Towards scalable electronic structure calculations for alloys
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.
Multilevel domain decomposition for electronic structure calculations
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.
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)
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.
Improving Boundary Conditions for Electronic Structure Calculations
NASA Astrophysics Data System (ADS)
Benesh, G. A.; Haydock, Roger
Boundary conditions imposed on a local system joined to a much larger substrate system routinely introduce unphysical reflections that affect the calculation of electronic properties such as energies, charge densities, and densities of states. These problems persist in atomic cluster, slab, and supercell calculations alike. However, wave functions in real, physical systems do not reflect at artificial boundaries. Instead, they carry current smoothly across the surface separating the local system from the underlying medium. Haydock and Nex have derived a non-reflecting boundary condition that works well for discrete systems [Phys. Rev. B 75, 205121 (2006)]. Solutions satisfying their maximal breaking of time-reversal symmetry (MBTS) boundary condition carry current away from the boundary at a maximal rate--in much the same way as exact wave functions in physical systems. The MBTS approach has now been extended to studies employing continuous basis functions. In model systems, MBTS boundary conditions work well for calculating wave functions, eigenenergies, and densities of states. Results are reported for an Al(001) surface. Comparisons are made with slab calculations, embedding calculations, and experiment.
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.
Probing Actinide Electronic Structure through Pu Cluster Calculations
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.
Basis functions for electronic structure calculations on spheres.
Gill, Peter M W; Loos, Pierre-François; Agboola, Davids
2014-12-28
We introduce a new basis function (the spherical Gaussian) for electronic structure calculations on spheres of any dimension D. We find general expressions for the one- and two-electron integrals and propose an efficient computational algorithm incorporating the Cauchy-Schwarz bound. Using numerical calculations for the D = 2 case, we show that spherical Gaussians are more efficient than spherical harmonics when the electrons are strongly localized. PMID:25554128
Electronic-structure calculation for metals by local optimization
Woodward, C.; Min, B.I.; Benedek, R.; Garner, J.
1989-03-15
Recent work by Car and Parrinello has generated considerable interest in the calculation of electronic structure by nonlinear optimization. The technique introduced by these authors, dynamical simulated annealing, is designed for problems that involve energy barriers. When local optimization suffices to determine the energy minimum, more direct methods are available. In this paper we apply the algorithm suggested by Williams and Soler to calculate the electronic structure of metals, using a plane-wave expansion for the electronic orbitals and an electron-ion pseudopotential of the Kleinman-Bylander form. Radial pseudopotentials were taken from the compilation of Bachelet, Hamann, and Schlueter. Calculations are performed to optimize the electronic structure (i) with fixed atomic configuration, or (ii) with the atomic volume being optimized simultaneously. It is found that the dual optimization (ii) converges in essentially the same number of steps as the static lattice optimization (i). Numerical results are presented for Li, K, Al, and simple-cubic P.
Spectral differences in real-space electronic structure calculations
NASA Astrophysics Data System (ADS)
Jordan, D. K.; Mazziotti, D. A.
2004-01-01
Real-space grids for electronic structure calculations are efficient because the potential is diagonal while the second derivative in the kinetic energy may be sparsely evaluated with finite differences or finite elements. In applications to vibrational problems in chemical physics a family of methods known as spectral differences has improved finite differences by several orders of magnitude. In this paper the use of spectral differences for electronic structure is studied. Spectral differences are implemented in two electronic structure programs PARSEC and HARES which currently employ finite differences. Applications to silicon clusters and lattices indicate that spectral differences achieve the same accuracy as finite differences with less computational work.
Parallel adaptive mesh refinement for electronic structure calculations
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.
Elongation method for electronic structure calculations of random DNA sequences.
Orimoto, Yuuichi; Liu, Kai; Aoki, Yuriko
2015-10-30
We applied ab initio order-N elongation (ELG) method to calculate electronic structures of various deoxyribonucleic acid (DNA) models. We aim to test potential application of the method for building a database of DNA electronic structures. The ELG method mimics polymerization reactions on a computer and meets the requirements for linear scaling computational efficiency and high accuracy, even for huge systems. As a benchmark test, we applied the method for calculations of various types of random sequenced A- and B-type DNA models with and without counterions. In each case, the ELG method maintained high accuracy with small errors in energy on the order of 10(-8) hartree/atom compared with conventional calculations. We demonstrate that the ELG method can provide valuable information such as stabilization energies and local densities of states for each DNA sequence. In addition, we discuss the "restarting" feature of the ELG method for constructing a database that exhaustively covers DNA species. PMID:26337429
New quinternary selenides: Syntheses, characterizations, and electronic structure calculations
Chung, Ming-Yan; Lee, Chi-Shen
2013-06-01
Five quinternary selenides, Sr₂.₆₃Y₀.₃₇Ge₀.₆₃Sb₂.₃₇Se₈ (I), Sr₂.₆₃La₀.₃₇Ge₀.₆₃Sb₂.₃₇Se₈ (II), Sr₂.₇₁La₀.₂₉Sn₀.₇₇Bi₂.₂₃Se₈ (III), Ba₂.₆₇ La₀.₃₃ Sn₀.₆₇Sb₂.₃₃Se₈ (IV), and Ba₂.₆₇ La₀.₃₃Sn₀.₆₇Bi₂.₃₃Se₈ (V), were synthesized by solid-state reaction in fused silica tubes. These compounds are isostructural and crystallize in the Sr₃GeSb₂Se₈ structural-type, which belongs to the orthorhombic space group Pnma (no. 62). Three structural units, ^{1}_{∞}[MSe₃], ^{1}_{∞}[M₄Se₁₀] (M=Tt, Pn) and M´ (M´=groups II and III element), comprise the entire one-dimensional structure, separated by M´. Measurements of electronic resistivity and diffused reflectance suggest that IV and V have semiconducting properties. Electronic structure calculations confirm the site preferences of Sr/La element discovered by crystal structure refinement. - Graphical abstract: Quinternary selenides Ae₂.₆₇M₀.₃₃Tt₀.₆₇Pn₂.₃₃Se₈ (Ae, M, Tt, Pn=Sr/Ba, Y/La, Ge/Sn, Sb/Bi) were synthesized and their site preferences were characterized by single-crystal X-ray diffraction and electronic structure calculation. Highlights: • Five new quinternary selenides were synthesized and characterized. • Structural units, ^{1}_{∞}[MSe₃] and ^{1}_{∞}[M₄Se₁₀] (M=Tt, Pn), construct the one-dimensional structure. • Calculations of electronic structure confirm site preference of Sr/La sites.
Exchange coupling in transition metal monoxides: Electronic structure calculations
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.
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.
Wavelets in self-consistent electronic structure calculations
Wei, S.; Chou, M.Y.
1996-04-01
We report the first implementation of orthonormal wavelet bases in self-consistent electronic structure calculations within the local-density approximation. These local bases of different scales efficiently describe localized orbitals of interest. As an example, we studied two molecules, H{sub 2} and O{sub 2}, using pseudopotentials and supercells. Considerably fewer bases are needed compared with conventional plane-wave approaches, yet calculated binding properties are similar. Our implementation employs fast wavelet and Fourier transforms, avoiding evaluating any three-dimensional integral numerically. {copyright} {ital 1996 The American Physical Society.}
Real-time feedback from iterative electronic structure calculations.
Vaucher, Alain C; Haag, Moritz P; Reiher, Markus
2016-04-01
Real-time feedback from iterative electronic structure calculations requires to mediate between the inherently unpredictable execution times of the iterative algorithm used and the necessity to provide data in fixed and short time intervals for real-time rendering. We introduce the concept of a mediator as a component able to deal with infrequent and unpredictable reference data to generate reliable feedback. In the context of real-time quantum chemistry, the mediator takes the form of a surrogate potential that has the same local shape as the first-principles potential and can be evaluated efficiently to deliver atomic forces as real-time feedback. The surrogate potential is updated continuously by electronic structure calculations and guarantees to provide a reliable response to the operator for any molecular structure. To demonstrate the application of iterative electronic structure methods in real-time reactivity exploration, we implement self-consistent semiempirical methods as the data source and apply the surrogate-potential mediator to deliver reliable real-time feedback. © 2015 Wiley Periodicals, Inc. PMID:26678030
Statistical learning for alloy design from electronic structure calculations
NASA Astrophysics Data System (ADS)
Broderick, Scott R.
The objective of this thesis is to explore how statistical learning methods can contribute to the interpretation and efficacy of electronic structure calculations. This study develops new applications of statistical learning and data mining methods to both semi-empirical and density functional theory (DFT) calculations. Each of these classes of electronic structure calculations serves as templates for different data driven discovery strategies for materials science applications. In our study of semi-empirical methods, we take advantage of the ability of data mining methods to quantitatively assess high dimensional parameterization schemes. The impact of this work includes the development of accelerated computational schemes for developing reduced order models. Another application is the use of these informatics based techniques to serve as a means for estimating parameters when data for such calculations are not available. Using density of states (DOS) spectra derived from DFT calculations we have demonstrated the classification power of singular value decomposition methods to accurately develop structural and stoichiometric classifications of compounds. Building on this work we have extended this analytical strategy to apply the predictive capacity of informatics methods to develop a new and far more robust modeling approach for DOS spectra, addressing an issue that has gone relatively unchallenged over two decades. By exploring a diverse array of materials systems (metals, ceramics, different crystal structures) this work has laid the foundations for expanding the linkages between statistical learning and statistical thermodynamics. The results of this work provide exciting new opportunities in computational based design of materials that have not been explored before.
Linear Multigrid Techniques in Self-consistent Electronic Structure Calculations
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.
Electronic Structure of Silicon Nanowires Matrix from Ab Initio Calculations.
Monastyrskii, Liubomyr S; Boyko, Yaroslav V; Sokolovskii, Bogdan S; Potashnyk, Vasylyna Ya
2016-12-01
An investigation of the model of porous silicon in the form of periodic set of silicon nanowires has been carried out. The electronic energy structure was studied using a first-principle band method-the method of pseudopotentials (ultrasoft potentials in the basis of plane waves) and linearized mode of the method of combined pseudopotentials. Due to the use of hybrid exchange-correlation potentials (B3LYP), the quantitative agreement of the calculated value of band gap in the bulk material with experimental data is achieved. The obtained results show that passivation of dangling bonds with hydrogen atoms leads to substantial transformation of electronic energy structure. At complete passivation of the dangling silicon bonds by hydrogen atoms, the band gap value takes the magnitude which substantially exceeds that for bulk silicon. The incomplete passivation gives rise to opposite effect when the band gap value decreases down the semimetallic range. PMID:26768147
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
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.
Supersampling method for efficient grid-based electronic structure calculations.
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. PMID:26957151
Efficient Execution of Electronic Structure Calculations on SMP Clusters
Nurzhan Ustemirov
2006-05-01
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.
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.
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.
Semiempirical electronic structure calculation on Ca and Pb apatites
NASA Astrophysics Data System (ADS)
Matos, Maria; Terra, Joice; Ellis, D. E.
A systematic study is made on the electronic structure of stoichiometric calcium and lead apatites, using the tight binding extended Hückel method (eHT). The aim is to investigate the applicability of the semiempirical theory to study this family of compounds. A10(BO4)6X2 (A = Ca, Pb) apatites, differing by substitutions in the BO4 tetrahedral unit (B = P, As, and V) and X-channel ion (X = OH, Cl), are considered. The calculations show that eHT is suitable to describe basic properties especially concerning trends with atomic substitution and geometry changes. Band structure, Mulliken charge distribution, and bond orders are in good agreement with results of ab initio density functional theory (DFT) found in the literature. Large variations in the optical gap due to vanadium and lead substitutions are newly found. Changes in the anion X-channel affect the optical gap, which is in close agreement with DFT results. Analysis involving subnets are performed to determine the role of halogenic orbitals in the electronic structure of chloroapatites, showing evidence of covalent Cl bonding. It was also found that Pb=OH bonding in hydroxy-vanadinite Pb10(VO4)6(OH)2, recently synthesized, is weaker than that of Ca=OH in vanadate Ca10(VO4)6(OH)2. Arsenium is found to be more weakely bound to the O-tetrahedron than phosphorous, although Ca=O bond is increased with the substitution. We investigate, in addition, the electronic structure of a model system Ca10(AsO4)6(OH)2, obtained from direct As substitution in the vanadate Ca10(VO4)6(OH)2.
Electronic structure calculations of hexaborides and boron carbide
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.
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.
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.
Auxiliary basis expansions for large-scale electronic structure calculations
Jung, Yousung; Sodt, Alexander; Gill, Peter W.M.; Head-Gordon, Martin
2005-04-04
One way to reduce the computational cost of electronic structure calculations is to employ auxiliary basis expansions to approximate 4 center integrals in terms of 2 and 3-center integrals, usually using the variationally optimum Coulomb metric to determine the expansion coefficients. However the long-range decay behavior of the auxiliary basis expansion coefficients has not been characterized. We find that this decay can be surprisingly slow. Numerical experiments on linear alkanes and a toy model both show that the decay can be as slow as 1/r in the distance between the auxiliary function and the fitted charge distribution. The Coulomb metric fitting equations also involve divergent matrix elements for extended systems treated with periodic boundary conditions. An attenuated Coulomb metric that is short-range can eliminate these oddities without substantially degrading calculated relative energies. The sparsity of the fit coefficients is assessed on simple hydrocarbon molecules, and shows quite early onset of linear growth in the number of significant coefficients with system size using the attenuated Coulomb metric. This means it is possible to design linear scaling auxiliary basis methods without additional approximations to treat large systems.
Adaptations in Electronic Structure Calculations in Heterogeneous Environments
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.
"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.
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.
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.
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.
Explicitly-correlated Gaussian geminals in electronic structure calculations
NASA Astrophysics Data System (ADS)
Szalewicz, Krzysztof; Jeziorski, Bogumił
2010-11-01
Explicitly correlated functions have been used since 1929, but initially only for two-electron systems. In 1960, Boys and Singer showed that if the correlating factor is of Gaussian form, many-electron integrals can be computed for general molecules. The capability of explicitly correlated Gaussian (ECG) functions to accurately describe many-electron atoms and molecules was demonstrated only in the early 1980s when Monkhorst, Zabolitzky and the present authors cast the many-body perturbation theory (MBPT) and coupled cluster (CC) equations as a system of integro-differential equations and developed techniques of solving these equations with two-electron ECG functions (Gaussian-type geminals, GTG). This work brought a new accuracy standard to MBPT/CC calculations. In 1985, Kutzelnigg suggested that the linear r 12 correlating factor can also be employed if n-electron integrals, n > 2, are factorised with the resolution of identity. Later, this factor was replaced by more general functions f (r 12), most often by ? , usually represented as linear combinations of Gaussian functions which makes the resulting approach (called F12) a special case of the original GTG expansion. The current state-of-art is that, for few-electron molecules, ECGs provide more accurate results than any other basis available, but for larger systems the F12 approach is the method of choice, giving significant improvements over orbital calculations.
