-principles calculation. The results show that the Cu doped SiC system prefers the anti-ferromagnetic (AFM) state. Compared to the Cu doped system, the ionicities of C-Cu and C-Si in Cu and N codoped SiC are respectively enhanced and weakened. Especially, the Cu and N codoped SiC systems favor the ferromagnetic (FM) coupling. The FM interactions can be explained by virtual hopping. However, higher N concentration will weaken the ferromagnetism. In order to keep the FM interaction, the N concentration should be restricted within 9.3% according to our analysis. Project supported by the Higher School Science Research Outstanding Youth Fund Project of Ningxia, China (Grant No. NGY2015049).

  18. Electronic structure and magnetic properties of (Cu, N)-codoped 3C-SiC studied by first-principles calculations

    NASA Astrophysics Data System (ADS)

    Pan, Feng-chun; Chen, Zhi-peng; Lin, Xue-ling; Zheng, Fu; Wang, Xu-ming; Chen, Huan-ming

    2016-09-01

    The electronic structures and magnetic properties of the Cu and N codoped 3C-SiC system have been investigated by the first-principles calculation. The results show that the Cu doped SiC system prefers the anti-ferromagnetic (AFM) state. Compared to the Cu doped system, the ionicities of C–Cu and C–Si in Cu and N codoped SiC are respectively enhanced and weakened. Especially, the Cu and N codoped SiC systems favor the ferromagnetic (FM) coupling. The FM interactions can be explained by virtual hopping. However, higher N concentration will weaken the ferromagnetism. In order to keep the FM interaction, the N concentration should be restricted within 9.3% according to our analysis. Project supported by the Higher School Science Research Outstanding Youth Fund Project of Ningxia, China (Grant No. NGY2015049).

  19. Energies of the X- and L-valleys in In0.53Ga0.47As from electronic structure calculations

    NASA Astrophysics Data System (ADS)

    Greene-Diniz, Gabriel; Fischetti, M. V.; Greer, J. C.

    2016-02-01

    Several theoretical electronic structure methods are applied to study the relative energies of the minima of the X- and L-conduction-band satellite valleys of InxGa1-xAs with x = 0.53. This III-V semiconductor is a contender as a replacement for silicon in high-performance n-type metal-oxide-semiconductor transistors. The energy of the low-lying valleys relative to the conduction-band edge governs the population of channel carriers as the transistor is brought into inversion, hence determining current drive and switching properties at gate voltages above threshold. The calculations indicate that the position of the L- and X-valley minima are ˜1 eV and ˜1.2 eV, respectively, higher in energy with respect to the conduction-band minimum at the Γ-point.

  20. The gas-phase molecular structure of 1,1-diethynylsilacyclobutane as determined by means of electron diffraction and ab initio calculations

    NASA Astrophysics Data System (ADS)

    Dakkouri, Marwan; Grosser, Martin

    2002-06-01

    As a continuation of our systematic investigation of the effect of substituents on the ring geometry and dynamics in silacyclobutanes and in order to explore the role of the silicon atom as a mediator for electronic interactions between the attached fragments, we studied the molecular structure of 1,1-diethynylsilacyclobutane (DESCB) by means of gas-phase electron diffraction and ab initio calculations. The structural refinement of the electron diffraction data yielded the following bond lengths ( ra) and bond angles (uncertainties are 3σ): r( Si- C)=1.874(2) Å, r( Si- C)=1.817(1) Å, r(- C C-)=1.209(1) Å, r( C- C)=1.563(2) Å, ∠(C-Si-C)=79.2(6)°, ∠(C-Si-C)=106.5(6)°. The geminal Si-CC moieties were found to be bent outwards by 3.1(15)° and the puckering angle was determined to be 30.0(15)°. The evidently short Si-C bond length, which was also reproduced by the ab initio calculations, could be rationalized as being the consequence of the electronic interaction between the outer π charges of the triple bond and the 3pπ orbitals at the silicon atom. It is also likely that the conjugation of the geminal ethynyl groups leads to an enhancement of this bond contraction. Electrostatic interactions and the subsequent reduction of the covalent radius of the silicon atom may also contribute to this bond shortening. It has been found that the endocyclic Si-C bond length fits nicely within a scheme describing a monotonous decrease of the Si-C bond length with the increase of the electronegativity of the substituent in various geminally substituted silacyclobutanes. A series of related silacyclobutanes and acyclic diethynylsilanes have been studied by applying various ab initio methods and their optimized structures were compared to the structure of DESCB. Among these compounds are 1,1-dicyanosilacyclobutane (DCYSCB), which is isoelectronic to DESCB, 1,1-diethynylcyclobutane (DECB) which is isovalent to DESCB, monoethynylsilacyclobutane (MESCB

  1. Approximate Bruechner orbitals in electron propagator calculations

    SciTech Connect

    Ortiz, J.V.

    1999-12-01

    Orbitals and ground-state correlation amplitudes from the so-called Brueckner doubles approximation of coupled-cluster theory provide a useful reference state for electron propagator calculations. An operator manifold with hold, particle, two-hole-one-particle and two-particle-one-hole components is chosen. The resulting approximation, third-order algebraic diagrammatic construction [2ph-TDA, ADC (3)] and 3+ methods. The enhanced versatility of this approximation is demonstrated through calculations on valence ionization energies, core ionization energies, electron detachment energies of anions, and on a molecule with partial biradical character, ozone.

  2. Local orbitals in electron scattering calculations*

    NASA Astrophysics Data System (ADS)

    Winstead, Carl L.; McKoy, Vincent

    2016-05-01

    We examine the use of local orbitals to improve the scaling of calculations that incorporate target polarization in a description of low-energy electron-molecule scattering. After discussing the improved scaling that results, we consider the results of a test calculation that treats scattering from a two-molecule system using both local and delocalized orbitals. Initial results are promising. Contribution to the Topical Issue "Advances in Positron and Electron Scattering", edited by Paulo Limao-Vieira, Gustavo Garcia, E. Krishnakumar, James Sullivan, Hajime Tanuma and Zoran Petrovic.

  3. Electronic structure and phase stability of oxide semiconductors: Performance of dielectric-dependent hybrid functional DFT, benchmarked against G W band structure calculations and experiments

    NASA Astrophysics Data System (ADS)

    Gerosa, Matteo; Bottani, Carlo Enrico; Caramella, Lucia; Onida, Giovanni; Di Valentin, Cristiana; Pacchioni, Gianfranco

    2015-04-01

    We investigate band gaps, equilibrium structures, and phase stabilities of several bulk polymorphs of wide-gap oxide semiconductors ZnO, TiO2,ZrO2, and WO3. We are particularly concerned with assessing the performance of hybrid functionals built with the fraction of Hartree-Fock exact exchange obtained from the computed electronic dielectric constant of the material. We provide comparison with more standard density-functional theory and GW methods. We finally analyze the chemical reduction of TiO2 into Ti2O3 , involving a change in oxide stoichiometry. We show that the dielectric-dependent hybrid functional is generally good at reproducing both ground-state (lattice constants, phase stability sequences, and reaction energies) and excited-state (photoemission gaps) properties within a single, fully ab initio framework.

  4. Quasiparticle virtual orbitals in electron propagator calculations.

    PubMed

    Flores-Moreno, R; Ortiz, J V

    2008-04-28

    The computational limits of accurate electron propagator methods for the calculation of electron binding energies of large molecules are usually determined by the rank of the virtual orbital space. Electron density difference matrices that correspond to these transition energies in the second-order quasiparticle approximation may be used to obtain a virtual orbital space of reduced rank that introduces only minor deviations with respect to the results produced with the full, original set of virtual orbitals. Numerical tests show the superior accuracy and efficiency of this approach compared to the usual practice of omission of virtual orbitals with the highest energies.

  5. Polarization calculations for electron storage rings

    SciTech Connect

    Mane, S.R.

    1988-05-01

    A computer program called SMILE has been developed to calculate the equilibrium polarization in a high-energy electron storage ring. It can calculate spin resonances to arbitrary orders, in principle. Results of polarization calculations are shown for a variety of storage ring models, to elucidate various aspects of the behaviour of the polarization, such as the effects of machine symmetry, beam energy spread, and transverse momentum recoils, etc. Reasonable agreement is obtained with some experimental data from measurements at SPEAR. 12 refs., 12 figs.

  6. First-principles calculations of structural stability, electronic, and electrical responses of GeC nanotube under electric field effect for use in nanoelectronic devices

    NASA Astrophysics Data System (ADS)

    Baei, Mohammad T.; Peyghan, Ali Ahmadi; Moghimi, Masoumeh; Hashemian, Saeedeh

    2012-12-01

    Density functional theory (DFT) calculations at the B3LYP/6-31G∗ level were performed to investigate the effect of external electric field on the H-capped (6, 0) zigzag single-walled germanium carbide nanotube (GeCNT). With increase in the applied external electric field strengths, the energy gap, dipole moment, and total energy of the (6, 0) zigzag CNT is increased. The length, tip diameters, and electronic spatial extent of the nanotube do not significantly change with increasing electric field strength. Analysis of the structural parameters indicates that the resistance of nanotube against the applied parallel electric field is less than the resistance of nanotube against the applied transverse electric field. The large variations of energy gap, quantum molecular descriptors, dipole moment, molecular orbital energy, and total energy of the (6, 0) zigzag germanium carbide nanotube with increase of the transverse electric field strengths shows that the transverse electric field has a much stronger interaction with the nanotube with respect to the parallel electric field strengths. Analysis of the parameters indicates that the properties of GeCNTs can be controlled by the proper external electric field for use in nano-electronic circuits.

  7. Electronic structure of Li2RuO3 studied by LDA and LDA+DMFT calculations and soft x-ray spectroscopy

    NASA Astrophysics Data System (ADS)

    Pchelkina, Z. V.; Pitman, A. L.; Moewes, A.; Kurmaev, E. Z.; Tan, Teck-Yee; Peets, D. C.; Park, Je-Geun; Streltsov, S. V.

    2015-03-01

    The electronic structure of Li2RuO3 was investigated using x-ray emission and absorption spectroscopy and by theoretical calculations employing two approaches: the local density approximation (LDA) and a combination of LDA with the cluster extension of dynamical mean-field theory (LDA+DMFT). The evolution of the spectral properties with the strength of electronic correlations is analyzed. We show that for moderate values of on-site Coulomb repulsion U and intra-atomic Hund's rule exchange JH,Li2RuO3 is in an orbital-selective strongly correlated state in the sense that a part of the t2 g manifold (i.e., x z /y z ) behaves as local atomic orbitals susceptible to Hubbard correlations, while the remaining (x y ) orbitals must be described as bond-centered molecular orbitals. Both theoretical approaches succeed in explaining the x-ray data, and a comparison of the theoretical and experimental spectra provides a reasonable estimate of the possible correlation strength (U ) and Hund's coupling (JH) in Li2RuO3 .

  8. Photoinduced reactions of both 2-formyl-2H-azirine and isoxazole: A theoretical study based on electronic structure calculations and nonadiabatic dynamics simulations

    SciTech Connect

    Cao, Jun

    2015-06-28

    In the present work, the combined electronic structure calculations and dynamics simulations have been performed to explore photocleavages of 2-formyl-2H-azirine and isoxazole in the gas phase and the subsequent rearrangement reactions. The carbonyl n → π{sup *} transition induces a cleavage of the C—N single bond of 2-formyl-2H-azirine to yield β-formylvinylnitrene in open-shell singlet state. However, the n → π{sup *} excitation of the imine chromophore results in a cleavage of the C—C single bond, producing a nitrile ylide intermediate through an internal conversion to the ground state. β-formylvinylnitrene and nitrile ylide with the carbonyl group are easily transformed into 2-formyl-2H-azirine and oxazole, respectively. The N—O bond cleavages on both S{sub 1}({sup 1}ππ{sup *}) and S{sub 2}({sup 1}n{sub N}π{sup *}) of isoxazole are ultrafast processes, and they give products of 2-formyl-2H-azirine, 3-formylketenimine, HCN + CHCHO, and HCO + CHCHN. Both 2H-azirines and ketenimines were suggested to be formed from the triplet vinylnitrenes by intersystem crossing in the previous studies. However, our calculations show that the singlet β-formylvinylnitrene is responsible for the formation of 2-formyl-2H-azirine and 3-formylketenimine, and the singlet vinylnitrenes can play a key role in the photoinduced reactions of both 2H-azirines and isoxazoles.

  9. Photoinduced reactions of both 2-formyl-2H-azirine and isoxazole: A theoretical study based on electronic structure calculations and nonadiabatic dynamics simulations.

    PubMed

    Cao, Jun

    2015-06-28

    In the present work, the combined electronic structure calculations and dynamics simulations have been performed to explore photocleavages of 2-formyl-2H-azirine and isoxazole in the gas phase and the subsequent rearrangement reactions. The carbonyl n → π(*) transition induces a cleavage of the C-N single bond of 2-formyl-2H-azirine to yield β-formylvinylnitrene in open-shell singlet state. However, the n → π(*) excitation of the imine chromophore results in a cleavage of the C-C single bond, producing a nitrile ylide intermediate through an internal conversion to the ground state. β-formylvinylnitrene and nitrile ylide with the carbonyl group are easily transformed into 2-formyl-2H-azirine and oxazole, respectively. The N-O bond cleavages on both S1((1)ππ(*)) and S2((1)nNπ(*)) of isoxazole are ultrafast processes, and they give products of 2-formyl-2H-azirine, 3-formylketenimine, HCN + CHCHO, and HCO + CHCHN. Both 2H-azirines and ketenimines were suggested to be formed from the triplet vinylnitrenes by intersystem crossing in the previous studies. However, our calculations show that the singlet β-formylvinylnitrene is responsible for the formation of 2-formyl-2H-azirine and 3-formylketenimine, and the singlet vinylnitrenes can play a key role in the photoinduced reactions of both 2H-azirines and isoxazoles.

  10. Crystallographic, magnetic, and electronic structures of ferromagnetic shape memory alloys Ni{sub 2}XGa (X=Mn,Fe,Co) from first-principles calculations

    SciTech Connect

    Bai, J.; Raulot, J. M.; Zhang, Y. D.; Esling, C.; Zhao, X.; Zuo, L.

    2011-01-01

    The crystallographic, magnetic and electronic structures of the ferromagnetic shape memory alloys Ni{sub 2}XGa (X=Mn, Fe, and Co), are systematically investigated by means of the first-principles calculations within the framework of density functional theory using the VIENNA AB INITIO SOFTWARE PACKAGE. The lattice parameters of both austenitic and martensitic phases in Ni{sub 2}MnGa have been calculated. The formation energies of the cubic phase of Ni{sub 2}XGa are estimated, and show a destabilization tendency if Mn atom is substituted by Fe or Co. From Ni{sub 2}MnGa to Ni{sub 2}CoGa, the down spin total density of states (DOS) at Fermi level is gradually increasing, whereas that of the up spin part remains almost unchanged. This is the main origin of the difference of the magnetic moment in these alloys. The partial DOS is dominated by the Ni and Mn 3d states in the bonding region below E{sub F}. There are two bond types existing in Ni{sub 2}XGa: one is between neighboring Ni atoms in Ni{sub 2}MnGa; the other is between Ni and X atoms in Ni{sub 2}FeGa and Ni{sub 2}CoGa alloys.

  11. Electronic structure and magneto-optical Kerr effect spectra of ferromagnetic shape-memory Ni-Mn-Ga alloys: Experiment and density functional theory calculations

    NASA Astrophysics Data System (ADS)

    Uba, S.; Bonda, A.; Uba, L.; Bekenov, L. V.; Antonov, V. N.; Ernst, A.

    2016-08-01

    In this joint experimental and ab initio study, we focused on the influence of the chemical composition and martensite phase transition on the electronic, magnetic, optical, and magneto-optical properties of the ferromagnetic shape-memory Ni-Mn-Ga alloys. The polar magneto-optical Kerr effect (MOKE) spectra for the polycrystalline sample of the Ni-Mn-Ga alloy of Ni60Mn13Ga27 composition were measured by means of the polarization modulation method over the photon energy range 0.8 ≤h ν ≤5.8 eV in magnetic field up to 1.5 T. The optical properties (refractive index n and extinction coefficient k ) were measured directly by spectroscopic ellipsometry using the rotating analyzer method. To complement experiments, extensive first-principles calculations were made with two different first-principles approaches combining the advantages of a multiple scattering Green function method and a spin-polarized fully relativistic linear-muffin-tin-orbital method. The electronic, magnetic, and MO properties of Ni-Mn-Ga Heusler alloys were investigated for the cubic austenitic and modulated 7M-like incommensurate martensitic phases in the stoichiometric and off-stoichiometric compositions. The optical and MOKE properties of Ni-Mn-Ga systems are very sensitive to the deviation from the stoichiometry. It was shown that the ab initio calculations reproduce well experimental spectra and allow us to explain the microscopic origin of the Ni2MnGa optical and magneto-optical response in terms of interband transitions. The band-by-band decomposition of the Ni2MnGa MOKE spectra is presented and the interband transitions responsible for the prominent structures in the spectra are identified.

  12. Energetics of the all-trans{yields}13-cis isomerization of the retinal chromophore of bacteriorhodopsin: Electronic structure calculations for a simple model system

    SciTech Connect

    Woywod, Clemens; Vallet, Valerie; Li, Jingrui; Goerling, Andreas

    2008-12-08

    Understanding the molecular mechanism for the photoinduced transmembrane proton pump in the bacteriorhodopsin system is of fundamental importance. This study attempts to investigate the energetics of the initial step of the proton transport cycle, the photoisomerization of the retinal chromophore. The exact reaction pathway and the question of how many excited electronic states are involved in the internal conversion process are still unresolved. The problem is approached by constructing a reaction coordinate suggested by crystallographic studies for a simplified chromophore model system. The CASSCF and CASPT2 electronic structure methods are employed to calculate the energies of the four lowest lying singlet states as a function of the reaction coordinate. The effect of negatively charged protein residues on the reaction is simulated by inclusion of a negative point charge in the model. The results indicate that trans{yields}cis isomerization around the C{sub {beta}} = C{sub {gamma}} bond may be accompanied by twisting around the C{sub {alpha}}-C{sub {beta}} bond in order to drive the proton pump. The presence of a counterion does not seem to reduce the barrier for isomerization or the S{sub 0}-S{sub 1} energy difference but clearly stabilizes the cis--product. At first sight the results appear to support the idea of a participation of no other electronic states beyond S{sub 0} and first singly {pi}{pi}* excited state in the photoreaction. However, the relevance of this prediction is rather limited because of the small size of the model system. Other states of retinal, corresponding in particular to the partly doubly {pi}{pi}* excited S{sub 2} state of the model, are likely to have a vertical excitation energy similar to the first singly {pi}{pi}* excited state or even below.

  13. Sulfur K-Edge XAS and DFT Calculations on NitrileHydratase: Geometric and Electronic Structure of the Non-heme Iron Active Site

    SciTech Connect

    Dey, Abhishek; Chow, Marina; Taniguchi, Kayoko; Lugo-Mas, Priscilla; Davin, Steven; Maeda, Mizuo; Kovacs, Julie A.; Odaka, Masafumi; Hodgson, Keith O.; Hedman, Britt; Solomon, Edward I.; /SLAC, SSRL

    2006-09-28

    The geometric and electronic structure of the active site of the non-heme iron enzyme nitrile hydratase (NHase) is studied using sulfur K-edge XAS and DFT calculations. Using thiolate (RS{sup -})-, sulfenate (RSO{sup -})-, and sulfinate (RSO{sub 2}{sup -})-ligated model complexes to provide benchmark spectral parameters, the results show that the S K-edge XAS is sensitive to the oxidation state of S-containing ligands and that the spectrum of the RSO- species changes upon protonation as the S-O bond is elongated (by {approx}0.1 {angstrom}). These signature features are used to identify the three cysteine residues coordinated to the low-spin Fe{sup III} in the active site of NHase as CysS{sup -}, CysSOH, and CysSO{sub 2}{sup -} both in the NO-bound inactive form and in the photolyzed active form. These results are correlated to geometry-optimized DFT calculations. The pre-edge region of the X-ray absorption spectrum is sensitive to the Z{sub eff} of the Fe and reveals that the Fe in [FeNO]{sup 6} NHase species has a Z{sub eff} very similar to that of its photolyzed Fe{sup III} counterpart. DFT calculations reveal that this results from the strong {pi} back-bonding into the {pi}* antibonding orbital of NO, which shifts significant charge from the formally t{sub 2}{sup 6} low-spin metal to the coordinated NO.

  14. Electronic structure investigations of 4-aminophthal hydrazide by UV-visible, NMR spectral studies and HOMO-LUMO analysis by ab initio and DFT calculations.

    PubMed

    Sambathkumar, K; Jeyavijayan, S; Arivazhagan, M

    2015-08-01

    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. PMID:25829160

  15. Calculations of financial incentives for providers in a pay-for-performance program: Manual review versus data from structured fields in electronic health records

    PubMed Central

    Urech, Tracy H.; Woodard, LeChauncy D.; Virani, Salim S.; Dudley, R. Adams; Lutschg, Meghan Z.; Petersen, Laura A.

    2015-01-01

    Background Hospital report cards and financial incentives linked to performance require clinical data that are reliable, appropriate, timely, and cost-effective to process. Pay-for-performance plans are transitioning to automated electronic health record (EHR) data as an efficient method to generate data needed for these programs. Objective To determine how well data from automated processing of structured EHR fields (AP-EHR) reflect data from manual chart review and the impact of these data on performance rewards. Research Design Cross-sectional analysis of performance measures used in a cluster randomized trial assessing the impact of financial incentives on guideline-recommended care for hypertension. Subjects A total of 2,840 patients with hypertension assigned to participating physicians at 12 Veterans Affairs hospital-based outpatient clinics. Fifty-two physicians and 33 primary care personnel received incentive payments. Measures Overall, positive and negative agreement indices and Cohen's kappa were calculated for assessments of guideline-recommended antihypertensive medication use, blood pressure (BP) control, and appropriate response to uncontrolled BP. Pearson's correlation coefficient was used to assess how similar participants’ calculated earnings were between the data sources. Results By manual chart review data, 72.3% of patients were considered to have received guideline-recommended antihypertensive medications compared to 65.0% by AP-EHR review (k=0.51). Manual review indicated 69.5% of patients had controlled BP compared to 66.8% by AP-EHR review (k=0.87). Compared to 52.2% of patients per the manual review, 39.8% received an appropriate response by AP-EHR review (k=0.28). Participants’ incentive payments calculated using the two methods were highly correlated (r≥0.98). Using the AP-EHR data to calculate earnings, participants’ payment changes ranged from a decrease of $91.00 (−30.3%) to an increase of $18.20 (+7.4%) for medication use

  16. Preparation of a diphosphine with persistent phosphinyl radical character in solution: characterization, reactivity with O2, S8, Se, Te, and P4, and electronic structure calculations.

    PubMed

    Giffin, Nick A; Hendsbee, Arthur D; Roemmele, Tracey L; Lumsden, Michael D; Pye, Cory C; Masuda, Jason D

    2012-11-01

    A new, easily synthesized diphosphine based on a heterocyclic 1,3,2-diazaphospholidine framework has been prepared. Due to the large, sterically encumbering Dipp groups (Dipp = 2,6-diisopropylphenyl) on the heterocyclic ring, the diphosphine undergoes homolytic cleavage of the P-P bond in solution to form two phosphinyl radicals. The diphosphine has been reacted with O(2), S(8), Se, Te, and P(4), giving products that involve insertion of elements between the P-P bond to yield the related phosphinic acid anhydride, sulfide/disulfide, selenide, telluride, and a butterfly-type perphospha-bicyclobutadiene structure with a trans,trans-geometry. All molecules have been characterized by multinuclear NMR spectroscopy, elemental analysis, and single-crystal X-ray crystallography. Variable-temperature EPR spectroscopy was utilized to study the nature of the phosphinyl radical in solution. Electronic structure calculations were performed on a number of systems from the parent diphosphine [H(2)P](2) to amino-substituted [(H(2)N)(2)P](2) and cyclic amino-substituted [(H(2)C)(2)(NH)(2)P](2); then, bulky substituents (Ph or Dipp) were attached to the cyclic amino systems. Calculations on the isolated diphosphine at the B3LYP/6-31+G* level show that the homolytic cleavage of the P-P bond to form two phosphinyl radicals is favored over the diphosphine by ~11 kJ/mol. Furthermore, there is a significant amount of relaxation energy stored in the ligands (52.3 kJ/mol), providing a major driving force behind the homolytic cleavage of the central P-P bond.

  17. Program Calculates Power Demands Of Electronic Designs

    NASA Technical Reports Server (NTRS)

    Cox, Brian

    1995-01-01

    CURRENT computer program calculates power requirements of electronic designs. For given design, CURRENT reads in applicable parts-list file and file containing current required for each part. Program also calculates power required for circuit at supply potentials of 5.5, 5.0, and 4.5 volts. Written by use of AWK utility for Sun4-series computers running SunOS 4.x and IBM PC-series and compatible computers running MS-DOS. Sun version of program (NPO-19590). PC version of program (NPO-19111).

  18. Structural, electronic and thermodynamic properties of R{sub 3}ZnH{sub 5} (R=K, Rb, Cs): A first-principle calculation

    SciTech Connect

    Li, Jia; Zhang, Shengli; Huang, Shiping; Wang, Peng; Tian, Huiping

    2013-02-15

    R{sub 3}ZnH{sub 5} (R=K, Rb, Cs) series have been investigated with respect to the crystal structure, electronic and thermodynamic properties using first-principle methods based on density functional theory with generalized gradient approximation. The optimized structures and atomic coordinates are in good agreement with the experimental data. The strong covalent interactions are obtained between Zn and H atoms in the 18-electron [ZnH{sub 4}]{sup 2-} complex, while an ionic interaction is found between [ZnH{sub 4}]{sup 2-} and R atom. The formation enthalpies show that the formations of R{sub 3}ZnH{sub 5} hydrides are all exothermic at 298 K. The vibration free energies of R{sub 3}ZnH{sub 5} show that the thermodynamic stabilities of R{sub 3}ZnH{sub 5} hydrides decrease with the increasing diameter of R atom. Two possible decomposition reactions of R{sub 3}ZnH{sub 5} series have been suggested in our work. One (reaction one) is that R{sub 3}ZnH{sub 5} hydrides decomposes to elements directly, and the other (reaction two) is that R{sub 3}ZnH{sub 5} hydrides decomposes to RH hydride. The results show that the first decomposition reaction is more favorable one. The spontaneous decomposition reaction of K{sub 3}ZnH{sub 5} hydrides occur upon 465 K via reaction one, and 564 K via reaction two, respectively. - Graphical abstract: Total charge density of K{sub 3}ZnH{sub 5}. Highlights: Black-Right-Pointing-Pointer Electronic and thermodynamic properties of R{sub 3}ZnH{sub 5} (R=K, Rb, Cs) were calculated. Black-Right-Pointing-Pointer The formations of R{sub 3}ZnH{sub 5} hydrides are all exothermic at 298 K. Black-Right-Pointing-Pointer The thermodynamic stabilities decrease with the increasing diameter of R atom. Black-Right-Pointing-Pointer Two possible decomposition pathways of R{sub 3}ZnH{sub 5} were investigated.

  19. Electron mobility calculation for graphene on substrates

    SciTech Connect

    Hirai, Hideki; Ogawa, Matsuto; Tsuchiya, Hideaki; Kamakura, Yoshinari; Mori, Nobuya

    2014-08-28

    By a semiclassical Monte Carlo method, the electron mobility in graphene is calculated for three different substrates: SiO{sub 2}, HfO{sub 2}, and hexagonal boron nitride (h-BN). The calculations account for polar and non-polar surface optical phonon (OP) scatterings induced by the substrates and charged impurity (CI) scattering, in addition to intrinsic phonon scattering in pristine graphene. It is found that HfO{sub 2} is unsuitable as a substrate, because the surface OP scattering of the substrate significantly degrades the electron mobility. The mobility on the SiO{sub 2} and h-BN substrates decreases due to CI scattering. However, the mobility on the h-BN substrate exhibits a high electron mobility of 170 000 cm{sup 2}/(V·s) for electron densities less than 10{sup 12 }cm{sup −2}. Therefore, h-BN should be an appealing substrate for graphene devices, as confirmed experimentally.

