Half-metallicity and spin-contamination of the electronic ground state of graphene nanoribbons and related systems: An impossible compromise?

NASA Astrophysics Data System (ADS)

Huzak, M.; Deleuze, M. S.; Hajgató, B.

2011-09-01

An analysis using the formalism of crystalline orbitals for extended systems with periodicity in one dimension demonstrates that any antiferromagnetic and half-metallic spin-polarization of the edge states in n-acenes, and more generally in zigzag graphene nanoislands and nanoribbons of finite width, would imply a spin contamination ⟨S2⟩ that increases proportionally to system size, in sharp and clear contradiction with the implications of Lieb's theorem for compensated bipartite lattices and the expected value for a singlet (S = 0) electronic ground state. Verifications on naphthalene, larger n-acenes (n = 3-10) and rectangular nanographene islands of increasing size, as well as a comparison using unrestricted Hartree-Fock theory along with basis sets of improving quality against various many-body treatments demonstrate altogether that antiferromagnetism and half-metallicity in extended graphene nanoribbons will be quenched by an exact treatment of electron correlation, at the confines of non-relativistic many-body quantum mechanics. Indeed, for singlet states, symmetry-breakings in spin-densities are necessarily the outcome of a too approximate treatment of static and dynamic electron correlation in single-determinantal approaches, such as unrestricted Hartree-Fock or Density Functional Theory. In this context, such as the size-extensive spin-contamination to which it relates, half-metallicity is thus nothing else than a methodological artefact.

Half-metallicity and spin-contamination of the electronic ground state of graphene nanoribbons and related systems: an impossible compromise?

PubMed

Huzak, M; Deleuze, M S; Hajgató, B

2011-09-14

An analysis using the formalism of crystalline orbitals for extended systems with periodicity in one dimension demonstrates that any antiferromagnetic and half-metallic spin-polarization of the edge states in n-acenes, and more generally in zigzag graphene nanoislands and nanoribbons of finite width, would imply a spin contamination S(2) that increases proportionally to system size, in sharp and clear contradiction with the implications of Lieb's theorem for compensated bipartite lattices and the expected value for a singlet (S = 0) electronic ground state. Verifications on naphthalene, larger n-acenes (n = 3-10) and rectangular nanographene islands of increasing size, as well as a comparison using unrestricted Hartree-Fock theory along with basis sets of improving quality against various many-body treatments demonstrate altogether that antiferromagnetism and half-metallicity in extended graphene nanoribbons will be quenched by an exact treatment of electron correlation, at the confines of non-relativistic many-body quantum mechanics. Indeed, for singlet states, symmetry-breakings in spin-densities are necessarily the outcome of a too approximate treatment of static and dynamic electron correlation in single-determinantal approaches, such as unrestricted Hartree-Fock or Density Functional Theory. In this context, such as the size-extensive spin-contamination to which it relates, half-metallicity is thus nothing else than a methodological artefact. © 2011 American Institute of Physics

The unrestricted Hartree-Fock self consistent field calculation for spin density wave state in metallic carbon nanotube

NASA Astrophysics Data System (ADS)

Kobayashi, Katsushi

1997-06-01

The possibility of a spin density wave (SDW) state in a metallic carbon nanotube (CN) and its electronic properties are investigated within the Hartree-Fock self consistent field (SCF) energy-band calculation. Two kinds of spatial SDW states are assumed in this study. Each assumed SDW on the wave function is constructed with the degenerate π orbital in the metallic CN system. The results calculated for the one SDW model of CN always have a relative stability (˜ 0.1 eV/cell) in SCF total energy compared with the original model in which no SDW is assumed. All the results calculated for another SDW model are completely equal to the original one. Moreover, in the energy dispersion of the former stable SDW model, the degenerate π level found in the original model disappears and the band gap (3-5 eV) occurs around at the Fermi level. The energetic stability and the band gap are also found in the π-electron band calculation within the Hubbard Hamiltonian.

Matrix Methods for Solving Hartree-Fock Equations in Atomic Structure Calculations and Line Broadening

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gomez, Thomas; Nagayama, Taisuke; Fontes, Chris

Atomic structure of N-electron atoms is often determined by solving the Hartree-Fock equations, which are a set of integro-differential equations. The integral part of the Hartree-Fock equations treats electron exchange, but the Hartree-Fock equations are not often treated as an integro-differential equation. The exchange term is often approximated as an inhomogeneous or an effective potential so that the Hartree-Fock equations become a set of ordinary differential equations (which can be solved using the usual shooting methods). Because the Hartree-Fock equations are an iterative-refinement method, the inhomogeneous term relies on the previous guess of the wavefunction. In addition, there are numericalmore » complications associated with solving inhomogeneous differential equations. This work uses matrix methods to solve the Hartree-Fock equations as an integro-differential equation. It is well known that a derivative operator can be expressed as a matrix made of finite-difference coefficients; energy eigenvalues and eigenvectors can be obtained by using linear-algebra packages. The integral (exchange) part of the Hartree-Fock equation can be approximated as a sum and written as a matrix. The Hartree-Fock equations can be solved as a matrix that is the sum of the differential and integral matrices. We compare calculations using this method against experiment and standard atomic structure calculations. This matrix method can also be used to solve for free-electron wavefunctions, thus improving how the atoms and free electrons interact. Here, this technique is important for spectral line broadening in two ways: it improves the atomic structure calculations, and it improves the motion of the plasma electrons that collide with the atom.« less

Matrix Methods for Solving Hartree-Fock Equations in Atomic Structure Calculations and Line Broadening

DOE PAGES

Gomez, Thomas; Nagayama, Taisuke; Fontes, Chris; ...

2018-04-23

Atomic structure of N-electron atoms is often determined by solving the Hartree-Fock equations, which are a set of integro-differential equations. The integral part of the Hartree-Fock equations treats electron exchange, but the Hartree-Fock equations are not often treated as an integro-differential equation. The exchange term is often approximated as an inhomogeneous or an effective potential so that the Hartree-Fock equations become a set of ordinary differential equations (which can be solved using the usual shooting methods). Because the Hartree-Fock equations are an iterative-refinement method, the inhomogeneous term relies on the previous guess of the wavefunction. In addition, there are numericalmore » complications associated with solving inhomogeneous differential equations. This work uses matrix methods to solve the Hartree-Fock equations as an integro-differential equation. It is well known that a derivative operator can be expressed as a matrix made of finite-difference coefficients; energy eigenvalues and eigenvectors can be obtained by using linear-algebra packages. The integral (exchange) part of the Hartree-Fock equation can be approximated as a sum and written as a matrix. The Hartree-Fock equations can be solved as a matrix that is the sum of the differential and integral matrices. We compare calculations using this method against experiment and standard atomic structure calculations. This matrix method can also be used to solve for free-electron wavefunctions, thus improving how the atoms and free electrons interact. Here, this technique is important for spectral line broadening in two ways: it improves the atomic structure calculations, and it improves the motion of the plasma electrons that collide with the atom.« less

Existence of Hartree-Fock excited states for atoms and molecules

NASA Astrophysics Data System (ADS)

Lewin, Mathieu

2018-04-01

For neutral and positively charged atoms and molecules, we prove the existence of infinitely many Hartree-Fock critical points below the first energy threshold (that is, the lowest energy of the same system with one electron removed). This is the equivalent, in Hartree-Fock theory, of the famous Zhislin-Sigalov theorem which states the existence of infinitely many eigenvalues below the bottom of the essential spectrum of the N-particle linear Schrödinger operator. Our result improves a theorem of Lions in 1987 who already constructed infinitely many Hartree-Fock critical points, but with much higher energy. Our main contribution is the proof that the Hartree-Fock functional satisfies the Palais-Smale property below the first energy threshold. We then use minimax methods in the N-particle space, instead of working in the one-particle space.

Tables Of Gaussian-Type Orbital Basis Functions

NASA Technical Reports Server (NTRS)

Partridge, Harry

1992-01-01

NASA technical memorandum contains tables of estimated Hartree-Fock wave functions for atoms lithium through neon and potassium through krypton. Sets contain optimized Gaussian-type orbital exponents and coefficients, and near Hartree-Fock quality. Orbital exponents optimized by minimizing restricted Hartree-Fock energy via scaled Newton-Raphson scheme in which Hessian evaluated numerically by use of analytically determined gradients.