Hartree-Fock electronic structure calculations for free atoms and immersed atoms in an electron gas
NASA Astrophysics Data System (ADS)
Walsh, Kenneth Charles
Electronic structure calculations for free and immersed atoms are performed in the context of unrestricted Hartree-Fock Theory. Spherical symmetry is broken, lifting degeneracies in electronic configurations involving the magnetic quantum number mℓ. Basis sets, produced from density functional theory, are then explored for completeness. Comparison to spectroscopic data is done by a configurational interaction of the appropriate L and S symmetry. Finally, a perturbation technique by Lowdin is used to couple the bound atomic states to a neutral, uniform background electronic gas (jellium).
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.
Calculation of exchange integrals and electronic structure for manganese ferrite
NASA Astrophysics Data System (ADS)
Zuo, Xu; Vittoria, Carmine
2002-11-01
The electrical and magnetic properties of manganese ferrite (MnFe2O4) are calculated with the density-functional theory (DFT) method for both normal and inverse spinel structures. The exchange functional is chosen to be a mixture of Becke exchange and Fock exchange with variable weight (w). The exchange integrals JAB (the exchange integral between the nearest-neighbor A and B sites) and JBB (the exchange integral between nearest-neighbor B sites) are calculated by substituting the total energies of different magnetic ground states into the Heisenberg model. The calculated value of JAB is in agreement with the experimental values measured by neutron diffraction and NMR. Also, the parameters U (Coulomb repulsion energy), Δ (charge-transfer energy), and EG (band gap) are extracted from the density of states (DOS) and plotted versus w. Our calculated band gap shows that MnFe2O4 is a complex insulator, in contrast to previous local spin-density approximation and generalized gradient approximation calculations, which showed it to be half metallic.
Cluster calculations of the electronic structure of copper oxide superconductors
Wang Yujuin.
1990-01-01
A semiempirical INDO model suitable for examination of the transition metal complexes is used to study the electronic structure of various clusters representing the La-Sr-Cu-O and Nd-Ce-Cu-O types of the high-{Tc} superconductors. The clusters are stabilized by embedding in an appropriate Madelung field. The results show a convergent picture independent of the cluster sizes. In the undoped clusters, all copper sites have a {approximately} d{sup 9} configuration with one unpaired spin coupled antiferromagnetically to the spin of adjacent Cu sites. Fitting the resulting energies to the Heisenberg spin Hamiltonian, the superexchange J values obtained were in excellent agreement with experiments. The hole carriers are mainly of planar O character, while the electron carriers are of Cu character.
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.
Unfolding method for first-principles LCAO electronic structure calculations
NASA Astrophysics Data System (ADS)
Lee, Chi-Cheng; Yamada-Takamura, Yukiko; Ozaki, Taisuke
2013-08-01
Unfolding the band structure of a supercell to a normal cell enables us to investigate how symmetry breakers such as surfaces and impurities perturb the band structure of the normal cell. We generalize the unfolding method, originally developed based on Wannier functions, to the linear combination of atomic orbitals (LCAO) method, and present a general formula to calculate the unfolded spectral weight. The LCAO basis set is ideal for the unfolding method because the basis functions allocated to each atomic species are invariant regardless of the existence of surface and impurity. The unfolded spectral weight is well defined by the property of the LCAO basis functions. In exchange for the property, the non-orthogonality of the LCAO basis functions has to be taken into account. We show how the non-orthogonality can be properly incorporated in the general formula. As an illustration of the method, we calculate the dispersive quantized spectral weight of a ZrB2 slab and show strong spectral broadening in the out-of-plane direction, demonstrating the usefulness of the unfolding method.
Unfolding method for first-principles LCAO electronic structure calculations.
Lee, Chi-Cheng; Yamada-Takamura, Yukiko; Ozaki, Taisuke
2013-08-28
Unfolding the band structure of a supercell to a normal cell enables us to investigate how symmetry breakers such as surfaces and impurities perturb the band structure of the normal cell. We generalize the unfolding method, originally developed based on Wannier functions, to the linear combination of atomic orbitals (LCAO) method, and present a general formula to calculate the unfolded spectral weight. The LCAO basis set is ideal for the unfolding method because the basis functions allocated to each atomic species are invariant regardless of the existence of surface and impurity. The unfolded spectral weight is well defined by the property of the LCAO basis functions. In exchange for the property, the non-orthogonality of the LCAO basis functions has to be taken into account. We show how the non-orthogonality can be properly incorporated in the general formula. As an illustration of the method, we calculate the dispersive quantized spectral weight of a ZrB2 slab and show strong spectral broadening in the out-of-plane direction, demonstrating the usefulness of the unfolding method. PMID:23912816
O(N) methods in electronic structure calculations
NASA Astrophysics Data System (ADS)
Bowler, D. R.; Miyazaki, T.
2012-03-01
Linear-scaling methods, or O(N) methods, have computational and memory requirements which scale linearly with the number of atoms in the system, N, in contrast to standard approaches which scale with the cube of the number of atoms. These methods, which rely on the short-ranged nature of electronic structure, will allow accurate, ab initio simulations of systems of unprecedented size. The theory behind the locality of electronic structure is described and related to physical properties of systems to be modelled, along with a survey of recent developments in real-space methods which are important for efficient use of high-performance computers. The linear-scaling methods proposed to date can be divided into seven different areas, and the applicability, efficiency and advantages of the methods proposed in these areas are then discussed. The applications of linear-scaling methods, as well as the implementations available as computer programs, are considered. Finally, the prospects for and the challenges facing linear-scaling methods are discussed.
Wood, R.F.; Wilson, T.M.
1981-01-01
The structure of the Hartree-Fock one-electron equations for simple point defects in ionic crystals are discussed. The importance of polarization effects due to the diffuse nature of the wavefunctions in the relaxed excited states are emphasized, and the usefulness of an effective mass approximation indicated. Several approaches to the calculation of the electronic structure are discussed and evaluated. The connection between electronic structure calculations and phonon perturbations are pointed out through a brief discussion of localized perturbation theory.
Electronic Structure Calculation of Permanent Magnets using the KKR Green's Function Method
NASA Astrophysics Data System (ADS)
Doi, Shotaro; Akai, Hisazumi
2014-03-01
Electronic structure and magnetic properties of permanent magnetic materials, especially Nd2Fe14B, are investigated theoretically using the KKR Green's function method. Important physical quantities in magnetism, such as magnetic moment, Curie temperature, and anisotropy constant, which are obtained from electronics structure calculations in both cases of atomic-sphere-approximation and full-potential treatment, are compared with past band structure calculations and experiments. The site preference of heavy rare-earth impurities are also evaluated through the calculation of formation energy with the use of coherent potential approximations. Further, the development of electronic structure calculation code using the screened KKR for large super-cells, which is aimed at studying the electronic structure of realistic microstructures (e.g. grain boundary phase), is introduced with some test calculations.
Electronic Structure Calculations of delta-Pu Based Alloys
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. %.
Electronic structure calculations on lithium battery electrolyte salts.
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
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.
Two-particle picture and electronic structure calculations
Gonis, A; Schulthess, T C; Turchi, P E A
1998-06-24
We derive exact formal expressions for the self-energy, (capital Sigma ^{(n)}, describing the in- teraction of n particles with one another and with the rest of the particles in an interacting quantum N-particle system In contrast to traditional treatments, in which the single-particle self-energy is built out of interactions of a particle with the rest of the system, here a general n-particle quantity, (capital sigma)^{(n)}, is obtained in a straight- forward fashion by integrating the exact N-particle Green function, G^{(N)}, over the coordinates of N ^{_} n particles and inverting An alternative expression, based on the canonical many-body equation of motion for the Green function is also discussed and compared with that derived through the integration process. The methodology is developed with respect to two-particle states, with the two-particle Green function being the central quantity from which the single-particle self-energy and Green function are derived It is suggested that the two-particle Green function be calculated directly in six-dimensional space in a two-particle generalization of density functional theory and the corresponding local density approximation. Methods for the calculation of the single-particle, n = 1, self-energy and effective single-particle t-matrix are discussed, and the methodology is illustrated by means of calculations on a model system.
Lagrange-Function Approach to Real-Space Order-N Electronic-Structure Calculations
Varga, Kalman; Pantelides, Sokrates T
2006-01-01
The Lagrange functions are a family of analytical, complete, and orthonormal basis sets that are suitable for efficient, accurate, real-space, order-N electronic-structure calculations. Convergence is controlled by a single monotonic parameter, the dimension of the basis set, and computational complexity is lower than that of conventional approaches. In this paper we review their construction and applications in linearscaling electronic-structure calculations.
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).
Hybrid functional calculation of electronic and phonon structure of BaSnO{sub 3}
Kim, Bog G.; Jo, J.Y.; Cheong, S.W.
2013-01-15
Barium stannate, BaSnO{sub 3} (BSO), with a cubic perovskite structure, has been highlighted as a promising host material for the next generation transparent oxide electrodes. This study examined theoretically the electronic structure and phonon structure of BSO using hybrid density functional theory based on the HSE06 functional. The electronic structure results of BSO were corrected by extending the phonon calculations based on the hybrid density functional. The fundamental thermal properties were also predicted based on a hybrid functional calculation. Overall, a detailed understanding of the electronic structure, phonon modes and phonon dispersion of BSO will provide a theoretical starting-point for engineering applications of this material. - Graphical Abstract: (a) Crystal structure of BaSnO{sub 3}. The center ball is Ba and small (red) ball on edge is oxygen and SnO{sub 6} octahedrons are plotted as polyhedron. (b) Electronic band structure along the high symmetry point in the Brillouin zone using the HSE06 hybrid functional. (c) The phonon dispersion curve calculated using the HSE06 hybrid functional (d) Zone center lowest energy F{sub 1u} phonon mode. Highlights: Black-Right-Pointing-Pointer We report the full hybrid functional calculation of not only the electronic structure but also the phonon structure for BaSnO{sub 3}. Black-Right-Pointing-Pointer The band gap calculation of HSE06 revealed an indirect gap with 2.48 eV. Black-Right-Pointing-Pointer The effective mass at the conduction band minimum and valence band maximum was calculated. Black-Right-Pointing-Pointer In addition, the phonon structure of BSO was calculated using the HSE06 functional. Black-Right-Pointing-Pointer Finally, the heat capacity was calculated and compared with the recent experimental result.
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
Electronic structure calculations of vacancies and their influence on materials properties
Sterne, P.A.; Van Ek, J.; Howell, R.H.
1997-08-01
We provide two examples to illustrate how electronic structure calculations contribute to our understanding of vacancies and their role in determining material properties. Diffusion and elctromigration in aluminium are known to depend strongly on vacancies. Electronic structure calculations show that the vacancy-impurity interaction oscillates with distance, and this leads to an explanation for both the increased elctromigration resistance and the slow impurity diffusion for copper in aluminium. Calculations of vacancies in plutonium have been used in conjunction with positron annihilation lifetime measurements to identify the presence of helium-filled vacanies. Helium stabilization of vacancies can provide the precursors for subsequent vacancy-related changes in materials properties.
Regularizing the molecular potential in electronic structure calculations. II. Many-body methods
Bischoff, Florian A.
2014-11-14
In Paper I of this series [F. A. Bischoff, “Regularizing the molecular potential in electronic structure calculations. I. SCF methods,” J. Chem. Phys. 141, 184105 (2014)] a regularized molecular Hamilton operator for electronic structure calculations was derived and its properties in SCF calculations were studied. The regularization was achieved using a correlation factor that models the electron-nuclear cusp. In the present study we extend the regularization to correlated methods, in particular the exact solution of the two-electron problem, as well as second-order many body perturbation theory. The nuclear and electronic correlation factors lead to computations with a smaller memory footprint because the singularities are removed from the working equations, which allows coarser grid resolution while maintaining the precision. Numerical examples are given.
NASA Astrophysics Data System (ADS)
Ghosh, Binita; Halder, Saswata; Das, Sayantani; Sinha, T. P.
2016-05-01
Europium-doped luminescent barium samarium tantalum oxide Ba2SmTaO6 (BST) has been investigated by first-principles calculation, and the crystal structure, electronic structure, and optical properties of pure BST and Eu-doped BST have been examined and compared. Based on the calculated results, the luminescence properties and mechanism of Eu-doped BST has been discussed. In the case of Eu-doped BST, there is an impurity energy band at the Fermi level, which is formed by seven spin up energy levels of Eu and act as the luminescent centre, which is evident from the band structure calculations.
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.
Variational quantum Monte Carlo calculation of electronic and structural properties of crystals
Louie, S.G.
1989-09-01
Calculation of the electronic and structural properties of solids using a variational quantum Monte Carlo nonlocal pseudopotential approach is described. Ionization potentials and electron affinities for atoms, and binding energies and structural properties for crystals are found to be in very good agreement with experiment. The approach employs a correlated many-electron wavefunction of the Jastrow-Slater form and the exact Coulomb interaction between valence electrons. One- and two-body terms in the Jastrow factor are used and found necessary for an accurate description of the electron-electron energy for the systems considered. The method has further been applied to compute various single-particle properties for solids including the single-particle orbital occupancy, electron pair correlation functions, and quasiparticle excitation energies. 23 refs., 3 figs., 3 tabs.
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.
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.
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.
Structure and properties of electronic and hole centers in CsBr from theoretical calculations
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.
Atomic and Electronic Structures of C_60+BN Nanopeapods from ab initio Pseudopotential Calculations
NASA Astrophysics Data System (ADS)
Trave, Andrea; Ribeiro, Filipe; Louie, Steven G.; Cohen, Marvin L.
2004-03-01
Nanopeapods are structures of nanometric size consisting of an external carbon nanotube encapsulating a chain or complex array of fullerenes. Recent calculations and experiments have proven that nanopeapods can be obtained assembling fullerenes within boron nitride nanotubes, creating novel materials of possible interest for electronic transport applications. To improve the understanding of the properties of these composite systems, as compared to empty nanotubes and carbon nanopeapods, ab-initio total energy calculations have been performed within the pseudopotential Density Functional Theory in local density approximation. Results of these calculations on the energetics and geometrical deformations involved in the encapsulation will be presented, followed by a discussion of the consequences on the electronic structures of these systems, with particular focus on aspects relevant to electronic transport phenomena. This work is supported by NFS (Grant DMR00-87088) and DOE (Contract DE-AC03-76SF00098), using computational resources at NERSC and NPACI.