  20. Molecular structure of mercury(II) thiocyanate complexes based on DFT calculations and experimental UV-electron spectroscopy and Raman studies

    NASA Astrophysics Data System (ADS)

    Elijošiutė, Erika; Eicher-Lorka, Olegas; Griškonis, Egidijus; Matulaitienė, Ieva; Jankūnaitė, Dalia; Denafas, Gintaras

    2013-11-01

    In this work, we report a combined experimental and theoretical study on molecular structure, vibrational and electronic spectra of [Hg(SCN)n]2-n complexes (where n = 2, 3, 4) in the aqueous solution. Molecular modeling of the mercury(II) complexes were done by the density functional theory (DFT) method using B3LYP functional with Stuttgart relativistic ECP 78MWB basis set for Hg and 6-311++G(d,p) basis set for all other atoms. The effect of different solvation models with explicit (ligand) and/or implicit water environment upon its geometry, vibrational frequencies and UV spectrum have been studied. The influence of H2O/D2O exchange on the experimental and calculated vibrational frequencies of studied complexes has been established. The double-peak character of the νHgsbnd S vibrational mode of the all analyzed mercury complexes and νCtbnd N mode of [Hg(SCN)3H2O]- complex, respectively, were proposed here for the first time. The formation of four-coordinated Hg(II) complexes with thiocyanate and (or) water ligands was verified.

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

    NASA Astrophysics Data System (ADS)

    Demkov, Alexander A.; Navrotsky, Alexandra

    2001-03-01

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

  2. Structure, electronic and magnetic properties of hexagonal boron nitride sheets doped by 5d transition metal atoms: First-principles calculations and molecular orbital analysis

    NASA Astrophysics Data System (ADS)

    Zhang, Zhaofu; Geng, Zhaohui; Cai, Danyun; Pan, Tongxi; Chen, Yixin; Dong, Liyuan; Zhou, Tiege

    2015-01-01

    A first-principles calculation based on density functional theory is carried out to reveal the geometry, electronic structures and magnetic properties of hexagonal boron nitride sheets (h-BNSs) doped by 5d transitional mental atoms (Lu, Hf, Ta, W, Re, Os, Ir, Pt, Au and Hg) at boron-site (B5d) and nitrogen-site (N5d). Results of pure h-BNS, h-BNS with B vacancy (VB) and N vacancy (VN) are also given for comparison. It is shown that all the h-BNSs doped with 5d atoms possess a C3v local symmetry except for NLu and NHg which have a clear deviation. For the same 5d dopant, the binding energy of B5d is larger than that of N5d, which indicates the substitution of a 5d atom for B is preferred. The total densities of states are presented, where impurity energy levels exist. Besides, the total magnetic moments (TMMs) change regularly with the increment of the 5d atomic number. Theoretical analyses by molecular orbital under C3v symmetry explain the impurity energy levels and TMMs.

  3. A Mathematica package for calculation of planar channeling radiation spectra of relativistic electrons channeled in a diamond-structure single crystal (quantum approach)

    NASA Astrophysics Data System (ADS)

    Azadegan, B.

    2013-03-01

    The presented Mathematica code is an efficient tool for simulation of planar channeling radiation spectra of relativistic electrons channeled along major crystallographic planes of a diamond-structure single crystal. The program is based on the quantum theory of channeling radiation which has been successfully applied to study planar channeling at electron energies between 10 and 100 MeV. Continuum potentials for different planes of diamond, silicon and germanium single crystals are calculated using the Doyle-Turner approximation to the atomic scattering factor and taking thermal vibrations of the crystal atoms into account. Numerical methods are applied to solve the one-dimensional Schrödinger equation. The code is designed to calculate the electron wave functions, transverse electron states in the planar continuum potential, transition energies, line widths of channeling radiation and depth dependencies of the population of quantum states. Finally the spectral distribution of spontaneously emitted channeling radiation is obtained. The simulation of radiation spectra considerably facilitates the interpretation of experimental data. Catalog identifier: AEOH_v1_0 Program summary URL:http://cpc.cs.qub.ac.uk/summaries/AEOH_v1_0.html Program obtainable from: CPC Program Library, Queen's University, Belfast, N. Ireland Licensing provisions: Standard CPC licence, http://cpc.cs.qub.ac.uk/licence/licence.html No. of lines in distributed program, including test data, etc.: 446 No. of bytes in distributed program, including test data, etc.: 209805 Distribution format: tar.gz Programming language: Mathematica. Computer: Platforms on which Mathematica is available. Operating system: Operating systems on which Mathematica is available. RAM: 1 MB Classification: 7.10. Nature of problem: Planar channeling radiation is emitted by relativistic charged particles during traversing a single crystal in direction parallel to a crystallographic plane. Channeling is modeled as the motion

  4. Sulfur on Nickel (100) and Hydrogen on Tungsten (100): Two Self-Consistent Lapw Electronic Structure Calculations of Simple Absorbates on Transition Metal Surfaces.

    NASA Astrophysics Data System (ADS)

    Richter, Roy

    1982-03-01

    The Film Linear Augmented Plane Wave (Film LAPW) method and accompanying potential construction is described and used in the self-consistent local density calculation of the electronic structure, charge density and potential for two absorbate-transition metal systems: c(2 x 2) sulfur on nickel {100}, a prototype p bonding system; and p(1 x 1) hydrogen on tungsten {100}, a prototype s bonding system. The nickel substrate was modelled by a three-atomic layer slab and the tungsten substrate was modelled by a five-atomic layer slab. The work function of the nickel surface increases by 0.5 eV upon sulfur adsorption from charge transfer of the surface nickel layer to the sulfur, agreeing with experimental values of 0.38 eV and 0.63 eV. The work function of the tungsten slab increases by 1.9 eV upon adsorption of a saturated monolayer of hydrogen, in contrast to an experimental value of 0.9 eV; the discrepancy is resolved by considering band-filling effects in the thin slab. For the sulfur on nickel system it is found that the sulfur 3p orbitals bond primarily with the 3d band of the nickel substrate, with a bonding-antibonding level splitting of 4-6 eV, straddling the nickel d band. The(' )k dispersion of the sulfur 3p-derived orbitals is (TURN)2 eV. A sulfur-nickel overlayer spacing of 1.3 (ANGSTROM) was used, obtained from electron diffraction measurements. For the hydrogen on tungsten system it is found the hydrogen 1s orbitals bond primarily with the localized 5d surface states of the tungsten substrate with a bonding -antibonding level splitting of 5 eV. The hydrogen 1s-derived orbitals are well described by a tight-binding band with a dispersion of 6-7 eV across the Brillouin zone, with the hydrogen-tungsten bonding states lying wholly in the d band of the tungsten substrate below the Fermi level and the hydrogen-tungsten antibonding states crossing through the Fermi level. To locate the hydrogen 1s-derived levels, two hydrogen-tungsten overlayer spacings of 1

  5. Molecular structures and conformational compositions of 2-chlorobutane and 2-bromobutane; an investigation using gas-phase electron-diffraction data and ab initio molecular orbital calculations

    NASA Astrophysics Data System (ADS)

    Aarset, Kirsten; Hagen, Kolbjørn; Stølevik, Reidar

    2001-06-01

    The structure and conformational composition of 2-chlorobutane and 2-bromobutane have been studied by gas-phase electron diffraction (GED) at 25°C, together with ab initio molecular orbital calculations (HF/6-311+G(d,p)). These molecules may exist as three distinguishable conformers (G+, A, and G-). The symbols refer to anti (A) with a torsion angle Φ2(X 8-C 2-C 3-C 4) of about 180° and gauche (G+ and G-) with torsion angles Φ2(X 8-C 2-C 3-C 4) of about +60° and 300°(-60°), respectively. It was not possible; from our GED-data alone, to accurately determine the conformational composition because the distance distributions for two of the conformers (G+ and G-) are very similar. The conformational composition for 2-chlorobutane obtained from the ab initio calculations (G+ 62%, A 25% G- 13%) was found to fit the experimental data quite well. For 2-bromobutane the ab initio calculated conformational composition (G+ 58%, A 28% G- 14%) did not, however, fit the experimental data. Here a much better fit was obtained by using only 10% of the A conformer and using the relative energy for the two gauche conformers, as obtained in the ab initio molecular orbital calculations, to calculate the relative amounts of the two gauche forms (G+ 73%, A 10% G- 17%). The results for the principal distances ( rg) and angles ∠ α for the G+ conformer of 2-chlorobutane, with estimated 2 σ uncertainties, obtained from the combined GED/ab initio study are: r( C1- C2)=1.524(3) Å, r( C2- C3)=1.528(3) Å, r( C3- C4)=1.539(3) Å, r( C- Cl)=1.812(3) Å, r( C- H) ave=1.098(4) Å, ∠C 1C 2C 3=111.5(16)°, ∠C 2C 3C 4=113.3(5)°, ∠C 1C 2C1=110.4(9)°. The results for the G+ conformer of 2-bromobutane are: r( C1- C2)=1.526(4) Å, r( C2- C3)=1.530(4) Å, r( C3- C4)=1.540(4) Å, r( C- Br)=1.982(5) Å, r( C- H) ave=1.111(8) Å, ∠C 1C 2C 3=112.5(16)°, ∠C 2C 3C 4=114.6(15)°, ∠C 1C 2Br=110.1(16)°. Only average values for r(C-C), r(C-H), ∠CCC, and ∠CCH could be determined in the

  6. Investigation on the electronic structures and optical performances of Si-S codoped anatase TiO2 by first-principles calculation

    NASA Astrophysics Data System (ADS)

    Zhou, S. W.; Peng, P.; Liu, J.; Tang, Y. H.; Meng, B.; Peng, Y. X.

    2016-04-01

    The electronic and optical properties of Si and/or S (co)doped anatase TiO2 are investigated by density function theory plus U calculations. Results show that the synergistic effects of Si and S codoping result in higher visible-light absorption compared with pure and Si or S monodoped TiO2. Moreover, with increasing S doping concentration, the band gap of Si/S-codoping system becomes narrower, and simultaneously the band edge positions may be suitable for water splitting. Additionally, the defect formation energy calculations indicate that Si doping can enhance the thermal stability of TiO2 under O-rich condition.

  7. Electronic structure and thermoelectric properties of (Mg2X)2 / (Mg2Y)2 (X, Y = Si, Ge, Sn) superlattices from first-principle calculations

    NASA Astrophysics Data System (ADS)

    Guo, San-Dong

    2016-05-01

    To identify thermoelectric materials containing abundant, low-cost and non-toxic elements, we have studied the electronic structures and thermoelectric properties of (Mg2X)2/ (Mg2Y)2 (X, Y = Si, Ge, Sn) superlattices with state-of-the-art first-principles calculations using a modified Becke and Johnson (mBJ) exchange potential. Our results show that (Mg2Ge)2/ (Mg2Sn)2 and (Mg2Si)2/ (Mg2Sn)2 are semi-metals using mBJ plus spin-orbit coupling (mBJ + SOC), while (Mg2Si)2/ (Mg2Ge)2 is predicted to be a direct-gap semiconductor with a mBJ gap value of 0.46 eV and mBJ + SOC gap value of 0.44 eV. Thermoelectric properties are predicted by through solving the Boltzmann transport equations within the constant scattering time approximation. It is found that (Mg2Si)2/ (Mg2Ge)2 has a larger Seebeck coefficient and power factor than (Mg2Ge)2/ (Mg2Sn)2 and (Mg2Si)2/ (Mg2Sn)2 for both p-type and n-type doping. The detrimental influence of SOC on the power factor of p-type (Mg2X)2/ (Mg2Y)2 (X, Y = Si, Ge, Sn) is analyzed as a function of the carrier concentration, but there is a negligible SOC effect for n-type. These results can be explained by the influence of SOC on their valence and conduction bands near the Fermi level.

  8. First principles reaction modeling of the electrochemical interface: Consideration and calculation of a tunable surface potential from atomic and electronic structure

    NASA Astrophysics Data System (ADS)

    Taylor, Christopher D.; Wasileski, Sally A.; Filhol, Jean-Sebastien; Neurock, Matthew

    2006-04-01

    A method for calculating and subsequently tuning the electrochemical potential of a half cell using periodic plane-wave density functional theory and a homogenous counter-charge is presented and evaluated by comparison to simulations which explicitly model the countercharge by a plane of ions. The method involves the establishment of two reference potentials, one related to the potential of the free electron in vacuo, and the other related to the potential of H2O species far from the electrode. The surface potential can be specifically adjusted by the explicit introduction of excess or deficit surface charges in the simulation cell and the application of periodic boundary conditions. We demonstrate the absence of field emission from the electrode over the range of realistic electrochemical potentials covered and confirm that the method can explicitly determine reaction energies and adsorption geometries as a function of electrochemical potential. This latter point is most useful as it asserts the viability of this method to model electrochemical and electrocatalytical systems of academic as well as applied interest. We present two case studies. The first examines the changes in the structure of water at the metal interface as a function of potential over Cu(111) . At cathodic potential, we observe the repulsion of H2O from the interface and the rotation of the water dipole toward the interface. The second study follows the initial pathways for the electrocatalytical activation of methanol over Pt(111) and the corresponding potential dependent reaction energetics for these paths. The results demonstrate that changes in the electrochemical potential can significantly alter the reaction energetics as well as the overall reaction selectivity. While the case studies presented herein described equilibrium geometries (i.e., the ideal forms at zero kelvin), the method is also suitable for application to ensembles of thermally activated systems.

  9. Numerical performance and throughput benchmark for electronic structure calculations in PC-Linux systems with new architectures, updated compilers, and libraries.

    PubMed

    Yu, Jen-Shiang K; Hwang, Jenn-Kang; Tang, Chuan Yi; Yu, Chin-Hui

    2004-01-01

    A number of recently released numerical libraries including Automatically Tuned Linear Algebra Subroutines (ATLAS) library, Intel Math Kernel Library (MKL), GOTO numerical library, and AMD Core Math Library (ACML) for AMD Opteron processors, are linked against the executables of the Gaussian 98 electronic structure calculation package, which is compiled by updated versions of Fortran compilers such as Intel Fortran compiler (ifc/efc) 7.1 and PGI Fortran compiler (pgf77/pgf90) 5.0. The ifc 7.1 delivers about 3% of improvement on 32-bit machines compared to the former version 6.0. Performance improved from pgf77 3.3 to 5.0 is also around 3% when utilizing the original unmodified optimization options of the compiler enclosed in the software. Nevertheless, if extensive compiler tuning options are used, the speed can be further accelerated to about 25%. The performances of these fully optimized numerical libraries are similar. The double-precision floating-point (FP) instruction sets (SSE2) are also functional on AMD Opteron processors operated in 32-bit compilation, and Intel Fortran compiler has performed better optimization. Hardware-level tuning is able to improve memory bandwidth by adjusting the DRAM timing, and the efficiency in the CL2 mode is further accelerated by 2.6% compared to that of the CL2.5 mode. The FP throughput is measured by simultaneous execution of two identical copies of each of the test jobs. Resultant performance impact suggests that IA64 and AMD64 architectures are able to fulfill significantly higher throughput than the IA32, which is consistent with the SpecFPrate2000 benchmarks.

  10. Numerical performance and throughput benchmark for electronic structure calculations in PC-Linux systems with new architectures, updated compilers, and libraries.

    PubMed

    Yu, Jen-Shiang K; Hwang, Jenn-Kang; Tang, Chuan Yi; Yu, Chin-Hui

    2004-01-01

    A number of recently released numerical libraries including Automatically Tuned Linear Algebra Subroutines (ATLAS) library, Intel Math Kernel Library (MKL), GOTO numerical library, and AMD Core Math Library (ACML) for AMD Opteron processors, are linked against the executables of the Gaussian 98 electronic structure calculation package, which is compiled by updated versions of Fortran compilers such as Intel Fortran compiler (ifc/efc) 7.1 and PGI Fortran compiler (pgf77/pgf90) 5.0. The ifc 7.1 delivers about 3% of improvement on 32-bit machines compared to the former version 6.0. Performance improved from pgf77 3.3 to 5.0 is also around 3% when utilizing the original unmodified optimization options of the compiler enclosed in the software. Nevertheless, if extensive compiler tuning options are used, the speed can be further accelerated to about 25%. The performances of these fully optimized numerical libraries are similar. The double-precision floating-point (FP) instruction sets (SSE2) are also functional on AMD Opteron processors operated in 32-bit compilation, and Intel Fortran compiler has performed better optimization. Hardware-level tuning is able to improve memory bandwidth by adjusting the DRAM timing, and the efficiency in the CL2 mode is further accelerated by 2.6% compared to that of the CL2.5 mode. The FP throughput is measured by simultaneous execution of two identical copies of each of the test jobs. Resultant performance impact suggests that IA64 and AMD64 architectures are able to fulfill significantly higher throughput than the IA32, which is consistent with the SpecFPrate2000 benchmarks. PMID:15032545

  11. Electronic structure of crystalline uranium nitrides UN, U2N3 and UN2: LCAO calculations with the basis set optimization

    NASA Astrophysics Data System (ADS)

    Evarestov, R. A.; Panin, A. I.; Bandura, A. V.; Losev, M. V.

    2008-06-01

    The results of LCAO DFT calculations of lattice parameters, cohesive energy and bulk modulus of the crystalline uranium nitrides UN, U2N3 and UN2 are presented and discussed. The LCAO computer codes Gaussian03 and Crystal06 are applied. The calculations are made with the uranium atom relativistic effective small core potential by Stuttgart-Cologne group (60 electrons in the core). The calculations include the U atom basis set optimization. Powell, Hooke-Jeeves, conjugated gradient and Box methods are implemented in the author's optimization package, being external to the codes for molecular and periodic calculations. The basis set optimization in LCAO calculations improves the agreement of the lattice parameter and bulk modulus of UN crystal with the experimental data, the change of the cohesive energy due to the optimization is small. The mixed metallic-covalent chemical bonding is found both in LCAO calculations of UN and U2N3 crystals; UN2 crystal has the semiconducting nature.

  12. Correlation of electronic structure and magnetic moment in Ga1-xMnxN : First-principles, mean field and high temperature series expansions calculations

    NASA Astrophysics Data System (ADS)

    Masrour, R.; Hlil, E. K.

    2016-08-01

    Self-consistent ab initio calculations based on density-functional theory and using both full potential linearized augmented plane wave and Korring-Kohn-Rostoker-coherent potential approximation methods, are performed to investigate both electronic and magnetic properties of the Ga1-xMnxN system. 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 such as the magnetic phase diagram and the critical exponent. The increasing of the dilution x in this system has allowed to verify a series of HTSEs predictions on the possibility of ferromagnetism in dilute magnetic insulators and to demonstrate that the interaction changes from antiferromagnetic to ferromagnetic passing through the spins glace phase.

  13. Global nuclear-structure calculations

    SciTech Connect

    Moeller, P.; Nix, J.R.

    1990-04-20

    The revival of interest in nuclear ground-state octupole deformations that occurred in the 1980's was stimulated by observations in 1980 of particularly large deviations between calculated and experimental masses in the Ra region, in a global calculation of nuclear ground-state masses. By minimizing the total potential energy with respect to octupole shape degrees of freedom in addition to {epsilon}{sub 2} and {epsilon}{sub 4} used originally, a vastly improved agreement between calculated and experimental masses was obtained. To study the global behavior and interrelationships between other nuclear properties, we calculate nuclear ground-state masses, spins, pairing gaps and {Beta}-decay and half-lives and compare the results to experimental qualities. The calculations are based on the macroscopic-microscopic approach, with the microscopic contributions calculated in a folded-Yukawa single-particle potential.

  14. DFT electronic structure calculations, spectroscopic studies, and normal coordinate analysis of 2-[(5-nitro-1,3-thiazol-2-yl)carbamoyl]phenyl acetate.

    PubMed

    Muthu, S; Elamuruguporchelvi, E; Varghese, Anitha

    2015-03-01

    The solid phase FTIR and FT-Raman spectra of 2-[(5-nitro-1,3-thiazol-2-yl)carbamoyl]phenyl acetate (25N2LCPA) have been recorded 450-4000cm(-1) and 100-4000cm(-1) respectively. The normal coordinate analysis was carried out to confirm the precision of the assignments. DFT calculations have been performed giving energies, optimized structures, harmonic vibrational frequencies and IR intensities. The structure of the molecule was optimized and the structural characteristics were determined by density functional theory (DFT) using B3LYP method with 6-31+G(d,p) basis set. The detailed interpretation of the vibrational spectra has been carried out with aid of normal coordinate analysis (NCA) following the scaled quantum mechanical force field methodology. The Vibrational frequencies are calculated in the above method and are compared with experimental frequencies which yield good agreement between observed and calculated frequencies. Stability of the molecule arising from hyper conjugative interactions, charge delocalization has been analyzed using natural bond orbital (NBO) analysis. In addition, Frontiers molecular orbital and molecular electrostatic potential were computed by using Density Functional Theory (DFT) B3LYP/6-31+G(d,p) basis set. The calculated HOMO and LUMO energies show that charge transfer occurs in the molecule.

  15. Electronic structure of Calcium hexaborides

    SciTech Connect

    Lee, Byounghak; Wang, Lin-Wang

    2005-06-15

    We present a theoretical study of crystal and electronic structures of CaB6 within a screened-exchange local density approximation (sX-LDA). Our ab initio total energy calculations show that CaB6 is a semiconductor with a gap of >1.2 eV, in agreement with recent experimental observations. We show a very sensitive band gap dependence on the crystal internal parameter, which might partially explain the scatter of previous theoretical results. Our calculation demonstrates that it is essential to study this system simultaneously for both crystal structures and electronic properties, and that the sX-LDA provides an ideal method for this problem.

  16. Study of V Substitution Effect on Structural and Electronic and Magnetic Properties of Zn1-xVxO0 ≤ x ≤ 0.5 by First Principles Calculations

    NASA Astrophysics Data System (ADS)

    Taghavi Mendi, R.; Majidiyan, M.; Boochani, A.; Elahi, S. M.; Bakhshayeshi, A.; Beryani Nezafat, N.

    2013-08-01

    In this paper some structural, magnetic and electronic properties of Zn1-xVxO for 0 ≤ x ≤ 0.5, such as optimized lattice constant, cohesive energy, formation enthalpy, density of states, band structure, effective mass and Fermi surface are being investigated. In calculating these properties first principle approach is being used. The calculations performed using DFT theory with full potential linear augmented plane wave (FP-LAPW) and GGA approximation. It is shown that by substituting V instead of Zn, Zn1-xVxO compound will gain magnetic properties. The band structure of Zn1-xVxO shows that metallic behavior increases with increasing substituted V. This substitution increases extremal area in Fermi surface around Γ point. The results obtained from calculated cohesive energy and formation enthalpy show that substituting V increases the stability of Zn1-xVxO. The calculated band gap is in a good agreement with other theoretical results.

  17. Molecular structure, electronic properties, NLO, NBO analysis and spectroscopic characterization of Gabapentin with experimental (FT-IR and FT-Raman) techniques and quantum chemical calculations

    NASA Astrophysics Data System (ADS)

    Sinha, Leena; Karabacak, Mehmet; Narayan, V.; Cinar, Mehmet; Prasad, Onkar

    2013-05-01

    Gabapentin (GP), structurally related to the neurotransmitter GABA (gamma-aminobutyric acid), mimics the activity of GABA and is also widely used in neurology for the treatment of peripheral neuropathic pain. It exists in zwitterionic form in solid state. The present communication deals with the quantum chemical calculations of energies, geometrical structure and vibrational wavenumbers of GP using density functional (DFT/B3LYP) method with 6-311++G(d,p) basis set. In view of the fact that amino acids exist as zwitterions as well as in the neutral form depending on the environment (solvent, pH, etc.), molecular properties of both the zwitterionic and neutral form of GP have been analyzed. The fundamental vibrational wavenumbers as well as their intensities were calculated and compared with experimental FT-IR and FT-Raman spectra. The fundamental assignments were done on the basis of the total energy distribution (TED) of the vibrational modes, calculated with scaled quantum mechanical (SQM) method. The electric dipole moment, polarizability and the first hyperpolarizability values of the GP have been calculated at the same level of theory and basis set. The nonlinear optical (NLO) behavior of zwitterionic and neutral form has been compared. Stability of the molecule arising from hyper-conjugative interactions and charge delocalization has been analyzed using natural bond orbital analysis. Ultraviolet-visible (UV-Vis) spectrum of the title molecule has also been calculated using TD-DFT method. The thermodynamic properties of both the zwitterionic and neutral form of GP at different temperatures have been calculated.

  18. Molecular structure, electronic properties, NLO, NBO analysis and spectroscopic characterization of Gabapentin with experimental (FT-IR and FT-Raman) techniques and quantum chemical calculations.

    PubMed

    Sinha, Leena; Karabacak, Mehmet; Narayan, V; Cinar, Mehmet; Prasad, Onkar

    2013-05-15

    Gabapentin (GP), structurally related to the neurotransmitter GABA (gamma-aminobutyric acid), mimics the activity of GABA and is also widely used in neurology for the treatment of peripheral neuropathic pain. It exists in zwitterionic form in solid state. The present communication deals with the quantum chemical calculations of energies, geometrical structure and vibrational wavenumbers of GP using density functional (DFT/B3LYP) method with 6-311++G(d,p) basis set. In view of the fact that amino acids exist as zwitterions as well as in the neutral form depending on the environment (solvent, pH, etc.), molecular properties of both the zwitterionic and neutral form of GP have been analyzed. The fundamental vibrational wavenumbers as well as their intensities were calculated and compared with experimental FT-IR and FT-Raman spectra. The fundamental assignments were done on the basis of the total energy distribution (TED) of the vibrational modes, calculated with scaled quantum mechanical (SQM) method. The electric dipole moment, polarizability and the first hyperpolarizability values of the GP have been calculated at the same level of theory and basis set. The nonlinear optical (NLO) behavior of zwitterionic and neutral form has been compared. Stability of the molecule arising from hyper-conjugative interactions and charge delocalization has been analyzed using natural bond orbital analysis. Ultraviolet-visible (UV-Vis) spectrum of the title molecule has also been calculated using TD-DFT method. The thermodynamic properties of both the zwitterionic and neutral form of GP at different temperatures have been calculated.

  19. Molecular structure, electronic properties, NLO, NBO analysis and spectroscopic characterization of Gabapentin with experimental (FT-IR and FT-Raman) techniques and quantum chemical calculations.

    PubMed

    Sinha, Leena; Karabacak, Mehmet; Narayan, V; Cinar, Mehmet; Prasad, Onkar

    2013-05-15

    Gabapentin (GP), structurally related to the neurotransmitter GABA (gamma-aminobutyric acid), mimics the activity of GABA and is also widely used in neurology for the treatment of peripheral neuropathic pain. It exists in zwitterionic form in solid state. The present communication deals with the quantum chemical calculations of energies, geometrical structure and vibrational wavenumbers of GP using density functional (DFT/B3LYP) method with 6-311++G(d,p) basis set. In view of the fact that amino acids exist as zwitterions as well as in the neutral form depending on the environment (solvent, pH, etc.), molecular properties of both the zwitterionic and neutral form of GP have been analyzed. The fundamental vibrational wavenumbers as well as their intensities were calculated and compared with experimental FT-IR and FT-Raman spectra. The fundamental assignments were done on the basis of the total energy distribution (TED) of the vibrational modes, calculated with scaled quantum mechanical (SQM) method. The electric dipole moment, polarizability and the first hyperpolarizability values of the GP have been calculated at the same level of theory and basis set. The nonlinear optical (NLO) behavior of zwitterionic and neutral form has been compared. Stability of the molecule arising from hyper-conjugative interactions and charge delocalization has been analyzed using natural bond orbital analysis. Ultraviolet-visible (UV-Vis) spectrum of the title molecule has also been calculated using TD-DFT method. The thermodynamic properties of both the zwitterionic and neutral form of GP at different temperatures have been calculated. PMID:23545435

  20. A Initio Mr-Rci Calculations of ((n - 1)D + Ns)(n) Atomic Bound States: Application to Hyperfine Structure and Electron Affinity Studies.