Development of the Nuclear-Electronic Orbital Approach and Applications to Ionic Liquids and Tunneling Processes

DTIC Science & Technology

2010-02-24

electronic Schrodinger equation . In previous grant cycles, we implemented the NEO approach at the Hartree-Fock (NEO-HF),13 configuration interaction...electronic and nuclear molecular orbitals. The resulting electronic and nuclear Hartree-Fock-Roothaan equations are solved iteratively until self...directly into the standard Hartree- Fock-Roothaan equations , which are solved iteratively to self-consistency. The density matrix representation

Optimized norm-conserving Hartree-Fock pseudopotentials

NASA Astrophysics Data System (ADS)

Walter, Eric J.; Al-Saidi, Wissam A.

2006-03-01

We report soft Hartree-Fock based pseudopotentials obtained using the optimized pseudopotential method. The spurious long range tail due to the non locality of the exchange potential is removed using a self-consistent damping mechanism as employed in exact exchange and recent Hartree-Fock pseudopotentials. The binding energies of several dimers computed using these pseudopotentials within a planewave Hartree-Fock code show good agreement with all-electron results. A. M. Rappe, K. M. Rabe, E. Kaxiras, and J. D. Joannopoulos, Phys. Rev. B 41, 1227 (1990). E. Engel, A. Höck, R. N. Schmid, R. M. Dreizler, and N. Chetty, Phys. Rev. B 64, 125111 (2001). J.R. Trail and R. J. Needs, J. Chem. Phys. 122, 014112 (2005).

Electron propagator calculations on the ionization energies of CrH -, MnH - and FeH -

NASA Astrophysics Data System (ADS)

Lin, Jyh-Shing; Ortiz, J. V.

1990-08-01

Electron propagator calculations with unrestricted Hartree-Fock reference states yield the ionization energies of the title anions. Spin contamination in the anionic reference state is small, enabling the use of second-and third-order self-energies in the Dyson equation. Feynman-Dyson amplitudes for these ionizations are essentially identical to canonical spin-orbitals. For most of the final states, these consist of an antibonding combination of an sp metal hybrid, polarized away from the hydrogen, and hydroegen s functions. In one case, the Feynman-Dyson amplitude consists of nonbonding d functions. Calculated ionization energies are within 0.5 eV of experiment.

Relativistic extended Thomas-Fermi calculations with exchange term contributions

NASA Astrophysics Data System (ADS)

Haddad, S.; Weigel, M. K.

1994-10-01

In this investigation we present self-consistent relativistic extended Thomas-Fermi (ETF) and extended Thomas-Fermi-Fock (ETFF) approaches, derived from the semiclassical treatment of the relativistic nuclear Hartree-Fock problem. The approximations are used to describe the ground-state properties of finite nuclei. The resulting equations are solved numerically for several one-boson-exchange (OBE) lagrangians. The results are discussed and compared with the outcome of full quantal Hartree and Hartree-Fock calculations, other semiclassical treatments and experimental data.

A finite-temperature Hartree-Fock code for shell-model Hamiltonians

NASA Astrophysics Data System (ADS)

Bertsch, G. F.; Mehlhaff, J. M.

2016-10-01

The codes HFgradZ.py and HFgradT.py find axially symmetric minima of a Hartree-Fock energy functional for a Hamiltonian supplied in a shell model basis. The functional to be minimized is the Hartree-Fock energy for zero-temperature properties or the Hartree-Fock grand potential for finite-temperature properties (thermal energy, entropy). The minimization may be subjected to additional constraints besides axial symmetry and nucleon numbers. A single-particle operator can be used to constrain the minimization by adding it to the single-particle Hamiltonian with a Lagrange multiplier. One can also constrain its expectation value in the zero-temperature code. Also the orbital filling can be constrained in the zero-temperature code, fixing the number of nucleons having given Kπ quantum numbers. This is particularly useful to resolve near-degeneracies among distinct minima.

Projected Hartree-Fock theory as a polynomial of particle-hole excitations and its combination with variational coupled cluster theory

NASA Astrophysics Data System (ADS)

Qiu, Yiheng; Henderson, Thomas M.; Scuseria, Gustavo E.

2017-05-01

Projected Hartree-Fock theory provides an accurate description of many kinds of strong correlations but does not properly describe weakly correlated systems. Coupled cluster theory, in contrast, does the opposite. It therefore seems natural to combine the two so as to describe both strong and weak correlations with high accuracy in a relatively black-box manner. Combining the two approaches, however, is made more difficult by the fact that the two techniques are formulated very differently. In earlier work, we showed how to write spin-projected Hartree-Fock in a coupled-cluster-like language. Here, we fill in the gaps in that earlier work. Further, we combine projected Hartree-Fock and coupled cluster theory in a variational formulation and show how the combination performs for the description of the Hubbard Hamiltonian and for several small molecular systems.

Restricted Closed Shell Hartree Fock Roothaan Matrix Method Applied to Helium Atom Using Mathematica

ERIC Educational Resources Information Center

Acosta, César R.; Tapia, J. Alejandro; Cab, César

2014-01-01

Slater type orbitals were used to construct the overlap and the Hamiltonian core matrices; we also found the values of the bi-electron repulsion integrals. The Hartree Fock Roothaan approximation process starts with setting an initial guess value for the elements of the density matrix; with these matrices we constructed the initial Fock matrix.…

Influence of the Dirac-Hartree-Fock starting potential on the parity-nonconserving electric-dipole-transition amplitudes in cesium and thallium

NASA Technical Reports Server (NTRS)

Perger, W. F.; Das, B. P.

1987-01-01

The parity-nonconserving electric-dipole-transition amplitudes for the 6s1/2-7s1/2 transition in cesium and the 6p1/2-7p1/2 transition in thallium have been calculated by the Dirac-Hartree-Fock method. The effects of using different Dirac-Hartree-Fock atomic core potentials are examined and the transition amplitudes for both the length and velocity gauges are given. It is found that the parity-nonconserving transition amplitudes exhibit a greater dependence on the starting potential for thallium than for cesium.

The any particle molecular orbital grid-based Hartree-Fock (APMO-GBHF) approach

NASA Astrophysics Data System (ADS)

Posada, Edwin; Moncada, Félix; Reyes, Andrés

2018-02-01

The any particle molecular orbital grid-based Hartree-Fock approach (APMO-GBHF) is proposed as an initial step to perform multi-component post-Hartree-Fock, explicitly correlated, and density functional theory methods without basis set errors. The method has been applied to a number of electronic and multi-species molecular systems. Results of these calculations show that the APMO-GBHF total energies are comparable with those obtained at the APMO-HF complete basis set limit. In addition, results reveal a considerable improvement in the description of the nuclear cusps of electronic and non-electronic densities.

Spatial and Spin Symmetry Breaking in Semidefinite-Programming-Based Hartree-Fock Theory.

PubMed

Nascimento, Daniel R; DePrince, A Eugene

2018-05-08

The Hartree-Fock problem was recently recast as a semidefinite optimization over the space of rank-constrained two-body reduced-density matrices (RDMs) [ Phys. Rev. A 2014 , 89 , 010502(R) ]. This formulation of the problem transfers the nonconvexity of the Hartree-Fock energy functional to the rank constraint on the two-body RDM. We consider an equivalent optimization over the space of positive semidefinite one-electron RDMs (1-RDMs) that retains the nonconvexity of the Hartree-Fock energy expression. The optimized 1-RDM satisfies ensemble N-representability conditions, and ensemble spin-state conditions may be imposed as well. The spin-state conditions place additional linear and nonlinear constraints on the 1-RDM. We apply this RDM-based approach to several molecular systems and explore its spatial (point group) and spin ( Ŝ 2 and Ŝ 3 ) symmetry breaking properties. When imposing Ŝ 2 and Ŝ 3 symmetry but relaxing point group symmetry, the procedure often locates spatial-symmetry-broken solutions that are difficult to identify using standard algorithms. For example, the RDM-based approach yields a smooth, spatial-symmetry-broken potential energy curve for the well-known Be-H 2 insertion pathway. We also demonstrate numerically that, upon relaxation of Ŝ 2 and Ŝ 3 symmetry constraints, the RDM-based approach is equivalent to real-valued generalized Hartree-Fock theory.