Dissociative recombination of interstellar ions: electronic structure calculations for HCO/sup +/
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.
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.
Moreno, M. S.; Egerton, R.F.; Rehr, J.J.; Midgley, P.A.
2005-01-15
The electronic structure of the tin oxides SnO and SnO{sub 2} is studied using the fine structure of the Sn-M{sub 4,5} and oxygen K-edges measured by electron energy loss spectroscopy (EELS). The experimental results are compared with real-space multiple scattering calculations. It is observed that both edges are overlapped. The calculations reveal that the observed fine structure is due largely to the oxygen states, and that it can be used to fingerprint each phase. The calculated densities of states are similar for both compounds and suggest a covalent nature. The structures appearing within the first 10 eV above the threshold arise from a covalent mixing of mainly O 2p and Sn 5s-p. For SnO the oxygen edge is satisfactorily reproduced. Discrepancies in the predicted energy position of the features in the EELS of SnO{sub 2} are briefly discussed.
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.
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.
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.
Flocke, N; Lotrich, V
2008-12-01
For the new parallel implementation of electronic structure methods in ACES III (Lotrich et al., in preparation) the present state-of-the-art algorithms for the evaluation of electronic integrals and their generalized derivatives were implemented in new object oriented codes with attention paid to efficient execution on modern processors with a deep hierarchy of data storage including multiple caches and memory banks. Particular attention has been paid to define proper integral blocks as basic building objects. These objects are stand-alone units and are no longer tied to any specific software. They can hence be used by any quantum chemistry code without modification. The integral blocks can be called at any time and in any sequence during the execution of an electronic structure program. Evaluation efficiency of these integral objects has been carefully tested and it compares well with other fast integral programs in the community. Correctness of the objects has been demonstrated by several application runs on real systems using the ACES III program. PMID:18496792
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.
Relativistic atomic structure calculations and electron impact excitations of Fe23+
NASA Astrophysics Data System (ADS)
El-Maaref, A. A.
2016-02-01
Relativistic calculations using the multiconfiguration Dirac-Fock method for energy levels, oscillator strengths, and electronic dipole transition probabilities of Li-like iron (Fe23+) are presented. A configuration state list with the quantum numbers nl, where n = 2 - 7 and l = s , p , d , f , g , h , i has been considered. Excitations up to three electrons and correlation contributions from higher orbitals up to 7 l have been included. Contributions from core levels have been taken into account, EOL (extended optimal level) type calculations have been applied, and doubly excited levels are considered. The calculations have been executed by using the fully relativistic atomic structure package GRASP2K. The present calculations have been compared with the available experimental and theoretical sources, the comparisons show a good agreement between the present results of energy levels and oscillator strengths with the literature. In the second part of the present study, the atomic data (energy levels, and radiative parameters) have been used to calculate the excitation and deexcitation rates of allowed transitions by electron impact, as well as the population densities of some excited levels at different electron temperatures.
HARES: an efficient method for first-principles electronic structure calculations of complex systems
NASA Astrophysics Data System (ADS)
Waghmare, U. V.; Kim, Hanchul; Park, I. J.; Modine, Normand; Maragakis, P.; Kaxiras, Efthimios
2001-07-01
We discuss our new implementation of the Real-space Electronic Structure method for studying the atomic and electronic structure of infinite periodic as well as finite systems, based on density functional theory. This improved version which we call HARES (for High-performance-Fortran Adaptive grid Real-space Electronic Structure) aims at making the method widely applicable and efficient, using high performance Fortran on parallel architectures. The scaling of various parts of a HARES 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. We illustrate the application of HARES to the study of elemental crystalline solids, molecules and complex crystalline materials, such as blue bronze and zeolites.
NASA Astrophysics Data System (ADS)
Suleiman, Mohammed S. H.; Joubert, Daniel P.
2015-11-01
In the present work, the atomic and the electronic structures of Au3N, AuN and AuN2 are investigated using first-principles density-functional theory (DFT). We studied cohesive energy vs. volume data for a wide range of possible structures of these nitrides. Obtained data were fitted to a Birch-Murnaghan third-order equation of state (EOS) so as to identify the most likely candidates for the true crystal structure in this subset of the infinite parameter space, and to determine their equilibrium structural parameters. The analysis of the electronic properties was achieved by the calculations of the band structure and the total and partial density of states (DOS). Some possible pressure-induced structural phase transitions have been pointed out. Further, we carried out GW0 calculations within the random-phase approximation (RPA) to the dielectric tensor to investigate the optical spectra of the experimentally suggested modification: Au3N(D09). Obtained results are compared with experiment and with some available previous calculations.
Density functional calculation of the structural and electronic properties of germanium quantum dots
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.
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.
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.
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.
Eberhart, M.E.; Woodward, C.; Giamei, A.F.
1999-08-01
Extracting full information from electronic structure calculations requires the ability to compare differences in bonding between two molecules or solids. Often these comparisons use qualitative models of the chemical bond in an unsuccessful attempt to account for subtle variations in molecular properties. Correlating electronic structure with properties requires an unambiguous and quantifiable description of the chemical bond. Here, the authors show that such a description is contained within the geometric properties of the charge density, which can be obtained from quantum mechanical calculations. This description is used to rationalize the previously unexplained variation in the mechanical properties of a series of ordered intermetallic alloys. The ease with which this description of chemical bonding can be applied to problems, which have defied simple bonding explanations, suggests that it may be useful in accounting for the properties of any molecular system which arise from the making, breaking, or rearrangement of bonds.
Multi-Center Electronic Structure Calculations for Plasma Equation of State
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.
Hao, Yajiang; Inhester, Ludger; Hanasaki, Kota; Son, Sang-Kil; Santra, Robin
2015-07-01
We present the implementation of an electronic-structure approach dedicated to ionization dynamics of molecules interacting with x-ray free-electron laser (XFEL) pulses. In our scheme, molecular orbitals for molecular core-hole states are represented by linear combination of numerical atomic orbitals that are solutions of corresponding atomic core-hole states. We demonstrate that our scheme efficiently calculates all possible multiple-hole configurations of molecules formed during XFEL pulses. The present method is suitable to investigate x-ray multiphoton multiple ionization dynamics and accompanying nuclear dynamics, providing essential information on the chemical dynamics relevant for high-intensity x-ray imaging. PMID:26798806
Efficient electronic structure calculation for molecular ionization dynamics at high x-ray intensity
Hao, Yajiang; Inhester, Ludger; Hanasaki, Kota; Son, Sang-Kil; Santra, Robin
2015-01-01
We present the implementation of an electronic-structure approach dedicated to ionization dynamics of molecules interacting with x-ray free-electron laser (XFEL) pulses. In our scheme, molecular orbitals for molecular core-hole states are represented by linear combination of numerical atomic orbitals that are solutions of corresponding atomic core-hole states. We demonstrate that our scheme efficiently calculates all possible multiple-hole configurations of molecules formed during XFEL pulses. The present method is suitable to investigate x-ray multiphoton multiple ionization dynamics and accompanying nuclear dynamics, providing essential information on the chemical dynamics relevant for high-intensity x-ray imaging. PMID:26798806
A new class of atomic basis functions for accurate electronic structure calculations of molecules
NASA Astrophysics Data System (ADS)
Laikov, Dimitri N.
2005-11-01
A new general approach is developed for obtaining systematic sequences of atomic single-particle basis sets for use in correlated electronic structure calculations of molecules. All the constituent functions are defined as the solutions of variational problems and are of three types: a minimal Hartree-Fock set, additional functions to represent low-lying excited configurations, and general functions for describing electron correlation. The latter are determined to minimize a functional derived from the closed-shell second-order correlation energy expression. Generally-contracted Gaussian expansions are developed to approximate these general functions in the non-relativistic case and within a scalar-relativistic approximation.
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.
A novel Gaussian-Sinc mixed basis set for electronic structure calculations.
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
A novel Gaussian-Sinc mixed basis set for electronic structure calculations
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.
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}
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.
Yang, Wenjuan; Wen, Yanwei; Chen, Rong; Zeng, Dawen; Shan, Bin
2014-10-21
First-principle calculations have been carried out to investigate structural stabilities, electronic structures and optical properties of tungsten doped bismuth oxychloride (BiOCl). The structures of substitutional and interstitial tungsten, and in the form of WO6-ligand-doped BiOCl are examined. The substitutional and interstitial tungsten doping leads to discrete midgap states within the forbidden band gap, which has an adverse effect on the photocatalytic properties. On the other hand, the WO6-ligand-doped BiOCl structure induces a continuum of hybridized states in the forbidden gap, which favors transport of electrons and holes and could result in enhancement of visible light activity. In addition, the band gap of WO6-BiOCl decreases by 0.25 eV with valence band maximum (VBM) shifting upwards compared to that of pure BiOCl. By calculating optical absorption spectra of pure BiOCl and WO6-ligand-doped BiOCl structure, it is found that the absorption peak of the WO6-ligand-doped BiOCl structure has a red shift towards visible light compared with that of pure BiOCl, which agrees well with experimental observations. These results reveal the tungsten doped BiOCl system as a promising material in photocatalytic decomposition of organics and water splitting under sunlight irradiation. PMID:25179434
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.
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. PMID:26677725
Mehrabova, M. A. Madatov, R. S.
2011-08-15
The Green's functions theory and the bond-orbital model are used as a basis for calculations of the electron structure of local defects-specifically, vacancies and their compensated states in III-VI semiconductors. The energy levels in the band gap are established, and the changes induced in the electron densities in the GaS, GaSe, and InSe semiconductors by anion and cation vacancies and their compensated states are calculated. It is established that, if a vacancy is compensated by an atom of an element from the same subgroup with the same tetrahedral coordination and if the ionic radius of the compensating atom is smaller than that of the substituted atom, the local levels formed by the vacancy completely disappear. It is shown that this mechanism of compensation of vacancies provides a means not only for recovering the parameters of the crystal, but for improving the characteristics of the crystal as well.
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.
Nekrashevich, S. S. Gritsenko, V. A.; Klauser, R.; Gwo, S.
2010-10-15
Charge transfer {Delta}Q = 0.35e at the Si-N bond in silicon nitride is determined experimentally using photoelectron spectroscopy, and the ionic formula of silicon nitride Si{sub 3}{sup +1.4}N{sub 4}{sup -1.05} is derived. The electronic structure of {alpha}-Si{sub 3}N{sub 4} is studied ab initio using the density functional method. The results of calculations (partial density of states) are compared with experimental data on X-ray emission spectroscopy of amorphous Si{sub 3}N{sub 4}. The electronic structure of the valence band of amorphous Si{sub 3}N{sub 4} is studied using synchrotron radiation at different excitation energies. The electron and hole effective masses m{sub e}{sup *} {approx} m{sub h}{sup *} {approx} 0.5m{sub e} are estimated theoretically. The calculated values correspond to experimental results on injection of electrons and holes into silicon nitride.
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.
Effect of tensile strain on the electronic structure of Ge: A first-principles calculation
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.
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.
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).
Genovese, Luigi; Deutsch, Thierry
2015-12-21
Discretizing an analytic function on a uniform real-space grid is often done via a straightforward collocation method. This is ubiquitous in all areas of computational physics and quantum chemistry. An example in density functional theory (DFT) is given by the external potential or the pseudo-potential describing the interaction between ions and electrons. The accuracy of the collocation method used is therefore very important for the reliability of subsequent treatments like self-consistent field solutions of the electronic structure problems. By construction, the collocation method introduces numerical artifacts typical of real-space treatments, like the so-called egg-box error, which may spoil the numerical stability of the description when the real-space grid is too coarse. As the external potential is an input of the problem, even a highly precise computational treatment cannot cope this inconvenience. We present in this paper a new quadrature scheme that is able to exactly preserve the moments of a given analytic function even for large grid spacings, while reconciling with the traditional collocation method when the grid spacing is small enough. In the context of real-space electronic structure calculations, we show that this method improves considerably the stability of the results for large grid spacings, opening up the path towards reliable low-accuracy DFT calculations with a reduced number of degrees of freedom. PMID:26372293
A Linear Scaling Three Dimensional Fragment Method for Large ScaleElectronic Structure Calculations
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.
A LDA calculation of the conformation and electronic structure of polyfluoroethylenes
Miao, M.S.; Van Camp, P.E.; Van Doren, V.E.
1996-12-31
Two different local density approximation (X{alpha} and Kohn-Sham exchange and Perdew-Zunger correlation) of the density funcitonal method have been used to calculate structural and electronic properties of six kinds of polyfluoroethylene, including polytetrafluoroethylene (PTFE), poly(1,2-difluorethylene) (PDFE), and others, for several different dihedral angles. For PTFE and PDFE, all the geometric parameters are optimized simultaneously in the stable helical conformation. The position of the minimum and the depth of the potential well are in good agreement with the experimental results. The stable helical conformation are found for PTFE and PDFE. For PDFE a shoulder close to the stable gauche conformation is found in the energy curve. The potential curves of another four kinds of polyfluorethylene are studied in detail close to the planar conformation. The side fluorine atoms strongly affect the conformation and the electronic structure. The band structure of PTFE and PDFE in optimized geometry and the other PFEs in planar zigzag conformation are calculated in good agreement with experimental results.
NASA Astrophysics Data System (ADS)
Chen, Hai-Hua; Bi, Yan; Cheng, Yan; Ji, Guangfu; Cai, Lingcang
2012-10-01
The elastic properties, electronic structure and thermodynamic behavior of the TaB have been investigated for the first time in this work. Using first-principles plane-wave ultrasoft-pseudopotential density functional theory (DFT), the ground state properties and equation of state of TaB have been obtained. The average zero-pressure bulk modulus of TaB is 302 GPa. By analyzing the elastically anisotropic behavior and the relative structure parameters of TaB, we found that the crystal cell along the b-axis was more compressible than along the a and c axes. The calculated ratio of bulk modulus and shear modulus (B/G) for TaB is 1.58, demonstrating that TaB is rather brittle. From the elastic stiffness constants, we found that TaB in the Cmcm phase is mechanically stable. The calculated hardness of TaB is 28.6 GPa which is close to the previous data. Moreover, using the Gibbs 2 model, the thermodynamic properties such as the thermal expansion and Debye temperature of TaB have been obtained firstly. At the ambient temperature, the Debye temperatures of TaB are 792 K and 845 K from GGA calculation and LDA calculation, respectively.
Linearly Scaling 3D Fragment Method for Large-Scale Electronic Structure Calculations
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.