    NASA Astrophysics Data System (ADS)

    Datta, Debasis

    Systematic inclusion of many-body effects in open d and f subshell atoms has long been known as a formidable challenge in atomic structure theory. Due to the presence of competing relativistic effects in such systems, an appropriate theoretical approach needs to incorporate electron correlation within the framework of the Special Theory of Relativity. To this aim, the Relativistic Configuration Interaction methodology as developed by Beck and others has been extended and applied to multi-reference situations in ((n - 1)d + ns) ^{rm N} type valence configurations. Specific focus has been on the hyperfine structure and electron affinity studies of the transition metal ions and the rare earths respectively. Energies and magnetic dipole and electric quadrupole hyperfine structure constants of all the fifteen Zr II (4d + 5s)^3 J = 0.5, 1.5 levels and the twenty one Nb II (4d + 5s)^4 J = 2 levels have been determined with unprecedented accuracies. The average errors in energy are 0.087 eV and 0.050 eV for Zr II J = 3/2 & 1/2 respectively while that for the ten bottom levels of Nb II J = 2 is 0.055 eV. For the levels known experimentally, the corresponding errors in magnetic dipole hyperfine structure constants are 9.2%, 31.8% and 3.8%. Quite a few of the many-body hyperfine constant values exhibit striking improvements over the Multi-Configurational Dirac Fock values. A new value of nuclear quadrupole moment has also been predicted for Zr II. In all cases certain previous level assignments have been corrected and five previously unknown levels have been identified in Nb II. The rigorous systematics of the many-body effects important for the energy level and hyperfine structure of these systems has been presented including core-valence and core-core effects. Contrary to the conventional wisdom and theoretical predictions of the last decade, the attachment of an f electron has been discarded as the most likely mechanism for the formation of Lanthanide and Actinide negative

  1. Influence of central metalloligand geometry on electronic communication between metals: syntheses, crystal structures, MMCT properties of isomeric cyanido-bridged Fe2Ru complexes, and TDDFT calculations.

    PubMed

    Ma, Xiao; Lin, Chen-Sheng; Hu, Sheng-Min; Tan, Chun-Hong; Wen, Yue-Hong; Sheng, Tian-Lu; Wu, Xin-Tao

    2014-06-01

    To investigate how the central metalloligand geometry influences distant or vicinal metal-to-metal charge-transfer (MMCT) properties of polynuclear complexes, cis- and trans-isomeric heterotrimetallic complexes, and their one- and two-electron oxidation products, cis/trans-[Cp(dppe)Fe(II)NCRu(II)(phen)2CN-Fe(II)(dppe)Cp][PF6]2 (cis/trans-1[PF6]2), cis/trans-[Cp(dppe)Fe(II)NCRu(II)(phen)2CNFe(III)-(dppe)Cp][PF6]3 (cis/trans-1[PF6]3) and cis/trans-[Cp(dppe)Fe(III)NCRu(II)(phen)2CN-Fe(III)(dppe)Cp][PF6]4 (cis/trans-1[PF6]4) have been synthesized and characterized. Electrochemical measurements show the presence of electronic interactions between the two external Fe(II) atoms of the cis- and trans-isomeric complexes cis/trans-1[PF6]2. The electronic properties of all these complexes were studied and compared by spectroscopic techniques and TDDFT//DFT calculations. As expected, both mixed valence complexes cis/trans-1[PF6]3 exhibited different strong absorption signals in the NIR region, which should mainly be attributed to a transition from an MO that is delocalized over the Ru(II)-CN-Fe(II) subunit to a Fe(III) d orbital with some contributions from the co-ligands. Moreover, the NIR transition energy in trans-1[PF6]3 is lower than that in cis-1[PF6]3, which is related to the symmetry of their molecular orbitals on the basis of the molecular orbital analysis. Also, the electronic spectra of the two-electron oxidized complexes show that trans-1[PF6]4 possesses lower vicinal Ru(II) → Fe(III) MMCT transition energy than cis-1[PF6]4. Moreover, the assignment of MMCT transition of the oxidized products and the differences of the electronic properties between the cis and trans complexes can be well rationalized using TDDFT//DFT calculations. PMID:24771667

  2. Electronic structure of Ca, Sr, and Ba under pressure.

    NASA Technical Reports Server (NTRS)

    Animalu, A. O. E.; Heine, V.; Vasvari, B.

    1967-01-01

    Electronic band structure calculations phase of Ca, Sr and Ba over wide range of atomic volumes under pressure electronic band structure calculations for fcc phase of Ca, Sr and Ba over wide range of atomic volumes under pressure electronic band structure calculations for fcc phase of Ca, Sr and Ba over wide range of atomic volumes under pressure

  3. Effects of the slab thickness on the crystal and electronic structures of In{sub 2}O{sub 3}(ZnO){sub m} revealed by first-principles calculations

    SciTech Connect

    Wen, Jing; Zhang, Xitian; Gao, Hong

    2015-02-15

    Many conflicting electron microscopy data for In{sub 2}O{sub 3}(ZnO){sub m} indicate that it may have the polymorphous and polytypoid structures. We investigate their stabilities based on four controversial models. The calculated results confirm that the models with the zigzag feature are more stable than the others and it is possible to form different zigzag configurations in the samples as observed in the experiments. The dynamic process of eliminating the dangling bonds and the requirements of maximizing the symmetry and the distances between the In atoms in the slabs can be regarded as the dominant rules to stabilize the system, but the statistical equilibrium processes have the chances to transform it from the ground state structures to the other model structures. The study of the electronic structures based on the plane and zigzag models reveals that their band gaps and effective masses increase monotonically with m. The predicted band gaps are consistent with the experimental results. The anisotropic feature of electron effective mass tensor exhibited in the plane model differs from that of the zigzag one, which is so notable that can be employed to determine which model is more close to the actual structure of a given sample. The calculated results confirm the possibilities of the separation of conduction electrons and defects and the existence of the natural optimized transport channels in the layered structures, which demonstrate its advantage over ZnO to transport electrons and benefit its applications in the optoelectronic devices. - Graphical abstract: The conduction electrons are mainly distributed around the boundaries of the plane or zigzag shape. The optimized transport channels can be formed around the boundaries. - Highlights: • The formation mechanisms for the polytypoid structure of In{sub 2}O{sub 3}(ZnO){sub m} are revealed. • The predicted band gaps are consistent with the experimental results. • The natural optimized transport channels

  4. Electronic correlation contributions to structural energies

    NASA Astrophysics Data System (ADS)

    Haydock, Roger

    2015-03-01

    The recursion method is used to calculate electronic excitation spectra including electron-electron interactions within the Hubbard model. The effects of correlation on structural energies are then obtained from these spectra and applied to stacking faults. http://arxiv.org/abs/1405.2288 Supported by the Richmond F. Snyder Fund and Gifts.

  5. Electronic structure of herbicides: Atrazine and bromoxynil

    NASA Astrophysics Data System (ADS)

    Novak, Igor; Kovač, Branka

    2011-06-01

    The electronic structures of herbicides atrazine and bromoxynil have been investigated by UV photoelectron spectroscopy (UPS), quantum chemical calculations and comparison with X-ray diffraction, molecular docking and molecular dynamics studies. Their electronic and molecular structures are discussed in the context of their biological activity. This is the first report which correlates the molecular mechanism of biological activity of these herbicides with their experimentally determined electronic and molecular structures.

  6. Controversial electronic structures and energies of Fe{sub 2}, Fe{sub 2}{sup +}, and Fe{sub 2}{sup −} resolved by RASPT2 calculations

    SciTech Connect

    Hoyer, Chad E.; Manni, Giovanni Li; Truhlar, Donald G. E-mail: gagliard@umn.edu; Gagliardi, Laura E-mail: gagliard@umn.edu

    2014-11-28

    The diatomic molecule Fe{sub 2} was investigated using restricted active space second-order perturbation theory (RASPT2). This molecule is very challenging to study computationally because predictions about the ground state and excited states depend sensitively on the choice of the quantum chemical method. For Fe{sub 2} we show that one needs to go beyond a full-valence active space in order to achieve even qualitative agreement with experiment for the dissociation energy, and we also obtain a smooth ground-state potential curve. In addition we report the first multireference study of Fe{sub 2}{sup +}, for which we predict an {sup 8}Σ{sub u}{sup −} ground state, which was not predicted by previous computational studies. By using an active space large enough to remove the most serious deficiencies of previous theoretical work and by explicitly investigating the interpretations of previous experimental results, this study elucidates previous difficulties and provides – for the first time – a qualitatively correct treatment of Fe{sub 2}, Fe{sub 2}{sup +}, and Fe{sub 2}{sup −}. Moreover, this study represents a record in terms of the number or active electrons and active orbitals in the active space, namely 16 electrons in 28 orbitals. Conventional CASPT2 calculations can be performed with at most 16 electrons in 16 orbitals. We were able to overcome this limit by using the RASPT2 formalism.

  7. Computational Chemistry Using Modern Electronic Structure Methods

    ERIC Educational Resources Information Center

    Bell, Stephen; Dines, Trevor J.; Chowdhry, Babur Z.; Withnall, Robert

    2007-01-01

    Various modern electronic structure methods are now days used to teach computational chemistry to undergraduate students. Such quantum calculations can now be easily used even for large size molecules.

  8. Instructional Approach to Molecular Electronic Structure Theory

    ERIC Educational Resources Information Center

    Dykstra, Clifford E.; Schaefer, Henry F.

    1977-01-01

    Describes a graduate quantum mechanics projects in which students write a computer program that performs ab initio calculations on the electronic structure of a simple molecule. Theoretical potential energy curves are produced. (MLH)

  9. Structural peculiarities of configurational isomers of 1-styrylpyrroles according to 1Н, 13С and 15N NMR spectroscopy and density functional theory calculations: electronic and steric hindrance for planar structure.

    PubMed

    Afonin, Andrei V; Ushakov, Igor A; Pavlov, Dmitry V; Schmidt, Elena Yu; Dvorko, Marina Yu

    2013-06-01

    Comparative analysis of the (1)Н and (13)С NMR data for a series of the E and Z-1-styrylpyrroles, E and Z-1-(1-propenyl)pyrroles, 1-vinylpyrroles and styrene suggests that the conjugation between the unsaturated fragments in the former compounds is reduced. This is the result of the mutual influence of the donor p-π and π-π conjugation having opposite directions. According to the NMR data combined with the density functional theory calculations, the Z isomer of 1-styrylpyrrole has essentially a nonplanar structure because of the steric hindrance. However, the E isomer of 1-styrylpyrrole is also an out-of-plane structure despite the absence of a sterical barrier for the planar one. Deviation of the E isomer from the planar structure seems to be caused by an electronic hindrance produced by a mutual influence of the p-π and π-π conjugation. The structure of the E isomer of the 2-substituted 1-styrylpyrroles is similar to that of the 2-substituted 1-vinylpyrroles. The steric effects in the Z isomer of the 2-substituted 1-styrylpyrroles result in the large increase of the dihedral angle between planes of the pyrrole ring and double bond. PMID:23558848

  10. Molecular structure calculations: A unified quantum mechanical description of electrons and nuclei using explicitly correlated Gaussian functions and the global vector representation

    SciTech Connect

    Matyus, Edit; Reiher, Markus

    2012-07-14

    We elaborate on the theory for the variational solution of the Schroedinger equation of small atomic and molecular systems without relying on the Born-Oppenheimer paradigm. The all-particle Schroedinger equation is solved in a numerical procedure using the variational principle, Cartesian coordinates, parameterized explicitly correlated Gaussian functions with polynomial prefactors, and the global vector representation. As a result, non-relativistic energy levels and wave functions of few-particle systems can be obtained for various angular momentum, parity, and spin quantum numbers. A stochastic variational optimization of the basis function parameters facilitates the calculation of accurate energies and wave functions for the ground and some excited rotational-(vibrational-)electronic states of H{sub 2}{sup +} and H{sub 2}, three bound states of the positronium molecule, Ps{sub 2}, and the ground and two excited states of the {sup 7}Li atom.

  11. CONDENSED MATTER: STRUCTURE, THERMAL AND MECHANICAL PROPERTIES: First-principles calculations on the electronic and vibrational properties of β-V2O5

    NASA Astrophysics Data System (ADS)

    Zhou, Bo; Su, Qing; He, De-Yan

    2009-11-01

    Using a first-principles approach based on density functional theory, this paper studies the electronic and dynamical properties of β-V2O5. A smaller band gap and much wider split-off bands have been observed in comparison with α-V2O5. The Raman- and infrared-active modes at the Γ point of the Brillouin zone are evaluated with LO/TO splitting, where the symbol denotes the longitudinal and transverse optical model. The nonresonant Raman spectrum of a β-V2O5 powder sample is also computed, providing benchmark theoretical results for the assignment of the experimental spectrum. The computed spectrum agrees with the available experimental data very well. This calculation helps to gain a better understanding of the transition from α- to β-V2O5.

  12. Molecular structure calculations: a unified quantum mechanical description of electrons and nuclei using explicitly correlated Gaussian functions and the global vector representation.

    PubMed

    Mátyus, Edit; Reiher, Markus

    2012-07-14

    We elaborate on the theory for the variational solution of the Schrödinger equation of small atomic and molecular systems without relying on the Born-Oppenheimer paradigm. The all-particle Schrödinger equation is solved in a numerical procedure using the variational principle, Cartesian coordinates, parameterized explicitly correlated Gaussian functions with polynomial prefactors, and the global vector representation. As a result, non-relativistic energy levels and wave functions of few-particle systems can be obtained for various angular momentum, parity, and spin quantum numbers. A stochastic variational optimization of the basis function parameters facilitates the calculation of accurate energies and wave functions for the ground and some excited rotational-(vibrational-)electronic states of H(2) (+) and H(2), three bound states of the positronium molecule, Ps(2), and the ground and two excited states of the (7)Li atom.

  13. Electronic, structural and magnetic studies of niobium borides of group 8 transition metals, Nb2MB2 (M=Fe, Ru, Os) from first principles calculations

    NASA Astrophysics Data System (ADS)

    Touzani, Rachid St.; Fokwa, Boniface P. T.

    2014-03-01

    The Nb2FeB2 phase (U3Si2-type, space group P4/mbm, no. 127) is known for almost 50 years, but until now its magnetic properties have not been investigated. While the synthesis of Nb2OsB2 (space group P4/mnc, no. 128, a twofold superstructure of U3Si2-type) with distorted Nb-layers and Os2-dumbbells was recently achieved, "Nb2RuB2" is still not synthesized and its crystal structure is yet to be revealed. Our first principles density functional theory (DFT) calculations have confirmed not only the experimental structures of Nb2FeB2 and Nb2OsB2, but also predict "Nb2RuB2" to crystalize with the Nb2OsB2 structure type. According to chemical bonding analysis, the homoatomic B-B interactions are optimized and very strong, but relatively strong heteroatomic M-B, B-Nb and M-Nb bonds (M=Fe, Ru, Os) are also found. These interactions, which together build a three-dimensional network, are mainly responsible for the structural stability of these ternary borides. The density-of-states at the Fermi level predicts metallic behavior, as expected, from metal-rich borides. Analysis of possible magnetic structures concluded preferred antiferromagnetic ordering for Nb2FeB2, originating from ferromagnetic interactions within iron chains and antiferromagnetic exchange interactions between them.

  14. Electronic band structure and optical properties of titanium oxyphosphates Li{sub 0.50}Co{sub 0.25}TiO(PO{sub 4}) single crystals: An ab-initio calculations

    SciTech Connect

    Reshak, Ali Hussain; Khenata, R.; Auluck, S.

    2011-08-15

    From the refined atomic positions obtained by Belmal et al. (2004) using X-ray diffraction for Li{sub 0.50}Co{sub 0.25}TiO(PO{sub 4}), we have performed a structural optimization by minimizing the forces acting on the atoms keeping the lattice parameters fixed at the experimental values. With this relaxed (optimized) geometry we have performed a comprehensive theoretical study of electronic properties and dispersion of the linear optical susceptibilities using the full potential linear augmented plane wave (FP-LAPW) method. The generalized gradient approximation (GGA) exchange-correlation potential was applied. In addition, the Engel-Vosko generalized gradient approximation (EVGGA) was used for comparison with GGA because it is known that EVGGA approach yields better band splitting compared to the GGA. We have calculated the band structure, and the total and partial densities of states. The electron charge densities and the bonding properties were analyzed and discussed. The complex dielectric optical susceptibilities were discussed in detail. - Graphical abstract: It is shown that P is tetrahedrally coordinated by four O ions. Highlights: > Comprehensive theoretical study of electronic and optical properties was performed. > Using X-ray diffraction data we have performed a structural optimization. > The electron charge densities and the bonding properties were analyzed and discussed. > Fermi surface was analyzed since it is useful for predicting thermal, magnetic, and optical properties. > The density of states at E{sub F} and the electronic specific heat coefficient were calculated.

  15. Electronic structures and formation energies of pentavalent-ion-doped SnO{sub 2}: First-principles hybrid functional calculations

    SciTech Connect

    Behtash, Maziar; Joo, Paul H.; Nazir, Safdar; Yang, Kesong

    2015-05-07

    We studied the electronic properties and relative thermodynamic stability of several pentavalent-ion (Ta, Nb, P, Sb, and I) doped SnO{sub 2} systems using first-principles hybrid density functional theory calculations, in order to evaluate their potential as transparent conducting oxides (TCOs). I-doped SnO{sub 2}, though conductive, shows a narrowed optical band gap with respect to the undoped system due to the formation of gap states above the valence band. Nb-doped SnO{sub 2} forms localized impurity states below the conduction band bottom, suggesting that the Nb dopant exists as an Nb{sup 4+}-like cation, which is consistent with the recent experimental finding of the formation of the impurity level below the conduction band bottom [Appl. Phys. Express 5, 061201 (2012)]. Ta- and Sb-doped SnO{sub 2} display n-type conductivity, high charge carrier density, and widened optical band gap. P-doped SnO{sub 2} shows similar n-type electronic properties with that of Sb- and Ta-doped systems, and thus P-doped SnO{sub 2} is proposed as a promising candidate TCO for further experimental validation.

  16. Effects of S/Ce-codoping on electronic structures and optical properties of anatase TiO2 from density functional theory calculations

    NASA Astrophysics Data System (ADS)

    Zhou, Shi Wen; Liu, Jian; Peng, Ping; Chen, Wen Qin

    2015-12-01

    The electronic and optical properties of S- and/or Ce-(co)doped anatase titanium dioxide (TiO2) are investigated using density functional theory plus U (DFT+U) calculations. The optimized total energy suggests that TiO2 codoping by Ce and S favours the configuration of one substitutional Ce atom occupied on a Ti site with one substitutional S atom either on its nearest neighboring O or Ti site. The calculated results show that all doping configurations exhibit remarkable red-shift and excellent photocatalytic properties compared with pure TiO2. These reinforced features can mainly be ascribed to the appearance of S 3p states in the top of valence band (VB) and Ce 4f states in the bottom of conduction band (CB) as well as the contribution from the increasing octahedral dipole moments. The synergetic effects of cationic Ce and anionic S can extend optical absorption edge, which results in higher absorption coefficient in the visible light region than that of the anionic S monodoping and cationic Ce monodoping case; in the same time, decreasing the codoping concentration leads to reduced optical absorption. Additionally, Ce and S as cations incorporating into TiO2 lattices can induce stronger redox potential with a lower defect formation energy under O-rich condition compared with other doping systems.

  17. Electronic structures of C{sub 28}H{sub 4} and HF@C{sub 28}H{sub 4} and their ions. SCF calculations

    SciTech Connect

    Tuan, D.F.T. |; Pitzer, R.M.

    1996-04-11

    Ab initio restricted Hartree-Fock calculations were performed on the ground and excited states of C{sub 28}H{sub 4}, Hf@C{sub 28}H{sub 4}, and their positive and negative ions. Relativistic core potentials were included in the calculations to take account of the relativistic effects of the heavy atom. Symmetry-adapted functions were used to reduce the time and effort of the computation. Ionization potentials, electron affinities, MO interaction diagrams, and population analyses of the systems were obtained. These results and those from our previous studies of Hf@C{sub 28} were used to interpret the mode of bonding in C{sub 28}H{sub 4} and Hf@C{sub 28}H{sub 4}, the mutual weakening of the bonding of the Hf and 4H to C{sub 28}, and the factors that affect the bonding. These results can also shed light on the characteristics of the bonding of endohedral and exohedral complexes of fullerenes in general. 25 refs., 5 figs., 4 tabs.

  18. New quantitative structure-fragmentation relationship strategy for chemical structure identification using the calculated enthalpy of formation as a descriptor for the fragments produced in electron ionization mass spectrometry: a case study with tetrachlorinated biphenyls.

    PubMed

    Dinca, Nicolae; Dragan, Simona; Dinca, Mihael; Sisu, Eugen; Covaci, Adrian

    2014-05-20

    Differential mass spectrometry correlated with quantum chemical calculations (QCC-ΔMS) has been shown to be an efficient tool for the chemical structure identification (CSI) of isomers with similar mass spectra. For this type of analysis, we report here a new strategy based on ordering (ORD), linear correlation (LCOR) algorithms, and their coupling, to filter the most probable structures corresponding to similar mass spectra belonging to a group with dozens of isomers (e.g., tetrachlorinated biphenyls, TeCBs). This strategy quantifies and compares the values of enthalpies of formation (Δ(f)H) obtained by QCC for some isobaric ions from the electron ionization (EI)-MS mass spectra, to the corresponding relative intensities. The result of CSI is provided in the form of lists of decreasing probabilities calculated for all the position-isomeric structures using the specialized software package CSI-Diff-MS Analysis 3.1.1. The simulation of CSI with ORD, LCOR, and their coupling of six TeCBs (IUPAC no. 44, 46, 52, 66, 74, and 77) has allowed us to find the best semiempirical molecular-orbital methods for several of their common isobaric fragments. The study of algorithms and strategy for the entire group of TeCBs (42 isomers) was made with one of the optimal variants for the computation of Δ(f)H using semiempirical molecular orbital methods of HyperChem: AM1 for M(+•) and [M - 4Cl](+•) ions and RM1 for [M - Cl](+) and [M - 2Cl](+•). The analytical performance of ORD, LCOR, and their coupling resulted from the CSI simulation of an analyte of known structure, using a decreasing number of isomeric standards, s = 5, 4, 3, and 2. Compared with the results obtained by a classical library search for TeCB isomers, the novel strategies of assigning structures of isomers with very similar mass spectra based on ORD, LCOR, and their coupling were much more efficient, because they provide the correct structure at the top of the probability list. Databases used in these CSI

  19. Structural, mechanical, electronic and thermal properties of KZnF3 and AgZnF3 Perovskites: FP-(L)APW+lo calculations

    NASA Astrophysics Data System (ADS)

    Hiadsi, S.; Bouafia, H.; Sahli, B.; Abidri, B.; Bouaza, A.; Akriche, A.

    2016-08-01

    This study presents a theoretical prediction of the structural, mechanical, electronic and thermal properties of the zinc-based Perovskites (AgZnF3 and KZnF3) within the framework of Density Functional Theory (DFT) using All-electron self consistent Full Potential Augmented Plane Waves plus local orbital FP-(L)APW + lo method. To make our work comparable and reliable, several functional were used for the exchange-correlation potential. Also, this study intends to provide a basis and an improvement for updating either the values already predicted by other previous work (by using obsolete functional) or to predict them for the first time. GGA-PBE and GGA-PBEsol were used to predict the structural properties of AgZnF3 and KZnF3 Perovskites such as lattice parameter, bulk modulus and its pressure derivative and the cohesive energy. For these properties, the found values are in very good agreement; also those found by GGA-PBEsol are closer to other available previous and experimental results. The electronic properties of these materials are investigated and compared to provide a consolidated prediction by using the modified Becke Johnson potential TB-mBJ with other functional; the values found by this potential are closer to the available proven results and show that these materials exhibit an indirect gap from R to Γ point. The charge densities plot for [110] direction and QTAIM (Quantum Theory of Atoms in Molecules) theory indicate that ionic character is predominate for (K, Ag, Zn)sbnd F bonds. Finally, the effect of temperature and pressure on the unit cell volume, the heat capacity CV and entropy were studied using the quasi-harmonic Debye model.

  20. Solid state {sup 1}H spin-lattice relaxation and isolated-molecule and cluster electronic structure calculations in organic molecular solids: The relationship between structure and methyl group and t-butyl group rotation

    SciTech Connect

    Wang, Xianlong E-mail: pbeckman@brynmawr.edu; Mallory, Frank B.; Mallory, Clelia W.; Odhner, Hosanna R.; Beckmann, Peter A. E-mail: pbeckman@brynmawr.edu

    2014-05-21

    We report ab initio density functional theory electronic structure calculations of rotational barriers for t-butyl groups and their constituent methyl groups both in the isolated molecules and in central molecules in clusters built from the X-ray structure in four t-butyl aromatic compounds. The X-ray structures have been reported previously. We also report and interpret the temperature dependence of the solid state {sup 1}H nuclear magnetic resonance spin-lattice relaxation rate at 8.50, 22.5, and 53.0 MHz in one of the four compounds. Such experiments for the other three have been reported previously. We compare the computed barriers for methyl group and t-butyl group rotation in a central target molecule in the cluster with the activation energies determined from fitting the {sup 1}H NMR spin-lattice relaxation data. We formulate a dynamical model for the superposition of t-butyl group rotation and the rotation of the t-butyl group's constituent methyl groups. The four compounds are 2,7-di-t-butylpyrene, 1,4-di-t-butylbenzene, 2,6-di-t-butylnaphthalene, and 3-t-butylchrysene. We comment on the unusual ground state orientation of the t-butyl groups in the crystal of the pyrene and we comment on the unusually high rotational barrier of these t-butyl groups.

  1. Second order distorted wave calculations for electron impact ionization processes

    NASA Astrophysics Data System (ADS)

    Chen, Zhangjin

    Electron impact ionization of atoms provides a fundamental test of the current understanding of atomic structure as well as our understanding of the three body problem. Triple differential cross sections (TDCS), measured in the coincidence experiment, provide the most sensitive test of the theory of electron impact ionization processes. It was found two decades ago that second-order effects were crucial in explaining both the positions and magnitudes of the binary and recoil peaks in the TDCS. However, the existing theoretical calculations of second-order amplitudes typically resort to simplifying approximations, such as the closure approximation or neglecting the real part of the Green's function, to make the calculation tractable. In this work, we have developed a second-order distorted wave (DWB2) theory for atomic ionization which does not make these approximations. The DWB2 theory has been used to calculate the TDCS for electron impact ionization of hydrogen. It is found that the DWB2 results are in good agreement with absolute experimental measurements for incident energy greater than 100 eV. We have also performed DWB2 calculations for electron impact ionization of helium with the residual ion left in the n=1 and 2 states at intermediate energies in coplanar asymmetric geometry. Both the neutral and ionic distorting potentials are employed for the projectile in the final state. It has been found that the DWB2 results with the ionic distorting potential are in better agreement with experiment for the case in which the residual ion is left in the excited states. We have also performed the calculations to check the validity of the closure approximation and the simplified Green's function approximation and found that these approximations are not accurate for non-coplanar geometry and low incident energies.

  2. Three-dimensional RF structure calculations

    NASA Astrophysics Data System (ADS)

    Cooper, R. K.; Browman, M. J.; Weiland, T.

    1989-04-01

    The calculation of three-dimensional rf structures is rapidly approaching adolescence, after having been in its infancy for the last four years. This paper will show the kinds of calculations that are currently being performed in the frequency domain and is a companion paper to one in which time-domain calculations are described.

  3. Three-dimensional rf structure calculations

    SciTech Connect

    Cooper, R.K.; Browman, M.J.; Weiland, T.

    1988-01-01

    The calculation of three-dimensional rf structures is rapidly approaching adolescence, after having been in its infancy for the last four years. This paper will show the kinds of calculations that are currently being performed in the frequency domain and is a companion paper to one in which time-domain calculations are described. 13 refs., 14 figs.