Electron impact ionization cross section studies of C2Fx (x = 1 - 6) and C3Fx (x = 1 - 8) fluorocarbon species

NASA Astrophysics Data System (ADS)

Gupta, Dhanoj; Choi, Heechol; Song, Mi-Young; Karwasz, Grzegorz P.; Yoon, Jung-Sik

2017-05-01

The total ionization cross section for C2Fx (x = 1 - 6) and C3Fx (x = 1 - 8) fluorocarbon species are studied with the Binary-Encounter Bethe (BEB) model using various orbital parameters calculated from restricted/unrestricted Hartree-Fock (RHF/UHF) and Density Functional Theory (DFT). All the targets were optimized for their minimal structures and energies with several ab-initio methods with the aug-cc-pVTZ basis set. Among them, the present results with RHF/UHF orbital energies showed good agreement with the experimental results for stable targets C2F6, C2F4, C3F6 and C3F8. The results with the DFT (ωB97X/ωB97X-D) showed a reasonable agreement with the recent calculation of Bull et al. [J.N. Bull, M. Bart, C. Vallance, P.W. Harland, Phys. Rev. A 88, 062710 (2013)] for C2F6, C3F6 and C3F8 targets. The ionization cross section for C2F, C2F2, C2F3, C3F, C3F2, C3F3, C3F4, C3F5 and C3F7 were computed for the first time in the present study. We have also computed the vertical ionization potentials and polarizability for all the targets and compared them with other experimental and theoretical values. A good agreement is found between the present and the previous results. The calculated polarizability in turn is used to study the correlation with maximum ionization cross section and in general a good correlation is found among them, confirming the consistency and reliability of the present data. The cross section data reported in this article are very important for plasma modeling especially related to fluorocarbon plasmas. Contribution to the Topical Issue "Atomic and Molecular Data and their Applications", edited by Gordon W.F. Drake, Jung-Sik Yoon, Daiji Kato, Grzegorz Karwasz.

Beyond computational difficulties: Survey of the two decades from the elaboration to the extensive application of the Hartree-Fock method

NASA Astrophysics Data System (ADS)

Martinez, Jean-Philippe

2017-11-01

The Hartree-Fock method, one of the first applications of the new quantum mechanics in the frame of the many-body problem, had been elaborated by Rayner Douglas Hartree in 1928 and Vladimir Fock in 1930. Promptly, the challenge of tedious computations was being discussed and it is well known that the application of the method benefited greatly from the development of computers from the mid-to-late 1950s. However, the years from 1930 to 1950 were by no means years of stagnation, as the method was the object of several considerations related to its mathematical formulation, possible extension, and conceptual understanding. Thus, with a focus on the respective attitudes of Hartree and Fock, in particular with respect to the concept of quantum exchange, the present work puts forward some mathematical and conceptual clarifications, which played an important role for a better understanding of the many-body problem in quantum mechanics.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu Kun; Zhao Hongmei; Wang Caixia

Bromoiodomethane photodissociation in the low-lying excited states has been characterized using unrestricted Hartree-Fock, configuration-interaction-singles, and complete active space self-consistent field calculations with the SDB-aug-cc-pVTZ, aug-cc-pVTZ, and 3-21g** basis sets. According to the results of the vertical excited energies and oscillator strengths of these low-lying excited states, bond selectivity is predicted. Subsequently, the minimum energy paths of the first excited singlet state and the third excited state for the dissociation reactions were calculated using the complete active space self-consistent field method with 3-21g** basis set. Good agreement is found between the calculations and experimental data. The relationships of excitations, the electronicmore » structures at Franck-Condon points, and bond selectivity are discussed.« less

Correlation study of sodium-atom chemisorption on the GaAs(110) surface

NASA Astrophysics Data System (ADS)

Song, K. M.; Khan, D. C.; Ray, A. K.

1994-01-01

Different possible adsorption sites of sodium atoms on a gallium arsenide surface have been investigated using ab initio self-consistent unrestricted Hartree-Fock total-energy cluster calculations with Hay-Wadt effective core potentials. The effects of electron correlation have been included by invoking the concepts of many-body perturbation theory and are found to be highly significant. We find that the Na-atom adsorption at a site modeled with an NaGa5As4H12 cluster is most favored energetically followed by Na adsorption at the site modeled with the NaGa4As5H12 cluster. The effects of charge transfer from Na to the GaAs surface as also possibilities of metallization are also analyzed and discussed.

A new near-linear scaling, efficient and accurate, open-shell domain-based local pair natural orbital coupled cluster singles and doubles theory.

PubMed

Saitow, Masaaki; Becker, Ute; Riplinger, Christoph; Valeev, Edward F; Neese, Frank

2017-04-28

The Coupled-Cluster expansion, truncated after single and double excitations (CCSD), provides accurate and reliable molecular electronic wave functions and energies for many molecular systems around their equilibrium geometries. However, the high computational cost, which is well-known to scale as O(N 6 ) with system size N, has limited its practical application to small systems consisting of not more than approximately 20-30 atoms. To overcome these limitations, low-order scaling approximations to CCSD have been intensively investigated over the past few years. In our previous work, we have shown that by combining the pair natural orbital (PNO) approach and the concept of orbital domains it is possible to achieve fully linear scaling CC implementations (DLPNO-CCSD and DLPNO-CCSD(T)) that recover around 99.9% of the total correlation energy [C. Riplinger et al., J. Chem. Phys. 144, 024109 (2016)]. The production level implementations of the DLPNO-CCSD and DLPNO-CCSD(T) methods were shown to be applicable to realistic systems composed of a few hundred atoms in a routine, black-box fashion on relatively modest hardware. In 2011, a reduced-scaling CCSD approach for high-spin open-shell unrestricted Hartree-Fock reference wave functions was proposed (UHF-LPNO-CCSD) [A. Hansen et al., J. Chem. Phys. 135, 214102 (2011)]. After a few years of experience with this method, a few shortcomings of UHF-LPNO-CCSD were noticed that required a redesign of the method, which is the subject of this paper. To this end, we employ the high-spin open-shell variant of the N-electron valence perturbation theory formalism to define the initial guess wave function, and consequently also the open-shell PNOs. The new PNO ansatz properly converges to the closed-shell limit since all truncations and approximations have been made in strict analogy to the closed-shell case. Furthermore, given the fact that the formalism uses a single set of orbitals, only a single PNO integral transformation is necessary, which offers large computational savings. We show that, with the default PNO truncation parameters, approximately 99.9% of the total CCSD correlation energy is recovered for open-shell species, which is comparable to the performance of the method for closed-shells. UHF-DLPNO-CCSD shows a linear scaling behavior for closed-shell systems, while linear to quadratic scaling is obtained for open-shell systems. The largest systems we have considered contain more than 500 atoms and feature more than 10 000 basis functions with a triple-ζ quality basis set.

A new near-linear scaling, efficient and accurate, open-shell domain-based local pair natural orbital coupled cluster singles and doubles theory

NASA Astrophysics Data System (ADS)

Saitow, Masaaki; Becker, Ute; Riplinger, Christoph; Valeev, Edward F.; Neese, Frank

2017-04-01

The Coupled-Cluster expansion, truncated after single and double excitations (CCSD), provides accurate and reliable molecular electronic wave functions and energies for many molecular systems around their equilibrium geometries. However, the high computational cost, which is well-known to scale as O(N6) with system size N, has limited its practical application to small systems consisting of not more than approximately 20-30 atoms. To overcome these limitations, low-order scaling approximations to CCSD have been intensively investigated over the past few years. In our previous work, we have shown that by combining the pair natural orbital (PNO) approach and the concept of orbital domains it is possible to achieve fully linear scaling CC implementations (DLPNO-CCSD and DLPNO-CCSD(T)) that recover around 99.9% of the total correlation energy [C. Riplinger et al., J. Chem. Phys. 144, 024109 (2016)]. The production level implementations of the DLPNO-CCSD and DLPNO-CCSD(T) methods were shown to be applicable to realistic systems composed of a few hundred atoms in a routine, black-box fashion on relatively modest hardware. In 2011, a reduced-scaling CCSD approach for high-spin open-shell unrestricted Hartree-Fock reference wave functions was proposed (UHF-LPNO-CCSD) [A. Hansen et al., J. Chem. Phys. 135, 214102 (2011)]. After a few years of experience with this method, a few shortcomings of UHF-LPNO-CCSD were noticed that required a redesign of the method, which is the subject of this paper. To this end, we employ the high-spin open-shell variant of the N-electron valence perturbation theory formalism to define the initial guess wave function, and consequently also the open-shell PNOs. The new PNO ansatz properly converges to the closed-shell limit since all truncations and approximations have been made in strict analogy to the closed-shell case. Furthermore, given the fact that the formalism uses a single set of orbitals, only a single PNO integral transformation is necessary, which offers large computational savings. We show that, with the default PNO truncation parameters, approximately 99.9% of the total CCSD correlation energy is recovered for open-shell species, which is comparable to the performance of the method for closed-shells. UHF-DLPNO-CCSD shows a linear scaling behavior for closed-shell systems, while linear to quadratic scaling is obtained for open-shell systems. The largest systems we have considered contain more than 500 atoms and feature more than 10 000 basis functions with a triple-ζ quality basis set.

Non-plane-wave Hartree-Fock states and nuclear homework potentials

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gutierrez, G.; Plastino, A.; de Llano, M.