Francisco, Juliano B; Martínez, José Mario; Martínez, Leandro
2004-12-01
As far as more complex systems are being accessible for quantum chemical calculations, the reliability of the algorithms used becomes increasingly important. Trust-region strategies comprise a large family of optimization algorithms that incorporates both robustness and applicability for a great variety of problems. The objective of this work is to provide a basic algorithm and an adequate theoretical framework for the application of globally convergent trust-region methods to electronic structure calculations. Closed shell restricted Hartree-Fock calculations are addressed as finite-dimensional nonlinear programming problems with weighted orthogonality constraints. A Levenberg-Marquardt-like modification of a trust-region algorithm for constrained optimization is developed for solving this problem. It is proved that this algorithm is globally convergent. The subproblems that ensure global convergence are easy-to-compute projections and are dependent only on the structure of the constraints, thus being extendable to other problems. Numerical experiments are presented, which confirm the theoretical predictions. The structure of the algorithm is such that accelerations can be easily associated without affecting the convergence properties. PMID:15634038
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.
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.
NASA Astrophysics Data System (ADS)
Nagabalasubramanian, P. B.; Periandy, S.; Karabacak, Mehmet; Govindarajan, M.
2015-06-01
The solid phase FT-IR and FT-Raman spectra of 4-vinylcyclohexene (abbreviated as 4-VCH) have been recorded in the region 4000-100 cm-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.
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. PMID:25795608
Tensor decomposition in electronic structure calculations on 3D Cartesian grids
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.
Polfus, Jonathan M; Bjørheim, Tor S; Norby, Truls; Haugsrud, Reidar
2012-09-01
The nitrogen related defect chemistry and electronic structure of wide band gap oxides are investigated by density functional theory defect calculations of N(O)(q), NH(O)(×), and (NH2)(O)(·) as well as V(O)(··) and OH(O)(·) in MgO, CaO, SrO, Al(2)O(3), In(2)O(3), Sc(2)O(3), Y(2)O(3), La(2)O(3), TiO(2), SnO(2), ZrO(2), BaZrO(3), and SrZrO(3). The N(O)(q) acceptor level is found to be deep and the binding energy of NH(O)(×) with respect to N(O)' and (OH(O)(·) is found to be significantly negative, i.e. binding, in all of the investigated oxides. The defect structure of the oxides was found to be remarkably similar under reducing and nitriding conditions (1 bar N(2), 1 bar H(2) and 1 × 10(-7) bar H(2)O): NH(O)(×) predominates at low temperatures and [N(O)'] = 2[V(O)(··) predominates at higher temperatures (>900 K for most of the oxides). Furthermore, we evaluate how the defect structure is affected by non-equilibrium conditions such as doping and quenching. In terms of electronic structure, N(O)' is found to introduce isolated N-2p states within the band gap, while the N-2p states of NH(O)(×) are shifted towards, or overlap with the VBM. Finally, we assess the effect of nitrogen incorporation on the proton conducting properties of oxides and comment on their corrosion resistance in nitriding atmospheres in light of the calculated defect structures. PMID:22828729
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.
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
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.
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
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.
Quantum Monte Carlo calculations of structural and electronic properties in the correlated oxide NiO
NASA Astrophysics Data System (ADS)
Mitra, Chandrima; Krogel, Jaron; Santana Palacio, Juan A.; Reboredo, Fernando A.
2015-03-01
Transition metal oxides pose difficulties for condensed matter theories due to the presence of strong electronic correlations. The complex interplay among correlation and exchange in d subshells, crystal field effects, p-d hybridization and charge transfer gives rise to a rich variety of structural and electronic phases. NiO is one such challenging d system, where conventional band theory fails. Compared to the experimental value, the cohesive energy of bulk NiO computed within DFT-LDA differs by almost a factor of 18 %. Band gap computed within standard local or semi-local functionals are off by a factor of 80 %. A quasi-particle correction like the G0W0 approach cannot correct the band gap and is still by far too low. In this work we adopt the Diffusion Quantum Monte (DMC) approach to study the structural and electronic properties of NiO. Trial wave-functions were self consistently generated in a Slater-Jastrow form. To test pseudopotentials used, DMC calculations were done on atomic Ni and O and their computed ionization potentials showed excellent agreement with experiments (within 0.04%). The equilibrium bond length and binding energy of the NiO dimer were also computed that were 0.001% and 0.03%, respectively, from experimental values. DMC calculations of equation of state and band gap of bulk NiO will be presented. We gratefully acknowledge support from U.S Department of Energy, Basic Energy Sciences, Materials Science and Engineering Division.
Ab initio calculation of structural stability, electronic and optical properties of Ag{sub 2}Se
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.
Atomic-scale calculations of interfacial structures and their properties in electronic materials
NASA Astrophysics Data System (ADS)
Liang, Tao
With the tremendous increase in computational power over the last two decades as well as the continuous shrinkage of Si-based Metal Oxide Semiconductor Field Effect Transistors (MOSFET), quantum mechanically based ab initio methods become indispensable tools in nano-scale device engineering. In this work, atomistic simulations including ab initio, nudged elastic band (NEB) and kinetic Monte Carlo methods have been used to (1) calculate the dopant segregation energy at silicon/gate oxide interfaces; (2) characterize the Si:Ge/SiO2 interfacial structure; (3) study the effects of impurity atoms on the diffusion process at Al and Al(Cu) grain boundaries. Using VASP, an ab initio simulation package, we calculated B segregation energy at different atomic sites in perfect and defected Si/SiO 2 interfaces and arsenic segregation energy in Si/LaAlO3 structures. With the presence of O vacancies and H in B doped systems, the predicted segregation energy is 0.85 eV for neutral systems and 1.12 eV for negatively charged systems, which is consistent with experimental measurements (0.51 to 1.47 eV). Recent ab initio structure calculations have examined the stability of various Si(001)/LaAlO3 interfaces and find that a LaO terminated interface with La deficiency or perfect stoichiometry depending on oxygen partial pressure has the lowest energy. Focussing on the La deficient Si/LaAlO3 interfacial structure, we find that the arsenic prefers energetically not to segregate into LaAlO3 nor does it pile up in front of the interface. In combation of atomic-resolution Z-contrast imaging and electron energy loss spectroscopy (EELS), we theorectically calculated the band structure and EELS of a Ge/SiO2 interface. We actually found a chemically abrupt Ge/SiO2 interface, which has never been reported before and which is quite desirable for applications. Furthermore, we formulated a kinetic Monte Carlo model to simulate the oxidation process of Ge ion-implanted Si. Our modeling suggests the
NASA Astrophysics Data System (ADS)
D'Yachkov, P. N.; Makaev, D. V.
2006-10-01
Electronic structure of double-wall carbon nanotubes (DWNTs) consisting of two concentric graphene cylinders with extremely strong covalent bonding of atoms within the individual graphitic sheets, but very weak van der Waals type interaction between them is calculated in the terms of the linear augmented cylindrical wave (LACW) method. A one-electron potential is used and the approximations are made in the sense of muffin-tin (MT) potentials and local density functional theory only. The atoms of DWNT are considered to be enclosed between cylinder-shaped potential barriers. In this approach, the electronic spectrum of the DWNTs is governed by the free movement of electron in the interatomic space of two cylindrical layers, by electron scattering on the MT spheres, and by electron tunneling between the layers. We have calculated the complete band structures and densities of states in the Fermi level region of the purely semiconducting zigzag DWNTs (n,0)@(n',0) ( 10⩽n⩽23 and 19⩽n'⩽32 ) with interlayer distance 3.2Å⩽Δd⩽3.7Å . Analogously data are obtained for metallic armchair (n,n)@(n',n') nanotubes ( n=5 or 4 and n'=10 or 9). According to the LACW calculations, the interwall coupling results in a distinctly stronger perturbation of the band structure of inner tube as compared to that of the outer one. In the case of semiconducting DWNTs, the minimum gap E11 between the singularities of the conduction and valence bands of the shell tubules decreases from 0.15to0.22eV or increases from 0.7to0.15eV , if dividing n' by three leaves a remainder of 1 or 2, respectively. In both cases, the ΔE11 shifts of the gap do not decay, but slightly oscillate as one goes to the tubules with larger diameters d . For inner tubules, the ΔE11 shift depends strongly on the d . For nmod3=2 series with 10⩽n⩽16 , the shifts ΔE11 are positive, the maximum values of ΔE11 being equal to 0.39 and 0.32eV , respectively. As one goes to the inner tubules with larger diameters
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.
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.
Model creation and electronic structure calculation of amorphous hydrogenated boron carbide
NASA Astrophysics Data System (ADS)
Belhadj Larbi, Mohammed
Boron-rich solids are of great interest for many applications, particularly, amorphous hydrogenated boron carbide (a-BC:H) thin films are a leading candidate for numerous applications such as: heterostructure materials, neutron detectors, and photovoltaic energy conversion. Despite this importance, the local structural properties of these materials are not well-known, and very few theoretical studies for this family of disordered solids exist in the literature. In order to optimize this material for its potential applications the structure property relationships need to be discovered. We use a hybrid method in this endeavor---which is to the best of our knowledge the first in the literature---to model and calculate the electronic structure of amorphous hydrogenated boron carbide (a-BC:H). A combination of classical molecular dynamics using the Large-scale Atomic/Molecular Massively Parallel Simulator (LAMMPS) and ab initio quantum mechanical simulations using the Vienna ab initio simulation package (VASP) have been conducted to create geometry optimized models that consist of a disordered hydrogenated twelve-vertex boron carbide icosahedra, with hydrogenated carbon cross-linkers. Then, the density functional theory (DFT) based orthogonalized linear combination of atomic orbitals (OLCAO) method was used to calculate the total and partial density of states (TDOS, PDOS), the complex dielectric function epsilon, and the radial pair distribution function (RPDF). The RPDF data stand as predictions that may be compared with future experimental electron or neutron diffraction data. The electronic structure simulations were not able to demonstrate a band gap of the same nature as that seen in prior experimental work, a general trend of the composition-properties relationship was established. The content of hydrogen and boron was found to be directly proportional to the decrease in the number of available states near the fermi energy, and inversely proportional to the
NASA Astrophysics Data System (ADS)
Duy, Truong Vinh Truong; Ozaki, Taisuke
2014-03-01
With tens of petaflops supercomputers already in operation and exaflops machines expected to appear within the next 10 years, efficient parallel computational methods are required to take advantage of such extreme-scale machines. In this paper, we present a three-dimensional domain decomposition scheme for enabling large-scale electronic structure calculations based on density functional theory (DFT) on massively parallel computers. It is composed of two methods: (i) the atom decomposition method and (ii) the grid decomposition method. In the former method, we develop a modified recursive bisection method based on the moment of inertia tensor to reorder the atoms along a principal axis so that atoms that are close in real space are also close on the axis to ensure data locality. The atoms are then divided into sub-domains depending on their projections onto the principal axis in a balanced way among the processes. In the latter method, we define four data structures for the partitioning of grid points that are carefully constructed to make data locality consistent with that of the clustered atoms for minimizing data communications between the processes. We also propose a decomposition method for solving the Poisson equation using the three-dimensional FFT in Hartree potential calculation, which is shown to be better in terms of communication efficiency than a previously proposed parallelization method based on a two-dimensional decomposition. For evaluation, we perform benchmark calculations with our open-source DFT code, OpenMX, paying particular attention to the O(N) Krylov subspace method. The results show that our scheme exhibits good strong and weak scaling properties, with the parallel efficiency at 131,072 cores being 67.7% compared to the baseline of 16,384 cores with 131,072 atoms of the diamond structure on the K computer.
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.
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.
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.
GPAW - massively parallel electronic structure calculations with Python-based software.
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.
Electronic Structure Calculations and Adaptation Scheme in Multi-core Computing Environments
Seshagiri, Lakshminarasimhan; Sosonkina, Masha; Zhang, Zhao
2009-05-20
Multi-core processing environments have become the norm in the generic computing environment and are being considered for adding an extra dimension to the execution of any application. The T2 Niagara processor is a very unique environment where it consists of eight cores having a capability of running eight threads simultaneously in each of the cores. Applications like General Atomic and Molecular Electronic Structure (GAMESS), used for ab-initio molecular quantum chemistry calculations, can be good indicators of the performance of such machines and would be a guideline for both hardware designers and application programmers. In this paper we try to benchmark the GAMESS performance on a T2 Niagara processor for a couple of molecules. We also show the suitability of using a middleware based adaptation algorithm on GAMESS on such a multi-core environment.
Is C50 a superaromat? Evidence from electronic structure and ring current calculations.
Matías, Ana Sanz; Havenith, Remco W A; Alcamí, Manuel; Ceulemans, Arnout
2016-04-28
The fullerene-50 is a 'magic number' cage according to the 2(N + 1)(2) rule. For the three lowest isomers of C50 with trigonal and pentagonal symmetries, we calculate the sphericity index, the spherical parentage of the occupied π-orbitals, and the current density in an applied magnetic field. The minimal energy isomer, with D3 symmetry, comes closest to a spherical aromat or a superaromat. In the D5h bond-stretch isomers the electronic structure shows larger deviations from the ideal spherical shells, with hybridisation or even reversal of spherical parentages. It is shown that relative stabilities of fullerene cages do not correlate well with aromaticity, unlike the magnetic properties which are very sensitive indicators of spherical aromaticity. Superaromatic diamagnetism in the D3 cage is characterized by global diatropic currents, which encircle the whole cage. The breakdown of sphericity in the D5h cages gives rise to local paratropic countercurrents. PMID:26444568
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.