  4. Electronic structure and optical properties of Ag{sub 3}PO{sub 4} photocatalyst calculated by hybrid density functional method

    SciTech Connect

    Liu, J. J.; Fu, X. L.; Chen, S. F.; Zhu, Y. F.

    2011-11-07

    The electronic structure and optical properties of Ag{sub 3}PO{sub 4} were studied by hybrid density functional theory. The results indicated that the band gap is 2.43 eV, which agrees well with the experimental value of 2.45 eV. The conduction bands of Ag{sub 3}PO{sub 4} are mainly attributable to Ag 5s and 5p states, while the valence bands are dominated by O 2p and Ag 4d states. The highest valence band edge potential was 2.67 V (vs. normal hydrogen electrode), which has enough driving force for photocatalytic water oxidation and pollutants degradation. The optical absorption spectrum showed that Ag{sub 3}PO{sub 4} is a visible light response photocatalyst.

  5. Synthesis, electronic structure investigation of 3-pentyl-2,6-di(furan-2-yl)piperidin-4-one by FT-IR, FT-Raman and UV-Visible spectral studies and ab initio/DFT calculations.

    PubMed

    Arockia Doss, M; Savithiri, S; Rajarajan, G; Thanikachalam, V; Anbuselvan, C

    2015-12-01

    FT-IR and FT-Raman spectra of 3-pentyl-2,6-di(furan-2-yl) piperidin-4-one (3-PFPO) were recorded in the solid phase. The structural and spectroscopic analyses of 3-PFPO were made by using B3LYP/HF level with 6-311++G(d, p) basis set. The fundamental vibrations are assigned on the basis of the total energy distribution (TED) of the vibrational modes, calculated with scaled quantum mechanics (SQM) method and PQS program. Comparison of the observed fundamental vibrational frequencies of 3-PFPO with calculated results by HF and DFT methods indicates that B3LYP is superior to HF method for molecular vibrational problems. The electronic properties such as excitation energies, oscillator strength, wavelengths and HOMO-LUMO energies were obtained by time-dependent DFT (TD-DFT) approach. The polarizability and first order hyperpolarizability of the title molecule were calculated and interpreted. The hyperconjugative interaction energy (E((2))) and electron densities of donor (i) and acceptor (j) bonds were calculated using NBO analysis. In addition, MEP and atomic charges of carbon, nitrogen, oxygen and hydrogen were calculated using B3LYP/6-311++G(d, p) level theory. Moreover, thermodynamic properties (heat capacities, entropy and enthalpy) of the title compound at different temperatures were calculated in gas phase. PMID:26172464

  6. Exploring the sloped-to-peaked S2/S1 seam of intersection of thymine with electronic structure and direct quantum dynamics calculations.

    PubMed

    Asturiol, David; Lasorne, Benjamin; Worth, Graham A; Robb, Michael A; Blancafort, Lluís

    2010-05-21

    The role of the seam of intersection between the lowest (pi,pi*) and (n,pi*) excited states in the decay of electronically excited singlet thymine has been investigated with ab initio complete active space self-consistent field (CASSCF) calculations and direct dynamics variational multiconfiguration Gaussian (DD-vMCG) quantum dynamics on the full-dimensional CASSCF surface, with 39 degrees of freedom. The seam has a sloped-to-peaked topography, and the dynamics at the different segments of the seam have been studied by varying the initial conditions of the propagation. When the wave packet is directed to the peaked segments, part of it traverses the seam, stays on the (pi,pi*) state and heads towards decay to the ground state. In contrast to this, when the wave packet is driven to sloped seam segments it bounces back to the minimum of the (pi,pi*) state. Significant population transfer to the (n,pi*) state is observed in both cases. The results suggest that a sloped-to-peaked topography can be used to control photochemical reactivity, by driving the wave packet to different regions of the seam where a different outcome of the propagation can be expected.

  7. Final disposal room structural response calculations

    SciTech Connect

    Stone, C.M.

    1997-08-01

    Finite element calculations have been performed to determine the structural response of waste-filled disposal rooms at the WIPP for a period of 10,000 years after emplacement of the waste. The calculations were performed to generate the porosity surface data for the final set of compliance calculations. The most recent reference data for the stratigraphy, waste characterization, gas generation potential, and nonlinear material response have been brought together for this final set of calculations.

  8. Structural, electronic, topological and vibrational properties of a series of N-benzylamides derived from Maca (Lepidium meyenii) combining spectroscopic studies with ONION calculations

    NASA Astrophysics Data System (ADS)

    Chain, Fernando E.; Ladetto, María Florencia; Grau, Alfredo; Catalán, César A. N.; Brandán, Silvia Antonia

    2016-02-01

    In the present work, the structural, topological and vibrational properties of four members of the N-benzylamides series derived from Maca (Lepidium meyenii) whose names are, N-benzylpentadecanamide, N-benzylhexadecanamide, N-benzylheptadecanamide and N-benzyloctadecanamide, were studied combining the FTIR, FT-Raman and 1H and 13C-NMR spectroscopies with density functional theory (DFT) and ONION calculations. Furthermore, the N-benzylacetamide, N-benzylpropilamide and N-benzyl hexanamide derivatives were also studied in order to compare their properties with those computed for the four macamides. These seven N-benzylamides series have a common structure, C8H8NO-R, being R the side chain [-(CH2)n-CH3] with a variable n number of CH2 groups. Here, the atomic charges, molecular electrostatic potentials, stabilization energies, topological properties of those macamides were analyzed as a function of the number of C atoms of the side chain while the frontier orbitals were used to compute the gap energies and some descriptors in order to predict their reactivities and behaviors in function of the longitude of the side chain. Here, the force fields, the complete vibrational assignments and the corresponding force constants were only reported for N-benzylacetamide, N-benzyl hexanamide and N-benzylpentadecanamide due to the high number of vibration normal modes that present the remains macamides.

  9. Ab initio cluster calculations on the electronic structure of oxygen vacancies at the polar ZnO(0001) surface and on the adsorption of H2, CO, and CO2 at these sites.

    PubMed

    Fink, Karin

    2006-04-01

    Oxygen vacancies at the polar O terminated (0001) surface of ZnO are of particular interest, because they are discussed as active sites in the methanol synthesis. In general, the polar ZnO surfaces are stabilized by OH groups, therefore O vacancies can be generated by removing either O atoms or OH or H2O groups from the surface. These defects differ in the number of electrons in the vacancy and the number of OH groups in the neighborhood. In the present study, the electronic structure and the adsorption properties of four different types of oxygen vacancies have been investigated by means of embedded cluster calculations. We performed ab initio calculations on F+ like surface excitations for the different defect types and found that the transition energies are above the optical band-gap, while F+ centers in bulk ZnO show a characteristic optical excitation at 3.19 eV. Furthermore, we studied the adsorption of CO2 and CO at the different defect sites by DFT calculations. We found that CO2 dissociates at electron rich vacancies into CO and an O atom which remains in the vacancy. At the OH vacancy which contains an unpaired electron CO2 adsorbed in the form of CO2-, while it adsorbed as a linear neutral molecule at the H2O defect. CO adsorbed preferentially at the H2O defect and the OH defect, both with a binding energy of 0.3 eV. PMID:16633631

  10. Calculation of electron wave functions and refractive index of Ne

    NASA Astrophysics Data System (ADS)

    Zhu, Min; Liu, Wei; Zhang, Tao

    2008-10-01

    The radial wave functions of inner electron shell and outer electron shell of a Ne atom were obtained by the approximate analytical method and tested by calculating the ground state energy of the Ne atom. The equivalent volume of electron cloud and the refractive index of Ne were calculated. The calculated refractive index agrees well with the experimental result. Relationship between the refractive index and the wave function of Ne was discovered.

  11. Self-healing diffusion quantum Monte Carlo algorithms: methods for direct reduction of the fermion sign error in electronic structure calculations

    SciTech Connect

    Reboredo, F A; Hood, R Q; Kent, P C

    2009-01-06

    We develop a formalism and present an algorithm for optimization of the trial wave-function used in fixed-node diffusion quantum Monte Carlo (DMC) methods. The formalism is based on the DMC mixed estimator of the ground state probability density. We take advantage of a basic property of the walker configuration distribution generated in a DMC calculation, to (i) project-out a multi-determinant expansion of the fixed node ground state wave function and (ii) to define a cost function that relates the interacting-ground-state-fixed-node and the non-interacting trial wave functions. We show that (a) locally smoothing out the kink of the fixed-node ground-state wave function at the node generates a new trial wave function with better nodal structure and (b) we argue that the noise in the fixed-node wave function resulting from finite sampling plays a beneficial role, allowing the nodes to adjust towards the ones of the exact many-body ground state in a simulated annealing-like process. Based on these principles, we propose a method to improve both single determinant and multi-determinant expansions of the trial wave function. The method can be generalized to other wave function forms such as pfaffians. We test the method in a model system where benchmark configuration interaction calculations can be performed and most components of the Hamiltonian are evaluated analytically. Comparing the DMC calculations with the exact solutions, we find that the trial wave function is systematically improved. The overlap of the optimized trial wave function and the exact ground state converges to 100% even starting from wave functions orthogonal to the exact ground state. Similarly, the DMC total energy and density converges to the exact solutions for the model. In the optimization process we find an optimal non-interacting nodal potential of density-functional-like form whose existence was predicted in a previous publication [Phys. Rev. B 77 245110 (2008)]. Tests of the method are

  12. Electronic structure of metal clusters. 4. Photoelectron spectra and molecular orbital calculations on cobalt, iron, ruthenium, and osmium sulfide nonacarbonyl clusters

    SciTech Connect

    Chesky, P.T.; Hall, M.B.

    1983-10-01

    Gas-phase, ultraviolet photoelectron (PE) spectra and molecular orbital (MO) calculations are reported for SCo/sub 3/(CO)/sub 9/, SH/sub n-//sub 1/Fe/sub n/Co/sub 3//sub -n/(CO)/sub 9/ (n = 1-3), S/sub 2/Fe/sub 3/(CO)/sub 9/, and SH/sub 2/M/sub 3/(CO)/sub 9/ (M = Fe, Ru, Os). The first PE spectra reported for mixed-metal clusters are included in this series. As Co atoms are replaced by the isoelectronic FeH unit, the spectra show the loss of a Co band and the appearance of an Fe band. This phenomenon suggests that the d bands localize upon ionization. In a comparison with the PE spectrum of M/sub 3/(CO)/sub 12/ (M = Fe, Ru, Os), the major spectral changes for SH/sub 2/M/sub 3/(CO)/sub 9/ (M = Fe, Ru, Os) are the loss of a band corresponding to direct M-M interactions and the appearance of bands due to a mixture of energy-equivalent M-H-M and M-S interactions. The spectra also show a substantial rearrangement of the bands due to the t/sub 2g/-like electrons, which are usually considered M-CO ..pi.. bonding. An antibonding interaction between a S orbital and the t/sub 2g/-like orbitals is responsible for a unique band in the spectra which occurs at high ionization energy between the M-M bonding band and the main t/sub 2//sub g/-like band. 12 figures, 9 tables

  13. The Calculation Of Absorbing Thin Film Optical Constants And Electronic Structure From Photometric Measures On Domain IR-VIS-UV Using Neural Networks

    SciTech Connect

    Bourouis, Chahrazed; Meddour, Ahcene; Moussaoui, Abdelkrim

    2008-09-23

    In this paper a new method using the combination of Neural Networks and the Newton-Raphson algorithm is developped. The technique consists of the use of the solution obtained by Newton-Raphson algorithm between 0.5 and 2.1eV for pure manganese (Mn) and for the amorphous metallic alloy Al{sub 88}Mn{sub 12}, to construct two parts of datasets; the first one is used for training the neural network and the second one for the validation tests. The validated neural network model is applied to the determination of optical constants of the two materials Mn and Al{sub 88}Mn{sub 12} in the range of 0.5 and 6.2eV (IR-VIS-UV). The results obtained over all the studied energy range are used to trace back to dielectric function, optical absorption and electronic structure of the same material. By using the partial solution obtained by Newton-Raphson as a database of the neural network prediction model, it is shown that the obtained results are in accordance with those of the literature which consolidate the efficiency of the suggested approach.

  14. Electronic structures and related thermoelectric properties of Pb7Bi4Se13 using first principle calculations and Boltzmann transport theory

    NASA Astrophysics Data System (ADS)

    Kanoun, Mohammed Benali

    The electronic structure, optical and thermoelectric properties of Pb7Bi4Se13 have been investigated using a combination of Density functional theory and Boltzmann transport theory. We applied the generalized gradient approximation as exchange-correlation energy functional added to the Coulomb energy (U Hubbard term). The existence of Bi and Pb has required the spin-orbit coupling. The intensity data for Pb7Bi4Se13 were measured at 100 K and 300 K leading to consider Pb7Bi4Se13 in two phases. The valence band maximum emerges predominantly from Se- p state with admixture of Bi - p and Pb - p states, while the conduction band minimum comes from Se- d states. The optical absorption shows the possibility of smaller multiple direct and indirect inter-band transitions in the visible region. We computed Seebeck coefficient, electrical and thermal conductivities, figure of merit and power factor, as function of temperature using the Boltzmann transport theory. Pb7Bi4Se13 is a potential shielding material that can be used at visible and UV region for thermoelectric devices. The present results were validated by comparison with the available experimental measurements.

  15. Structures and Electronic Properties of (KI)n(-/0) (n = 1-4) and K(KI)n(-/0) (n = 1-3) Clusters: Photoelectron Spectroscopy, Isomer-Depletion, and ab Initio Calculations.

    PubMed

    Hou, Gao-Lei; Feng, Gang; Zhao, Li-Juan; Xu, Hong-Guang; Zheng, Wei-Jun

    2015-11-12

    The (KI)n(-) (n = 1-4) and K(KI)n(-) (n = 1-3) clusters were studied by negative ion photoelectron spectroscopy and ab initio calculations. Comparison between the theoretical vertical detachment energies and the experimental values revealed that multiple isomers may coexist in the experiments. The existence of two isomers for K(KI)(-) and K(KI)2(-) were confirmed directly by isomer-depletion experiments, in which the low adiabatic detachment energy isomers were depleted by a 1064 nm laser beam before the anions were photodetached by a 532 nm laser beam. Our results show that the most stable structures of the K(KI)(-), (KI)2(-), and K(KI)2(-) anions are chain structures, while those of their neutral counterparts are planar. Three-dimensional structures start to appear at n = 3 for (KI)n(-/0) and K(KI)n(-/0). In the K(KI)n(-) cluster anions, the excess electron is localized on the extra K atom and forms an electron pair with the existing s electron of the K atom; the resulting negatively charged K prefers to interact with the other positively charged K atoms rather than with the I atoms. Both the anionic and neutral (KI)4 clusters have cuboid structures, which may be regarded as the smallest structural motif of KI crystal. PMID:26473992

  16. FEL gain calculation for imperfectly matched electron beams

    NASA Astrophysics Data System (ADS)

    Swent, R. L.; Berryman, K. W.

    1995-04-01

    We present here the details of an analytical small-signal gain calculation. The analysis builds on the basic one-dimensional analytical calculation by modeling the effects of finite electron beam size and imperfect matching of the electron beam to the wiggler. The calculation uses TRANSPORT [SLAC-91, Rev. 2 (1977)] parameters to describe the electron beam in order to easily take the output of beam transport calculations and use them as the input for FEL gain calculations. The model accepts an arbitrary TRANSPORT beam and includes the effects of energy spread, beam size, betatron oscillations, and focussing in the wiggle plane. The model has allowed us to calculate the range over which our FEL can be tuned by changing the electron energy alone (i.e., without changing any magnets).

  17. Electronic band structure and photoemission: A review and projection

    SciTech Connect

    Falicov, L.M.

    1987-09-01

    A brief review of electronic-structure calculations in solids, as a means of interpreting photoemission spectra, is presented. The calculations are, in general, of three types: ordinary one-electron-like band structures, which apply to bulk solids and are the basis of all other calculations; surface modified calculations, which take into account, self-consistently if at all possible, the presence of a vacuum-solid interface and of the electronic modifications caused thereby; and many-body calculations, which go beyond average-field approximations and consider dynamic rearrangement effects caused by electron-electron correlations during the photoemission process. 44 refs.

  18. Local density functional calculations of the electronic structures of the intermetallic systems U{sub 2}Fe{sub 2}Sn and UFe{sub 2}Ge{sub 2}

    SciTech Connect

    Matar, S.F.; Chevalier, B.; Etourneau, J.; Eyert, V.

    1997-02-05

    The electronic structures of U{sub 2}Fe{sub 2}Sn and UFe{sub 2}Ge{sub 2} are self-consistently calculated within the local density functional theory using the augmented spherical wave (ASW) method. Calculations are scalar relativistic. The experimentally observed Pauli paramagnetic behavior of the two systems is accounted for and the influence of hybridization between the different l-states on the chemical bonding is discussed from the site-projected densities of states (DOS) as well as from the modulation of the DOS by the sign and magnitude of the overlap integral, i.e., with the so-called COOP. From this, we propose a mechanism for the evolution of bonding within the series to which the two compounds belong. 12 refs., 3 figs.

  19. Electronic Structure of Small Lanthanide Containing Molecules

    NASA Astrophysics Data System (ADS)

    Kafader, Jared O.; Ray, Manisha; Topolski, Josey E.; Chick Jarrold, Caroline

    2016-06-01

    Lanthanide-based materials have unusual electronic properties because of the high number of electronic degrees of freedom arising from partial occupation of 4f orbitals, which make these materials optimal for their utilization in many applications including electronics and catalysis. Electronic spectroscopy of small lanthanide molecules helps us understand the role of these 4f electrons, which are generally considered core-like because of orbital contraction, but are energetically similar to valence electrons. The spectroscopy of small lanthanide-containing molecules is relatively unexplored and to broaden this understanding we have completed the characterization of small cerium, praseodymium, and europium molecules using photoelectron spectroscopy coupled with DFT calculations. The characterization of PrO, EuH, EuO/EuOH, and CexOy molecules have allowed for the determination of their electron affinity, the assignment of numerous anion to neutral state transitions, modeling of anion/neutral structures and electron orbital occupation.

  20. Mixed lithium-sodium (LiNaCO3) and lithium-potassium (LiKCO3) carbonates for low temperature electrochemical applications: Structure, electronic properties and surface reconstruction from ab-initio calculations

    NASA Astrophysics Data System (ADS)

    Ricca, Chiara; Ringuedé, Armelle; Cassir, Michel; Adamo, Carlo; Labat, Frédéric

    2016-05-01

    The structural, electronic and surface properties of the mixed lithium-sodium (LiNaCO3) and lithium-potassium (LiKCO3) carbonates were studied through periodic calculations performed at the density functional theory (DFT) level, using three different exchange-correlation functionals. The hybrid functional PBE0 was found to be the best one to describe both geometric and electronic features of bulk LiNaCO3 and LiKCO3. Polar (001) and non-polar (110) low index surfaces were taken into account, the first one being found the most stable in both cases, after reconstruction. Both introduction of vacancies (R1) and octopolar terminations (R2) of (001), exposing Li ((001)Li) or Na ((001)Na) were described in detail. The computed stability order for the reconstructed surfaces in gas phase is: (001)R1Na > > (001)R1Li > (001)R2Na ≈ (001)R2Li. The obtained information, in particular regarding the electronic and surface properties, could be used in future to help understanding the role of mixed carbonates as component of oxide-carbonate electrolytes for low temperature solid oxide fuel cells (LT-SOFCs) applications, especially as reasonable starting points for dynamics calculations of liquid molten carbonates based systems.

  1. Calculating Buckling And Vibrations Of Lattice Structures

    NASA Technical Reports Server (NTRS)

    Anderson, M. S.; Durling, B. J.; Herstrom, C. L.; Williams, F. W.; Banerjee, J. R.; Kennedy, D.; Warnaar, D. B.

    1989-01-01

    BUNVIS-RG computer program designed to calculate vibration frequencies or buckling loads of prestressed lattice structures used in outer space. For buckling and vibration problems, BUNVIS-RG calculates deadload axial forces caused in members by any combination of externally-applied static point forces and moments at nodes, axial preload or prestrain in members, and such acceleration loads as those due to gravity. BUNVIS-RG is FORTRAN 77 computer program implemented on CDC CYBER and VAX computer.

  2. Enhancing Scalability of Parallel Structured AMR Calculations

    SciTech Connect

    Wissink, A M; Hysom, D; Hornung, R D

    2003-02-10

    This paper discusses parallel scaling performance of large scale parallel structured adaptive mesh refinement (SAMR) calculations in SAMRAI. Previous work revealed that poor scaling qualities in the adaptive gridding operations in SAMR calculations cause them to become dominant for cases run on up to 512 processors. This work describes algorithms we have developed to enhance the efficiency of the adaptive gridding operations. Performance of the algorithms is evaluated for two adaptive benchmarks run on up 512 processors of an IBM SP system.

  3. Electronic Structure and Optical Properties of Cu2ZnGeSe4. First-Principles Calculations and Vacuum-Ultraviolet Spectroscopic Ellipsometric Studies

    SciTech Connect

    Choi, Sukgeun; Park, Ji-Sang; Donohue, Andrea; Christensen, Steven T.; To, Bobby; Beall, Carolyn; Wei, Su-Huai; Repins, Ingid L.

    2015-11-19

    Cu2ZnGeSe4 is of interest for the development of next-generation thin-film photovoltaic technologies. To understand its electronic structure and related fundamental optical properties, we perform first-principles calculations for three structural variations: kesterite, stannite, and primitive-mixed CuAu phases. The calculated data are compared with the room-temperature dielectric functionϵ=ϵ1+iϵ2 spectrum of polycrystalline Cu2ZnGeSe4 determined by vacuum-ultraviolet spectroscopic ellipsometry in the photon-energy range of 0.7 to 9.0 eV. Ellipsometric data are modeled with the sum of eight Tauc-Lorentz oscillators, and the best-fit model yields the band-gap and Tauc-gap energies of 1.25 and 1.19 eV, respectively. A comparison of overall peak shapes and relative intensities between experimental spectra and the calculated ϵ data for three structural variations suggests that the sample may not have a pure (ordered) kesterite phase. We found that the complex refractive index N=n+ik, normal-incidence reflectivity R, and absorption coefficients α are calculated from the modeled ϵ spectrum, which are also compared with those of Cu2ZnSnSe4 . The spectral features for Cu2ZnGeSe4 appear to be weaker and broader than those for Cu2ZnSnSe4 , which is possibly due to more structural imperfections presented in Cu2ZnGeSe4 than Cu2ZnSnSe4 .

  4. Electronic Structure of the Aqueous Vanadyl Ion Probed by 9 and 94 GHz EPR and Pulsed ENDOR Spectroscopies and Density Functional Theory Calculations

    PubMed Central

    Grant, Christopher V.; Cope, William; Ball, James A.; Maresch, Guenter G.; Gaffney, Betty J.; Fink, William

    2005-01-01

    The aqueous vanadyl ion ([VO(H2O)5]2+) has been investigated by X-band EPR, 94 GHz W-band EPR, and ESE-ENDOR. These experiments reveal information about the hyperfine (|Axx| = 208.5 MHz, |Ayy| = 208.5 MHz, |Azz| = 547.0 MHz), and nuclear quadrupole coupling (|e2qQ| = 5.6 MHz) of the 51V nucleus. The measured nuclear quadrupole coupling parameters are compared to values determined by density functional theory calculations (|e2qQ| = 5.2 MHz). These theoretical calculations illustrate that axial ligands and molecular distortions can alter the magnitude of the nuclear quadrupole interaction. PMID:16467924

  5. Electronic structure interpolation via atomic orbitals.

    PubMed

    Chen, Mohan; Guo, G-C; He, Lixin

    2011-08-17

    We present an efficient scheme for accurate electronic structure interpolation based on systematically improvable optimized atomic orbitals. The atomic orbitals are generated by minimizing the spillage value between the atomic basis calculations and the converged plane wave basis calculations on some coarse k-point grid. They are then used to calculate the band structure of the full Brillouin zone using the linear combination of atomic orbitals algorithms. We find that usually 16-25 orbitals per atom can give an accuracy of about 10 meV compared to the full ab initio calculations, and the accuracy can be systematically improved by using more atomic orbitals. The scheme is easy to implement and robust, and works equally well for metallic systems and systems with complicated band structures. Furthermore, the atomic orbitals have much better transferability than Shirley's basis and Wannier functions, which is very useful for perturbation calculations.

  6. Benchmark Calculations for Electron-Impact Excitation of Krypton.

    NASA Astrophysics Data System (ADS)

    Grum-Grzhimailo, A. N.; Bartschat, K.

    2000-06-01

    Angular correlation and polarization studies of electron-impact excitation of the heavy rare gases provide important benchmarks for testing theoretical approaches. For e--Kr collisions, simulations must treat a complex target structure and the scattering dynamics, both with the inclusion of relativistic effects. A variety of observables calculated with our improved model will be presented, the convergence of the results with the number of coupled channels will be analyzed, and the results will be compared with detailed experimental data [1,2]. Finally, our predictions for the angular momentum transfer L_⊥ at small scattering angles suggest a promising test for a deeper understanding of propensity rules in these transitions. [1] X. Guo et al. (1999), J. Phys. B 32 L155. [2] M. Dümmler et al. (1995), J. Phys. B 28 2985.

  7. Structural, Electronic, and Optical Properties of BiOX1-xYx (X, Y = F, Cl, Br, and I) Solid Solutions from DFT Calculations.

    PubMed

    Zhao, Zong-Yan; Liu, Qing-Lu; Dai, Wen-Wu

    2016-01-01

    Six BiOX1-xYx (X, Y = F, Cl, Br, and I) solid solutions have been systematically investigated by density functional theory calculations. BiOCl1-xBrx, BiOBr1-xIx, and BiOCl1-xIx solid solutions have very small bowing parameters; as such, some of their properties increase almost linearly with increasing x. For BiOF1-xYx solid solutions, the bowing parameters are very large and it is extremely difficult to fit the related calculated data by a single equation. Consequently, BiOX1-xYx (X, Y = Cl, Br, and I) solid solutions are highly miscible, while BiOF1-xYx (Y = Cl, Br, and I) solid solutions are partially miscible. In other words, BiOF1-xYx solid solutions have miscibility gaps or high miscibility temperature, resulting in phase separation and F/Y inhomogeneity. Comparison and analysis of the calculated results and the related physical-chemical properties with different halogen compositions indicates that the parameters of BiOX1-xYx solid solutions are determined by the differences of the physical-chemical properties of the two halogen compositions. In this way, the large deviation of some BiOX1-xYx solid solutions from Vegard's law observed in experiments can be explained. Moreover, the composition ratio of BiOX1-xYx solid solutions can be measured or monitored using optical measurements.

  8. Structural, Electronic, and Optical Properties of BiOX1-xYx (X, Y = F, Cl, Br, and I) Solid Solutions from DFT Calculations.