1979-12-01

It is shown that non-plane-wave single-particle Hartree-Fock orbitals giving rise to a ''spin-density-wave-like'' structure give lower energy than plane waves beyond a certain relatively low density in both nuclear and neutron matter with homework pair potentials v/sub 1/ and v/sub 2/.

The fractal geometry of Hartree-Fock

NASA Astrophysics Data System (ADS)

Theel, Friethjof; Karamatskou, Antonia; Santra, Robin

2017-12-01

The Hartree-Fock method is an important approximation for the ground-state electronic wave function of atoms and molecules so that its usage is widespread in computational chemistry and physics. The Hartree-Fock method is an iterative procedure in which the electronic wave functions of the occupied orbitals are determined. The set of functions found in one step builds the basis for the next iteration step. In this work, we interpret the Hartree-Fock method as a dynamical system since dynamical systems are iterations where iteration steps represent the time development of the system, as encountered in the theory of fractals. The focus is put on the convergence behavior of the dynamical system as a function of a suitable control parameter. In our case, a complex parameter λ controls the strength of the electron-electron interaction. An investigation of the convergence behavior depending on the parameter λ is performed for helium, neon, and argon. We observe fractal structures in the complex λ-plane, which resemble the well-known Mandelbrot set, determine their fractal dimension, and find that with increasing nuclear charge, the fragmentation increases as well.

Self-consistent description of the SHFB equations for 112Sn

NASA Astrophysics Data System (ADS)

Ghafouri, M.; Sadeghi, H.; Torkiha, M.

2018-03-01

The Hartree-Fock (HF) method is an excellent approximation of the closed shell magic nuclei. Pair correlation is essential for the description of open shell nuclei and has been derived for even-even, odd-odd and even-odd nuclei. These effects are reported by Hartree-Fock with BCS (HFBCS) or Hartree-Fock-Bogolyubov (HFB). These issues have been investigated, especially in the nuclear charts, and such studies have been compared with the observed information. We compute observations such as total binding energy, charge radius, densities, separation energies, pairing gaps and potential energy surfaces for neutrons and protons, and compare them with experimental data and the result of the spherical codes. In spherical even-even neutron-rich nuclei are considered in the Skyrme-Hartree-Fock-Bogolyubov (SHFB) method with density-dependent pairing interaction. Zero-range density-dependent interactions is used in the pairing channel. We solve SHF or SHFB equations in the spatial coordinates with spherical symmetry for tin isotopes such as 112Sn. The numerical accuracy of solving equations in the coordinate space is much greater than the fundamental extensions, which yields almost precise results.

Skyrme-Hartree-Fock calculation on He, Li, and Be isotopes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shen, Y.; Ren, Z.

1996-09-01

The ground-state properties of He, Li, and Be nuclei are investigated by the Skyrme-Hartree-Fock approach with new force parameters SKI4 of Reinhard and Flocard [Nucl. Phys. A {bold 584}, 467 (1995)] plus a density-dependent pairing correlation. Calculations show that the Skyrme-Hartree-Fock model with above force parameters provides a good description on the binding energy and radii of He, Li, and Be isotopes. It also succeeds in reproducing neutron halos in nuclei {sup 6}He, {sup 8}He, {sup 11}Li, and {sup 14}Be. A detailed discussion on numerical results is provided and an explanation for the above success is given. {copyright} {ital 1996more » The American Physical Society.}« less

A theoretical study of bond selective photochemistry in CH2BrI

NASA Astrophysics Data System (ADS)

Liu, Kun; Zhao, Hongmei; Wang, Caixia; Zhang, Aihua; Ma, Siyu; Li, Zonghe

2005-01-01

Bromoiodomethane photodissociation in the low-lying excited states has been characterized using unrestricted Hartree-Fock, configuration-interaction-singles, and complete active space self-consistent field calculations with the SDB-aug-cc-pVTZ, aug-cc-pVTZ, and 3-21g** basis sets. According to the results of the vertical excited energies and oscillator strengths of these low-lying excited states, bond selectivity is predicted. Subsequently, the minimum energy paths of the first excited singlet state and the third excited state for the dissociation reactions were calculated using the complete active space self-consistent field method with 3-21g** basis set. Good agreement is found between the calculations and experimental data. The relationships of excitations, the electronic structures at Franck-Condon points, and bond selectivity are discussed.

Charge renormalization at the large-D limit for N-electron atoms and weakly bound systems

NASA Astrophysics Data System (ADS)

Kais, S.; Bleil, R.

1995-05-01

We develop a systematic way to determine an effective nuclear charge ZRD such that the Hartree-Fock results will be significantly closer to the exact energies by utilizing the analytically known large-D limit energies. This method yields an expansion for the effective nuclear charge in powers of (1/D), which we have evaluated to the first order. This first order approximation to the desired effective nuclear charge has been applied to two-electron atoms with Z=2-20, and weakly bound systems such as H-. The errors for the two-electron atoms when compared with exact results were reduced from ˜0.2% for Z=2 to ˜0.002% for large Z. Although usual Hartree-Fock calculations for H- show this to be unstable, our results reduce the percent error of the Hartree-Fock energy from 7.6% to 1.86% and predicts the anion to be stable. For N-electron atoms (N=3-18, Z=3-28), using only the zeroth order approximation for the effective charge significantly reduces the error of Hartree-Fock calculations and recovers more than 80% of the correlation energy.

Semiempirical evaluation of post-Hartree-Fock diagonal-Born-Oppenheimer corrections for organic molecules.

PubMed

Mohallem, José R

2008-04-14

Recent post-Hartree-Fock calculations of the diagonal-Born-Oppenheimer correction empirically show that it behaves quite similar to atomic nuclear mass corrections. An almost constant contribution per electron is identified, which converges with system size for specific series of organic molecules. This feature permits pocket-calculator evaluation of the corrections within thermochemical accuracy (10(-1) mhartree or kcal/mol).

Uniform in N global well-posedness of the time-dependent Hartree-Fock-Bogoliubov equations in R^{1+1}

NASA Astrophysics Data System (ADS)

Chong, Jacky Jia Wei

2018-04-01

We prove the global well-posedness of the time-dependent Hartree-Fock-Bogoliubov (TDHFB) equations in R^{1+1} with two-body interaction potential of the form N^{-1}v_N(x) = N^{β -1} v(N^β x) where v≥0 is a sufficiently regular radial function, i.e., v \\in L^1(R)\\cap C^∞ (R) . In particular, using methods of dispersive PDEs similar to the ones used in Grillakis and Machedon (Commun Partial Differ Equ 42:24-67, 2017), we are able to show for any scaling parameter β >0 the TDHFB equations are globally well-posed in some Strichartz-type spaces independent of N, cf. (Bach et al. in The time-dependent Hartree-Fock-Bogoliubov equations for Bosons, 2016. arXiv:1602.05171).

Positron and electron energy bands in several ionic crystals using restricted Hartree-Fock method

NASA Astrophysics Data System (ADS)

Kunz, A. B.; Waber, J. T.

1981-08-01

Using a restricted Hartree-Fock formalism and suitably localized and symmetrized wave functions, both the positron and electron energy bands were calculated for NaF, MgO and NiO. The lowest positron state at Γ 1 lies above the vacuum level and negative work functions are predicted. Positron annihilation rates were calculated and found to be in good agreement with measured lifetimes.

Near Hartree-Fock quality GTO basis sets for the first- and third-row atoms

NASA Technical Reports Server (NTRS)

Partridge, Harry

1989-01-01

Energy-optimized Gaussian-type-orbital (GTO) basis sets of accuracy approaching that of numerical Hartree-Fock computations are compiled for the elements of the first and third rows of the periodic table. The methods employed in calculating the sets are explained; the applicability of the sets to electronic-structure calculations is discussed; and the results are presented in tables and briefly characterized.

Multiorbital kinetic effects on charge ordering of frustrated electrons on the triangular lattice

NASA Astrophysics Data System (ADS)

Février, C.; Fratini, S.; Ralko, A.

2015-06-01

The role of the multiorbital effects on the emergence of frustrated electronic orders on the triangular lattice at half filling is investigated through an extended spinless fermion Hubbard model. By using two complementary approaches, unrestricted Hartree-Fock and exact diagonalizations, we unravel a very rich phase diagram controlled by the strength of both local and off-site Coulomb interactions and by the interorbital hopping anisotropy ratio t'/t . Three robust unconventional electronic phases, a pinball liquid, an inverse pinball liquid, and a large-unit-cell √{12 }×√{12 } droplet phase, are found to be generic in the triangular geometry, being controlled by the band structure parameters. The latter are also stabilized in the isotropic limit of our microscopic model, which recovers the standard SU(2) spinful extended single-band Hubbard model.