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
NASA Astrophysics Data System (ADS)
Takeshima, Tsuguhide; Takeuchi, Hiroshi; Egawa, Toru; Konaka, Shigehiro
2005-01-01
The molecular structure of arecoline (methyl 1,2,5,6-tetrahydro-1-methylnicotinate, ? has been determined by gas electron diffraction. Diffraction patterns were taken at about 370 K. Structural constraints for the data analysis were obtained from MP2/6-31G** calculations. Vibrational mean amplitudes and shrinkage corrections were calculated from the force constants obtained from the gas-phase vibrational frequencies and the B3LYP/6-31G** calculations. The electron diffraction data were well reproduced by assuming the mixture of four conformers. The determined structural parameters ( rg (Å) and ∠ (°)) for the main conformer with 3 σ in parentheses are as follows: < rg(N-C ring)>=1.456(4); rg(N-C methyl)=1.451 (d.p.); rg(C dbnd6 C)=1.339(9); < rg(C-C)>=1.512(3); rg(O-C methyl)=1.434(5); rg(C(O)-O)=1.355 (d.p.); rg(C dbnd6 O)=1.209(4); the out-of-plane angle of the methyl group=50.3(23); ∠C ringN ringC ring=112.8(30); ∠N ringC ringC ring(H 2)=110.5(16); <∠C ringC ringC ring>=118.4(5); ∠C dbnd6 CC(O)=116.8(7); ∠CC dbnd6 O=127.6(9); ∠CC-O=109.8(8), where the angle brackets denote averaged values and d.p. denotes dependent parameters. Fixing the abundances of the minor conformers, Ax-s- cis and Ax-s- trans, at the theoretical values (13% in total), those of the Eq-s- cis and Eq-s- trans conformers were determined to be 46(16) and 41(16)%, respectively. Here Ax and Eq denote the axial and equatorial directions of the N-CH 3 bond and s- cis and s- trans show the orientation of the methoxycarbonyl group expressed by the configuration of the C dbnd6 O and C dbnd6 C bonds. The N⋯O carbonyl distances of the Eq-s- cis and Ax-s- cis conformers are 4.832(13) and 4.874(16) Å, respectively. They are close to the N⋯N distance of the most abundant conformer of nicotine, 4.885(6) Å, suggesting that the Eq-s- cis and Ax-s- cis conformers have nicotinic activity.
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
NASA Astrophysics Data System (ADS)
Bhatta, Ram S.; Perry, David S.
2010-06-01
The inter-ring torsional potentials of poly (3-methyl thiophene) (P3MT) oligomers are investigated by means of electronic structure calculations. Single layer and ONIOM calculations were performed at B3LYP level with 6-31++G(d,p) basis on the partially optimized geometries of dimer, tetramer and hexamer of P3MT oligomers. Potential energy surfaces are computed as a function of the multiple inter-ring torsional angles involved. The following conclusions are reached: (i) A mixture of cis and trans geometries can be expected in a disordered polymer. (ii) The cis-trans barrier is low enough to allow cis-trans conversion at room temperature. (iii) In the dimer, the potential energy minima are about 30^0 from the cis and trans planar geometries, but planar geometries are stabilized as the chain length increases. (iv) The extended conjugation causes the torsional potential about one inter-ring bond to be coupled to other torsions along the oligomer chain.
The linearly scaling 3D fragment method for large scale electronic structure calculations
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.
The Linearly Scaling 3D Fragment Method for Large Scale Electronic Structure Calculations
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.
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.
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.
NASA Astrophysics Data System (ADS)
Lavrentyev, A. A.; Gabrelian, B. V.; Vu, V. T.; Shkumat, P. N.; Myronchuk, G. L.; Khvyshchun, M.; Fedorchuk, A. O.; Parasyuk, O. V.; Khyzhun, O. Y.
2015-04-01
High-quality single crystal of cesium mercury tetraiodide, Cs2HgI4, has been synthesized by the vertical Bridgman-Stockbarger method and its crystal structure has been refined. In addition, electronic structure and optical properties of Cs2HgI4 have been studied. For the crystal under study, X-ray photoelectron core-level and valence-band spectra for pristine and Ar+-ion irradiated surfaces have been measured. The present X-ray photoelectron spectroscopy (XPS) results indicate that the Cs2HgI4 single crystal surface is very sensitive with respect to Ar+ ion-irradiation. In particular, Ar+ bombardment of the single crystal surface alters the elemental stoichiometry of the Cs2HgI4 surface. To elucidate peculiarities of the energy distribution of the electronic states within the valence-band and conduction-band regions of the Cs2HgI4 compound, we have performed first-principles band-structure calculations based on density functional theory (DFT) as incorporated in the WIEN2k package. Total and partial densities of states for Cs2HgI4 have been calculated. The DFT calculations reveal that the I p states make the major contributions in the upper portion of the valence band, while the Hg d, Cs p and I s states are the dominant contributors in its lower portion. Temperature dependence of the light absorption coefficient and specific electrical conductivity has been explored for Cs2HgI4 in the temperature range of 77-300 K. Main optical characteristics of the Cs2HgI4 compound have been elucidated by the first-principles calculations.
NASA Astrophysics Data System (ADS)
Ding, Yi; Wang, Yanli
2015-01-01
Using first-principles calculations, we investigate the geometric structures and electronic properties of porous silicene and germanene nanosheets, which are the Si and Ge analogues of α-graphyne (referred to as silicyne and germanyne). It is found that the elemental silicyne and germanyne sheets are energetically unfavourable. However, after the C-substitution, the hybrid graphyne-like sheets (c-silicyne/c-germanyne) possess robust energetic and dynamical stabilities. Different from silicene and germanene, c-silicyne is a flat sheet, and c-germanyne is buckled with a distinct half-hilled conformation. Such asymmetric buckling structure causes the semiconducting behaviour into c-germanyne. While in c-silicyne, the semimetallic Dirac-like property is kept at the nonmagnetic state, but a spontaneous antiferromagnetism produces the massive Dirac fermions and opens a sizeable gap between Dirac cones. A tensile strain can further enhance the antiferromagnetism, which also linearly modulates the gap value without altering the direct-bandgap feature. Through strain engineering, c-silicyne can form a type-II band alignment with the MoS 2 sheet. The combined c-silicyne/MoS 2 nanostructure has a high power conversion efficiency beyond 20% for photovoltaic solar cells, enabling a fascinating utilization in the fields of solar energy and nano-devices.
Ding, Yi; Wang, Yanli
2015-01-01
Using first-principles calculations, we investigate the geometric structures and electronic properties of porous silicene and germanene nanosheets, which are the Si and Ge analogues of α-graphyne (referred to as silicyne and germanyne). It is found that the elemental silicyne and germanyne sheets are energetically unfavourable. However, after the C-substitution, the hybrid graphyne-like sheets (c-silicyne/c-germanyne) possess robust energetic and dynamical stabilities. Different from silicene and germanene, c-silicyne is a flat sheet, and c-germanyne is buckled with a distinct half-hilled conformation. Such asymmetric buckling structure causes the semiconducting behaviour into c-germanyne. While in c-silicyne, the semimetallic Dirac-like property is kept at the nonmagnetic state, but a spontaneous antiferromagnetism produces the massive Dirac fermions and opens a sizeable gap between Dirac cones. A tensile strain can further enhance the antiferromagnetism, which also linearly modulates the gap value without altering the direct-bandgap feature. Through strain engineering, c-silicyne can form a type-II band alignment with the MoS 2 sheet. The combined c-silicyne/MoS 2 nanostructure has a high power conversion efficiency beyond 20% for photovoltaic solar cells, enabling a fascinating utilization in the fields of solar energy and nano-devices. PMID:25852311
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.
Marino, Maria, M.; Ermler, Walter C
2006-01-27
It is now possible to calculate many properties including the energetics (total bond dissociation energies or heats of formation) of molecules containing light elements to high accuracy by using correlation-consistent basis sets, coupled cluster theory and including additive corrections for core-valence and relativistic effects and careful treatment of the zero point energy. We propose to develop software for ab initio electronic structure calculations based on molecular orbital theory and density functional theory with the proper treatment of relativistic effects to study complexes of heavy elements in order to assist in understanding and predicting the chemistry of the actinides, lanthanides, and heavy transition metals, molecules critical to DOE missions including environmental management. The proposed work will focus on the development of these electronic structure methods and their implementation in software on advanced massively parallel processor (MPP) computer architectures capable of multi-tens of teraflops to petaflops. The core of the software will be developed within the NWChem and Columbus software suites. We propose to make the software broadly available so that other scientists can use these tools to address the complex environmental problems facing the Department of Energy's nuclear production sites as well as other waste sites in the Nation. Our implementation of relativistic quantum chemical methods for massively parallel computers will enable us to simulate the behavior of heavy-element compounds at the same type of level currently available for light-element compounds. In addition, this work will enable us to provide better methods for benchmarks of the additive energetic schemes currently available for light atom compounds. The theoretical and computational methodology so developed will be an invaluable supplement to current, very expensive experimental studies of the actinides, lanthanides, and radioactive heavy transition metal elements
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.
NASA Astrophysics Data System (ADS)
Wood, Douglas A.
The focus of this thesis is the application of electron structure calculations, particularly density functional theory, to the analysis of the process by which oxygen is able to migrate through a perovskite crystal. This property creates the possibility of using perovskite membranes to separate oxygen from air. This could be applied to the generation of syngas directly from natural gas without the need for a separate air separation unit. A perovskite has the nominal formula ABO3 where A is a rare earth type cation and B is a transition type cation. The structure consists of the B cations arranged in a cube with the A cation in the center. The oxygen ions are located at the midpoint of each B-B cube edge and form an octahedron centered on each B cation. Any real perovskite crystal will contain a certain fraction of vacancies at the oxygen sites. Oxygen migrates through the crystal by jumping from a neighboring site to the vacancy. The permeability of the crystal is thus a function of the concentration of vacancies and the activation energy of the jump from a neighboring site to the vacancy. These properties can be modified by adding dopants for the A and B cations. The literature contains a substantial amount of experimental work on the effect of such dopants. The overall migration process can be divided into components (i) the concentration of oxygen vacancies, (ii) the activation energy for a neighboring on-site oxygen atom to jump to the vacant site, (iii) the concentration of surface vacancies, and (iv) the processes by which oxygen ions transfer back and forth between the perovskite surface and the contiguous vapor space. Using SrTiO3 and LaCoO3 as model compounds, DFT calculations have been used to (i) calculate various properties of the perovskite crystal, (ii) estimate the activation energy of a jump between an occupied oxygen site and an adjacent vacant oxygen site, (iii) predict the effects of various dopants at the A and B site and (iv) analyze the
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
NASA Astrophysics Data System (ADS)
Wu, Hai-Ying; Chen, Ya-Hong; Zhou, Ping; Han, Xiang-Yu; Liu, Zi-Jiang
2014-09-01
The structural, electronic, and mechanical stability properties of magnesium sulfide in different phases are presented using the plane wave pseudopotential method within the generalized gradient approximation. Eight different phases such as rocksalt (B1), zincblende (B3), wurtzite (B4), nickel arsenide (B8), cesium chloride (B2), PH4I-type (B11), FeSi-type (B28), and MnP-type (B31) are considered in great detail. The calculated ground-state properties of these phases are consistent with available experimental and theoretical data. It is found that MgS in the B1 and B8 phases are indirect band gap materials, the B3, B4, B11, B28, and B31 phases are all direct gap materials, while the B2 phase displays the metallic character. The B1, B3, B4, B8, B28, and B31 phases are mechanically stable at ambient conditions, but the B2 and B11 phases are mechanically unstable under zero pressure and zero temperature
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
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).
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.
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.
Multi-Jastrow trial wavefunctions for electronic structure calculations with quantum Monte Carlo.
Bouabça, Thomas; Braïda, Benoît; Caffarel, Michel
2010-07-28
A new type of electronic trial wavefunction suitable for quantum Monte Carlo calculations of molecular systems is presented. In contrast with the standard Jastrow-Slater form built with a unique global Jastrow term, it is proposed to introduce individual Jastrow factors attached to molecular orbitals. Such a form is expected to be more physical since it allows to describe differently the local electronic correlations associated with various molecular environments (1s-core orbitals, 3d-magnetic orbitals, localized two-center sigma-orbitals, delocalized pi-orbitals, atomic lone pairs, etc.). In contrast with the standard form, introducing different Jastrow terms allows us to change the nodal structure of the wavefunction, a point which is important in the context of building better nodes for more accurate fixed-node diffusion Monte Carlo (FN-DMC) calculations. Another important aspect resulting from the use of local Jastrow terms is the possibility of defining and preoptimizing local and transferable correlated units for building complex trial wavefunctions from simple parts. The practical aspects associated with the computation of the intricate derivatives of the multi-Jastrow trial function are presented in detail. Some first illustrative applications for atoms of increasing size (O, S, and Cu) and for the potential energy curve and spectroscopic constants of the FH molecule are presented. In the case of the copper atom, the use of the multi-Jastrow form at the variational Monte Carlo level has allowed us to improve significantly the value of the total ground-state energy (about 75% of the correlation energy with only one determinant and three atomic orbital Jastrow factors). In the case of the FH molecule (fluorine hydride), it has been found that the multi-Jastrow nodes lead to an almost exact FN-DMC value of the dissociation energy [D(0)=-140.7(4) kcal/mol instead of the estimated nonrelativistic Born-Oppenheimer exact value of -141.1], which is not the case
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
Structural phase transition and 5f-electrons localization of PuSe explored by ab initio calculations
Cui Shouxin; Feng Wenxia; Hu Haiquan; Gong Zizheng; Liu Hong
2010-04-15
An investigation into the structural phase transformation, electronic and optical properties of PuSe under high pressure was conducted by using the full potential linearized augmented plane wave plus local orbitals (FP-LAPW+lo) method, in the presence and in the absence of spin-orbit coupling (SOC). Our results demonstrate that there exists a structural phase transition from rocksalt (B 1) structure to CsCl-type (B 2) structure at the transition pressure of 36.3 GPa (without SOC) and 51.3 GPa (with SOC). The electronic density of states (DOS) for PuSe show that the f-electrons of Pu are more localized and concentrated in a narrow peak near the Fermi level, which is consistent with the experimental studies. The band structure shows that B 1-PuSe is metallic. A pseudogap appears around the Fermi level of the total density of states of B 1 phase PuSe, which may contribute to its stability. The calculated reflectivity R(omega) shows agreement with the available experimental results. Furthermore, the absorption spectrum, refractive index, extinction coefficient, energy-loss spectrum and dielectric function were calculated. The origin of the spectral peaks was interpreted based on the electronic structures. - Abstract: Graphical Abstract Legend (TOC Figure): 5f-electrons are more localized by the analysis of the density of states (SOC). The origin spectra peaks was interpreted based on electronic structures.
Calculation of Electron Trajectories
Energy Science and Technology Software Center (ESTSC)
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
NASA Astrophysics Data System (ADS)
Newton, M. D.
1987-08-01
Model calculations have been employed to elucidate the mechanism of electron transfer reactions in aqueous solution. The contribution of inner shell OH bonds to activation barriers has been estimated from calculation for metal ion hydrates. Calculated electron transfer matrix elements H sub if for redox processes of the type, ML sub 6 sup 2(+)+ ML sub 6 sup 3(+) in equilibrium ML sub 6 sup 3(+) + ML sub 6 sup 2(+), M = Fe, Co, or Ru, L = H2O or NH3, have been analyzed in terms of various orbital concepts. The matrix elements are based on ab initio wavefunctions for model supermolecule clusters of the type, (ML sub n ...L sub n M) sup 5(+), with n = 1 or 3. The analysis shows that the many-electron H sub if quantities can in fact be expressed to good approximation as effective 1-electron expressions of the type, H sub if proportional to lambda' sup 2 N sub c h sub L1Lr, where lambda' is the metal-ligand covalency parameter, h sub L1Lr is a local 1-electron matrix element for ligand orbitals in contact in the transition state, and N sub c is the number of such contacts. A least-squares fit of the data implies a value of approx. 5000/cm for h sub L1Lr, showing that significant coupling can occur in the absence of formal bonding between reactants.