    PubMed

    Zhao, Zong-Yan; Liu, Qing-Lu; Dai, Wen-Wu

    2016-01-01

    Six BiOX1-xYx (X, Y = F, Cl, Br, and I) solid solutions have been systematically investigated by density functional theory calculations. BiOCl1-xBrx, BiOBr1-xIx, and BiOCl1-xIx solid solutions have very small bowing parameters; as such, some of their properties increase almost linearly with increasing x. For BiOF1-xYx solid solutions, the bowing parameters are very large and it is extremely difficult to fit the related calculated data by a single equation. Consequently, BiOX1-xYx (X, Y = Cl, Br, and I) solid solutions are highly miscible, while BiOF1-xYx (Y = Cl, Br, and I) solid solutions are partially miscible. In other words, BiOF1-xYx solid solutions have miscibility gaps or high miscibility temperature, resulting in phase separation and F/Y inhomogeneity. Comparison and analysis of the calculated results and the related physical-chemical properties with different halogen compositions indicates that the parameters of BiOX1-xYx solid solutions are determined by the differences of the physical-chemical properties of the two halogen compositions. In this way, the large deviation of some BiOX1-xYx solid solutions from Vegard's law observed in experiments can be explained. Moreover, the composition ratio of BiOX1-xYx solid solutions can be measured or monitored using optical measurements. PMID:27549344

  9. Structural, Electronic, and Optical Properties of BiOX1‑xYx (X, Y = F, Cl, Br, and I) Solid Solutions from DFT Calculations

    NASA Astrophysics Data System (ADS)

    Zhao, Zong-Yan; Liu, Qing-Lu; Dai, Wen-Wu

    2016-08-01

    Six BiOX1‑xYx (X, Y = F, Cl, Br, and I) solid solutions have been systematically investigated by density functional theory calculations. BiOCl1‑xBrx, BiOBr1‑xIx, and BiOCl1‑xIx solid solutions have very small bowing parameters; as such, some of their properties increase almost linearly with increasing x. For BiOF1‑xYx solid solutions, the bowing parameters are very large and it is extremely difficult to fit the related calculated data by a single equation. Consequently, BiOX1‑xYx (X, Y = Cl, Br, and I) solid solutions are highly miscible, while BiOF1‑xYx (Y = Cl, Br, and I) solid solutions are partially miscible. In other words, BiOF1‑xYx solid solutions have miscibility gaps or high miscibility temperature, resulting in phase separation and F/Y inhomogeneity. Comparison and analysis of the calculated results and the related physical–chemical properties with different halogen compositions indicates that the parameters of BiOX1‑xYx solid solutions are determined by the differences of the physical–chemical properties of the two halogen compositions. In this way, the large deviation of some BiOX1‑xYx solid solutions from Vegard’s law observed in experiments can be explained. Moreover, the composition ratio of BiOX1‑xYx solid solutions can be measured or monitored using optical measurements.

  10. Structural, Electronic, and Optical Properties of BiOX1−xYx (X, Y = F, Cl, Br, and I) Solid Solutions from DFT Calculations

    PubMed Central

    Zhao, Zong-Yan; Liu, Qing-Lu; Dai, Wen-Wu

    2016-01-01

    Six BiOX1−xYx (X, Y = F, Cl, Br, and I) solid solutions have been systematically investigated by density functional theory calculations. BiOCl1−xBrx, BiOBr1−xIx, and BiOCl1−xIx solid solutions have very small bowing parameters; as such, some of their properties increase almost linearly with increasing x. For BiOF1−xYx solid solutions, the bowing parameters are very large and it is extremely difficult to fit the related calculated data by a single equation. Consequently, BiOX1−xYx (X, Y = Cl, Br, and I) solid solutions are highly miscible, while BiOF1−xYx (Y = Cl, Br, and I) solid solutions are partially miscible. In other words, BiOF1−xYx solid solutions have miscibility gaps or high miscibility temperature, resulting in phase separation and F/Y inhomogeneity. Comparison and analysis of the calculated results and the related physical–chemical properties with different halogen compositions indicates that the parameters of BiOX1−xYx solid solutions are determined by the differences of the physical–chemical properties of the two halogen compositions. In this way, the large deviation of some BiOX1−xYx solid solutions from Vegard’s law observed in experiments can be explained. Moreover, the composition ratio of BiOX1−xYx solid solutions can be measured or monitored using optical measurements. PMID:27549344

  11. An electronic structure perspective of graphene interfaces

    NASA Astrophysics Data System (ADS)

    Schultz, Brian J.; Dennis, Robert V.; Lee, Vincent; Banerjee, Sarbajit

    2014-03-01

    The unusual electronic structure of graphene characterized by linear energy dispersion of bands adjacent to the Fermi level underpins its remarkable transport properties. However, for practical device integration, graphene will need to be interfaced with other materials: 2D layered structures, metals (as ad-atoms, nanoparticles, extended surfaces, and patterned metamaterial geometries), dielectrics, organics, or hybrid structures that in turn are constituted from various inorganic or organic components. The structural complexity at these nanoscale interfaces holds much promise for manifestation of novel emergent phenomena and provides a means to modulate the electronic structure of graphene. In this feature article, we review the modifications to the electronic structure of graphene induced upon interfacing with disparate types of materials with an emphasis on iterative learnings from theoretical calculations and electronic spectroscopy (X-ray absorption fine structure (XAFS) spectroscopy, scanning transmission X-ray microscopy (STXM), angle-resolved photoemission spectroscopy (ARPES), and X-ray magnetic circular dichroism (XMCD)). We discuss approaches for engineering and modulating a bandgap in graphene through interfacial hybridization, outline experimental methods for examining electronic structure at interfaces, and overview device implications of engineered interfaces. A unified view of how geometric and electronic structure are correlated at interfaces will provide a rational means for designing heterostructures exhibiting emergent physical phenomena with implications for plasmonics, photonics, spintronics, and engineered polymer and metal matrix composites.

  12. An electronic structure perspective of graphene interfaces.

    PubMed

    Schultz, Brian J; Dennis, Robert V; Lee, Vincent; Banerjee, Sarbajit

    2014-04-01

    The unusual electronic structure of graphene characterized by linear energy dispersion of bands adjacent to the Fermi level underpins its remarkable transport properties. However, for practical device integration, graphene will need to be interfaced with other materials: 2D layered structures, metals (as ad-atoms, nanoparticles, extended surfaces, and patterned metamaterial geometries), dielectrics, organics, or hybrid structures that in turn are constituted from various inorganic or organic components. The structural complexity at these nanoscale interfaces holds much promise for manifestation of novel emergent phenomena and provides a means to modulate the electronic structure of graphene. In this feature article, we review the modifications to the electronic structure of graphene induced upon interfacing with disparate types of materials with an emphasis on iterative learnings from theoretical calculations and electronic spectroscopy (X-ray absorption fine structure (XAFS) spectroscopy, scanning transmission X-ray microscopy (STXM), angle-resolved photoemission spectroscopy (ARPES), and X-ray magnetic circular dichroism (XMCD)). We discuss approaches for engineering and modulating a bandgap in graphene through interfacial hybridization, outline experimental methods for examining electronic structure at interfaces, and overview device implications of engineered interfaces. A unified view of how geometric and electronic structure are correlated at interfaces will provide a rational means for designing heterostructures exhibiting emergent physical phenomena with implications for plasmonics, photonics, spintronics, and engineered polymer and metal matrix composites.

  13. Electronic structure of f{sup 1} actinide complexes. 1. Nonrelativistic and relativistic calculations of the optical transition energies of AnX{sub 6}{sup q{minus}} complexes

    SciTech Connect

    Kaltsoyannis, N.; Bursten, B.E.

    1995-05-10

    The ground-state electronic structures of PaX{sub 6}{sup 2{minus}} (X = F, Cl, Br, I), UX{sub 6}{sup {minus}} (X = F, Cl, Br), and NpF{sub 6} have been calculated, using both nonrelativistic implementations of the discrete-variational X{alpha} (DV-X{alpha}) method. A significant amount of metal-ligand covalent bonding is found, involving both 6d and 5f metal orbitals. The 5f contribution to the bonding levels increases significantly from PaX{sub 6}{sup 2{minus}} to UX{sub 6}{sup {minus}} to NpF{sub 6} but remains approximately constant as the halogen is altered in PaX{sub 6}{sup 2{minus}} and UX{sub 6}{sup {minus}}. In contrast, the 6d atomic orbital character of the halogen-based levels increases from UF{sub 6}{sup {minus}} to UBr{sub 6}{sup {minus}} and a similar, through less marked, trend is observed in PaX{sub 6}{sup 2{minus}}. The electronic transition energies have been calculated using the transition state method. The relativistic calculations are far superior to the nonrelativistic ones in both qualitatively and quantitatively describing the electronic spectra. The stabilization of the metal 5f atomic orbitals with respect to the halogen np levels from protactinium to neptunium results in the more energetic f {yields} f transitions in NpF{sub 6} being masked by the onset of a ligand-to-metal charge-transfer band. In the remaining molecules, the f {yields} F transitions in NpF{sub 6} being masked by the onset of a ligand-to-metal charge-transfer band. In the remaining molecules, the f {yields} f transitions occur well removed from charge-transfer bands.

  14. Structural and Electronic Properties of Reduced Transition Metal Oxide Clusters, M 3 O 8 and M 3 O 8 - (M = Cr, W), from Photoelectron Spectroscopy and Quantum Chemical Calculations

    SciTech Connect

    Li, Shenggang; Zhai, Hua-Jin; Wang, Lai-Sheng; Dixon, David A.

    2009-09-28

    We report a comparative study of reduced transition metal oxide clusters, M₃O₈⁻ (M = Cr, W) anions and their neutrals, via anion photoelectron spectroscopy (PES) and density functional theory (DFT) and molecular orbital theory (CCSD(T)) calculations. Well-resolved PES spectra are obtained for M₃O₈⁻ (M = Cr, W) at 193 and 157 nm photon energies. Different PES spectra are observed for M = Cr versus M = W. ExtensiveDFT and CCSD(T) calculations are performed to locate the ground and low-lying excited states for the neutrals and anions. The ground states of Cr₃O₈ and Cr₃O₈⁻ are predicted to be the ³B₂ and ⁴B₂ states of a C₂v structure, respectively, revealing ferromagnetic spin coupling for Cr 3d electrons. In contrast, the ground states of W₃O₈ and W₃O₈⁻ are predicted to be the ¹A' state (Cs symmetry) and the ²A₁ state (C₂v symmetry), respectively, showing metal-metal d-d bonding in the anion. The current cluster geometries are in qualitative agreement with prior DFT studies at the PBE level for M = Cr and the B3LYP level for M = W. The BP86 and PW91 functionals significantly outperform the B3LYP functional for the Cr species, in terms of relative energies, electron detachment energies, and electronic excitation energies, whereas the B3LYP functional is better for the W species. Accurate heats of formation for the ground states of M₃O₈ are calculated from the clustering energies and the heats of formation of MO₂ and MO₃. The energetics have been used to predict redox reaction thermochemistry.

  15. Multiscale real-space quantum-mechanical tight-binding calculations of electronic structure in crystals with defects using perfectly matched layers

    NASA Astrophysics Data System (ADS)

    Pourmatin, Hossein; Dayal, Kaushik

    2016-10-01

    We consider the scattering of incident plane-wave electrons from a defect in a crystal modeled by the time-harmonic Schrödinger equation. While the defect potential is localized, the far-field potential is periodic, unlike standard free-space scattering problems. Previous work on the Schrödinger equation has been almost entirely in free-space conditions; a few works on crystals have been in one-dimension. We construct absorbing boundary conditions for this problem using perfectly matched layers in a tight-binding formulation. Using the example of a point defect in graphene, we examine the efficiency and convergence of the proposed absorbing boundary condition.

  16. Benchmark Calculations of Electron-Impact Differential Cross Sections

    SciTech Connect

    Bray, I.; Bostock, C. J.; Fursa, D. V.; Hines, C. W.; Kadyrov, A. S.; Stelbovics, A. T.

    2011-05-11

    The calculation of electron-atom excitation and ionization cross section is considered in both the non-relativistic and relativistic scattering theory. We consider electron collisions with H, He, Cs, and Hg. Differential cross sections for elastic scattering and ionization are presented.

  17. Structural increments in UV spectra of conjugated carbonyl compounds. Part II. CNDO/S-CI calculations of electronic spectra of enamino aldehydes, enamino ketones and enamino amides

    NASA Astrophysics Data System (ADS)

    Kania, L.; Kamieńska-Trela, K.; Witanowski, M.

    1984-06-01

    The semiempirical molecular orbital CNDO/S-CI spectral parameterization is used in order to evaluate structural increments in UV spectra of a series of β-amino-α,β-un- saturated carbonyl compounds. For most of the compounds, theoretical values of con formational and configurational spectral effects are lower than the experimental ones. It is suggested that a substantial part of the discrepancy is associated with the neglect by the CNDO/S-CI approximation of the changes in the nonbonded interaction energies caused by conformational and configurational isomerizaticns. We show that the applica tion of due corrections based on simple electrostatic and van der Waals interactions according to the Lennard-Jones potentials leads to a good agreement in magnitude and sign between the experimental and theoretical increments.

  18. Electronics for Piezoelectric Smart Structures

    NASA Technical Reports Server (NTRS)

    Warkentin, D. J.; Tani, J.

    1997-01-01

    This paper briefly presents work addressing some of the basic considerations for the electronic components used in smart structures incorporating piezoelectric elements. After general remarks on the application of piezoelectric elements to the problem of structural vibration control, three main topics are described. Work to date on the development of techniques for embedding electronic components within structural parts is presented, followed by a description of the power flow and dissipation requirements of those components. Finally current work on the development of electronic circuits for use in an 'active wall' for acoustic noise is introduced.

  19. Calculating electron beam properties in an ionized benzene channel

    SciTech Connect

    Goosman, D.R.

    1986-08-01

    We have derived formulas for the equilibrium-beam radius and other properties of an electron beam propagating in an ionized benzene channel. These formulas have been determined for two special cases. The first was for Gaussian spatial profiles for both the electron and laser beams. We obtained an analytical result for the equilibrium-beam radius, even though we included both KrF laser-induced and collisional sources of ionization of different sizes. The second case we considered was for laser and electron beams with flat radial profiles. These calculations were performed to determine if a laser-guided electron beam could reduce the focal size of an electron accelerator. We also developed a personal-computer spreadsheet program that receives 10 inputs and calculates 26 dependent quantities relating to the beam and ionization properties.

  20. Structural, vibrational, electronic, NMR, NLO and reactivity analyses of (3Z)-3-(2-oxo-2-phenylethylidene)-1,3-dihydro-2H-indol-2-one (OPEDI) by ab initio HF and DFT calculations.

    PubMed

    Sridevi, C; Velraj, G

    2013-04-15

    This study represents the vibrational, electronic, NMR, NLO, reactivity and structural aspects of (3Z)-3-(2-oxo-2-phenylethylidene)-1,3-dihydro-2H-indol-2-one (OPEDI). A detailed interpretation of the FT-IR, FT-Raman, UV and NMR spectra were reported. Theoretical calculations were performed by ab initio HF and density functional theory (DFT)/B3LYP method using 6-311++G(d,p) basis sets. The most preferred Z isomer (cis-configuration) was confirmed through PES scan studies. The vibrational wavenumbers and potential energy distribution (PED) of various normal modes were calculated. The lower frontier orbital energy gap and high dipole moment of OPEDI illustrates the high reactivity. The stability and charge delocalization of the molecule was studied by natural bond orbital (NBO) analysis. OPEDI exhibited good nonlinear optical activity and was 13 times greater than that of urea. Molecular electrostatic potential (MEP) was carried out for predicting the reactive sites. The NMR results indicated that the observed chemical shifts depend not only on the structure of the molecule being studied, but also on the solvent used.

  1. Influence of halide composition on the structural, electronic, and optical properties of mixed CH3NH3Pb (I1-xBrx) 3 perovskites calculated using the virtual crystal approximation method

    NASA Astrophysics Data System (ADS)

    Jong, Un-Gi; Yu, Chol-Jun; Ri, Jin-Song; Kim, Nam-Hyok; Ri, Guk-Chol

    2016-09-01

    Extensive studies have demonstrated the promising capability of the organic-inorganic hybrid halide perovskite CH3NH3PbI3 in solar cells with a high power conversion efficiency exceeding 20%. However, the intrinsic as well as extrinsic instabilities of this material remain the major challenge to the commercialization of perovskite-based solar cells. Mixing halides is expected to resolve this problem. Here, we investigate the effect of chemical substitution in the position of the halogen atom on the structural, electronic, and optical properties of mixed halide perovskites CH3NH3Pb (I1-xBrx) 3 with a pseudocubic phase using the virtual crystal approximation method within density functional theory. With an increase of Br content x from 0.0 to 1.0, the lattice constant decreases in proportion to x with the function of a (x )=6.420 -0.333 x (Å), while the band gap and the exciton binding energy increase with the quadratic function of Eg(x ) =1.542 +0.374 x +0.185 x2 (eV) and the linear function of Eb(x ) =0.045 +0.057 x (eV), respectively. The photoabsorption coefficients are also calculated, showing a blueshift of the absorption onsets for higher Br contents. We calculate the phase decomposition energy of these materials and analyze the electronic charge density difference to estimate the material stability. Based on the calculated results, we suggest that the best match between efficiency and stability can be achieved at x ≈0.2 in CH3NH3Pb (I1-xBrx) 3 perovskites.

  2. Electronic structures of TiO2-TCNE, -TCNQ, and -2,6-TCNAQ surface complexes studied by ionization potential measurements and DFT calculations: Mechanism of the shift of interfacial charge-transfer bands

    NASA Astrophysics Data System (ADS)

    Fujisawa, Jun-ichi; Hanaya, Minoru

    2016-06-01

    Interfacial charge-transfer (ICT) transitions between inorganic semiconductors and π-conjugated molecules allow direct charge separation without loss of energy. This feature is potentially useful for efficient photovoltaic conversions. Charge-transferred complexes of TiO2 nanoparticles with 7,7,8,8-tetracyanoquinodimethane (TCNQ) and its analogues (TCNX) show strong ICT absorption in the visible region. The ICT band was reported to be significantly red-shifted with extension of the π-conjugated system of TCNX. In order to clarify the mechanism of the red-shift, in this work, we systematically study electronic structures of the TiO2-TCNX surface complexes (TCNX; TCNE, TCNQ, 2,6-TCNAQ) by ionization potential measurements and density functional theory (DFT) calculations.

  3. A new algorithm to handle finite nuclear mass effects in electronic calculations: the ISOTOPE program.

    PubMed

    Gonçalves, Cristina P; Mohallem, José R

    2004-11-15

    We report the development of a simple algorithm to modify quantum chemistry codes based on the LCAO procedure, to account for the isotope problem in electronic structure calculations. No extra computations are required compared to standard Born-Oppenheimer calculations. An upgrade of the Gamess package called ISOTOPE is presented, and its applicability is demonstrated in some examples. PMID:15362130

  4. Electronic and crystallographic structure of apatites

    NASA Astrophysics Data System (ADS)

    Calderín, L.; Stott, M. J.; Rubio, A.

    2003-04-01

    An ab initio study of four different stoichiometric apatites (oxyapatite, hydroxyapatite, fluorapatite, and chlorapatite) is presented. The calculations were performed using density-functional theory with the local-density approximation for exchange and correlation, and a full relaxation of the electronic structure, the atomic arrangement, and the unit cell. Hexagonal unit cells were obtained for all four apatites, and the calculated atomic arrangements are in close agreement with observation in those cases for which the structure is firmly established. A zero-temperature structure is predicted for oxyapatite, and two possible configurations were found for the Cl- ions in chlorapatite. The possibility of the monoclinic structure in hydroxyapatite and chlorapatite was also studied but no indication of greater stability with respect to the hexagonal structure was found. A relationship between the structure of the apatites and that of pure calcium is discussed.

  5. Structural and electronic properties of thallium compounds

    NASA Astrophysics Data System (ADS)

    Paliwal, Neetu; Srivastava, Vipul

    2016-05-01

    The tight binding linear muffin-tin-orbital (TB-LMTO) method within the local density approximation (LDA has been used to calculate structural and electronic properties of thallium pnictides TlX (X=Sb, Bi) at high pressure. As a function of volume, the total energy is evaluated. Apart from this, the lattice parameter (a0), bulk modulus (B0), band structure (BS) and density of states (DOS) are calculated. From energy band diagram we observed metallic behaviour in TlSb and TlBi compounds. The values of equilibrium lattice constants and bulk modulus are agreed well with the available data.

  6. Electron/Photon Verification Calculations Using MCNP4B

    SciTech Connect

    D. P. Gierga; K. J. Adams

    1999-04-01

    MCNP4BW was released in February 1997 with significant enhancements to electron/photon transport methods. These enhancements have been verified against a wide range of published electron/photon experiments, spanning high energy bremsstrahlung production to electron transmission and reflection. The impact of several MCNP tally options and physics parameters was explored in detail. The agreement between experiment and simulation was usually within two standard deviations of the experimental and calculational errors. Furthermore, sub-step artifacts for bremsstrahlung production were shown to be mitigated. A detailed suite of electron depth dose calculations in water is also presented. Areas for future code development have also been explored and include the dependence of cell and detector tallies on different bremsstrahlung angular models and alternative variance reduction splitting schemes for bremsstrahlung production.

  7. Electronic structure of disordered conjugated polymers: Polythiophenes

    SciTech Connect

    Vukmirovic, Nenad; Wang, Lin-Wang

    2008-11-26

    Electronic structure of disordered semiconducting conjugated polymers was studied. Atomic structure was found from a classical molecular dynamics simulation and the charge patching method was used to calculate the electronic structure with the accuracy similar to the one of density functional theory in local density approximation. The total density of states, the local density of states at different points in the system and the wavefunctions of several states around the gap were calculated in the case of poly(3-hexylthiophene) (P3HT) and polythiophene (PT) systems to gain insight into the origin of disorder in the system, the degree of carrier localization and the role of chain interactions. The results indicated that disorder in the electronic structure of alkyl substituted polythiophenes comes from disorder in the conformation of individualchains, while in the case of polythiophene there is an additional contribution due to disorder in the electronic coupling between the chains. Each of the first several wavefunctions in the conduction and valence band of P3HT is localized over several rings of a single chain. It was shown that the localization can be caused in principle both by ring torsions and chain bending, however the effect of ring torsions is much stronger. PT wavefunctions are more complicated due to larger interchain electronic coupling and are not necessarily localized on a single chain.

  8. The calculation of free electron density in CASSANDRA

    NASA Astrophysics Data System (ADS)

    Pattison, L. K.; Crowley, B. J. B.; Harris, J. W. O.; Upcraft, L. M.

    2010-01-01

    CASSANDRA is an AWE opacity code used to model plasmas in local thermal equilibrium: there is a desire to expand its use to calculating plasma equations of state. CASSANDRA's self-consistent field calculation ( SCF) uses the local density approximation for bounds states and has a free electron contribution based upon the Thomas-Fermi model [B.J.B. Crowley et al., J. Quant. Spectro. Radiat. Trans. 71, 257(2001)]. Whilst this is applicable for very high temperature or low density plasmas; in hot and dense matter the effect of ionization will lead to discontinuities in the effective ionisation, Z⋆. The electron contribution to hydrostatic pressure is associated with Z⋆, thus these discontinuities produce unphysical jumps in the resulting calculated material pressure. We describe a procedure to mitigate the effect by calculating the free electron wave functions within the generalized ion-cell model [B.J.B. Crowley et al., Phys. Rev. A 41, 2179(1990)], and thus explicitly calculate free-electron resonances.

  9. Calculation of electrostatic fields in periodic structures of complex shape

    NASA Technical Reports Server (NTRS)

    Kravchenko, V. F.

    1978-01-01

    A universal algorithm is presented for calculating electrostatic fields in an infinite periodic structure consisting of electrodes of arbitrary shape which are located in mirror-symmetrical manner along the axis of electron-beam propagation. The method is based on the theory of R-functions, and the differential operators which are derived on the basis of the functions. Numerical results are presented and the accuracy of the results is examined.

  10. Monte Carlo Code System for Electron (Positron) Dose Kernel Calculations.

    SciTech Connect

    CHIBANI, OMAR

    1999-05-12

    Version 00 KERNEL performs dose kernel calculations for an electron (positron) isotropic point source in an infinite homogeneous medium. First, the auxiliary code PRELIM is used to prepare cross section data for the considered medium. Then the KERNEL code simulates the transport of electrons and bremsstrahlung photons through the medium until all particles reach their cutoff energies. The deposited energy is scored in concentric spherical shells at a radial distance ranging from zero to twice the source particle range.

  11. The molecular structure of TbI 3, DyI 3, HoI 3 and ErI 3 as determined by synchronous gas-phase electron diffraction and mass spectrometric experiment assisted by quantum chemical calculations

    NASA Astrophysics Data System (ADS)

    Shlykov, Sergey A.; Giricheva, Nina I.; Lapykina, Elena A.; Girichev, Georgiy V.; Oberhammer, Heinz

    2010-08-01

    A first gas electron diffraction study of TbI 3, DyI 3, HoI 3 and ErI 3 has been carried out in combination with mass spectrometric vapour monitoring at 1117(10), 1117(10), 1132(10) and 1102(10) K, respectively. Up to 4 mol.% of dimeric species was observed in addition to the dominating monomeric molecules. The change of the thermal-averaged rg-configuration parameters of the molecules in the series TbI 3 → ErI 3 reflect the lanthanide contraction. A low value of the shrinkage δ(I…I) even at such a high temperatures may be considered due to vibration effects in molecule whose equilibrium geometric nuclear structure is planar and which correspond to configurationally-averaged 4f n electronic state. B3LYP and МР2 calculations performed in this work with large core potential for lanthanide atoms also resulted in equilibrium geometry of D 3h symmetry. According to the both quantum chemical methods applied the potential function the non-planar vibration is essentially anharmonic, which is therefore to be taken into account to correctly describe nuclear dynamics in molecules such as LnI 3. Different models applied in this study predict the equilibrium distance re(Ln-I) to be shorter than the thermal-averaged rg(Ln-I) distance by 0.002-0.018(1) Å.

  12. The Band Structure of Polymers: Its Calculation and Interpretation. Part 3. Interpretation.

    ERIC Educational Resources Information Center

    Duke, B. J.; O'Leary, Brian

    1988-01-01

    In this article, the third part of a series, the results of ab initio polymer calculations presented in part 2 are discussed. The electronic structure of polymers, symmetry properties of band structure, and generalizations are presented. (CW)

  13. [An empirical model for calculating electron dose distributions].

    PubMed

    Leistner, H; Schüler, W

    1990-01-01

    Dose-distributions in radiation fields are calculated for purpose of irradiation planning from measured depth dose and cross-distributions predominantly. Especially in electron fields the measuring effort is high to this, because these distributions have to be measured for all occurring irradiation parameters and in many different tissue depths. At the very least it can be shown for the 6...10 MeV electron radiation of the linear accelerator Neptun 10p that all required distributions can be calculated from each separately measured depth dose and cross-distribution. For this depth dose distribution and the measured border decrease of cross-distribution are tabulated and the abscissas are submitted to a linear transformation x' = k.x. In case of depth dose distribution the transformation factor k is dependent on electron energy only and in cross-distribution on tissue depth and source-surface-distance additionally. PMID:2356295

  14. Study of the thymine molecule: equilibrium structure from joint analysis of gas-phase electron diffraction and microwave data and assignment of vibrational spectra using results of ab initio calculations.

    PubMed

    Vogt, Natalja; Khaikin, Leonid S; Grikina, Olga E; Rykov, Anatolii N; Vogt, Jürgen

    2008-08-21

    Thymine is one of the nucleobases which forms the nucleic acid (NA) base pair with adenine in DNA. The study of molecular structure and dynamics of nucleobases can help to understand and explain some processes in biological systems and therefore it is of interest. Because the scattered intensities on the C, N, and O atoms as well as some bond lengths in thymine are close to each other the structural problem cannot been solved by the gas phase electron diffraction (GED) method alone. Therefore the rotational constants from microvawe (MW) studies and differences in the groups of N-C, C=O, N-H, and C-H bond lengths from MP2 (full)/cc-pVQZ calculations were used as supplementary data. The analysis of GED data was based on the C(s) molecular symmetry according to results of the structure optimizations at the MP2 (full) level using 6-311G (d,p), cc-pVTZ, and cc-pVQZ basis sets confirmed by vibrational frequency calculations with 6-311G (d,p) and cc-pVTZ basis sets. Mean-square amplitudes as well as harmonic and anharmonic vibrational corrections to the internuclear distances (r(e)-r(a)) and to the rotational constants (B(e)(k)-B(0)(k), where k = A, B, C) were calculated from the quadratic (MP2 (full)/cc-pVTZ) and cubic (MP2 (full)/6-311G (d,p)) force constants (the latter were used only for anharmonic corrections). The harmonic force field was scaled using published IR and Raman spectra of the parent and N1,N3-dideuterated species, which were for the first time completely assigned in the present work. The main equilibrium structural parameters of the thymine molecule determined from GED data supplemented by MW rotational constants and results of MP2 calculations are the following (bond lengths in Angstroms and bond angles in degrees with 3sigma in parentheses): r(e) (C5=C6) = 1.344 (16), r(e) (C5-C9) = 1.487 (8), r(e) (N1-C6) = 1.372 (3), r(e) (N1-C2) = 1.377 (3), r(e) (C2-N3) = 1.378 (3), r(e) (N3-C4) = 1.395 (3), r(e) (C2=O7) = 1.210 (1), r(e) (C4=O8) = 1.215 (1

  15. Electronic Structure of Iridium Clusters on Graphene

    NASA Astrophysics Data System (ADS)

    Barker, Bradford A.; Bradley, Aaron J.; Ugeda, Miguel M.; Coh, Sinisa; Zettl, Alex; Crommie, Michael F.; Cohen, Marvin L.; Louie, Steven G.