Localization of holes near charged defects in orbitally degenerate, doped Mott insulators

NASA Astrophysics Data System (ADS)

Avella, Adolfo; Oleś, Andrzej M.; Horsch, Peter

2018-05-01

We study the role of charged defects, disorder and electron-electron (e-e) interactions in a multiband model for t2g electrons in vanadium perovskites R1-xCaxVO3 (R = La,…,Y). By means of unrestricted Hartree-Fock calculations, we find that the atomic multiplet structure persists up to 50% Ca doping. Using the inverse participation number, we explore the degree of localization and its doping dependence for all electronic states. The observation of strongly localized wave functions is consistent with our conjecture that doped holes form spin-orbital polarons that are strongly bound to the charged Ca2+ defects. Interestingly, the long-range e-e interactions lead to a discontinuity in the wave function size across the chemical potential, where the electron removal states are more localized than the addition states.

Relativistic effects on magnetic circular dichroism studied by GUHF/SECI method

NASA Astrophysics Data System (ADS)

Honda, Y.; Hada, M.; Ehara, M.; Nakatsuji, H.; Downing, J.; Michl, J.

2002-04-01

Quasi-relativistic formulation of the Magnetic circular dichroism (MCD) Faraday terms are presented using the generalized unrestricted Hartree-Fock (GUHF)/single excitation configuration interaction (SECI) method combined with the finite perturbation method and applied to the MCD of the three n-σ ∗ states ( 3Q1, 3Q0, 1Q1) of CH 3I. The Faraday B term for the 1Q1 state was 0.1976( Debye) 2( Bohr magneton )/(10 3 cm-1) in the non-relativistic theory, but was dramatically improved by the relativistic effect and became 0.0184 in agreement with the experimental values, 0.014 and 0.0257. This change was mainly due to the one-electron spin-orbit (SO1) term rather than the spin-free relativistic (SFR) and the two-electron spin-orbit (SO2) terms.

Linear scaling computation of the Fock matrix. II. Rigorous bounds on exchange integrals and incremental Fock build

NASA Astrophysics Data System (ADS)

Schwegler, Eric; Challacombe, Matt; Head-Gordon, Martin

1997-06-01

A new linear scaling method for computation of the Cartesian Gaussian-based Hartree-Fock exchange matrix is described, which employs a method numerically equivalent to standard direct SCF, and which does not enforce locality of the density matrix. With a previously described method for computing the Coulomb matrix [J. Chem. Phys. 106, 5526 (1997)], linear scaling incremental Fock builds are demonstrated for the first time. Microhartree accuracy and linear scaling are achieved for restricted Hartree-Fock calculations on sequences of water clusters and polyglycine α-helices with the 3-21G and 6-31G basis sets. Eightfold speedups are found relative to our previous method. For systems with a small ionization potential, such as graphitic sheets, the method naturally reverts to the expected quadratic behavior. Also, benchmark 3-21G calculations attaining microhartree accuracy are reported for the P53 tetramerization monomer involving 698 atoms and 3836 basis functions.

Parallel scalability of Hartree-Fock calculations

NASA Astrophysics Data System (ADS)

Chow, Edmond; Liu, Xing; Smelyanskiy, Mikhail; Hammond, Jeff R.

2015-03-01

Quantum chemistry is increasingly performed using large cluster computers consisting of multiple interconnected nodes. For a fixed molecular problem, the efficiency of a calculation usually decreases as more nodes are used, due to the cost of communication between the nodes. This paper empirically investigates the parallel scalability of Hartree-Fock calculations. The construction of the Fock matrix and the density matrix calculation are analyzed separately. For the former, we use a parallelization of Fock matrix construction based on a static partitioning of work followed by a work stealing phase. For the latter, we use density matrix purification from the linear scaling methods literature, but without using sparsity. When using large numbers of nodes for moderately sized problems, density matrix computations are network-bandwidth bound, making purification methods potentially faster than eigendecomposition methods.

Optimizing the Navy’s Investment in Space Professionals

DTIC Science & Technology

2011-09-01

UFO Ultra High Frequency Follow-On UHF Ultra High Frequency URL Unrestricted Line USA United States Army USAF United States Air Force USCYBERCOM...LEASAT), and eight UHF Follow-On ( UFO ) satellites all flying in geostationary orbit (GEO). NAVSOC is the principle Navy command that operates, manages...and maintains the DoD’s narrowband UHF capability from five different ground stations. The replacement satellite for the aging UFO system is the

Reconciling phase diffusion and Hartree-Fock approximation in condensate systems

NASA Astrophysics Data System (ADS)

Giorgi, Gian Luca; de Pasquale, Ferdinando

2012-01-01

Despite the weakly interacting regime, the physics of Bose-Einstein condensates is widely affected by particle-particle interactions. They determine quantum phase diffusion, which is known to be the main cause of loss of coherence. Studying a simple model of two interacting Bose systems, we show how to predict the appearance of phase diffusion beyond the Bogoliubov approximation, providing a self-consistent treatment in the framework of a generalized Hartree-Fock-Bogoliubov perturbation theory.

Attenuated coupled cluster: a heuristic polynomial similarity transformation incorporating spin symmetry projection into traditional coupled cluster theory

NASA Astrophysics Data System (ADS)

Gomez, John A.; Henderson, Thomas M.; Scuseria, Gustavo E.

2017-11-01

In electronic structure theory, restricted single-reference coupled cluster (CC) captures weak correlation but fails catastrophically under strong correlation. Spin-projected unrestricted Hartree-Fock (SUHF), on the other hand, misses weak correlation but captures a large portion of strong correlation. The theoretical description of many important processes, e.g. molecular dissociation, requires a method capable of accurately capturing both weak and strong correlation simultaneously, and would likely benefit from a combined CC-SUHF approach. Based on what we have recently learned about SUHF written as particle-hole excitations out of a symmetry-adapted reference determinant, we here propose a heuristic CC doubles model to attenuate the dominant spin collective channel of the quadratic terms in the CC equations. Proof of principle results presented here are encouraging and point to several paths forward for improving the method further.

Theoretical study of the density of states and magnetic properties of LaCoO3

NASA Astrophysics Data System (ADS)

Zhuang, Min; Zhang, Weiyi; Hu, Cheng; Ming, Naiben

1998-05-01

The density of states and magnetic properties of low-spin, high-spin, and mixing states of LaCoO3 have been studied within the unrestricted Hartree-Fock approximation. The real-space recursion method is adopted for computing the electronic structure of the disordered system. The paramagnetic high-spin state is dealt with using the usual binary alloy coherent potential approximation (CPA); an extended trinary alloy CPA approximation is developed to describe the mixing state. In agreement with experiments, our results show that the main features of the quasiparticle spectra in the mixing state are not a sensitive function of the high-spin component, but the spectrum does get broadened due to spin scattering. The increasing of the high-spin component also results in a pileup of the density of states at the Fermi energy which indicates an insulator to metal phase transition. Some limitations of the present approach are also discussed.

Roothaan approach in the thermodynamic limit

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gutierrez, G.; Plastino, A.

1982-02-01

A systematic method for the solution of the Hartree-Fock equations in the thermodynamic limit is presented. The approach is seen to be a natural extension of the one usually employed in the finite-fermion case, i.e., that developed by Roothaan. The new techniques developed here are applied, as an example, to neutron matter, employing the so-called V/sub 1/ Bethe homework potential. The results obtained are, by far, superior to those that the ordinary plane-wave Hartree-Fock theory yields.

Electron correlation in Hooke's law atom in the high-density limit.

PubMed

Gill, P M W; O'Neill, D P

2005-03-01

Closed-form expressions for the first three terms in the perturbation expansion of the exact energy and Hartree-Fock energy of the lowest singlet and triplet states of the Hooke's law atom are found. These yield elementary formulas for the exact correlation energies (-49.7028 and -5.807 65 mE(h)) of the two states in the high-density limit and lead to a pair of necessary conditions on the exact correlation kernel G(w) in Hartree-Fock-Wigner theory.

Superdeformed bands in neutron-rich sulfur isotopes suggested by cranked Skyrme-Hartree-Fock calculations

NASA Astrophysics Data System (ADS)

Inakura, T.; Mizutori, S.; Yamagami, M.; Matsuyanagi, K.

2003-12-01

On the basis of the cranked Skyrme-Hartree-Fock calculations in the three-dimensional coordinate-mesh representation, we suggest that, in addition to the well-known candidate 32S, the neutron-rich nucleus 36S and the drip-line nuclei, 48S and 50S, are also good candidates for finding superdeformed rotational bands in sulfur isotopes. Calculated density distributions for the superdeformed states in 48S and 50S exhibit superdeformed neutron skins.