Ab-initio calculations of electronic, transport, and structural properties of boron phosphide
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.
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.
NASA Astrophysics Data System (ADS)
Vazart, Fanny; Latouche, Camille; Skouteris, Dimitrios; Balucani, Nadia; Barone, Vincenzo
2015-09-01
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 + CH2 = 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)0.152 × e(-0.0948/T). According to the present study, the more stable Z-C-cyanomethanimine isomer is formed with a slightly larger yield (4.59 × 10-10 × (T/300)0.153 × e(-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 + CH2 = 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.
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.
First principle calculations of structural phase transition and electronic properties in AmTe
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.
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.
Nonrelativistic structure calculations of two-electron ions in a strongly coupled plasma environment
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.
A. Afanasev, I. Akushevich, A. Ilyichev, N. Merenkov
2003-09-01
The main features of the electron structure method for calculations of the higher order QED radiative effects to polarized deep-inelastic ep-scattering are presented. A new FORTRAN code ESFRAD based on this method was developed. A detailed quantitative comparison between the results of ESFRAD and other methods implemented in the codes POLRAD and RADGEN for calculation of the higher order radiative corrections is performed.
Wang, Lin-Wang; Zhao, Zhengji; Meza, Juan; Wang, Lin-Wang
2008-07-11
We present a new linear scaling ab initio total energy electronic structure calculation method based on the divide-and-conquer strategy. This method is simple to implement, easily to parallelize, and produces very accurate results when compared with the direct ab initio method. The method has been tested using up to 8,000 processors, and has been used to calculate nanosystems up to 15,000 atoms.
Self-consistent calculation of the electron structure and x-ray spectra of chromium nitride
Bekenev, V.L.; Lisenko, A.A.; Zhurakovskii, E.A.
1986-02-01
The authors calculate the energy band structure of cubic chromium nitride by the self-consistent method of associated plane waves for a broad energy range. Self-consistency led to overlapping of the p-band of nitrogen and the d-band of chromium and to the appearance of an energy discontinuity in the region of unbounded states. The total and local partial densities of the states are calculated. With allowance for the probability of transition, the KB/sub 5/ and L/sub 111/ -emission bands of chromium, the Ka -band of nitrogen, and the K-edge of absorption of chromium in chromium nitride are calculated in a dipole approximation. The possibility of calculating the absorption edge with allowance for the effect of shell holes is discussed. Satisfactory agreement is obtained with experimental data.
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.
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) =
NASA Astrophysics Data System (ADS)
Belosevic-Cavor, Jelena; Koteski, Vasil; Concas, Giorgio; Cekic, Bozidar; Novakovic, Nikola; Spano, Giorgio
2005-10-01
A detailed theoretical study of the structure, electronic properties and the electric field gradients of the Hf2Fe intermetallic compound is presented. Using all-electron full-potential linearized augmented plane wave (FP-LAPW) formalism the equilibrium volume, bulk modulus and electric field gradients are calculated. The obtained results are compared with EFG values inferred from measurements performed using Mössbauer spectroscopy and the earlier reported time differential perturbed angular correlation (TDPAC) measurements. The lattice relaxation and the supercell calculations are found to be essential for the correct interpretation of the experimental results.
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.
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.
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.
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.
Photophysics of Auramine-O: electronic structure calculations and nonadiabatic dynamics simulations.
Xie, Bin-Bin; Xia, Shu-Hua; Chang, Xue-Ping; Cui, Ganglong
2016-01-01
Diphenylmethane dyes are very useful photoinduced molecular rotors; however, their photophysical mechanisms are still elusive until now. In this work, we adopted combined static electronic structure calculations (MS-CASPT2//CASSCF) and trajectory-based surface-hopping dynamics simulations (OM2/MRCI) to study the S1 excited-state relaxation mechanism of a representative diphenylmethane dye Auramine-O. On the basis of the optimized S1 minima and the computed emission bands, we have for the first time assigned experimentally proposed three transient states (i.e. S1-LE, S1-I1 or S1-I2, and S1-II). Mechanistically, upon irradiation to the S1 state, the system first relaxes to the locally excited S1 minimum (S1-LE). Starting from this point, there exist two kinds of relaxation paths to S1-II. In the sequential path, the system first evolves into S1-I1 or S1-I2 and then runs into S1-II; in the concerted one, the system, bypassing S1-I1 and S1-I2, directly runs into S1-II. In addition, the system can decay to the S0 state in the vicinity of three S1/S0 conical intersections i.e. S1S0-I1, S1S0-I2, and S1S0-II. In the S1 dynamic simulations, 54% trajectories decay to the S0 state via S1S0-II; the remaining trajectories are de-excited to the S0 state via S1S0-I1 (11%) and S1S0-I2 (35%). Our present theoretical investigation does not support the experimentally proposed S1 excited-state hypothesis that the intramolecular rotation of the two dimethyl groups around the C-N bond is responsible for the rapid decay of the emission band at about 500 nm; instead, it should be heavily interrelated with the rotation of the two dimethylanilino groups. Finally, this work provides important mechanistic insights into similar diphenylmethane dyes. PMID:26615798
Pipek, János; Nagy, Szilvia
2013-03-01
The wave function of a many electron system contains inhomogeneously distributed spatial details, which allows to reduce the number of fine detail wavelets in multiresolution analysis approximations. Finding a method for decimating the unnecessary basis functions plays an essential role in avoiding an exponential increase of computational demand in wavelet-based calculations. We describe an effective prediction algorithm for the next resolution level wavelet coefficients, based on the approximate wave function expanded up to a given level. The prediction results in a reasonable approximation of the wave function and allows to sort out the unnecessary wavelets with a great reliability. PMID:23115109
State-of-the-art eigensolvers for electronic structure calculations of large scale nano-systems
NASA Astrophysics Data System (ADS)
Vömel, Christof; Tomov, Stanimire Z.; Marques, Osni A.; Canning, A.; Wang, Lin-Wang; Dongarra, Jack J.
2008-07-01
The band edge states determine optical and electronic properties of semiconductor nano-structures which can be computed from an interior eigenproblem. We study the reliability and performance of state-of-the-art iterative eigensolvers on large quantum dots and wires, focusing on variants of preconditioned CG, Lanczos, and Davidson methods. One Davidson variant, the GD + k (Olsen) method, is identified to be as reliable as the commonly used preconditioned CG while consistently being between two and three times faster.
Atomistic and electronic structure calculation of defects at the surfaces of oxides
NASA Astrophysics Data System (ADS)
Watson, G. W.
We present the results of simulations using both atomistic and density functional theory (DFT) approaches that illustrate the uses of these techniques for investigating the structure and electronic structure of defects at the surfaces of oxides. Atomistic simulation studies of the low index surfaces of spinel (MgAl2O4) will show the role of vacancy configuration and surface rearrangement. Atomistic and DFT studies on Li doped MgO illustrate the importance of both the defect structure and its effect of morphology. We will also illustrate using DFT electronic defects at the surface of CeO2 , which are of great importance in redox reactions and catalytic activity. Finally we will present a novel atomistic approach for predicting the structure of supported oxide nanoclusters giving rise to a wide range of defects including a range of surface terminations, grain formation, mixed screw edge dislocations and misfit dislocations. We will illustrate this using the structure of a BaO supported MgO nanocluster.
NASA Astrophysics Data System (ADS)
Bertoni, Giovanni; Calmels, Lionel; Altibelli, Anne; Serin, Virginie
2005-02-01
A spin-polarized first-principles calculation of the atomic and electronic structure of the graphene/Ni(111) interface is presented. Different structural models have been considered, which differ in the positions of the carbon atoms with respect to the nickel topmost layer. The most probable structure, which has the lowest energy, has been determined. The distance between the floating carbon layer and the nickel surface is found smaller than the distance between graphene sheets in bulk graphite, in accordance with experimental measurements. The electronic structure of the graphene layer is strongly modified by interaction with the substrate and the magnetic moment of the surface nickel atoms is lowered in the presence of the graphene layer. Several interface states have been identified in different parts of the interface two-dimensional Brillouin zone. Their influence on the electron energy loss spectra has been evaluated.
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
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.
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.
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.
Iterative diagonalization in augmented plane wave based methods in electronic structure calculations
Blaha, P.; Laskowski, R.; Schwarz, K.
2010-01-20
Due to the increased computer power and advanced algorithms, quantum mechanical calculations based on Density Functional Theory are more and more widely used to solve real materials science problems. In this context large nonlinear generalized eigenvalue problems must be solved repeatedly to calculate the electronic ground state of a solid or molecule. Due to the nonlinear nature of this problem, an iterative solution of the eigenvalue problem can be more efficient provided it does not disturb the convergence of the self-consistent-field problem. The blocked Davidson method is one of the widely used and efficient schemes for that purpose, but its performance depends critically on the preconditioning, i.e. the procedure to improve the search space for an accurate solution. For more diagonally dominated problems, which appear typically for plane wave based pseudopotential calculations, the inverse of the diagonal of (H - ES) is used. However, for the more efficient 'augmented plane wave + local-orbitals' basis set this preconditioning is not sufficient due to large off-diagonal terms caused by the local orbitals. We propose a new preconditioner based on the inverse of (H - {lambda}S) and demonstrate its efficiency for real applications using both, a sequential and a parallel implementation of this algorithm into our WIEN2k code.
The use of quadratic forms in the calculation of ground state electronic structures
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.
NASA Astrophysics Data System (ADS)
Chen, L.; Ouyang, Y.; Pan, H. Z.; Sun, Y. Y.; Wang, Y. L.
A spin-polarized first-principles calculation of the atomic and electronic structure of the graphene/Ni(111) interface is studied. The electronic structure of the graphene layer is strongly modified by interaction with the substrate and a behavior where magnetic moments are localized at the edges of nanoscale holes of isolated graphene does not happen in the defect-graphene/Ni(111) system. The magnetic moment of the surface nickel atoms is lowered in the presence of the graphene layer and nanoscale holes of graphene, which control the strength of the hybridization between electronic states of graphene and Ni substrate. Our findings show that an electron spin in the graphene/Ni(111) interface can be manipulated in a controlled way and have important implications for graphene-based spintronic devices.
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. PMID:24387056
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.
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 , dxy, and 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. PMID:26525099
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.
Lattice vibrations and instabilities in tungsten phases from electronic structure calculations
NASA Astrophysics Data System (ADS)
Grimvall, G.; Einarsdotter, K.; Sadigh, B.; Köpe, B.; Ozolinš, V.
1998-03-01
Phonon dispersion curves are calculated for bcc and fcc W, as a function of atomic volume. The range of phonon stability in the fcc phase is mapped out in the Brillouin zone. Incipient instabilities in the bcc phase are studied, and compared with related instabilities in, e.g., bcc Ti and Zr. A molecular-dynamics type analysis is also performed. Implications are discussed for binary phase diagrams AB where elements A and B have different lattice structures, one of them being dynamically unstable.
Ding, Li-Ping; Shao, Peng; Zhang, Fang-Hui; Lu, Cheng; Ding, Lei; Ning, Shu Ya; Huang, Xiao Fen
2016-07-18
On the basis of the first-principles techniques, we perform the structure prediction for MoB2. Accordingly, a new ground-state crystal structure WB2 (P63/mmc, 2 fu/cell) is uncovered. The experimental synthesized rhombohedral R3̅m and hexagonal AlB2, as well as theoretical predicted RuB2 structures, are no longer the most favorite structures. By analyzing the elastic constants, formation enthalpies, and phonon dispersion, we find that the WB2 phase is thermodynamically and mechanically stable. The high bulk modulus B, shear modulus G, low Poisson's ratio ν, and small B/G ratio are benefit to its low compressibility. When the pressure is 10 GPa, a phase transition is observed between the WB2-MoB2 and the rhombohedral R3̅m MoB2 phases. By analyzing the density of states and electron density, we find that the strong covalent is formed in MoB2 compounds, which contributes a great deal to its low compressibility. Furthermore, the low compressibility is also correlated with the local buckled structure. PMID:27387577
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].
Sarkar, Kanchan; Sharma, Rahul; Bhattacharyya, S P
2010-03-01
A density matrix based soft-computing solution to the quantum mechanical problem of computing the molecular electronic structure of fairly long polythiophene (PT) chains is proposed. The soft-computing solution is based on a "random mutation hill climbing" scheme which is modified by blending it with a deterministic method based on a trial single-particle density matrix [P((0))(R)] for the guessed structural parameters (R), which is allowed to evolve under a unitary transformation generated by the Hamiltonian H(R). The Hamiltonian itself changes as the geometrical parameters (R) defining the polythiophene chain undergo mutation. The scale (λ) of the transformation is optimized by making the energy [E(λ)] stationary with respect to λ. The robustness and the performance levels of variants of the algorithm are analyzed and compared with those of other derivative free methods. The method is further tested successfully with optimization of the geometry of bipolaron-doped long PT chains. PMID:26613302
A Initio Lcao Electronic Structure Calculations of Layered Transition Metal Compounds.
NASA Astrophysics Data System (ADS)
Dawson, William G.
1987-09-01
Available from UMI in association with The British Library. In this work the electronic structure of three systems of layered transition metal compounds are examined using an ab initio tight binding (LCAO) method using the Xalpha exchange/correlation approximation: group VI ditellurides, group IV trichalcogenides and quaternary copper oxide defect-perovskites. A chemical pseudopotential argument is presented in order to justify the use of a small basis set of atomic orbitals. The group VI transition metal compounds MoTe_2 and WTe _2 show strong metal-metal interactions and MoTe_2 undergoes an unusual phase transition with the lattice parameter perpendicular to the layers decreasing with increasing temperature. The group IV transition metal trichalcogenides provide a useful series for study due to their quasi-1-dimensional character and the occurrence of two closely related structural variants. The atypical compound ZrTe_3 is given special attention because of its apparent semimetallic nature. The final group of compounds studied are the high Tc superconducting ceramics Ba-La-Cu-O and Ba-Y-Cu-O. The technological importance of compounds with zero resistance and showing the Meissner effect (expelling magnetic fields) above liquid nitrogen temperatures and the, as yet, undefined nature of the mechanism of superconductivity stresses the need to carefully examine the electronic structure of these materials. The role of oxygen vacancies, the charge state of the copper ions and the possibility of structural phase transitions are some of the topics considered here. The use of an atomic-orbital basis allows a comparatively straightforward description of the chemical bonding in a crystal--especially useful when the unit cell contains a large number of atoms.