    2015-03-01

    Graphene was predicted to exhibit non-trivial Z2 topology, but its exceedingly weak spin-orbit coupling prevented this from being observed. Previous theoretical work has proposed enhancing the spin-orbit coupling strength by depositing individual adatoms adsorbed onto the surface of graphene. We show experimental evidence that the iridium adatoms cluster, with a cluster size of at least two atoms. We investigate through theoretical calculations the orientation of the iridium dimers on graphene, contrast the electronic structure of iridium dimers with iridium monomers, and compare the theoretical iridium dimer electronic structure calculations with the experimental results determined via scanning tunneling spectroscopy. This work was supported by NSF Grant No. DMR10-1006184 and U.S. DOE under Contract No. DE-AC02-05CH11231. Computational resources have been provided by DOE at LBNL's NERSC facility.

  16. Atomic Structure Calculations from the Los Alamos Atomic Physics Codes

    DOE Data Explorer

    Cowan, R. D.

    The well known Hartree-Fock method of R.D. Cowan, developed at Los Alamos National Laboratory, is used for the atomic structure calculations. Electron impact excitation cross sections are calculated using either the distorted wave approximation (DWA) or the first order many body theory (FOMBT). Electron impact ionization cross sections can be calculated using the scaled hydrogenic method developed by Sampson and co-workers, the binary encounter method or the distorted wave method. Photoionization cross sections and, where appropriate, autoionizations are also calculated. Original manuals for the atomic structure code, the collisional excitation code, and the ionization code, are available from this website. Using the specialized interface, you will be able to define the ionization stage of an element and pick the initial and final configurations. You will be led through a series of web pages ending with a display of results in the form of cross sections, collision strengths or rates coefficients. Results are available in tabular and graphic form.

  17. Electronic structure of bacterial surface protein layers

    SciTech Connect

    Maslyuk, Volodymyr V.; Mertig, Ingrid; Bredow, Thomas; Mertig, Michael; Vyalikh, Denis V.; Molodtsov, Serguei L.

    2008-01-15

    We report an approach for the calculation of the electronic density of states of the dried two-dimensional crystalline surface protein layer (S layer) of the bacterium Bacillus sphaericus NCTC 9602. The proposed model is based on the consideration of individual amino acids in the corresponding conformation of the peptide chain which additively contribute to the electronic structure of the entire protein complex. The derived results agree well with the experimental data obtained by means of photoemission (PE), resonant PE, and near-edge x-ray absorption spectroscopy.

  18. Electronic structure of metallic glasses

    SciTech Connect

    Oelhafen, P.; Lapka, R.; Gubler, U.; Krieg, J.; DasGupta, A.; Guentherodt, H.J.; Mizoguchi, T.; Hague, C.; Kuebler, J.; Nagel, S.R.

    1981-01-01

    This paper is organized in six sections and deals with (1) the glassy transition metal alloys, their d-band structure, the d-band shifts on alloying and their relation to the alloy heat of formation (..delta..H) and the glass forming ability, (2) the glass to crystal phase transition viewed by valence band spectroscopy, (3) band structure calculations, (4) metallic glasses prepared by laser glazing, (5) glassy normal metal alloys, and (6) glassy hydrides.

  19. Monte Carlo Code System for Electron (Positron) Dose Kernel Calculations.

    1999-05-12

    Version 00 KERNEL performs dose kernel calculations for an electron (positron) isotropic point source in an infinite homogeneous medium. First, the auxiliary code PRELIM is used to prepare cross section data for the considered medium. Then the KERNEL code simulates the transport of electrons and bremsstrahlung photons through the medium until all particles reach their cutoff energies. The deposited energy is scored in concentric spherical shells at a radial distance ranging from zero to twicemore » the source particle range.« less

  20. Electronic Structure Principles and Aromaticity

    ERIC Educational Resources Information Center

    Chattaraj, P. K.; Sarkar, U.; Roy, D. R.

    2007-01-01

    The relationship between aromaticity and stability in molecules on the basis of quantities such as hardness and electrophilicity is explored. The findings reveal that aromatic molecules are less energetic, harder, less polarizable, and less electrophilic as compared to antiaromatic molecules, as expected from the electronic structure principles.

  1. Metallic impurities induced electronic transport in WSe2: First-principle calculations

    NASA Astrophysics Data System (ADS)

    Li, Hongping; Liu, Shuai; Huang, Songlei; Zhang, Quan; Li, Changsheng; Liu, Xiaojuan; Meng, Jian; Tian, Yi

    2016-08-01

    Using density functional theory calculations, we have systematically explored the effect of V, Nb and Ta impurities on the electronic transport properties of 2H-WSe2. The formation energies elucidate dopants are preferred to substitute W atoms, and the incorporation of Nb into WSe2 is most thermodynamically favorable. The crystal structures almost hold the pristine WSe2 structure-type in spite of with slightly bond relaxation. More importantly, a pronounced electronic transport behavior has realized in all doped systems, which is mainly triggered by metal impurities. Our calculation suggests chemical doping is an effective way to precisely modulate WSe2 performance for target technological applications.

  2. QED calculation of transition probabilities in two-electron ions

    NASA Astrophysics Data System (ADS)

    Andreev, Oleg Yu.; Labzowsky, Leonti N.; Plunien, Günter

    2009-03-01

    An accurate QED calculation of transition probabilities for the low-lying two-electron configurations of multicharged ions is presented. The calculation is performed for the nondegenerate states (1s2s)S31 , (1s2p3/2)P32 ( M1 and M2 transitions, respectively) and for the quasidegenerate states (1s2p)P11 , (1s2p)P31 ( E1 transitions) decaying to the ground state (1s1s)S10 . Two-electron ions with nuclear-charge numbers Z=10-92 are considered. The line profile approach is employed for the description of the process in multicharged ions within the framework of QED.

  3. Structural and electronic properties for atomic clusters

    NASA Astrophysics Data System (ADS)

    Sun, Yan

    We have studied the structural and electronic properties for different groups of atomic clusters by doing a global search on the potential energy surface using the Taboo Search in Descriptors Space (TSDS) method and calculating the energies with Kohn-Sham Density Functional Theory (KS-DFT). Our goal was to find the structural and electronic principles for predicting the structure and stability of clusters. For Ben (n = 3--20), we have found that the evolution of geometric and electronic properties with size reflects a change in the nature of the bonding from van der Waals to metallic and then bulk-like. The cluster sizes with extra stability agree well with the predictions of the jellium model. In the 4d series of transition metal (TM) clusters, as the d-type bonding becomes more important, the preferred geometric structure changes from icosahedral (Y, Zr), to distorted compact structures (Nb, Mo), and FCC or simple cubic crystal fragments (Tc, Ru, Rh) due to the localized nature of the d-type orbital. Analysis of relative isomer energies and their electronic density of states suggest that these clusters tend to follow a maximum hardness principle (MHP). For A4B12 clusters (A is divalent, B is monovalent), we found unusually large (on average 1.95 eV) HOMO-LUMO gap values. This shows the extra stability at an electronic closed shell (20 electrons) predicted by the jellium model. The importance of symmetry, closed electronic and ionic shells in stability is shown by the relative stability of homotops of Mg4Ag12 which also provides support for the hypothesis that clusters that satisfy more than one stability criterion ("double magic") should be particularly stable.

  4. Calculating merit increases: a structured approach.

    PubMed

    Seithel, W W; Emans, J S

    1983-01-01

    Determining the amount of salary increase appropriate for each employee poses a major dilemma for many human resources managers and/or compensation managers (not to mention the employee's supervisor). This task requires complying with the company's compensation philosophy, meeting market competition, and rewarding employees fairly and equitably. Authors William W. Seithel, vice president, personnel of the Midwest Stock Exchange, Inc., and Jeff S. Emans, director, employee compensation of the Kemper Group, describe a method for pinpointing a salary rate increase that is not only structured enough to move people through the salary range in accordance with a reward philosophy, but precise enough to provide a basis for projecting costs and flexible enough to meet the needs of various performance levels. The method entails the use of a structured matrix that spells out the target percentage raises for various levels of performance. By using both the matrix-which is constructed to meet the individual company's needs-and a guide chart provided by the authors, it is possible to calculate a specific percentage increase for each employee. The manager who uses this system will find that the matrix is a mechanism for control as well as a means for projecting costs. PMID:10262948

  5. Structure determination of propanal by joint analysis of gas electron diffraction, microwave and infrared spectroscopy, including constraints and a valence force field from geometry relaxed ab-initio calculations

    NASA Astrophysics Data System (ADS)

    Van Nuffel, P.; Van Den Enden, L.; Van Alsenoy, C.; Geise, H. J.

    1984-04-01

    The structure and conformational equilibrium of CH 3-SYN and CH 3-SKEW conformers of propanal were studied by joint analysis of gas electron diffraction, microwave and infrared data, including constraints obtained after ab-initio relaxations (4-21G basis set) of the molecule. A valence force field was calculated for both conformers and scaled upon experimental IR frequencies; theoretical frequencies and band intensities are compared to experimental ones. Rotamer populations of CH 3-SYN and CH 3-SKEW were found to be 81 and 19%, respectively, at 300 K. The following best-fitting rg/ rα parameters were obtained as: r(OC) = 1.209(4) Å, r(C2C3) = 1.515(9) Å, r(C3C4) = 1.521(9) Å for CH 3-SYN and (with lower reliability) 1.569(45) Å for CH 3-SKEW, = 1.127(4) Å, ∠O=CC = 124.5(3)°(SYN) and 125.1(3)° (SKEW), ∠CCC = 113.8(4)° (SYN) and 110.2(4)° (SKEW), torsion angle around C2C3 = 123.7(2.6)° for CH 3-SKEW.

  6. Graph-based linear scaling electronic structure theory.

    PubMed

    Niklasson, Anders M N; Mniszewski, Susan M; Negre, Christian F A; Cawkwell, Marc J; Swart, Pieter J; Mohd-Yusof, Jamal; Germann, Timothy C; Wall, Michael E; Bock, Nicolas; Rubensson, Emanuel H; Djidjev, Hristo

    2016-06-21

    We show how graph theory can be combined with quantum theory to calculate the electronic structure of large complex systems. The graph formalism is general and applicable to a broad range of electronic structure methods and materials, including challenging systems such as biomolecules. The methodology combines well-controlled accuracy, low computational cost, and natural low-communication parallelism. This combination addresses substantial shortcomings of linear scaling electronic structure theory, in particular with respect to quantum-based molecular dynamics simulations. PMID:27334148

  7. Composite electron propagator methods for calculating ionization energies

    NASA Astrophysics Data System (ADS)

    Díaz-Tinoco, Manuel; Dolgounitcheva, O.; Zakrzewski, V. G.; Ortiz, J. V.

    2016-06-01

    Accurate ionization energies of molecules may be determined efficiently with composite electron-propagator (CEP) techniques. These methods estimate the results of a calculation with an advanced correlation method and a large basis set by performing a series of more tractable calculations in which large basis sets are used with simpler approximations and small basis sets are paired with more demanding correlation techniques. The performance of several CEP methods, in which diagonal, second-order electron propagator results with large basis sets are combined with higher-order results obtained with smaller basis sets, has been tested for the ionization energies of closed-shell molecules from the G2 set. Useful compromises of accuracy and computational efficiency employ complete-basis-set extrapolation for second-order results and small basis sets in third-order, partial third-order, renormalized partial-third order, or outer valence Green's function calculations. Analysis of results for vertical as well as adiabatic ionization energies leads to specific recommendations on the best use of regular and composite methods. Results for 22 organic molecules of interest in the design of photovoltaic devices, benzo[a]pyrene, Mg-octaethylporphyrin, and C60 illustrate the capabilities of CEP methods for calculations on large molecules.

  8. Composite electron propagator methods for calculating ionization energies.

    PubMed

    Díaz-Tinoco, Manuel; Dolgounitcheva, O; Zakrzewski, V G; Ortiz, J V

    2016-06-14

    Accurate ionization energies of molecules may be determined efficiently with composite electron-propagator (CEP) techniques. These methods estimate the results of a calculation with an advanced correlation method and a large basis set by performing a series of more tractable calculations in which large basis sets are used with simpler approximations and small basis sets are paired with more demanding correlation techniques. The performance of several CEP methods, in which diagonal, second-order electron propagator results with large basis sets are combined with higher-order results obtained with smaller basis sets, has been tested for the ionization energies of closed-shell molecules from the G2 set. Useful compromises of accuracy and computational efficiency employ complete-basis-set extrapolation for second-order results and small basis sets in third-order, partial third-order, renormalized partial-third order, or outer valence Green's function calculations. Analysis of results for vertical as well as adiabatic ionization energies leads to specific recommendations on the best use of regular and composite methods. Results for 22 organic molecules of interest in the design of photovoltaic devices, benzo[a]pyrene, Mg-octaethylporphyrin, and C60 illustrate the capabilities of CEP methods for calculations on large molecules. PMID:27305999

  9. QWalk: A quantum Monte Carlo program for electronic structure

    SciTech Connect

    Wagner, Lucas K. Bajdich, Michal Mitas, Lubos

    2009-05-20

    We describe QWalk, a new computational package capable of performing quantum Monte Carlo electronic structure calculations for molecules and solids with many electrons. We describe the structure of the program and its implementation of quantum Monte Carlo methods. It is open-source, licensed under the GPL, and available at the web site (http://www.qwalk.org)

  10. Electronic structures of endohedral fullerenes

    SciTech Connect

    Jin, Changming; Hettich, R.L.; Puretzky, A.A.; Ying, Z.C.; Haufler, R.E.; Compton, R.N.

    1994-12-31

    Fullerenes with different elements trapped inside the cage have been the subject of active research both experimentally and theoretically ever since the initial discovery of C{sub 60}. La@C{sub n}, were the first endohedral fullerenes produced both in gas phase and in macroscopic quantities. Early electron spin resonance investigation of La@C{sub 82} by R.D. Johnson, et.al indicated that La transfer nearly all of the three valence electrons to the fullerene cage, forming a La{sup 3+}@C{sub 82}{sup 3-} complex. Theoretical calculations also have shown that La transfers its valence electrons to the fullerene cage in molecules of La@C{sub n}. Investigations with ultraviolet photoelectron spectroscopy by L. Wang, et.al. indicated that attaching a potassium atom outside the C{sub 60} cage lowers the electron affinity (EA) while trapping Ca atom inside the C{sub 60} sphere increases the EA compared with parent C{sub 60} molecule. These results indicate that metallofullerenes appear to have substantially lower ionization potentials (IP) and higher EA than empty fullerenes.

  11. Linear Scaling Electronic Structure Methods with Periodic Boundary Conditions

    SciTech Connect

    Gustavo E. Scuseria

    2008-02-08

    The methodological development and computational implementation of linear scaling quantum chemistry methods for the accurate calculation of electronic structure and properties of periodic systems (solids, surfaces, and polymers) and their application to chemical problems of DOE relevance.

  12. Electronic Structure of B12 coenzymes

    NASA Astrophysics Data System (ADS)

    Ouyang, Lizhi; Ching, W. Y.; Randaccio, Lucio

    2001-06-01

    We have carried out an ab-initio local density functional calculations of the two most important B12 coenzymes, adoensyl-cobalamin (Ado-Cbl) and methyl-cobalamin (Me-Cbl). The crystal structures were determined by accurate X-ray synchrotron radiation measurements. Both crystals have space group P2121 with four molecules, or about 800 atoms, per unit cell. Our electronic structure calculation is based on one full molecule including the side chains. Results are analyzed in terms of atom and orbital resolved partial density of states (PDOS), Mulliken effective charges and bond orders. The PDOS analysis shows that the Co complexes of both B12 coenzymes had a HOMO/LUMO gap of about 1.5 eV. The Co-C bond order in Me-Cbl is smaller than that in Ado-Cbl. This appears to be in contradiction with the measured bond dissociated energies. However, this could also indicate the importance of the effects of solvents, which were not included in the calculation. We are investigating whether the effect of the solvents could dramatically modify the electronic structures of Ado-Cbl and Me-Cbl.

  13. Effective Interactions for Nuclear Structure Calculations

    NASA Astrophysics Data System (ADS)

    Signoracci, Angelo

    Experimental interest in nuclei far from stability, especially due to proposed advancements in rare isotope facilities, has stimulated improvements in theoretical predictions of exotic isotopes. However, standard techniques developed for nuclear structure calculations, Configuration Interaction theory and Energy Density Functional methods, lack either the generality or the accuracy necessary for reliable calculations away from stability. Hybrid methods, which combine Configuration Interaction theory and Energy Density Functional methods in order to exploit their beneficial properties, are currently under investigation for improved theoretical capabilities. A new technique to produce nuclear Hamiltonians has been developed, implementing renormalization group methods, many-body perturbative techniques, and Energy Density Functional methods. Connection to the underlying physics is a primary focus, limiting the number of free parameters necessary in the procedure. The main benefit of this approach is the improvement in the quality of effective interactions outside of standard model spaces. In the Hybrid Renormalization Procedure developed in this dissertation, Skyrme energy density functionals provide a realistic single particle basis that accounts for the long tail of loosely bound orbits, especially significant for valence orbits of exotic isotopes. A microscopic nucleon-nucleon potential is softened with renormalization group techniques to eliminate the hard core of the nuclear interaction. Many-body perturbative techniques, in the form of Rayleigh-Schrodinger theory, implement the realistic basis to convert the low-momentum interaction into a model space of interest. The basis is an important ingredient in the renormalization and greatly affects the results obtained with the Hybrid Renormalization Procedure, specifically through the single particle energies derived from Skyrme functionals. A comparison of the standard harmonic oscillator basis and the realistic

  14. Electron Coherence in Mesoscopic Structures

    SciTech Connect

    Kamenev, Alex; Glazman, Leonid

    2011-03-20

    The recent rapid progress in nanofabrication and experimental techniques made it possible to investigate a variety of meso-- and nano--scale systems, which were unavailable only a few years ago. Examples include fabrication of high-quality quantum wires in semiconductor heterostructures, of nanoscale hybrid superconductor--normal metal structures, and of a variety of novel (and much smaller) quantum dot and q-bit designs. These technological advances have led to formulation of a number of condensed matter theory problems which are equally important for applications and for the fundamental science. The present proposal aims at filling the exposed gaps in knowledge and at facilitating further development of experimental and theoretical physics of nanoscale structures. Specifically, the two PIs address the following issues: (i) The theory of interacting electrons in a quantum wire which accounts adequately for the non-linear dispersion relation of the electrons. The existing approaches rely on models with {\\em linearized} electron spectrum, which fall short of addressing a growing list of experimentally relevant phenomena. (ii) Dynamics of hybrid normal--superconducting systems. A reliable treatment of dissipative phenomena in such structures is not developed as of yet, while rapid progress in fabrication makes finding the proper theoretical treatment methods highly desirable. (iii)~The fundamental limits on relaxation times of a superconducting charge q-bit. The latter is one of the most advanced scalable realizations of a quantum computing device. (iv)~The dynamics and relaxation times of a spin of an electron in a small semiconductor quantum dot. Besides the fundamental importance, these structures are also valuable candidates for quantum computing applications.

  15. Electronic structure theory of the superheavy elements

    NASA Astrophysics Data System (ADS)

    Eliav, Ephraim; Fritzsche, Stephan; Kaldor, Uzi

    2015-12-01

    High-accuracy calculations of atomic properties of the superheavy elements (SHE) up to element 122 are reviewed. The properties discussed include ionization potentials, electron affinities and excitation energies, which are associated with the spectroscopic and chemical behavior of these elements, and are therefore of considerable interest. Accurate predictions of these quantities require high-order inclusion of relativity and electron correlation, as well as large, converged basis sets. The Dirac-Coulomb-Breit Hamiltonian, which includes all terms up to second order in the fine-structure constant α, serves as the framework for the treatment; higher-order Lamb shift terms are considered in some selected cases. Electron correlation is treated by either the multiconfiguration self-consistent-field approach or by Fock-space coupled cluster theory. The latter is enhanced by the intermediate Hamiltonian scheme, allowing the use of larger model (P) spaces. The quality of the calculations is assessed by applying the same methods to lighter homologs of the SHEs and comparing with available experimental information. Very good agreement is obtained, within a few hundredths of an eV, and similar accuracy is expected for the SHEs. Many of the properties predicted for the SHEs differ significantly from what may be expected by straightforward extrapolation of lighter homologs, demonstrating that the structure and chemistry of SHEs are strongly affected by relativity. The major scientific challenge of the calculations is to find the electronic structure and basic atomic properties of the SHE and assign its proper place in the periodic table. Significant recent developments include joint experimental-computational studies of the excitation spectrum of Fm and the ionization energy of Lr, with excellent agreement of experiment and theory, auguring well for the future of research in the field.

  16. Monte Carlo calculation of monitor unit for electron arc therapy

    SciTech Connect

    Chow, James C. L.; Jiang Runqing

    2010-04-15

    Purpose: Monitor unit (MU) calculations for electron arc therapy were carried out using Monte Carlo simulations and verified by measurements. Variations in the dwell factor (DF), source-to-surface distance (SSD), and treatment arc angle ({alpha}) were studied. Moreover, the possibility of measuring the DF, which requires gantry rotation, using a solid water rectangular, instead of cylindrical, phantom was investigated. Methods: A phase space file based on the 9 MeV electron beam with rectangular cutout (physical size=2.6x21 cm{sup 2}) attached to the block tray holder of a Varian 21 EX linear accelerator (linac) was generated using the EGSnrc-based Monte Carlo code and verified by measurement. The relative output factor (ROF), SSD offset, and DF, needed in the MU calculation, were determined using measurements and Monte Carlo simulations. An ionization chamber, a radiographic film, a solid water rectangular phantom, and a cylindrical phantom made of polystyrene were used in dosimetry measurements. Results: Percentage deviations of ROF, SSD offset, and DF between measured and Monte Carlo results were 1.2%, 0.18%, and 1.5%, respectively. It was found that the DF decreased with an increase in {alpha}, and such a decrease in DF was more significant in the {alpha} range of 0 deg. - 60 deg. than 60 deg. - 120 deg. Moreover, for a fixed {alpha}, the DF increased with an increase in SSD. Comparing the DF determined using the rectangular and cylindrical phantom through measurements and Monte Carlo simulations, it was found that the DF determined by the rectangular phantom agreed well with that by the cylindrical one within {+-}1.2%. It shows that a simple setup of a solid water rectangular phantom was sufficient to replace the cylindrical phantom using our specific cutout to determine the DF associated with the electron arc. Conclusions: By verifying using dosimetry measurements, Monte Carlo simulations proved to be an alternative way to perform MU calculations effectively

  17. Radial Moment Calculations of Coupled Electron-Photon Beams

    SciTech Connect

    FRANKE,BRIAN C.; LARSEN,EDWARD W.

    2000-07-19

    The authors consider the steady-state transport of normally incident pencil beams of radiation in slabs of material. A method has been developed for determining the exact radial moments of 3-D beams of radiation as a function of depth into the slab, by solving systems of 1-D transport equations. They implement these radial moment equations in the ONEBFP discrete ordinates code and simulate energy-dependent, coupled electron-photon beams using CEPXS-generated cross sections. Modified P{sub N} synthetic acceleration is employed to speed up the iterative convergence of the 1-D charged particle calculations. For high-energy photon beams, a hybrid Monte Carlo/discrete ordinates method is examined. They demonstrate the efficiency of the calculations and make comparisons with 3-D Monte Carlo calculations. Thus, by solving 1-D transport equations, they obtain realistic multidimensional information concerning the broadening of electron-photon beams. This information is relevant to fields such as industrial radiography, medical imaging, radiation oncology, particle accelerators, and lasers.

  18. Coupled Electron-Ion Monte Carlo calculations of atomic hydrogen

    NASA Astrophysics Data System (ADS)

    Holzmann, Markus; Pierleoni, Carlo; Ceperley, David M.

    2005-07-01

    We present a new Monte Carlo method which couples Path Integral for finite temperature protons with Quantum Monte Carlo for ground state electrons, and we apply it to metallic hydrogen for pressures beyond molecular dissociation. This method fills the gap between high temperature electron-proton Path Integral and ground state Diffusion Monte Carlo methods. Our data exhibit more structure and higher melting temperatures of the proton crystal than Car-Parrinello Molecular Dynamics results using LDA. We further discuss the quantum motion of the protons and the zero temperature limit.

  19. Structural phase transition and electronic properties of NdBi

    SciTech Connect

    Sahu, Ashvini K.; Patiya, Jagdish; Sanyal, Sankar P.

    2015-06-24

    The structural and electronic properties of NdBi from an electronic structure calculation have been presented. The calculation is performed using self-consistent tight binding linear muffin tin orbital (TB-LMTO) method within the local density approximation (LDA). The calculated equilibrium structural parameters are in good agreement with the available experimental results. It is found that this compound shows metallic behavior under ambient condition and undergoes a structural phase transition from the NaCl structure to the CsCl structure at the pressure 20.1 GPa. The electronic structures of NdBi under pressure are investigated. It is found that NdBi have metallization and the hybridizations of atoms in NdBi under pressure become stronger.

  20. Electronic Structure of Few-Electron Quantum Dot Molecules

    NASA Astrophysics Data System (ADS)

    Popsueva, V.; Hansen, J. P.; Caillat, J.

    2007-12-01

    We present a study of strongly correlated few-electron quantum dots, exploring the spectra of various few-electron quantum dot molecules: a double (diatomic) structure a quadruple two-electron quantum dot, and a three-electron double dot. Electron energy spectra are computed for different values of dot separation. All spectra show clear band structures and can be understood from asymptotical properties of the system.

  1. Calculation of the Ionization Potentials and Electron Affinities for Atoms

    NASA Astrophysics Data System (ADS)

    Chen, Jiqiang; Krieger, J. B.; Iafrate, G. J.; Savin, A.

    1998-03-01

    The method employing the self-interaction-corrected correlation energy functional obtained from the homogeneous electron gas with a gap is extended to atoms and ions with non-zero spin polarization. As in the case for atoms and ions with ζ=3D0, the error in the calculated Ec is significantly smaller than in the LSD approximation with zero gap for atoms and ions with Z<=18. Comparison of the resulting ionization potentials and electron affinities with experimental values will also be presented. Finally, we will discuss the possibility of obtaining saturation for Ec for the He, Li, N, O, F and Ne isoelectronic series, but a divergent Ec for the Be, B and C isoelectronic series, in the large Z limit.

  2. Calculation of electron scattering from the ground state of ytterbium

    SciTech Connect

    Bostock, Christopher J.; Fursa, Dmitry V.; Bray, Igor

    2011-05-15

    We report on the application of the convergent close-coupling method, in both relativistic and nonrelativistic formulations, to electron scattering from ytterbium. Angle-differential and integrated cross sections are presented for elastic scattering and excitation of the states (6s6p){sup 3}P{sub 0,1,2}, (6s6p){sup 1}P{sub 1}{sup o}, (6s7p){sup 1}P{sub 1}{sup o}, and (6s5d){sup 1}D{sub 2}{sup e} for a range of incident electron energies. We also present calculations of the total cross section, and angle-differential Stokes parameters for excitation of the (6s6p){sup 3}P{sub 1}{sup o} state from the ground state. A comparison is made with the relativistic distorted-wave method and experiments.

  3. Calculation of Cross Sections in Electron-Nuclear Dynamics

    NASA Astrophysics Data System (ADS)

    Cabrera-Trujillo, R.; Sabin, John R.; Deumens, E.; Öhrn, Y.