Tensor numerical methods in quantum chemistry: from Hartree-Fock to excitation energies.

PubMed

Khoromskaia, Venera; Khoromskij, Boris N

2015-12-21

We resume the recent successes of the grid-based tensor numerical methods and discuss their prospects in real-space electronic structure calculations. These methods, based on the low-rank representation of the multidimensional functions and integral operators, first appeared as an accurate tensor calculus for the 3D Hartree potential using 1D complexity operations, and have evolved to entirely grid-based tensor-structured 3D Hartree-Fock eigenvalue solver. It benefits from tensor calculation of the core Hamiltonian and two-electron integrals (TEI) in O(n log n) complexity using the rank-structured approximation of basis functions, electron densities and convolution integral operators all represented on 3D n × n × n Cartesian grids. The algorithm for calculating TEI tensor in a form of the Cholesky decomposition is based on multiple factorizations using algebraic 1D "density fitting" scheme, which yield an almost irreducible number of product basis functions involved in the 3D convolution integrals, depending on a threshold ε > 0. The basis functions are not restricted to separable Gaussians, since the analytical integration is substituted by high-precision tensor-structured numerical quadratures. The tensor approaches to post-Hartree-Fock calculations for the MP2 energy correction and for the Bethe-Salpeter excitation energies, based on using low-rank factorizations and the reduced basis method, were recently introduced. Another direction is towards the tensor-based Hartree-Fock numerical scheme for finite lattices, where one of the numerical challenges is the summation of electrostatic potentials of a large number of nuclei. The 3D grid-based tensor method for calculation of a potential sum on a L × L × L lattice manifests the linear in L computational work, O(L), instead of the usual O(L(3) log L) scaling by the Ewald-type approaches.

Stiffness-constant variation in nickel-based alloys: Experiment and theory

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hennion, M.; Hennion, B.

1979-01-01

Recent measurements of the spin-wave stiffness constant in several nickel alloys at various concentrations are interpreted within a random-phase approximation, coherent-potential approximation (RPA-CPA) band model which uses the Hartree-Fock approximation to treat the intraatomic correlations. We give a theoretical description of the possible impurity states in the Hartree-Fock approximation. This allows the determination of the Hartree-Fock solutions which can account for the stiffness-constant behavior and the magnetic moment on the impurity for all the investigated alloys. For alloys such as NiCr, NiV, NiMo, and NiRu, the magnetizations of which deviate from the Slater-Pauling curve, our determination does not correspond tomore » previous works and is consequently discussed. The limits of the model appear mainly due to local-environment effects; in the case of NiMn, it is found that a ternary-alloy model with some Mn atoms in the antiferromagnetic state can account for both stiffness-constant and magnetization behaviors.« less

Investigation of nuclear structure of 30-44S isotopes using spherical and deformed Skyrme-Hartree-Fock method

NASA Astrophysics Data System (ADS)

Alzubadi, A. A.

2015-06-01

Nuclear many-body system is usually described by a mean-field built upon a nucleon-nucleon effective interaction. In this work, we investigate ground state properties of the sulfur isotopes covering a wide range from the line of stability up to the dripline region (30-44S). For this purpose the Hartree-Fock mean field theory in coordinate space with a Skyrme parameterization SkM* has been utilized. In particular, we calculate the nuclear charge, neutrons, protons, mass densities, the associated radii, neutron skin thickness and binding energy. The charge form factors have been also investigated using SkM*, SkO, SkE, SLy4 and Skxs15 Skyrme parameterizations and the results obtained using the theoretical approach are compared with the available experimental data. To investigate the potential energy surface as a function of the quadrupole deformation for isotopic sulfur chains, Skyrme-Hartree-Fock-Bogoliubov theory has been adopted with SLy4 parameterization.

Hyperfine coupling constants of the nitrogen and phosphorus atoms: A challenge for exact-exchange density-functional and post-Hartree-Fock methods

NASA Astrophysics Data System (ADS)

Kaupp, Martin; Arbuznikov, Alexei V.; Heßelmann, Andreas; Görling, Andreas

2010-05-01

The isotropic hyperfine coupling constants of the free N(S4) and P(S4) atoms have been evaluated with high-level post-Hartree-Fock and density-functional methods. The phosphorus hyperfine coupling presents a significant challenge to both types of methods. With large basis sets, MP2 and coupled-cluster singles and doubles calculations give much too small values for the phosphorus atom. Triple excitations are needed in coupled-cluster calculations to achieve reasonable agreement with experiment. None of the standard density functionals reproduce even the correct sign of this hyperfine coupling. Similarly, the computed hyperfine couplings depend crucially on the self-consistent treatment in exact-exchange density-functional theory within the optimized effective potential (OEP) method. Well-balanced auxiliary and orbital basis sets are needed for basis-expansion exact-exchange-only OEP approaches to come close to Hartree-Fock or numerical OEP data. Results from the localized Hartree-Fock and Krieger-Li-Iafrate approximations deviate notably from exact OEP data in spite of very similar total energies. Of the functionals tested, only full exact-exchange methods augmented by a correlation functional gave at least the correct sign of the P(S4) hyperfine coupling but with too low absolute values. The subtle interplay between the spin-polarization contributions of the different core shells has been analyzed, and the influence of even very small changes in the exchange-correlation potential could be identified.

Hartree-Fock theory of the inhomogeneous electron gas at a jellium metal surface: Rigorous upper bounds to the surface energy and accurate work functions

NASA Astrophysics Data System (ADS)

Sahni, V.; Ma, C. Q.

1980-12-01

The inhomogeneous electron gas at a jellium metal surface is studied in the Hartree-Fock approximation by Kohn-Sham density functional theory. Rigorous upper bounds to the surface energy are derived by application of the Rayleigh-Ritz variational principle for the energy, the surface kinetic, electrostatic, and nonlocal exchange energy functionals being determined exactly for the accurate linear-potential model electronic wave functions. The densities obtained by the energy minimization constraint are then employed to determine work-function results via the variationally accurate "displaced-profile change-in-self-consistent-field" expression. The theoretical basis of this non-self-consistent procedure and its demonstrated accuracy for the fully correlated system (as treated within the local-density approximation for exchange and correlation) leads us to conclude these results for the surface energies and work functions to be essentially exact. Work-function values are also determined by the Koopmans'-theorem expression, both for these densities as well as for those obtained by satisfaction of the constraint set on the electrostatic potential by the Budd-Vannimenus theorem. The use of the Hartree-Fock results in the accurate estimation of correlation-effect contributions to these surface properties of the nonuniform electron gas is also indicated. In addition, the original work and approximations made by Bardeen in this attempt at a solution of the Hartree-Fock problem are briefly reviewed in order to contrast with the present work.

Electric dipole transitions for four-times ionized cerium (Ce V)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Usta, Betül Karaçoban, E-mail: bkaracoban@sakarya.edu.tr; Akgün, Elif, E-mail: elif.akgun@ogr.sakarya.edu.tr; Alparslan, Büşra, E-mail: busra.alparslan1@ogr.sakarya.edu.tr

2016-03-25

We have calculated the transition parameters, such as wavelengths, oscillator strengths, and transition probabilities (or rates), for the electric dipole (E1) transitions in four-times ionized cerium (Ce V, Z = 58) by using the multiconfiguration Hartree-Fock method within the framework of Breit-Pauli (MCHF+BP) relativistic corrections and the relativistic Hartree-Fock (HFR) method. The obtained results have been compared with other works available in literature. A discussion of these calculations for Ce V in this study has also been in view of the MCHF+BP and HFR methods.

Second-Order Moller-Plesset Perturbation Theory for Molecular Dirac-Hartree-Fock Wave Functions

NASA Technical Reports Server (NTRS)

Dyall, Kenneth G.; Arnold, James O. (Technical Monitor)

1994-01-01

Moller-Plesset perturbation theory is developed to second order for a selection of Kramers restricted Dirac-Hartree-Fock closed and open-shell reference wave functions. The open-shell wave functions considered are limited to those with no more than two electrons in open shells, but include the case of a two-configuration SCF reference. Denominator shifts are included in the style of Davidson's OPT2 method. An implementation which uses unordered integrals with labels is presented, and results are given for a few test cases.

Accurate Gaussian basis sets for atomic and molecular calculations obtained from the generator coordinate method with polynomial discretization.