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.
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.
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
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.
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).
NASA Astrophysics Data System (ADS)
Guo, San-Dong
2014-03-01
We investigate the electronic structures of {{\\rm{X}}_{3}}{\\rm{Sb}} (X = Li, K, Cs) by using Tran and Blaha's modified Becke and Johnson exchange potential. Calculated energy gaps are substantially better than previous first-principles results with respect to experimental values. The substantial improvement is achieved because the conduction bands are correctly calculated with the new exchange potential. The approach should be applicable to other similar materials. The elastic properties of {{\\rm{X}}_{3}}{\\rm{Sb}} (X = Li, K, Cs) are also studied in detail with the generalized gradient approximation such as bulk modulus, shear modulus, Young's modulus, Poisson's ratio, sound velocities, and Debye temperature.
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.
Electronic Structure of Organic/Inorganic Interfaces: Insights from First Principles Calculations
NASA Astrophysics Data System (ADS)
Segev, Lior
Electronic devices based on molecules draw a lot of attention in both scientific and industrial activities. Molecules in electronic devices can serve as the heart of the device, featuring versatile physical properties i.e. electronical, optical, magnetic, etc. Molecules can also function as an assist mechanism in which the electronic properties of the underlying material are modified in a predictable fashion according to the molecular monolayer properties. But, the route to applications in both these directions lies in answering fundamental questions related to band offsets between two materials, full electronic structure determination of molecule and substrates, work function modifications, etc. To tackle these questions, we chose to study the interface formed by an alkyl monolayer adsorbed on a Si substrate by utilizing two ab initio methods. First, the density functional theory (DFT) utilizing the local density or the B3LYP approximations for the exchange-correlation potential and, second, the many-body perturbation theory based on the GW approximation. We adapted a "divide and conquer" approach to our system by simulating the infinite counterpart, polyethylene, of our finite alkyl chain to test how the band gap of the two molecules changes when moving from an infinite 1D molecule to a finite length molecule. We find excellent agreement between our GW simulation results for polyethylene and experimental results for the bandstructure, ionization potential and band gap values. From DFT simulations, we analyze the ultra-violet photoelectron spectra (UPS) of odd and even number of carbons alkyl chains and identify the origin of their differences in spectral signature. GW simulations of the full alkyl monolayer/Si(111) system reveal that the projected density of states (DOS) of the upper alkyl chain have an excellent agreement to experimental UPS and inverse-photoemission spectra results. Based on this correspondence, we find the band alignment between the alkyl
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.
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.
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.
Du, Jincheng; Devanathan, Ramaswami; Corrales, Louis R.; Weber, William J.
2012-05-01
First-principles periodic density functional theory (DFT) calculations have been performed to understand the electronic structure, chemical bonding, phase transition, and physical properties of the mineral 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 electronic density of states and atomic charges analyses show that bonding in the high-pressure reidite phase has a stronger covalent character.
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.
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.
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.
Wang, Xue B.; Fu, Qiang; Yang, Jinlong
2010-09-02
Hydroxyl substituted phenoxide, o-, m-, p- HO(C6H4)O– and the corresponding neutral radicals are important species, in particularly, the p- isomer pair is directly involved in the proton-coupled electron transfer in biological photosynthetic centers. Here we report the first spectroscopic study of these species in the gas phase by means of low-temperature photoelectron spectroscopy (PES) and ab initio calculations. Vibrationally resolved PES spectra were obtained at 70 K and several photon energies for each anion, directly yielding electron affinity (EA) and electronic structure information of the corresponding hydroxyphenoxyl radical. The EAs are found to vary with OH positions, from 1.990 ± 0.010 eV (p-) to 2.315 ± 0.010 (o-) and 2.330 ± 0.010 (m-). Theoretical calculations were carried out to identify the optimized molecular structures for both anions and neutral radicals. The electron binding energies and excited state energies were also calculated to compare with experimental data. Excellent agreement is found between calculations and experiments. Molecular orbital analyses indicate strong OH anti-bonding interaction with the phenoxide moiety for o- as well as p- isomers, whereas such interaction is largely missing for the m- anion. The variance of EAs among three isomers is interpreted primarily due to the interplay between two competing factors: the OH anti-bonding interaction and H-bonding stabilization (existed only in the o- anion).
Atomic and electronic structure of hydrogen on ZnO (1bar 100) surface: ab initio hybrid calculations
NASA Astrophysics Data System (ADS)
Usseinov, A. B.; Kotomin, E. A.; Zhukovskii, Yu F.; Purans, J.; Sorokin, A. V.; Akilbekov, A. T.
2013-12-01
Hydrogen atoms unavoidably incorporated into ZnO during growth of bulk samples and thin films considerably affect their electrical conductivity. The results of first principles hybrid LCAO calculations are discussed for hydrogen atoms in the bulk and on the non-polar ZnO (1bar 100) surface. The incorporation energy, the atomic relaxation, the electronic density redistribution and the electronic structure modifications are compared for the surface adsorption and bulk interstitial H positions. It is shown that hydrogen has a strong binding with the surface O ions (2.7 eV) whereas its incorporation into bulk is energetically unfavorable. Surface hydrogen atoms are very shallow donors, thus, contributing to the electronic conductivity.
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.
NASA Astrophysics Data System (ADS)
Noble-Eddy, Robert; Masters, Sarah L.; Rankin, David W. H.; Robertson, Heather E.; Guillemin, Jean-Claude
2010-08-01
The molecular structures of vinylarsine (CH 2dbnd CHAsH 2), vinyldichloroarsine (CH 2dbnd CHAsCl 2) and arsine (AsH 3) have been determined from gas-phase electron diffraction data and, in the case of vinylarsine, rotation constants, employing the SARACEN method. The structure of vinylarsine represents the first complete gas-phase structure of a primary arsine. The experimental geometric parameters generally show good agreement with those obtained using ab initio calculations. Key structural parameters ( rh1) for vinylarsine are rAs-H = 150.5(4) pm, rAs-C = 195.1(1) pm and ∠C-C-As = 119.4(2)°. The bonding and conformational trends in both vinylarsine and vinyldichloroarsine are compared to those found in the analogous amines and phosphines.
NASA Technical Reports Server (NTRS)
Long, E. R., Jr.
1979-01-01
The Bethe-Bloch stopping power relations for inelastic collisions were used to determine the absorption of electron and proton energy in cured neat epoxy resin and the absorption of electron energy in a graphite/epoxy composite. Absorption of electron energy due to bremsstrahlung was determined. Electron energies from 0.2 to 4.0 MeV and proton energies from 0.3 to 1.75 MeV were used. Monoenergetic electron energy absorption profiles for models of pure graphite, cured neat epoxy resin, and graphite/epoxy composites are reported. A relation is determined for depth of uniform energy absorption in a composite as a function of fiber volume fraction and initial electron energy. Monoenergetic proton energy absorption profiles are reported for the neat resin model. A relation for total proton penetration in the epoxy resin as a function of initial proton energy is determined. Electron energy absorption in the composite due to bremsstrahlung is reported. Electron and proton energy absorption profiles in cured neat epoxy resin are reported for environments approximating geosynchronous earth orbit.
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).
NASA Astrophysics Data System (ADS)
Li, Yanli; Dabo, Ismaila
2011-10-01
Plane-wave electronic-structure predictions based upon orbital-dependent density-functional theory (OD-DFT) approximations, such as hybrid density-functional methods and self-interaction density-functional corrections, are severely affected by computational inaccuracies in evaluating electron interactions in the plane-wave representation. These errors arise from divergence singularities in the plane-wave summation of electrostatic and exchange interaction contributions. Auxiliary-function corrections are reciprocal-space countercharge corrections that cancel plane-wave singularities through the addition of an auxiliary function to the point-charge electrostatic kernel that enters into the expression of interaction terms. At variance with real-space countercharge corrections that are employed in the context of density-functional theory (DFT), reciprocal-space corrections are computationally inexpensive, making them suited to more demanding OD-DFT calculations. Nevertheless, there exists much freedom in the choice of auxiliary functions and various definitions result in different levels of performance in eliminating plane-wave inaccuracies. In this work we derive exact point-charge auxiliary functions for the description of molecular structures of arbitrary translational symmetry, including the yet unaddressed one-dimensional case. In addition, we provide a critical assessment of different reciprocal-space countercharge corrections and demonstrate the improved accuracy of point-charge auxiliary functions in predicting the electronic levels and electrical response of conjugated polymers from plane-wave OD-DFT calculations.
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.
NASA Astrophysics Data System (ADS)
Borghi, Giovanni; Fabrizio, Michele; Tosatti, Erio
2014-09-01
The Gutzwiller projector technique has long been known as a method to include correlations in electronic structure calculations. We describe a model implementation for a Gutzwiller +LDA calculation in a localized-orbital restricted basis framework, emphasizing the protocol step by step and illustrating our specific procedure for this and future applications. We demonstrate the method with a classic problem, the ferromagnetism of bulk bcc Fe, whose nature is attracting fresh interest. In the conventional Stoner-Wohlfarth model, and in spin-polarized LDA calculations, the ferromagnetic ordering of iron sets in so that the electrons can reduce their mutual Coulomb repulsion, at the cost of some increase of electron kinetic energy. This balance may, however, be altered by correlations, which are strong for localized d orbitals. The present localized basis Gutzwiller +LDA calculation demonstrates how the ferromagnetic ordering of Fe may, in fact, entrain a decrease of kinetic energy at the cost of some increase of potential energy. This happens because, as foreshadowed long ago by Goodenough and others and more recently supported by LDA-DMFT calculations, correlations cause eg and t2g d orbitals to behave differently, with the weakly propagating eg states fully spin polarized and almost localized, and only t2g states forming a broad partly filled itinerant band. Owing to an intra-atomic Hund's rule exchange that aligns eg and t2g spins, the propagation of itinerant t2g holes is favored when different atomic spins are ferromagnetically aligned. This suggests a strong analogy with double exchange in iron ferromagnetism.
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.
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.
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. PMID:26525099
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.
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…
NASA Astrophysics Data System (ADS)
Amadon, B.; Lechermann, F.; Georges, A.; Jollet, F.; Wehling, T. O.; Lichtenstein, A. I.
2008-05-01
The description of realistic strongly correlated systems has recently advanced through the combination of density functional theory in the local density approximation (LDA) and dynamical mean field theory (DMFT). This LDA+DMFT method is able to treat both strongly correlated insulators and metals. Several interfaces between LDA and DMFT have been used, such as ( Nth order) linear muffin-tin orbitals or maximally localized Wannier functions. Such schemes are, however, either complex in use or additional simplifications are often performed (i.e., the atomic sphere approximation). We present an alternative implementation of LDA+DMFT , which keeps the precision of the Wannier implementation, but which is lighter. It relies on the projection of localized orbitals onto a restricted set of Kohn-Sham states to define the correlated subspace. The method is implemented within the projector augmented wave and within the mixed-basis pseudopotential frameworks. This opens the way to electronic structure calculations within LDA+DMFT for more complex structures with the precision of an all-electron method. We present an application to two correlated systems, namely, SrVO3 and β -NiS (a charge-transfer material), including ligand states in the basis set. The results are compared to calculations done with maximally localized Wannier functions, and the physical features appearing in the orbitally resolved spectral functions are discussed.
NASA Astrophysics Data System (ADS)
Zhang, Yu; Tang, Fu-Ling; Xue, Hong-Tao; Lu, Wen-Jiang; Liu, Jiang-Fei; Huang, Min
2015-02-01
Using first-principles plane-wave calculations within density functional theory, we theoretically studied the atomic structure, bonding energy and electronic properties of the perfect Mo (110)/MoSe2 (100) interface with a lattice mismatch less than 4.2%. Compared with the perfect structure, the interface is somewhat relaxed, and its atomic positions and bond lengths change slightly. The calculated interface bonding energy is about -1.2 J/m2, indicating that this interface is very stable. The MoSe2 layer on the interface has some interface states near the Fermi level, the interface states are mainly caused by Mo 4d orbitals, while the Se atom almost have no contribution. On the interface, Mo-5s and Se-4p orbitals hybridize at about -6.5 to -5.0 eV, and Mo-4d and Se-4p orbitals hybridize at about -5.0 to -1.0 eV. These hybridizations greatly improve the bonding ability of Mo and Se atom in the interface. By Bader charge analysis, we find electron redistribution near the interface which promotes the bonding of the Mo and MoSe2 layer.
NASA Astrophysics Data System (ADS)
Harish, R. Sugan; Jayalakshmi, D. S.; Viswanathan, E.; Sundareswari, M.
2016-05-01
The mechanical, electronic, thermodynamic properties and structural stability of tetragonal structured CaNi2P2 and CaNi2Sb2 intermetallic compounds has been studied using the FP-LAPW method based on density functional theory. The PBE-GGA exchange correlation has been applied. Using the computed elastic constants, various elastic moduli such as bulk, shear, Young’s modulus, Poisson’s ratio and anisotropy constant are calculated and discussed. Stability of the compounds is confirmed by using their elastic constants. Pugh’s ratio is calculated to analyze the mechanical nature of the compound.
Kafafi, S.A. ); LaFemina, J.P. ); Nauss, J.L. )
1990-11-21
Full geometry optimizations using molecular mechanics and the quantum chemical AM1 method have been carried out to determine the minimum energy conformation of pyromellitic dianhydride-oxydianiline polyimide (PMDA-ODA PI). The phenyl-imide twist angle for this compound was determined to be {approximately}30. These computations also provided a quantitative determination of the energy gap (7 eV), electron affinity ({minus}2 eV), and ionization potential (8.97 eV). Computations on the PMDA-ODA PI radical anion provided an estimate of the hopping barrier for an electron to hop from one chain to another (3.2 eV), the mechanism believed responsible for photoconduction. Moreover, the use of qualitative molecular orbital theory (QMOT) arguments provided an interpretation of these results in a simple molecular orbital framework.
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.
NASA Astrophysics Data System (ADS)
Rivelino, Roberto; Malaspina, Thaciana; Fileti, Eudes E.