    In this work, we present an overview of the study of total and differential cross section calculations within the electron-nuclear dynamics (END). END is a method to solve the time-dependent Schrödinger equation in a non-adiabatic approach to direct dynamics. The method takes advantage of a coherent state representation of the molecular wave function. A quantum-mechanical Lagrangian formulation is employed to approximate the Schrödinger equation, via the time-dependent variational principle, to a set of coupled first-order differential equations in time for the END. We obtain the final wave function for the system allowing the determination of collisional properties of interest, as for example, deflection functions, charge exchange probabilities and amplitudes, and differential cross sections. We discuss the use and selection of basis sets for both the electronic description of the colliding systems as well as for their importance in the description of electron capture. As quantum effects are important in many cases and lacking for classical nuclei, we discuss the Schiff methodology and its advantages over other traditional methods for including semiclassical corrections. Time-lapse rendering of the dynamics of the participating electrons and atomic nuclei provides for a detailed view of dynamical and reactive processes. Comparison to experimental and other theoretical results is provided where appropriate data are available.

  4. First-principles mobility calculations and atomic-scale interface roughness in nanoscale structures.

    PubMed

    Evans, M H; Zhang, X-G; Joannopoulos, J D; Pantelides, S T

    2005-09-01

    Calculations of mobilities have so far been carried out using approximate methods that suppress atomic-scale detail. Such approaches break down in nanoscale structures. Here we report the development of a method to calculate mobilities using atomic-scale models of the structures and density functional theory at various levels of sophistication and accuracy. The method is used to calculate the effect of atomic-scale roughness on electron mobilities in ultrathin double-gate silicon-on-insulator structures. The results elucidate the origin of the significant reduction in mobility observed in ultrathin structures at low electron densities.

  5. First-Principles Mobility Calculations and Atomic-Scale Interface Roughness in Nanoscale Structures

    SciTech Connect

    Evans, Matthew H; Zhang, Xiaoguang; Joannopoulos, J. D.; Pantelides, Sokrates T

    2005-01-01

    Calculations of mobilities have so far been carried out using approximate methods that suppress atomic-scale detail. Such approaches break down in nanoscale structures. Here we report the development of a method to calculate mobilities using atomic-scale models of the structures and density functional theory at various levels of sophistication and accuracy. The method is used to calculate the effect of atomic-scale roughness on electron mobilities in ultrathin double-gate silicon-on-insulator structures. The results elucidate the origin of the significant reduction in mobility observed in ultrathin structures at low electron densities.

  6. Accurate characterization of Monte Carlo calculated electron beams for radiotherapy.

    PubMed

    Ma, C M; Faddegon, B A; Rogers, D W; Mackie, T R

    1997-03-01

    Monte Carlo studies of dose distributions in patients treated with radiotherapy electron beams would benefit from generalized models of clinical beams if such models introduce little error into the dose calculations. Methodology is presented for the design of beam models, including their evaluation in terms of how well they preserve the character of the clinical beam, and the effect of the beam models on the accuracy of dose distributions calculated with Monte Carlo. This methodology has been used to design beam models for electron beams from two linear accelerators, with either a scanned beam or a scattered beam. Monte Carlo simulations of the accelerator heads are done in which a record is kept of the particle phase-space, including the charge, energy, direction, and position of every particle that emerges from the treatment head, along with a tag regarding the details of the particle history. The character of the simulated beams are studied in detail and used to design various beam models from a simple point source to a sophisticated multiple-source model which treats particles from different parts of a linear accelerator as from different sub-sources. Dose distributions calculated using both the phase-space data and the multiple-source model agree within 2%, demonstrating that the model is adequate for the purpose of Monte Carlo treatment planning for the beams studied. Benefits of the beam models over phase-space data for dose calculation are shown to include shorter computation time in the treatment head simulation and a smaller disk space requirement, both of which impact on the clinical utility of Monte Carlo treatment planning.

  7. Structural Dynamics of Electronic Systems

    NASA Astrophysics Data System (ADS)

    Suhir, E.

    2013-03-01

    The published work on analytical ("mathematical") and computer-aided, primarily finite-element-analysis (FEA) based, predictive modeling of the dynamic response of electronic systems to shocks and vibrations is reviewed. While understanding the physics of and the ability to predict the response of an electronic structure to dynamic loading has been always of significant importance in military, avionic, aeronautic, automotive and maritime electronics, during the last decade this problem has become especially important also in commercial, and, particularly, in portable electronics in connection with accelerated testing of various surface mount technology (SMT) systems on the board level. The emphasis of the review is on the nonlinear shock-excited vibrations of flexible printed circuit boards (PCBs) experiencing shock loading applied to their support contours during drop tests. At the end of the review we provide, as a suitable and useful illustration, the exact solution to a highly nonlinear problem of the dynamic response of a "flexible-and-heavy" PCB to an impact load applied to its support contour during drop testing.

  8. Relativistic Calculating the Spectral Lines Hyperfine Structure Parameters for Heavy Ions

    SciTech Connect

    Khetselius, O. Yu.

    2008-10-22

    The energies and constants of the hyperfine structure, derivatives of the one-electron characteristics on nuclear radius, nuclear electric quadrupole, magnetic dipole moments for some Li-like multicharged ions are calculated.

  9. Electronic instrumentation for smart structures

    NASA Astrophysics Data System (ADS)

    Blanar, George J.

    1995-04-01

    The requirements of electronic instrumentation for smart structures are similar to those of data acquisition systems at our national particle physics laboratories. Modern high energy and heavy ion physics experiments may have tens of thousands of channels of data sources producing data that must be converted to digital form, compacted, stored and interpreted. In parallel, multiple sensors distributed in and around smart structures generate either binary or analog signals that are voltage, charge, or time like in their information content. In all cases, they must be transmitted, converted and preserved into a unified digital format for real-time processing. This paper will review the current status of practical large scale electronic measurement systems with special attention to architectures and physical organization. Brief surveys of the current state of the art will include preamplifiers and amplifiers, comparators and discriminators, voltage or charge analog-to-digital converters, time internal meters or time-to-digital converters, and finally, counting or scalar systems. The paper will conclude by integrating all of these ideas in a concept for an all-digital readout of a smart structure using the latest techniques used in physics research today.

  10. Calculation of Electronic Absorption Spectra with Account of Thermal Geometry Fluctuations

    NASA Astrophysics Data System (ADS)

    Guzha, Maris V.; Svitenkov, Andrew I.

    2016-08-01

    An influence of thermal fluctuations of molecule's geometry on calculated electronic-absorption Vis/Uv spectra is considered. Paper presents the quantum chemical modeling of the electronic-absorption spectra for the collection of graphene samples (44, 56, 60, 68 atoms). The calculations were performed by time dependent density functional theory (TDDFT) method in combination with molecular dynamics (MD) simulation at T=300 K. The noticeable changing of spectra relative to single point TDDFT calculation was discovered for two of four structures. We associate achieved results with perturbation of hydrogen and carbon atoms on the edges of the structures. We believe that suggested methodology will be useful in application engineering researches of novel molecules and molecular complexes.

  11. Electronic structure and optical properties of resin

    NASA Astrophysics Data System (ADS)

    Rao, Zhi-Fan; Zhou, Rong-Feng

    2013-03-01

    We used the density of functional theory (DFT) to study the electronic structure and density of states of resin by ab initio calculation. The results show the band gap of resin is 1.7 eV. The covalent bond is combined C/O atoms with H atoms. The O 2p orbital is the biggest effect near the Fermi level. The results of optical properties show the reflectivity is low, and the refractive index is 1.7 in visible light range. The highest absorption coefficient peak is in 490 nm and the value is 75,000.

  12. Assessing the effect of electron density in photon dose calculations

    SciTech Connect

    Seco, J.; Evans, P. M.

    2006-02-15

    Photon dose calculation algorithms (such as the pencil beam and collapsed cone, CC) model the attenuation of a primary photon beam in media other than water, by using pathlength scaling based on the relative mass density of the media to water. In this study, we assess if differences in the electron density between the water and media, with different atomic composition, can influence the accuracy of conventional photon dose calculations algorithms. A comparison is performed between an electron-density scaling method and the standard mass-density scaling method for (i) tissues present in the human body (such as bone, muscle, etc.), and for (ii) water-equivalent plastics, used in radiotherapy dosimetry and quality assurance. We demonstrate that the important material property that should be taken into account by photon dose algorithms is the electron density, and not the mass density. The mass-density scaling method is shown to overestimate, relative to electron-density predictions, the primary photon fluence for tissues in the human body and water-equivalent plastics, where 6%-7% and 10% differences were observed respectively for bone and air. However, in the case of patients, differences are expected to be smaller due to the large complexity of a treatment plan and of the patient anatomy and atomic composition and of the smaller thickness of bone/air that incident photon beams of a treatment plan may have to traverse. Differences have also been observed for conventional dose algorithms, such as CC, where an overestimate of the lung dose occurs, when irradiating lung tumors. The incorrect lung dose can be attributed to the incorrect modeling of the photon beam attenuation through the rib cage (thickness of 2-3 cm in bone upstream of the lung tumor) and through the lung and the oversimplified modeling of electron transport in convolution algorithms. In the present study, the overestimation of the primary photon fluence, using the mass-density scaling method, was shown

  13. Incidence of the muffin-tin approximation on the electronic structure of large clusters calculated by the MS-LSD method: The typical case of C{sub 60}

    SciTech Connect

    Razafinjanahary, H.; Rogemond, F.; Chermette, H.

    1994-08-15

    The MS-LSD method remains a method of interest when rapidity and small computer resources are required; its main drawback is some lack of accuracy, mainly due to the muffin-tin distribution of the potential. In the case of large clusters or molecules, the use of an empty sphere to fill, in part, the large intersphere region can improve greatly the results. Calculations bearing on C{sub 60} has been undertaken to underline this trend, because, on the one hand, the fullerenes exhibit a remarkable possibility to fit a large empty sphere in the center of the cluster and, on the other hand, numerous accurate calculations have already been published, allowing quantitative comparison with results. The author`s calculations suggest that in case of added empty sphere the results compare well with the results of more accurate calculations. The calculated electron affinity for C{sub 60} and C{sub 60}{sup {minus}} are in reasonable agreement with experimental values, but the stability of C{sub 60}{sup 2-} in gas phase is not found. 35 refs., 3 figs., 5 tabs.

  14. Spatial and electron structure of substituted gold clusters

    NASA Astrophysics Data System (ADS)

    Yarzhemsky, V. G.; Kazaryan, M. A.; Bulychev, N. A.; Dyakov, Y. A.; Kosheleva, O. K.; Chen, C. H.

    2015-12-01

    The structure of intermetallic clusters Au12M (M=Hf, Ta, W, Re, Os) and features of their interaction with electron donors and acceptor atoms, i.e. H and F, were investigated making use computer calculation based of density functional theory. In was found that metal clusters with effective electron number equal to 18 have more symmetrical shape then that with a number of electrons differing from 18. The interaction of gold nanoparticles with silica was modeled by attachment of SiO4H groups and the connection of the electronic structure with electronic transitions in spaser is discussed.

  15. Revealing Dissociative Electron Attachment Dynamics in Polyatomic Molecules Using Momentum Imaging Experiments and Electron Scattering Calculations

    NASA Astrophysics Data System (ADS)

    Belkacem, Ali; Slaughter, Daniel

    2015-05-01

    Understanding electron-driven chemical reactions is important for improving a variety of technological applications such as materials processing and the important role they play in the radiation damage in bulk matter. Furthermore, dissociative electron attachment often exhibits site-selective bond cleavage, which holds promise for prediction and precise control of electron-driven chemical reactions. Recent dynamical studies of these reactions have demonstrated that an understanding of anion dissociation dynamics beyond simple one-dimensional models is crucial in interpreting the measured fragment angular distributions. We combine ion fragment momentum imaging experiments with electron attachment entrance amplitude calculations to interrogate the non-Born-Oppenheimer dynamics of dissociative electron attachment in polyatomic molecules. We will report recent experimental developments in molecules of technological interest including methanol, methane and uracil. Work supported by Chemical Sciences, Geosciences and Biosciences division of BES/DOE.

  16. Pu electronic structure and photoelectron spectroscopy

    SciTech Connect

    Joyce, John J; Durakiewicz, Tomasz; Graham, Kevin S; Bauer, Eric D; Moore, David P; Mitchell, Jeremy N; Kennison, John A; Martin, Richard L; Roy, Lindsay E; Scuseria, G. E.

    2010-01-01

    The electronic structure of PuCoGa{sub 5}, Pu metal, and PuO{sub 2} is explored using photoelectron spectroscopy. Ground state electronic properties are inferred from temperature dependent photoemission near the Fermi energy for Pu metal. Angle-resolved photoemission details the energy vs. crystaJ momentum landscape near the Fermi energy for PuCoGa{sub 5} which shows significant dispersion in the quasiparticle peak near the Fermi energy. For the Mott insulators AnO{sub 2}(An = U, Pu) the photoemission results are compared against hybrid functional calculations and the model prediction of a cross over from ionic to covalent bonding is found to be reasonable.

  17. Dramatic changes in electronic structure revealed by fractionally charged nuclei

    SciTech Connect

    Cohen, Aron J.; Mori-Sánchez, Paula

    2014-01-28

    Discontinuous changes in the electronic structure upon infinitesimal changes to the Hamiltonian are demonstrated. These are revealed in one and two electron molecular systems by full configuration interaction (FCI) calculations when the realm of the nuclear charge is extended to be fractional. FCI electron densities in these systems show dramatic changes in real space and illustrate the transfer, hopping, and removal of electrons. This is due to the particle nature of electrons seen in stretched systems and is a manifestation of an energy derivative discontinuity at constant number of electrons. Dramatic errors of density functional theory densities are seen in real space as this physics is missing from currently used approximations. The movements of electrons in these simple systems encapsulate those in real physical processes, from chemical reactions to electron transport and pose a great challenge for the development of new electronic structure methods.

  18. Calculation of electron transfer in ruthenium-modified derivatives of cytochrome b562

    NASA Astrophysics Data System (ADS)

    Glukhova, O. E.; Prytkova, T. R.; Shunaev, V. V.

    2016-03-01

    Quantitative theoretical studies of long-range electron transfer are still quite rare and require further development of computational methods for the analysis of such reactions. We considered the electron transfer reaction in rutenium-modified derivatives of cytochrome b562 with advanced modeling techniques. We conducted a series of ab initio calculations of the donor/acceptor interaction in protein fragments and compared the calculated electron velocity with available experimental data. Our approach takes into account the co-factor of the electronic structure and the impact of the solution on a donor-acceptor interaction. This allows us to predict the absolute values of the electron transfer rate unlike other computational methods which provide only qualitative results. Our estimates with good accuracy repeat the experimental values of electron transfer rate. It was found that the electron transfer in certain derivatives of cytochrome b562 is mainly caused by "shortcut" conformations in which the donor/acceptor interactions are mediated by the interaction of Ru-unbound ligands with groups of the protein surface. We argue that a quantitative theoretical analysis is essential for detailed understanding of electron transfer in proteins and mechanisms of biological redox reactions.

  19. Analysis of boron carbides' electronic structure

    NASA Technical Reports Server (NTRS)

    Howard, Iris A.; Beckel, Charles L.

    1986-01-01

    The electronic properties of boron-rich icosahedral clusters were studied as a means of understanding the electronic structure of the icosahedral borides such as boron carbide. A lower bound was estimated on bipolaron formation energies in B12 and B11C icosahedra, and the associated distortions. While the magnitude of the distortion associated with bipolaron formation is similar in both cases, the calculated formation energies differ greatly, formation being much more favorable on B11C icosahedra. The stable positions of a divalent atom relative to an icosahedral borane was also investigated, with the result that a stable energy minimum was found when the atom is at the center of the borane, internal to the B12 cage. If incorporation of dopant atoms into B12 cages in icosahedral boride solids is feasible, novel materials might result. In addition, the normal modes of a B12H12 cluster, of the C2B10 cage in para-carborane, and of a B12 icosahedron of reduced (D sub 3d) symmetry, such as is found in the icosahedral borides, were calculated. The nature of these vibrational modes will be important in determining, for instance, the character of the electron-lattice coupling in the borides, and in analyzing the lattice contribution to the thermal conductivity.

  20. Electronic structure and magnetism of ThFeAsN

    NASA Astrophysics Data System (ADS)

    Wang, Guangtao; Shi, Xianbiao

    2016-03-01

    The electronic structure and magnetic properties of ThFeAsN, a newly discovered superconductor, are investigated by means of first-principles calculations. ThFeAsN shares electronic structure and magnetic properties similar to those of LaOFeAs. Its calculated ground state is the stripe antiferromagnetic state. The hole-like Fermi surfaces (FSs) along the Γ\\text-Z line largely overlap with the electron-like FS along the M\\text-A line with the vector q= (π, π, 0) . Such significant FS nesting induces a peak of the bare susceptibility χ0(q ) at the M-point.

  1. Electronic Structure and Bonding in Complex Biomolecule

    NASA Astrophysics Data System (ADS)

    Ouyang, Lizhi

    2005-03-01

    For over a century vitamin B12 and its enzyme cofactor derivates have persistently attracted research efforts for their vital biological role, unique Co-C bonding, rich red-ox chemistry, and recently their candidacies as drug delivery vehicles etc. However, our understanding of this complex metalorganic molecule's efficient enzyme activated catalytic power is still controversial. We have for the first time calculated the electronic structure, Mulliken effective charge and bonding of a whole Vitamin B12 molecule without any structural simplification by first- principles approaches based on density functional theory using structures determined by high resolution X-ray diffraction. A partial density of states analysis shows excellent agreement with X-ray absorption data and has been used successfully to interpret measured optical absorption spectra. Mulliken bonding analysis of B12 and its derivatives reveal noticeable correlations between the two axial ligands which could be exploited by the enzyme to control the catalytic process. Our calculated X-ray near edge structure of B12 and its derivates using Slater's transition state theory are also in good agreement with experiments. The same approach has been applied to other B12 derivatives, ferrocene peptides, and recently DNA molecules.

  2. Determining the Structure of Oxalate Anion Using Infrared and Raman Spectroscopy Coupled with Gaussian Calculations

    ERIC Educational Resources Information Center

    Peterson, Karen I.; Pullman, David P.

    2016-01-01

    A laboratory project for the upper-division physical chemistry laboratory is described, and it combines IR and Raman spectroscopies with Gaussian electronic structure calculations to determine the structure of the oxalate anion in solid alkali oxalates and in aqueous solution. The oxalate anion has two limiting structures whose vibrational spectra…

  3. Structural Investigation of Layered Niobates by DFT Calculations

    NASA Astrophysics Data System (ADS)

    Adhikari Subin, Jhashanath

    Layered forms of inorganic niobates have been used for various applications, such as charge transport and storage, photo-catalysis, solid acids, magnetic materials, superconductors, magneto-resistors and photo-luminescence devices. The layered niobates exists in different geometrical forms and composition with variation in the packing of oxide lattice by the constituting monovalent, divalent/trivalent and pentavalent cations. Four different types of lamellar niobates are studied in this research by theoretical methods, namely the all-electron full-potential DFT method using plane wave and periodic boundary conditions. A common feature of all the layered niobates is that the basic building block, NbO6 octahedral units are shared with each other at the corners and edges forming a covalent network and that the sharing is terminated in a particular direction. These octahedral units get modulated along with the geometry of interlayer interface with the change in the composition of the material. The macroscopic structure change is reflected by the alteration of the unit cell axes whereas the local change at various sites in the structure is revealed by the variation of the atomic distances and angles/tilt. The different properties of the layered compounds are a function of these structural variations and thus understanding the mechanism and the characteristics requires atomic level analysis. Calculations reveal the local bonding details and the bulk geometry of a material and can be compared to that obtained from powder diffraction methods. The EFG tensor which is a sensitive probe of the electronic environment around a quadrupolar nucleus can be used to monitor the minor changes in the bond lengths and angles in various structures. Among the configurations lying in the minima of the potential energy surfaces, the one representing the real material would be the one matching with the EFG tensor calculated from DFT methods with that determined from the SSNMR experiments

  4. Electronic properties of tantalum pentoxide polymorphs from first-principles calculations

    SciTech Connect

    Lee, J.; Lu, W.; Kioupakis, E.

    2014-11-17

    Tantalum pentoxide (Ta{sub 2}O{sub 5}) is extensively studied for its attractive properties in dielectric films, anti-reflection coatings, and resistive switching memory. Although various crystalline structures of tantalum pentoxide have been reported, its structural, electronic, and optical properties still remain a subject of research. We investigate the electronic and optical properties of crystalline and amorphous Ta{sub 2}O{sub 5} structures using first-principles calculations based on density functional theory and the GW method. The calculated band gaps of the crystalline structures are too small to explain the experimental measurements, but the amorphous structure exhibits a strong exciton binding energy and an optical band gap (∼4 eV) in agreement with experiment. We determine the atomic orbitals that constitute the conduction band for each polymorph and analyze the dependence of the band gap on the atomic geometry. Our results establish the connection between the underlying structure and the electronic and optical properties of Ta{sub 2}O{sub 5}.

  5. QED calculations in heavy many-electron atoms and one-electron quasi-molecules

    NASA Astrophysics Data System (ADS)

    Tupitsyn, I. I.; Safronova, M. S.; Kozlov, M. G.; Porsev, S. G.; Shabaev, V. M.

    2016-05-01

    Construction of simple one-electron approach to one-loop QED operator is an important task for the relativistic quantum theory of atoms and molecules. In this work we used two modifications of the model QED potential approach to calculations of the Lamb shift in many-electron atoms and one-electron quasi-molecules. The model potential is constructed as a sum of local and nonlocal (separable) potentials. The nonlocal part of the model potential was introduced to reproduce exactly the diagonal elements and also off-diagonal elements of the one-loop ab initio QED operator. The one-particle model QED operator was introduced in the Dirac-Fock and CI+MBPT relativistic calculations of the heavy and super-heavy atoms and in the calculations of the diatomic quasi-molecules. The comparison of the data obtained in different approaches to the one-loop QED operator is presented. Model QED potential is applied to calculate Lamb shift in the U91+- U92+ dimer. The results are compared with Ref..

  6. Study of electronic structures of solids with strongly interacting electrons

    NASA Astrophysics Data System (ADS)

    Su, Yen-Sheng

    This work contains studies of two classes of perovskite transition metal oxides. The first class is the layered perovskite cuprates and the related nickelate. The second class is the three dimensional perovskite manganites. Both model and ab initio calculations are carried out for the two classes of systems. The dissertation is therefore divided into the following four parts. The first part is about the 3-band Hubbard model. The model is commonly used for describing the electronic properties of the important CuO2 layers in the crystals of high-Tc superconducting cuprates, such as doped La2CuO4 and YBa2Cu3O 7. The straightforward perturbation expansion on the model taking tpd/ɛpd (~0.36 for the cuprates) as the small parameter does not converge. In this work, I show that there exist canonical transformations on the model Hamiltonian such that the perturbation expansion based on the transformed Hamiltonians converges. In the second part, crystal Hartree-Fock calculations are carried out for La2NiO4 and La2CuO4. The results predict correctly that these two materials are antiferromagnetic insulators, in contrast to the wrong predictions made by the density functional calculations using the local spin density approximation (LSDA). The spin form factors of the materials are also calculated. The results agree with previous theoretical works using an embedded cluster model. The calculated spin form factor of La2CuO4 is consistent with the few experimental data currently available, while the results for La2NiO4 show a large discrepancy between theory and experiment. We question the accuracy of the experimental results of La2NiO4 and call for more experiments to settle the issue. In the third part, crystal Hartree-Fock calculations are carried out for LaMnO3. Our main focus is on the magnetic and orbital orderings, the effect of the crystal distortion from the cubic perovskite structure, and the analysis of the projected density of states. In addition, we also find

  7. Electronic and structural properties of metallic microclusters

    SciTech Connect

    Maiti, A.

    1992-04-01

    The first part of this thesis presents a first-order pseudopotential calculation at T=O of the total energy of small sodium clusters of size N<800. The calculation is based on a local-pseudopotential scheme and local-density correlation and exchange. A temperature-size (T-N) phase-diagram is then derived using the T=O results and Lindemann`s criterion for melting. The phase-diagram contains three regions of stability: (1) a liquid (jellium) phase at temperatures above the melting line T{sub M}(N) where cluster-stability occurs at electronic magic numbers: (2) a phase related to complete geometrical shells of body-centered-cubic structure at temperatures below the melting line; and (3) a close-packed structure at very low temperatures and sufficiently large N. The melting line drops to T{sub M}(N)=O for N<65, where electronic magic numbers are stable even at T=O. The phase diagram reduces asymptotically to the known phases of sodium as N{yields}{infinity}, including the known martensitic transformation at T{approximately}5 K. The second and the last part of this thesis consists of a study of small-cluster many-body systems by means of an on-site ``local`` chemical potential which allows the continuous variation of local electron-density. This method yields a criterion to distinguish particular features of a small cluster that are likely to survive in the large-N thermodynamic limit from those discontinuities that arise only from finite-size effects.

  8. Electronic and structural properties of metallic microclusters

    SciTech Connect

    Maiti, A.

    1992-04-01

    The first part of this thesis presents a first-order pseudopotential calculation at T=O of the total energy of small sodium clusters of size N<800. The calculation is based on a local-pseudopotential scheme and local-density correlation and exchange. A temperature-size (T-N) phase-diagram is then derived using the T=O results and Lindemann's criterion for melting. The phase-diagram contains three regions of stability: (1) a liquid (jellium) phase at temperatures above the melting line T{sub M}(N) where cluster-stability occurs at electronic magic numbers: (2) a phase related to complete geometrical shells of body-centered-cubic structure at temperatures below the melting line; and (3) a close-packed structure at very low temperatures and sufficiently large N. The melting line drops to T{sub M}(N)=O for N<65, where electronic magic numbers are stable even at T=O. The phase diagram reduces asymptotically to the known phases of sodium as N{yields}{infinity}, including the known martensitic transformation at T{approximately}5 K. The second and the last part of this thesis consists of a study of small-cluster many-body systems by means of an on-site local'' chemical potential which allows the continuous variation of local electron-density. This method yields a criterion to distinguish particular features of a small cluster that are likely to survive in the large-N thermodynamic limit from those discontinuities that arise only from finite-size effects.

  9. Calculation of diffraction patterns associated with electron irradiation induced amorphization of CuTi

    SciTech Connect

    Devanathan, R.; Meshii, M. . Dept. of Materials Science and Engineering); Lam, N.Q.; Okamoto, P. ); Sabochik, M.J. . Dept. of Engineering Physics)

    1990-11-01

    A new approach that uses the multislice method in conjunction with molecular dynamics simulations to study electron irradiation induced amorphisation is presented. Diffraction patterns were calculated for CuTi and found to be more sensitive than the pair correlation function to the structural changes preceding amorphisation. The results from this approach and from a study of long range order are presented. 16 refs., 8 figs.

  10. Calculating electron momentum densities and Compton profiles using the linear tetrahedron method.

    PubMed

    Ernsting, D; Billington, D; Haynes, T D; Millichamp, T E; Taylor, J W; Duffy, J A; Giblin, S R; Dewhurst, J K; Dugdale, S B

    2014-12-10

    A method for computing electron momentum densities and Compton profiles from ab initio calculations is presented. Reciprocal space is divided into optimally-shaped tetrahedra for interpolation, and the linear tetrahedron method is used to obtain the momentum density and its projections such as Compton profiles. Results are presented and evaluated against experimental data for Be, Cu, Ni, Fe3Pt, and YBa2Cu4O8, demonstrating the accuracy of our method in a wide variety of crystal structures.

  11. Cross section calculations for electron scattering from platinum chemotherapeutic compounds. Electron scattering from carboplatin and oxaliplatin

    NASA Astrophysics Data System (ADS)

    Żywicka, B.; Możejko, P.