PubMed

Celeste, Ricardo; Maringolo, Milena P; Comar, Moacyr; Viana, Rommel B; Guimarães, Amanda R; Haiduke, Roberto L A; da Silva, Albérico B F

2015-10-01

Accurate Gaussian basis sets for atoms from H to Ba were obtained by means of the generator coordinate Hartree-Fock (GCHF) method based on a polynomial expansion to discretize the Griffin-Wheeler-Hartree-Fock equations (GWHF). The discretization of the GWHF equations in this procedure is based on a mesh of points not equally distributed in contrast with the original GCHF method. The results of atomic Hartree-Fock energies demonstrate the capability of these polynomial expansions in designing compact and accurate basis sets to be used in molecular calculations and the maximum error found when compared to numerical values is only 0.788 mHartree for indium. Some test calculations with the B3LYP exchange-correlation functional for N2, F2, CO, NO, HF, and HCN show that total energies within 1.0 to 2.4 mHartree compared to the cc-pV5Z basis sets are attained with our contracted bases with a much smaller number of polarization functions (2p1d and 2d1f for hydrogen and heavier atoms, respectively). Other molecular calculations performed here are also in very good accordance with experimental and cc-pV5Z results. The most important point to be mentioned here is that our generator coordinate basis sets required only a tiny fraction of the computational time when compared to B3LYP/cc-pV5Z calculations.

DOE Office of Scientific and Technical Information (OSTI.GOV)

San Fabián, J.; Omar, S.; García de la Vega, J. M., E-mail: garcia.delavega@uam.es

The effect of a fraction of Hartree-Fock exchange on the calculated spin-spin coupling constants involving fluorine through a hydrogen bond is analyzed in detail. Coupling constants calculated using wavefunction methods are revisited in order to get high-level calculations using the same basis set. Accurate MCSCF results are obtained using an additive approach. These constants and their contributions are used as a reference for density functional calculations. Within the density functional theory, the Hartree-Fock exchange functional is split in short- and long-range using a modified version of the Coulomb-attenuating method with the SLYP functional as well as with the original B3LYP.more » Results support the difficulties for calculating hydrogen bond coupling constants using density functional methods when fluorine nuclei are involved. Coupling constants are very sensitive to the Hartree-Fock exchange and it seems that, contrary to other properties, it is important to include this exchange for short-range interactions. Best functionals are tested in two different groups of complexes: those related with anionic clusters of type [F(HF){sub n}]{sup −} and those formed by difluoroacetylene and either one or two hydrogen fluoride molecules.« less

Molecular modeling studies of interactions between sodium polyacrylate polymer and calcite surface

NASA Astrophysics Data System (ADS)

Ylikantola, A.; Linnanto, J.; Knuutinen, J.; Oravilahti, A.; Toivakka, M.

2013-07-01

The interactions between calcite pigment and sodium polyacrylate dispersing agent, widely used in papermaking as paper coating components, were investigated using classical force field and quantum chemical approaches. The objective was to understand interactions between the calcite surface and sodium polyacrylate polymer at 300 K using molecular dynamics simulations. A quantum mechanical ab initio Hartree-Fock method was also used to obtain detailed information about the sodium polyacrylate polymer structure. The effect of water molecules (moisture) on the interactions was also examined. Calculations showed that molecular weight, branching and the orientation of sodium polyacrylate polymers influence the interactions between the calcite surface and the polymer. The force field applied, and also water molecules, were found to have an impact on all systems studied. Ab initio Hartree-Fock calculations indicated that there are two types of coordination between sodium atoms and carboxylate groups of the sodium polyacrylate polymer, inter- and intra-carboxylate group coordination. In addition, ab initio Hartree-Fock calculations of the structure of the sodium polyacrylate polymer produced important information regarding interactions between the polymers and carboxylated styrene-butadiene latex particles.

Global Futures: a multithreaded execution model for Global Arrays-based applications

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chavarría-Miranda, Daniel; Krishnamoorthy, Sriram; Vishnu, Abhinav

2012-05-31

We present Global Futures (GF), an execution model extension to Global Arrays, which is based on a PGAS-compatible Active Message-based paradigm. We describe the design and implementation of Global Futures and illustrate its use in a computational chemistry application benchmark (Hartree-Fock matrix construction using the Self-Consistent Field method). Our results show how we used GF to increase the scalability of the Hartree-Fock matrix build to up to 6,144 cores of an Infiniband cluster. We also show how GF's multithreaded execution has comparable performance to the traditional process-based SPMD model.

Self-consistent collective coordinate for reaction path and inertial mass

NASA Astrophysics Data System (ADS)

Wen, Kai; Nakatsukasa, Takashi

2016-11-01

We propose a numerical method to determine the optimal collective reaction path for a nucleus-nucleus collision, based on the adiabatic self-consistent collective coordinate (ASCC) method. We use an iterative method, combining the imaginary-time evolution and the finite amplitude method, for the solution of the ASCC coupled equations. It is applied to the simplest case, α -α scattering. We determine the collective path, the potential, and the inertial mass. The results are compared with other methods, such as the constrained Hartree-Fock method, Inglis's cranking formula, and the adiabatic time-dependent Hartree-Fock (ATDHF) method.

Theoretical dissociation energies for the alkali and alkaline-earth monofluorides and monochlorides

NASA Technical Reports Server (NTRS)

Langhoff, S. R.; Bauschlicher, C. W., Jr.; Partridge, H.

1986-01-01

Spectroscopic parameters are accurately determined for the alkali and alkaline-earth monofluorides and monochlorides by means of ab initio self-consistent field and correlated wave function calculations. Numerical Hartree-Fock calculations are performed on selected systems to ensure that the extended Slater basis sets employed are near the Hartree-Fock limit. Since the bonding is predominantly electrostatic in origin, a strong correlation exists between the dissociation energy (to ions) and the spectroscopic parameter r(e). By dissociating to the ionic limits, most of the differential correlation effects can be embedded in the accurate experimental electron affinities and ionization potentials.

Hartree-Fock studies of hypernuclear properties

NASA Astrophysics Data System (ADS)

Lanskoy, D. E.

1998-08-01

The Skyrme-Hartree-Fock approach is approved as a powerful tool to reproduce general properties of Λ hypernuclear spectra [1-4] and to relate hypernuclear observables to effective interaction features. In this contribution, we consider briefly some less common hypernuclear systems, which appear to be quite sensitive to details of the relevant interactions. Particularly, we address possible manifestations of the polarization of a hypernuclear core (i.e. core distortion due to hyperon addition), which is driven in terms of the Skyrme force mainly by counterbalance between the two-body ΛN force and the three-body ΛNN (or density-dependent ΛN) one.

Singlet-paired coupled cluster theory for open shells

NASA Astrophysics Data System (ADS)

Gomez, John A.; Henderson, Thomas M.; Scuseria, Gustavo E.

2016-06-01

Restricted single-reference coupled cluster theory truncated to single and double excitations accurately describes weakly correlated systems, but often breaks down in the presence of static or strong correlation. Good coupled cluster energies in the presence of degeneracies can be obtained by using a symmetry-broken reference, such as unrestricted Hartree-Fock, but at the cost of good quantum numbers. A large body of work has shown that modifying the coupled cluster ansatz allows for the treatment of strong correlation within a single-reference, symmetry-adapted framework. The recently introduced singlet-paired coupled cluster doubles (CCD0) method is one such model, which recovers correct behavior for strong correlation without requiring symmetry breaking in the reference. Here, we extend singlet-paired coupled cluster for application to open shells via restricted open-shell singlet-paired coupled cluster singles and doubles (ROCCSD0). The ROCCSD0 approach retains the benefits of standard coupled cluster theory and recovers correct behavior for strongly correlated, open-shell systems using a spin-preserving ROHF reference.

Study on the spin-states of cobalt-based double-layer perovskite Sr2Y0.5Ca0.5Co2O7

NASA Astrophysics Data System (ADS)

He, H.; Zhang, W. Y.

2008-02-01

The spin-states of cobalt based perovskite compounds depend sensitively on the valence state and local crystal environment of Co ions and the rich physical properties arise from strong coupling among charge, spin, and orbital degrees of freedom. While extensive studies have been carried out in the past, most of them concentrated on the isotropic compound LaCoO3. In this paper, using the unrestricted Hartree-Fock approximation and the real-space recursion method, we have investigated the competition of various magnetically ordered spin-states of anisotropic double-layered perovskite Sr2Y0.5Ca0.5Co2O7. The energy comparison among these states shows that the nearest-neighbor high-spin-intermediate-spin ferromagnetically ordered state is the relevant magnetic ground state of the compound. The magnetic structure and sizes of magnetic moments are consistent with the recent experimental observation.

Optical properties of 3d transition-metal-doped MgAl2O4 spinels

NASA Astrophysics Data System (ADS)

Izumi, K.; Miyazaki, S.; Yoshida, S.; Mizokawa, T.; Hanamura, E.