2009-01-01
We have investigated the stability, electronic properties, Rayleigh (elastic), and Raman (inelastic) depolarization ratios, infrared and Raman absorption vibrational spectra of fullerenols [C60(OH)n] with different degrees of hydroxylation by using all-electron density-functional-theory (DFT) methods. Stable arrangements of these molecules were found by means of full geometry optimizations using Becke’s three-parameter exchange functional with the Lee, Yang, and Parr correlation functional. This DFT level has been combined with the 6-31G(d,p) Gaussian-type basis set, as a compromise between accuracy and capability to treat highly hydroxylated fullerenes, e.g., C60(OH)36 . Thus, the molecular properties of fullerenols were systematically analyzed for structures with n=1 , 2, 3, 4, 8, 10, 16, 18, 24, 32, and 36. From the electronic structure analysis of these molecules, we have evidenced an important effect related to the weak chemical reactivity of a possible C60(OH)24 isomer. To investigate Raman scattering and the vibrational spectra of the different fullerenols, frequency calculations are carried out within the harmonic approximation. In this case a systematic study is only performed for n=1-4 , 8, 10, 16, 18, and 24. Our results give good agreements with the expected changes in the spectral absorptions due to the hydroxylation of fullerenes.
Properties of Cerium Hydroxides from Matrix Infrared Spectra and Electronic Structure Calculations.
Fang, Zongtang; Thanthiriwatte, K Sahan; Dixon, David A; Andrews, Lester; Wang, Xuefeng
2016-02-15
Reactions of laser ablated cerium atoms with hydrogen peroxide or hydrogen and oxygen mixtures diluted in argon and condensed at 4 K produced the Ce(OH)3 and Ce(OH)2 molecules and Ce(OH)2(+) cation as major products. Additional minor products were identified as the Ce(OH)4, HCeO, and OCeOH molecules. These new species were identified from their matrix infrared spectra with D2O2, D2, and (18)O2 isotopic substitution and correlating observed frequencies with values calculated by density functional theory. We find that the amounts of Ce(OH)3 and of the Ce(OH)2(+) cation increase on UV (λ > 220 nm) photolysis, while Ce(OH)2, Ce(OH)4, and HCeO are photosensitive. The observed major species for Ce are in the +III or +II oxidation state, and the minor product, Ce(OH)4, is in the +IV oxidation state. The calculations for the vibrational frequencies with the B3LYP functional agree well with the experiment. The NBO analysis shows significant backbonding to the metal 4f and 5d orbitals for the closed shell species. Most open shell species have the excess spin in the 4f with paired spin in the 5d due to backbonding. The heats of formation of the observed species were derived from the available data from experiment and the calculated reaction energies. The major products in this study are different from similar reactions for Th where the tetrahydroxide was the major species. PMID:26814626
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.
NASA Astrophysics Data System (ADS)
Drablia, S.; Meradji, H.; Ghemid, S.; Labidi, S.; Bouhafs, B.
2009-04-01
First principles calculations have been used to investigate the structural, electronic, thermodynamic and optical properties of boron ternary alloy BAs1 - x Px, using a hybrid full-potential (linear) augmented plane wave plus the local orbitals (APW + lo) method within the density-functional theory (DFT). The Perdew-Burke-Ernzerhof generalized gradient approximation (PBE-GGA) as well as the Engel-Vosko (EV)-GGA are used to calculate the band gap. We investigated the effect of composition on lattice constant, bulk modulus and band gap. Deviations of the lattice constant from Vegard's law and the bulk modulus from linear concentration dependence (LCD) were observed for the alloy. Using the approach of Zunger and co-workers, the microscopic origins of the gap bowing are explained. The thermodynamic stability of the alloy is investigated by calculating the excess enthalpy of mixing ΔHm as well as the phase diagram. The calculated phase diagram showed a broad miscibility gap for the alloy of interest with a high critical temperature. For optical properties, the compositional dependence of the refractive index and the dielectric constant is studied.
García-Risueño, Pablo; Alberdi-Rodriguez, Joseba; Oliveira, Micael J T; Andrade, Xavier; Pippig, Michael; Muguerza, Javier; Arruabarrena, Agustin; Rubio, Angel
2014-03-01
We present an analysis of different methods to calculate the classical electrostatic Hartree potential created by charge distributions. Our goal is to provide the reader with an estimation on the performance-in terms of both numerical complexity and accuracy-of popular Poisson solvers, and to give an intuitive idea on the way these solvers operate. Highly parallelizable routines have been implemented in a first-principle simulation code (Octopus) to be used in our tests, so that reliable conclusions about the capability of methods to tackle large systems in cluster computing can be obtained from our work. PMID:24249048
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}.
NASA Astrophysics Data System (ADS)
Nakamura, H.; Hayashi, N.; Nakai, N.; Okumura, M.; Machida, M.
2009-10-01
In order to resolve a discrepancy of the magnetic moment on Fe between the experimental and calculation results, we perform first-principle electronic structure calculations for iron-based superconductors LaFeAsO1-x and LiFeAs also show similar SDW. So far, the first-principle calculations on LaFeAsO actually predicted the SDW state as a ground state. However, the predicted magnetic moment (∼2 μB) per an Fe atom is much larger than the observed one (∼0.35 μB) in experiments [2,4]. The authors suggested that the discrepancy can be resolved by expanding U into a negative U range within LSDA + U framework. In this paper, we revisit the discrepancy and clarify why the negative correction is essential in these compounds. See Ref. [5] for the details of calculation data by LSDA + negative U. In the first-principle calculation on compounds including transition metals, the total energy is frequently corrected by “LSDA + U” approach. The parameter U is theoretically re-expressed as U(≡U-J), where U is the on-site Coulomb repulsion (Hubbard U) and J is the atomic-orbital intra-exchange energy (Hund’s coupling parameter) [6]. The parameter U employed in the electronic structure calculations is usually positive. The positivity promotes the localized character of d-electrons and enhances the magnetic moment in the cases of magnetically ordered compounds. Normally, this positive correction successfully works. In choosing the parameter, one can principally extend the parameter U range to a negative region. The negative case [7] is not popular, but it can occur in the following two cases [8]: (i) the Hubbard U becomes negative and (ii) the intra-exchange J is effectively larger than the Hubbard U. The case (i) has been suggested by many authors based on various theoretical considerations. Here, we note that U should be estimated once screening effects on the long-range Coulomb interaction are taken into account. In fact, small U has been reported [9]. Thus, when the
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).
NASA Astrophysics Data System (ADS)
Kutorasinski, K.; Wiendlocha, B.; Kaprzyk, S.; Tobola, J.
2015-05-01
We present results of the electronic band structure, Fermi surface, and electron transport property calculations in the orthorhombic n - and p -type SnSe, applying the Korringa-Kohn-Rostoker method and the Boltzmann transport approach. The analysis accounted for the temperature effect on crystallographic parameters in P n m a structure as well as the phase transition to C m C m structure at Tc˜807 K. Remarkable modifications of the conduction and valence bands were noticed upon varying crystallographic parameters within the structure before Tc, while the phase transition mostly leads to the jump in the band-gap value. The diagonal components of the kinetic parameter tensors (velocity, effective mass) and resulting transport quantity tensors [electrical conductivity σ , thermopower S , and power factor (PF)] were computed for a wide range of temperature (15-900 K) and hole (p -type) and electron (n -type) concentrations (1017-1021cm-3 ). SnSe is shown to have a strong anisotropy of the electron transport properties for both types of charge conductivity, as expected for the layered structure, with the generally heavier p -type effective masses compared to n -type ones. Interestingly, p -type SnSe has strongly nonparabolic dispersion relations, with the "pudding-mold-like" shape of the highest valence band. The analysis of σ ,S , and PF tensors indicates that the interlayer electron transport is beneficial for thermoelectric performance in n -type SnSe, while this direction is blocked in p -type SnSe, where in-plane transport is preferred. Our results predict that n -type SnSe is potentially even better thermoelectric material than p -type SnSe. Theoretical results are compared with the single-crystal p -SnSe measurements, and good agreement is found below 600 K. The discrepancy between the computational and experimental data, appearing at higher temperatures, can be explained assuming an increase of the hole concentration versus T , which is correlated with the
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.
A method for calculating surface electronic structures using semi-infinite boundary conditions
NASA Astrophysics Data System (ADS)
Abraham, Yonas
2005-03-01
We have developed a new formalism for solving the Kohn-Sham equations in the layer geometry appropriate for studying equilibrium and transport properties of surfaces and interfaces. The formalism assumes that the electron-lattice interactions are modeled by pseudopotentials containing both local contributions and non-local terms represented by separable functions, and works especially well with the projector augmented wave ``PAW'' method. Based on the Numerov algorithm, a two-point recurrence relation is used to integrate the differential equations. The recurrence formalism is used to find the generalized Bloch waves in the bulk regions of the system as well as to find the propagating and surface states in the interface regions of the system. The wavefunction is matched at the boundary between the bulk and interface regions and at intermediate points to ensure stability. The formalism is demonstrated for a simple model of a semi-infinite system and compared with a boundary matching formalism developed by Choi and Ihm.
Atomic partial charges on CH3NH3PbI3 from first-principles electronic structure calculations
NASA Astrophysics Data System (ADS)
Madjet, Mohamed E.; El-Mellouhi, Fedwa; Carignano, Marcelo A.; Berdiyorov, Golibjon R.
2016-04-01
We calculated the partial charges in methylammonium (MA) lead-iodide perovskite CH3NH3PbI3 in its different crystalline phases using different first-principles electronic charge partitioning approaches, including the Bader, ChelpG, and density-derived electrostatic and chemical (DDEC) schemes. Among the three charge partitioning methods, the DDEC approach provides chemically intuitive and reliable atomic charges for this material, which consists of a mixture of transition metals, halide ions, and organic molecules. The DDEC charges are also found to be robust against the use of hybrid functionals and/or upon inclusion of spin-orbit coupling or dispersive interactions. We calculated explicitly the atomic charges with a special focus on the dipole moment of the MA molecules within the perovskite structure. The value of the dipole moment of the MA is reduced with respect to the isolated molecule due to charge redistribution involving the inorganic cage. DDEC charges and dipole moment of the organic part remain nearly unchanged upon its rotation within the octahedral cavities. Our findings will be of both fundamental and practical importance, as the accurate and consistent determination of the atomic charges is important in order to understand the average equilibrium distribution of the electrons and to help in the development of force fields for larger scale atomistic simulations to describe static, dynamic, and thermodynamic properties of the material.
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.
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.
Revised self-consistent continuum solvation in electronic-structure calculations.
Andreussi, Oliviero; Dabo, Ismaila; Marzari, Nicola
2012-02-14
The solvation model proposed by Fattebert and Gygi [J. Comput. Chem. 23, 662 (2002)] and Scherlis et al. [J. Chem. Phys. 124, 074103 (2006)] is reformulated, overcoming some of the numerical limitations encountered and extending its range of applicability. We first recast the problem in terms of induced polarization charges that act as a direct mapping of the self-consistent continuum dielectric; this allows to define a functional form for the dielectric that is well behaved both in the high-density region of the nuclear charges and in the low-density region where the electronic wavefunctions decay into the solvent. Second, we outline an iterative procedure to solve the Poisson equation for the quantum fragment embedded in the solvent that does not require multigrid algorithms, is trivially parallel, and can be applied to any Bravais crystallographic system. Last, we capture some of the non-electrostatic or cavitation terms via a combined use of the quantum volume and quantum surface [M. Cococcioni, F. Mauri, G. Ceder, and N. Marzari, Phys. Rev. Lett. 94, 145501 (2005)] of the solute. The resulting self-consistent continuum solvation model provides a very effective and compact fit of computational and experimental data, whereby the static dielectric constant of the solvent and one parameter allow to fit the electrostatic energy provided by the polarizable continuum model with a mean absolute error of 0.3 kcal/mol on a set of 240 neutral solutes. Two parameters allow to fit experimental solvation energies on the same set with a mean absolute error of 1.3 kcal/mol. A detailed analysis of these results, broken down along different classes of chemical compounds, shows that several classes of organic compounds display very high accuracy, with solvation energies in error of 0.3-0.4 kcal/mol, whereby larger discrepancies are mostly limited to self-dissociating species and strong hydrogen-bond-forming compounds. PMID:22360164
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
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. PMID:26882275
Atomic and Electronic Structure of the P3HT/PCBM Interface From First-Principle Calculations
NASA Astrophysics Data System (ADS)
Li, Longhua; Kontsevoi, Oleg; Freeman, Arthur J.
2013-03-01
Fundamental research on donor/acceptor (D/A) interfaces of organic photovoltaics (OPV) have drawn immense interest because of their crucial roles in charge separation (CS), charge transfer (CT) and charge recombination (CR). The blend system consisting of regioregular poly(3-hexylthiophene) (rr-P3HT) and fullerene derivative [6,6]-phenyl C61 butyric acid methyl ester (PCBM) is a widely investigated binary system. Despite significant efforts that have been done to optimize the OPV, such as the D/A ratio, detailed information on their structure, interfaces, and morphology are far from complete. Additionally, fewer investigations have focused on the elementary charge transfer processes. In this work, such a hetero-interface was carried out by annealing simulation; and then interfacial electronic structure and charge transfer were studied by DFT calculations. The process of PCBM assembly on the P3HT surface were shown and the carrier mobilities could be tuned by PCBM orientations.Our calculations provide an important understanding on the assembly of PCBM and charge transfer at the binary interface. Supported by ANSER, an Energy Frontier Research Center funded by the U.S. Department of Energy.
Řezáč, Jan; Huang, Yuanhang; Hobza, Pavel; Beran, Gregory J O
2015-07-14
Many-body noncovalent interactions are increasingly important in large and/or condensed-phase systems, but the current understanding of how well various models predict these interactions is limited. Here, benchmark complete-basis set coupled cluster singles, doubles, and perturbative triples (CCSD(T)) calculations have been performed to generate a new test set for three-body intermolecular interactions. This "3B-69" benchmark set includes three-body interaction energies for 69 total trimer structures, consisting of three structures from each of 23 different molecular crystals. By including structures that exhibit a variety of intermolecular interactions and packing arrangements, this set provides a stringent test for the ability of electronic structure methods to describe the correct physics involved in the interactions. Both MP2.5 (the average of second- and third-order Møller-Plesset perturbation theory) and spin-component-scaled CCSD for noncovalent interactions (SCS-MI-CCSD) perform well. MP2 handles the polarization aspects reasonably well, but it omits three-body dispersion. In contrast, many widely used density functionals corrected with three-body D3 dispersion correction perform comparatively poorly. The primary difficulty stems from the treatment of exchange and polarization in the functionals rather than from the dispersion correction, though the three-body dispersion may also be moderately underestimated by the D3 correction. PMID:26575743
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.