    2013-10-01

    Cross section for electron impact ionization of carboplatin, C6H12N2O4Pt, and oxaliplatin, C8H14N2O4Pt, have been calculated within binary-encounter-Bethe model for energies from the ionization threshold up to 5000 eV. Cross section for elastic electron scattering from carboplatin and oxaliplatin molecules have also been derived using independent atom method (IAM) and additivity rule for collision energies ranging from 50 eV to 3000 eV. Obtained cross sections have been compared with relevant cross sections for cisplatin molecules.

  12. Electronic correlation in magnetic contributions to structural energies

    NASA Astrophysics Data System (ADS)

    Haydock, Roger

    For interacting electrons the density of transitions [see http://arxiv.org/abs/1405.2288] replaces the density of states in calculations of structural energies. Extending previous work on paramagnetic metals, this approach is applied to correlation effects on the structural stability of magnetic transition metals. Supported by the H. V. Snyder Gift to the University of Oregon.

  13. Coupled Electron-Ion Monte Carlo Calculations of Dense Metallic Hydrogen

    NASA Astrophysics Data System (ADS)

    Pierleoni, Carlo; Ceperley, David M.; Holzmann, Markus

    2004-09-01

    We present an efficient new Monte Carlo method which couples path integrals for finite temperature protons with quantum Monte Carlo calculations for ground state electrons, and we apply it to metallic hydrogen for pressures beyond molecular dissociation. We report data for the equation of state for temperatures across the melting of the proton crystal. Our data exhibit more structure and higher melting temperatures of the proton crystal than do Car-Parrinello molecular dynamics results. This method fills the gap between high temperature electron-proton path integral and ground state diffusion Monte Carlo methods and should have wide applicability.

  14. Assignment of absolute stereostructures through quantum mechanics electronic and vibrational circular dichroism calculations.

    PubMed

    Dai, Peng; Jiang, Nan; Tan, Ren-Xiang

    2016-01-01

    Elucidation of absolute configuration of chiral molecules including structurally complex natural products remains a challenging problem in organic chemistry. A reliable method for assigning the absolute stereostructure is to combine the experimental circular dichroism (CD) techniques such as electronic and vibrational CD (ECD and VCD), with quantum mechanics (QM) ECD and VCD calculations. The traditional QM methods as well as their continuing developments make them more applicable with accuracy. Taking some chiral natural products with diverse conformations as examples, this review describes the basic concepts and new developments of QM approaches for ECD and VCD calculations in solution and solid states.

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

    NASA Astrophysics Data System (ADS)

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

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

  16. Electronic structure and stability of some silicon compounds

    NASA Astrophysics Data System (ADS)

    Novak, Igor; Abu-Izneid, Tareq; Kovač, Branka

    2010-05-01

    The electronic structures of N,1,3-tris(1,1-dimethylethyl)-cyclodisilazan-2-amine ( I) and 2,3,5,5-tetrakis(trimethylsilyl)cyclopentadiene ( II) have been investigated by HeI and HeII UV photoelectron spectroscopy (UPS) and quantum chemical calculations. We discuss the influence of substituent effects on their electronic structure and thermodynamic stability. Our study shows that trimethylsilyl substituents have strong influence on the electronic structure of cyclopentadiene via inductive effect. Their influence on thermodynamic stability is also pronounced. In substituted cyclodisilazanes hyperconjugative influence of alkylsilyl groups was shown to cause relative thermodynamic stabilization of the cyclodisilazane system.

  17. Electronic structure and enthalpy of hydrogen and helium mixtures

    NASA Astrophysics Data System (ADS)

    Ross, M.; Klepeis, J. E.; Schafer, K. J.; Barbee, T. W., III

    1992-11-01

    The first local density approximation (LDA) calculations of the electronic structure, equation of state, and enthalpy of mixing were carried out for a number of different compositions of hydrogen and helium in bcc and fcc lattices. These are fully quantum mechanical, self-consistent calculations utilizing state-of-the-art methods of electron band theory, which make no assumptions regarding pressure ionization. The major approximation in the LDA method is that the exchange and correlation energy is given by a free electron functional in terms of the local electron density. The majority of previous mixture calculations start with the assumption that both hydrogen and helium are pressure-ionized so that the electronic structure is approximately that of free or weakly screened electrons in the presence of positive ions. Stevenson used a hard-sphere mixture model for the ions with an ion-ion pseudopotential to account for electron screening and predicted that a mixture containing 7% helium by number, the composition believed to be present in Jupiter and Saturn, would phase separate at a temperature of about 7000 K at 8 Mbar. Subsequent calculations carried out for the fully ionized mixture and for a mixture of screened ions (linear response theory) have all arrived at predictions similar to those of Stevenson. MacFarlane and Hubbard performed Thomas-Fermi-Dirac calculations for mixing enthalpies of hydrogen and helium in bcc and fcc lattices and predicted that phase separation would not occur at any temperature.

  18. Considerations of beta and electron transport in internal dose calculations

    SciTech Connect

    Bolch, W.E.; Poston, J.W. Sr. . Dept. of Nuclear Engineering)

    1990-12-01

    Ionizing radiation has broad uses in modern science and medicine. These uses often require the calculation of energy deposition in the irradiated media and, usually, the medium of interest is the human body. Energy deposition from radioactive sources within the human body and the effects of such deposition are considered in the field of internal dosimetry. In July of 1988, a three-year research project was initiated by the Nuclear Engineering Department at Texas A M University under the sponsorship of the US Department of Energy. The main thrust of the research was to consider, for the first time, the detailed spatial transport of electron and beta particles in the estimation of average organ doses under the Medical Internal Radiation Dose (MIRD) schema. At the present time (December of 1990), research activities are continuing within five areas. Several are new initiatives begun within the second or third year of the current contract period. They include: (1) development of small-scale dosimetry; (2) development of a differential volume phantom; (3) development of a dosimetric bone model; (4) assessment of the new ICRP lung model; and (5) studies into the mechanisms of DNA damage. A progress report is given for each of these tasks within the Comprehensive Report. In each use, preliminary results are very encouraging and plans for further research are detailed within this document. 22 refs., 13 figs., 1 tab.

  19. Considerations of beta and electron transport in internal dose calculations

    SciTech Connect

    Bolch, W.E.; Poston, J.W. Sr.

    1990-12-01

    Ionizing radiation has broad uses in modern science and medicine. These uses often require the calculation of energy deposition in the irradiated media and, usually, the medium of interest is the human body. Energy deposition from radioactive sources within the human body and the effects of such deposition are considered in the field of internal dosimetry. In July of 1988, a three-year research project was initiated by the Nuclear Engineering Department at Texas A M University under the sponsorship of the US Department of Energy. The main thrust of the research was to consider, for the first time, the detailed spatial transport of electron and beta particles in the estimation of average organ doses under the Medical Internal Radiation Dose (MIRD) schema. At the present time (December of 1990), research activities are continuing within five areas. Several are new initiatives begun within the second or third year of the current contract period. They include: (1) development of small-scale dosimetry; (2) development of a differential volume phantom; (3) development of a dosimetric bone model; (4) assessment of the new ICRP lung model; and (5) studies into the mechanisms of DNA damage. A progress report is given for each of these tasks within the Comprehensive Report. In each case, preliminary results are very encouraging and plans for further research are detailed within this document.

  20. First-principles calculations of electronic and magnetic properties of CeN: The LDA + U method

    NASA Astrophysics Data System (ADS)

    Hao, Ai-Min; Bai, Jing

    2013-10-01

    Electronic and magnetic properties of CeN are investigated using first-principles calculations based on density functional theory (DFT) with the LDA + U method. Our results show that CeN is a half-metal. The majority-spin electron band structure has metallic intersections, whereas the minority-spin electron band structure has a semiconducting gap straddling the Fermi level. A small indirect energy gap occurs between X and W. The calculated magnetic moment is 0.99 μB per unit cell.

  1. Angle-resolved auger electron spectra for a Ni(110) surface: Calculations with the reduced angular momentum expansion

    NASA Astrophysics Data System (ADS)

    Fritzsche, V.; Chassé, A.; Mróz, S.

    1990-05-01

    Results of multiple-scattering cluster calculations are presented for angle-resolved M 2,3VV Auger electron intensities from a clean Ni(110) surface, which are obtained using the reduced angular momentum expansion (RAME). This method goes beyond the popular plane-wave approximation and takes into account both the spherical character and the anisotropy of the electron waves. The positions of the maxima and minima in the calculated polar intensity profiles agree well with the experimentally determined structures.

  2. Reversible Hydrogen Storage Materials – Structure, Chemistry, and Electronic Structure

    SciTech Connect

    Robertson, Ian M.; Johnson, Duane D.

    2014-06-21

    To understand the processes involved in the uptake and release of hydrogen from candidate light-weight metal hydride storage systems, a combination of materials characterization techniques and first principle calculation methods have been employed. In addition to conventional microstructural characterization in the transmission electron microscope, which provides projected information about the through thickness microstructure, electron tomography methods were employed to determine the three-dimensional spatial distribution of catalyst species for select systems both before and after dehydrogenation. Catalyst species identification as well as compositional analysis of the storage material before and after hydrogen charging and discharging was performed using a combination of energy dispersive spectroscopy, EDS, and electron energy loss spectroscopy, EELS. The characterization effort was coupled with first-principles, electronic-structure and thermodynamic techniques to predict and assess meta-stable and stable phases, reaction pathways, and thermodynamic and kinetic barriers. Systems studied included:NaAlH4, CaH2/CaB6 and Ca(BH4)2, MgH2/MgB2, Ni-Catalyzed Magnesium Hydride, TiH2-Catalyzed Magnesium Hydride, LiBH4, Aluminum-based systems and Aluminum

  3. Extraordinary electronic properties in uncommon structure types

    NASA Astrophysics Data System (ADS)

    Ali, Mazhar Nawaz

    In this thesis I present the results of explorations into several uncommon structure types. In Chapter 1 I go through the underlying idea of how we search for new compounds with exotic properties in solid state chemistry. The ideas of exploring uncommon structure types, building up from the simple to the complex, using chemical intuition and thinking by analogy are discussed. Also, the history and basic concepts of superconductivity, Dirac semimetals, and magnetoresistance are briefly reviewed. In chapter 2, the 1s-InTaS2 structural family is introduced along with the discovery of a new member of the family, Ag0:79VS2; the synthesis, structure, and physical properties of two different polymorphs of the material are detailed. Also in this chapter, we report the observation of superconductivity in another 1s structure, PbTaSe2. This material is especially interesting due to it being very heavy (resulting in very strong spin orbit coulping (SOC)), layered, and noncentrosymmetric. Electronic structure calculations reveal the presence of a bulk 3D Dirac cone (very similar to graphene) that is gapped by SOC originating from the hexagonal Pb layer. In Chapter 3 we show the re-investigation of the crystal structure of the 3D Dirac semimetal, Cd3As2. It is found to be centrosymmetric, rather than noncentrosymmetric, and as such all bands are spin degenerate and there is a 4-fold degenerate bulk Dirac point at the Fermi level, making Cd3As2 a 3D electronic analog to graphene. Also, for the first time, scanning tunneling microscopy experiments identify a 2x2 surface reconstruction in what we identify as the (112) cleavage plane of single crystals; needle crystals grow with a [110] long axis direction. Lastly, in chapter 4 we report the discovery of "titanic" (sadly dubbed ⪉rge, nonsaturating" by Nature editors and given the acronym XMR) magnetoresistance (MR) in the non-magnetic, noncentrosymmetric, layered transition metal dichalcogenide WTe2; over 13 million% at 0.53 K in

  4. Electronic and thermal properties of germanene and stanene by first-principles calculations

    NASA Astrophysics Data System (ADS)

    Jomehpour Zaveh, S.; Roknabadi, M. R.; Morshedloo, T.; Modarresi, M.

    2016-03-01

    The electronic, vibrational and thermal properties of germanene and stanene have been investigated based on density functional theory (DFT) and density functional perturbation theory (DFPT). The electronic band structure, total and partial density of states and phonon dispersion spectrum and states are analyzed. The phonon spectrum is positive for all modes in the first Brillouin zone and there is a phonon energy band gap between acoustic and optical modes which is around 50 cm-1 for both structure. The constant-volume specific heats of two structures are calculated by using phonon spectrum and density of states. The spin-orbit coupling (SOC) opens a direct energy band gap at the Dirac point, softens phonon spectrum and decreases phonon group velocity of ZA mode.

  5. PLATON SQUEEZE: a tool for the calculation of the disordered solvent contribution to the calculated structure factors.

    PubMed

    Spek, Anthony L

    2015-01-01

    The completion of a crystal structure determination is often hampered by the presence of embedded solvent molecules or ions that are seriously disordered. Their contribution to the calculated structure factors in the least-squares refinement of a crystal structure has to be included in some way. Traditionally, an atomistic solvent disorder model is attempted. Such an approach is generally to be preferred, but it does not always lead to a satisfactory result and may even be impossible in cases where channels in the structure are filled with continuous electron density. This paper documents the SQUEEZE method as an alternative means of addressing the solvent disorder issue. It conveniently interfaces with the 2014 version of the least-squares refinement program SHELXL [Sheldrick (2015). Acta Cryst. C71. In the press] and other refinement programs that accept externally provided fixed contributions to the calculated structure factors. The PLATON SQUEEZE tool calculates the solvent contribution to the structure factors by back-Fourier transformation of the electron density found in the solvent-accessible region of a phase-optimized difference electron-density map. The actual least-squares structure refinement is delegated to, for example, SHELXL. The current versions of PLATON SQUEEZE and SHELXL now address several of the unnecessary complications with the earlier implementation of the SQUEEZE procedure that were a necessity because least-squares refinement with the now superseded SHELXL97 program did not allow for the input of fixed externally provided contributions to the structure-factor calculation. It is no longer necessary to subtract the solvent contribution temporarily from the observed intensities to be able to use SHELXL for the least-squares refinement, since that program now accepts the solvent contribution from an external file (.fab file) if the ABIN instruction is used. In addition, many twinned structures containing disordered solvents are now also

  6. PLATON SQUEEZE: a tool for the calculation of the disordered solvent contribution to the calculated structure factors.

    PubMed

    Spek, Anthony L

    2015-01-01

    The completion of a crystal structure determination is often hampered by the presence of embedded solvent molecules or ions that are seriously disordered. Their contribution to the calculated structure factors in the least-squares refinement of a crystal structure has to be included in some way. Traditionally, an atomistic solvent disorder model is attempted. Such an approach is generally to be preferred, but it does not always lead to a satisfactory result and may even be impossible in cases where channels in the structure are filled with continuous electron density. This paper documents the SQUEEZE method as an alternative means of addressing the solvent disorder issue. It conveniently interfaces with the 2014 version of the least-squares refinement program SHELXL [Sheldrick (2015). Acta Cryst. C71. In the press] and other refinement programs that accept externally provided fixed contributions to the calculated structure factors. The PLATON SQUEEZE tool calculates the solvent contribution to the structure factors by back-Fourier transformation of the electron density found in the solvent-accessible region of a phase-optimized difference electron-density map. The actual least-squares structure refinement is delegated to, for example, SHELXL. The current versions of PLATON SQUEEZE and SHELXL now address several of the unnecessary complications with the earlier implementation of the SQUEEZE procedure that were a necessity because least-squares refinement with the now superseded SHELXL97 program did not allow for the input of fixed externally provided contributions to the structure-factor calculation. It is no longer necessary to subtract the solvent contribution temporarily from the observed intensities to be able to use SHELXL for the least-squares refinement, since that program now accepts the solvent contribution from an external file (.fab file) if the ABIN instruction is used. In addition, many twinned structures containing disordered solvents are now also

  7. Electronic structures of reconstructed zigzag silicene nanoribbons

    SciTech Connect

    Ding, Yi E-mail: wangyanli-04@tsinghua.org.cn; Wang, Yanli E-mail: wangyanli-04@tsinghua.org.cn

    2014-02-24

    Edge states and magnetism are crucial for spintronic applications of nanoribbons. Here, using first-principles calculations, we explore structural stabilities and electronic properties of zigzag silicene nanoribbons (ZSiNRs) with Klein and pentagon-heptagon reconstructions. Comparing to unreconstructed zigzag edges, deformed bare pentagon-heptagon ones are favored under H-poor conditions, while H-rich surroundings stabilize di-hydrogenated Klein edges. These Klein edges have analogous magnetism to zigzag ones, which also possess the electric-field-induced half-metallicity of nanoribbons. Moreover, diverse magnetic states can be achieved by asymmetric Klein and zigzag edges into ZSiNRs, which could be transformed from antiferromagnetic-semiconductors to bipolar spin-gapless-semiconductors and ferromagnetic-metals depending on edge hydrogenations.

  8. Electronic structures of reconstructed zigzag silicene nanoribbons

    NASA Astrophysics Data System (ADS)

    Ding, Yi; Wang, Yanli

    2014-02-01

    Edge states and magnetism are crucial for spintronic applications of nanoribbons. Here, using first-principles calculations, we explore structural stabilities and electronic properties of zigzag silicene nanoribbons (ZSiNRs) with Klein and pentagon-heptagon reconstructions. Comparing to unreconstructed zigzag edges, deformed bare pentagon-heptagon ones are favored under H-poor conditions, while H-rich surroundings stabilize di-hydrogenated Klein edges. These Klein edges have analogous magnetism to zigzag ones, which also possess the electric-field-induced half-metallicity of nanoribbons. Moreover, diverse magnetic states can be achieved by asymmetric Klein and zigzag edges into ZSiNRs, which could be transformed from antiferromagnetic-semiconductors to bipolar spin-gapless-semiconductors and ferromagnetic-metals depending on edge hydrogenations.

  9. Comparison of electronic structure between monolayer silicenes on Ag (111)

    NASA Astrophysics Data System (ADS)

    Chun-Liang, Lin; Ryuichi, Arafune; Maki, Kawai; Noriaki, Takagi

    2015-08-01

    The electronic structures of monolayer silicenes (4 × 4 and ) grown on Ag (111) surface are studied by scanning tunneling spectroscopy (STS) and density functional theory (DFT) calculations. While both phases have similar electronic structures around the Fermi level, significant differences are observed in the higher energy unoccupied states. The DFT calculations show that the contributions of Si 3pz orbitals to the unoccupied states are different because of their different buckled configurations. Project supported by the Ministry of Education, Culture, Sports, Science and Technology (MEXT) through Grants-in-Aid for Scientific Research (Grant Nos. 24241040 and 25110008) and the World Premier International Research Center Initiative (WPI), MEXT, Japan.

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

    NASA Astrophysics Data System (ADS)

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

    2014-04-01

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

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

    SciTech Connect

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

    2014-04-28

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

  12. Heats of Formation of XeF₃⁺, XeF₃⁻, XeF₅⁺, XeF₇⁺, XeF₇⁻,and XeF₈ from High Level Electronic Structure Calculations

    SciTech Connect

    Grant, Daniel J.; Wang, Tsang-Hsiu; Dixon, David A.; Christe, Karl O.

    2010-01-04

    Atomization energies at 0 K and heats of formation at 0 and 298 K are predicted for XeF₃⁺, XeF₃⁻, XeF₅⁺, XeF₇⁻, and XeF₈ from coupled cluster theory (CCSD(T)) calculations with effective core potential correlation-consistent basis sets for Xe and including correlation of the nearest core electrons. Additional corrections are included to achieve near chemical accuracy of ±1 kcal/mol. Vibrational zero point energies were computed at the MP2 level of theory. Unlike the other neutral xenon fluorides, XeF₈ is predicted to be thermodynamically unstable with respect to loss of F₂ with the reaction calculated to be exothermic by 22.3 kcal/mol at 0 K. XeF₇⁺ is also predicted to be thermodynamically unstable with respect to the loss of F₂ by 24.1 kcal/mol at 0 K. For XeF₃⁺, XeF₅⁺, XeF₃⁻, XeF₅⁻ and XeF₇⁻, the reactions for loss of F₂ are endothermic by 14.8, 37.8, 38.2, 59.6, and 31.9 kcal/mol at 0 K, respectively. The F⁻ affinities of Xe, XeF₂, XeF₄, and XeF₆ are predicted to be 165.1, 155.3, 172.7, and 132.5 kcal/mol, and the corresponding F⁻ affinities are 6.3, 19.9, 59.1, and 75.0 kcal/mol at 0 K, respectively.

  13. Heavy ion track-structure calculations for radial dose in arbitrary materials

    NASA Technical Reports Server (NTRS)

    Cucinotta, Francis A.; Katz, Robert; Wilson, John W.; Dubey, Rajendra R.

    1995-01-01

    The delta-ray theory of track structure is compared with experimental data for the radial dose from heavy ion irradiation. The effects of electron transmission and the angular dependence of secondary electron ejection are included in the calculations. Several empirical formulas for electron range and energy are compared in a wide variety of materials in order to extend the application of the track-structure theory. The model of Rudd for the secondary electron-spectrum in proton collisions, which is based on a modified classical kinematics binary encounter model at high energies and a molecular promotion model at low energies, is employed. For heavier projectiles, the secondary electron spectrum is found by scaling the effective charge. Radial dose calculations for carbon, water, silicon, and gold are discussed. The theoretical data agreed well with the experimental data.

  14. Transmission zero in a quantum dot with strong electron-electron interaction: Perturbative conductance calculations

    NASA Astrophysics Data System (ADS)

    Kim, Sejoong; Lee, Hyun-Woo

    2006-05-01

    A pioneering experiment [E. Schuster, E. Buks, M. Heiblum, D. Mahalu, V. Umansky, and Hadas Shtrikman, Nature 385, 417 (1997)] reported the measurement of the transmission phase of an electron traversing a quantum dot and found the intriguing feature of a sudden phase drop in the conductance valleys. Based on the Friedel sum rule for a spinless effective one-dimensional system, it has been previously argued [H.-W. Lee, Phys. Rev. Lett. 82, 2358 (1999)] that the sudden phase drop should be accompanied by the vanishing of the transmission amplitude, or transmission zero. Here we address roles of strong electron-electron interactions on the electron transport through a two-level quantum dot where one level couples with the leads much more strongly than the other level does [P. G. Silvestrov and Y. Imry, Phys. Rev. Lett. 85, 2565 (2000)]. We perform a perturbative conductance calculation with an explicit account of large charging energy and verify that the resulting conductance exhibits transmission zero, in agreement with the analysis based on the Friedel sum rule.

  15. Electronic structure and photoelectron spectra of osmium and ruthenium tetraoxides

    SciTech Connect

    Topol', I.A.; Vovna, V.I.; Kazachek, M.V.

    1988-01-01

    The X/sub ..cap alpha../-SW method has been used in the nonrelativistic and quasirelativistic approximations to calculate the electronic structures of OsO/sub 4/, RuO/sub 4/, and FeO/sub 4/. When the 5d element is replaced by a 4d or 3d one, the electron-density redistribution is due mainly to the d electrons. All the d electrons in FeO/sub 4/ are localized on the iron atom, which markedly reduced the ionic and covalent bonding on the transition from RuO/sub 4/ to FeO/sub 4/, which explains the instability of FeO/sub 4/. The calculated spin-orbit splittings agree well with the structure of the PES bands, which enables one to establish the sequence of MO ionization energies unambiguously.

  16. DFT Calculations with van der Waals Interactions of Hydrated Calcium Carbonate Crystals CaCO3·(H2O, 6H2O): Structural, Electronic, Optical, and Vibrational Properties.

    PubMed

    Costa, Stefane N; Freire, Valder N; Caetano, Ewerton W S; Maia, Francisco F; Barboza, Carlos A; Fulco, Umberto L; Albuquerque, Eudenilson L

    2016-07-21

    The role of hydration on the structural, electronic, optical, and vibrational properties of monohydrated (CaCO3·H2O, hexagonal, P31, Z = 9) and hexahydrated (CaCO3·6H2O, monoclinic, C2/c, Z = 4) calcite crystals is assessed with the help of published experimental and theoretical data applying density functional theory within the generalized gradient approximation and a dispersion correction scheme. We show that the presence of water increases the main band gap of monohydrocalcite by 0.4 eV relative to the anhydrous structure, although practically not changing the hexahydrocalcite band gap. The gap type, however, is modified from indirect to direct as one switches from the monohydrated to the hexahydrated crystal. A good agreement was obtained between the simulated vibrational infrared and Raman spectra and the experimental data, with an infrared signature of hexahydrocalcite relative to monohydrocalcite being observed at 837 cm(-1). Other important vibrational signatures of the lattice, water molecules, and CO3(2-) were identified as well. Analysis of the phonon dispersion curves shows that, as the hydration level of calcite increases, the longitudinal optical-transverse optical phonon splitting becomes smaller. The thermodynamics properties of hexahydrocalcite as a function of temperature resemble closely those of calcite, while monohydrocalcite exhibits a very distinct behavior. PMID:27409458

  17. Stacking dependent electronic structures of transition metal dichalcogenides heterobilayer

    NASA Astrophysics Data System (ADS)

    Lee, Yea-Lee; Park, Cheol-Hwan; Ihm, Jisoon

    The systematic study of the electronic structures and optical properties of the transition metal dichalcogenides (TMD) heterobilayers can significantly improve the designing of new electronic and optoelectronic devices. Here, we theoretically study the electronic structures and optical properties of TMD heterobilayers using the first-principles methods. The band structures of TMD heterobilayer are shown to be determined by the band alignments of the each layer, the weak interlayer interactions, and angle dependent stacking patterns. The photoluminescence spectra are investigated using the calculated band structures, and the optical absorption spectra are examined by the GW approximations including the electron-hole interaction through the solution of the Bethe-Salpeter equation. It is expected that the weak interlayer interaction gives rise to the substantial interlayer optical transition which will be corresponding to the interlayer exciton.

  18. Electron tomography of dislocation structures

    SciTech Connect

    Liu, G.S.; House, S.D.; Kacher, J.; Tanaka, M.; Higashida, K.; Robertson, I.M.

    2014-01-15

    Recent developments in the application of electron tomography for characterizing microstructures in crystalline solids are described. The underlying principles for electron tomography are presented in the context of typical challenges in adapting the technique to crystalline systems and in using diffraction contrast imaging conditions. Methods for overcoming the limitations associated with the angular range, the number of acquired images, and uniformity of image contrast are introduced. In addition, a method for incorporating the real space coordinate system into the tomogram is presented. As the approach emphasizes development of experimental solutions to the challenges, the solutions developed and implemented are presented in the form of examples.

  19. First-principles calculation of the structural stability of 6d transition metals

    SciTech Connect

    Oestlin, A.; Vitos, L.

    2011-09-15

    The phase stability of the 6d transition metals (elements 103-111) is investigated using first-principles electronic-structure calculations. Comparison with the lighter transition metals reveals that the structural sequence trend is broken at the end of the 6d series. To account for this anomalous behavior, the effect of relativity on the lattice stability is scrutinized, taking different approximations into consideration. It is found that the mass-velocity and Darwin terms give important contributions to the electronic structure, leading to changes in the interstitial charge density and, thus, in the structural energy difference.

  20. Electron gun controlled smart structure

    DOEpatents

    Martin, Jeffrey W.; Main, John Alan; Redmond, James M.; Henson, Tammy D.; Watson, Robert D.

    2001-01-01

    Disclosed is a method and system for actively controlling the shape of a sheet of electroactive material; the system comprising: one or more electrodes attached to the frontside of the electroactive sheet; a charged particle generator, disposed so as to direct a beam of charged particles (e.g. electrons) onto the electrode; a conductive substrate attached to the backside of the sheet; and a power supply electrically connected to the conductive substrate; whereby the sheet changes its shape in response to an electric field created across the sheet by an accumulation of electric charge within the electrode(s), relative to a potential applied to the conductive substrate. Use of multiple electrodes distributed across on the frontside ensures a uniform distribution of the charge with a single point of e-beam incidence, thereby greatly simplifying the beam scanning algorithm and raster control electronics, and reducing the problems associated with "blooming". By placing a distribution of electrodes over the front surface of a piezoelectric film (or other electroactive material), this arrangement enables improved control over the distribution of surface electric charges (e.g. electrons) by creating uniform (and possibly different) charge distributions within each individual electrode. Removal or deposition of net electric charge can be affected by controlling the secondary electron yield through manipulation of the backside electric potential with the power supply. The system can be used for actively controlling the shape of space-based deployable optics, such as adaptive mirrors and inflatable antennae.