2007-08-01

Strong emission bands in the visible region are observed in MgAl2O4 crystals doped with transition-metal ions under excitation at the band-to-band transitions. We report optical responses of Cr-, Co-, and Ni-doped MgAl2O4 and present optical models for M -doped MgAl2O4 ( M=Ti , V, Cr, Mn, Co, and Ni) to describe the charge-transfer transitions and the transitions between multiplet levels of 3d electrons, which are observed competitively or coexisting, depending on the number of 3d electrons. While the optical responses of Cr- and Ni-doped MgAl2O4 are dominated by the multiplet-multiplet transitions, those of Ti- and V-doped MgAl2O4 are governed by the charge-transfer transitions. The two kinds of transitions coexist in the Mn- and Co-doped MgAl2O4 . These behaviors are well understood based on the numerical results of unrestricted Hartree-Fock approximation.

Solutions of the two-dimensional Hubbard model: Benchmarks and results from a wide range of numerical algorithms

DOE PAGES

LeBlanc, J. P. F.; Antipov, Andrey E.; Becca, Federico; ...

2015-12-14

Numerical results for ground-state and excited-state properties (energies, double occupancies, and Matsubara-axis self-energies) of the single-orbital Hubbard model on a two-dimensional square lattice are presented, in order to provide an assessment of our ability to compute accurate results in the thermodynamic limit. Many methods are employed, including auxiliary-field quantum Monte Carlo, bare and bold-line diagrammatic Monte Carlo, method of dual fermions, density matrix embedding theory, density matrix renormalization group, dynamical cluster approximation, diffusion Monte Carlo within a fixed-node approximation, unrestricted coupled cluster theory, and multireference projected Hartree-Fock methods. Comparison of results obtained by different methods allows for the identification ofmore » uncertainties and systematic errors. The importance of extrapolation to converged thermodynamic-limit values is emphasized. Furthermore, cases where agreement between different methods is obtained establish benchmark results that may be useful in the validation of new approaches and the improvement of existing methods.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gomez, John A.; Henderson, Thomas M.; Scuseria, Gustavo E.

Restricted single-reference coupled cluster theory truncated to single and double excitations accurately describes weakly correlated systems, but often breaks down in the presence of static or strong correlation. Good coupled cluster energies in the presence of degeneracies can be obtained by using a symmetry-broken reference, such as unrestricted Hartree-Fock, but at the cost of good quantum numbers. A large body of work has shown that modifying the coupled cluster ansatz allows for the treatment of strong correlation within a single-reference, symmetry-adapted framework. The recently introduced singlet-paired coupled cluster doubles (CCD0) method is one such model, which recovers correct behavior formore » strong correlation without requiring symmetry breaking in the reference. Here, we extend singlet-paired coupled cluster for application to open shells via restricted open-shell singlet-paired coupled cluster singles and doubles (ROCCSD0). The ROCCSD0 approach retains the benefits of standard coupled cluster theory and recovers correct behavior for strongly correlated, open-shell systems using a spin-preserving ROHF reference.« less

Predicted NMR properties of noble gas hydride cations RgH +

NASA Astrophysics Data System (ADS)

Cukras, Janusz; Sadlej, Joanna

2008-12-01

The NMR shielding constants and, for the first time, the spin-spin coupling constants of Rg and H in RgH + compounds for Rg = Ne, Ar, Kr, Xe have been investigated by non-relativistic Hartree-Fock (HF) and relativistic Dirac-Hartree-Fock (DHF) methods. Electron-correlation effects have been furthermore calculated using SOPPA and CCSD at the non-relativistic level. The correlation effects are large on both parameters and opposite to the relativistic effects. The results indicate that both the relativistic and correlation effects need to be taken into account in a quantitative computations, especially in the case of the spin-spin coupling constants.

Conserving and gapless Hartree-Fock-Bogoliubov theory for the three-dimensional dilute Bose gas

NASA Astrophysics Data System (ADS)

Zhang, Ya-Hui; Li, Dingping

2013-11-01

The excitation spectrum for the three-dimensional Bose gas in the Bose-Einstein condensation phase is calculated nonperturbatively with the modified Hartree-Fock-Bogoliubov theory, which is both conserving and gapless. From improved Φ-derivable theory, the diagrams needed to preserve the Ward-Takahashi identity are re-summed in a systematic and nonperturbative way. It is valid up to the critical temperature where the dispersion relation of the low-energy excitation spectrum changes from linear to quadratic. Because including the higher-order fluctuation, the results show significant improvement on the calculation of the shift of critical temperature with other conserving and gapless theories.

Hartree-Fock limit values of multipole moments, polarizabilities, and hyperpolarizabilities for atoms and diatomic molecules

NASA Astrophysics Data System (ADS)

Kobus, Jacek

2015-02-01

Recently it has been demonstrated that the finite difference Hartree-Fock method can be used to deliver highly accurate values of electric multipole moments together with polarizabilities αz z,Az ,z z , and hyperpolarizabilities βz z z, γz z z,Bz z ,z z , for the ground states of various atomic and diatomic systems. Since these results can be regarded as de facto Hartree-Fock limit values their quality is of the utmost importance. This paper reexamines the use of the finite field method to calculate these electric properties, discusses its accuracy, and presents an updated list of the properties for the following atoms and diatomic molecules: H-, He, Li, Li+,Li2 +,Li-,Be2 + , Be, B+,C2 + , Ne, Mg2 +, Mg, Al+,Si2 + , Ar, K+,Ca2 +,Rb+,Sr2 +,Zr4 +,He2 , Be2,N2,F2,O2 , HeNe, LiH2 +, LiCl, LiBr, BH, CO, FH, NaCl, and KF. The potential energy curves and the dependence of the electric properties on the internuclear distance is also studied for He2,LiH+,Be2 , and HeNe systems.

Proper and improper zero energy modes in Hartree-Fock theory and their relevance for symmetry breaking and restoration.

PubMed

Cui, Yao; Bulik, Ireneusz W; Jiménez-Hoyos, Carlos A; Henderson, Thomas M; Scuseria, Gustavo E

2013-10-21

We study the spectra of the molecular orbital Hessian (stability matrix) and random-phase approximation (RPA) Hamiltonian of broken-symmetry Hartree-Fock solutions, focusing on zero eigenvalue modes. After all negative eigenvalues are removed from the Hessian by following their eigenvectors downhill, one is left with only positive and zero eigenvalues. Zero modes correspond to orbital rotations with no restoring force. These rotations determine states in the Goldstone manifold, which originates from a spontaneously broken continuous symmetry in the wave function. Zero modes can be classified as improper or proper according to their different mathematical and physical properties. Improper modes arise from symmetry breaking and their restoration always lowers the energy. Proper modes, on the other hand, correspond to degeneracies of the wave function, and their symmetry restoration does not necessarily lower the energy. We discuss how the RPA Hamiltonian distinguishes between proper and improper modes by doubling the number of zero eigenvalues associated with the latter. Proper modes in the Hessian always appear in pairs which do not double in RPA. We present several pedagogical cases exemplifying the above statements. The relevance of these results for projected Hartree-Fock methods is also addressed.

Straightening the Hierarchical Staircase for Basis Set Extrapolations: A Low-Cost Approach to High-Accuracy Computational Chemistry

NASA Astrophysics Data System (ADS)

Varandas, António J. C.

2018-04-01

Because the one-electron basis set limit is difficult to reach in correlated post-Hartree-Fock ab initio calculations, the low-cost route of using methods that extrapolate to the estimated basis set limit attracts immediate interest. The situation is somewhat more satisfactory at the Hartree-Fock level because numerical calculation of the energy is often affordable at nearly converged basis set levels. Still, extrapolation schemes for the Hartree-Fock energy are addressed here, although the focus is on the more slowly convergent and computationally demanding correlation energy. Because they are frequently based on the gold-standard coupled-cluster theory with single, double, and perturbative triple excitations [CCSD(T)], correlated calculations are often affordable only with the smallest basis sets, and hence single-level extrapolations from one raw energy could attain maximum usefulness. This possibility is examined. Whenever possible, this review uses raw data from second-order Møller-Plesset perturbation theory, as well as CCSD, CCSD(T), and multireference configuration interaction methods. Inescapably, the emphasis is on work done by the author's research group. Certain issues in need of further research or review are pinpointed.

Twist-averaged boundary conditions for nuclear pasta Hartree-Fock calculations

DOE PAGES

Schuetrumpf, B.; Nazarewicz, W.

2015-10-21

Nuclear pasta phases, present in the inner crust of neutron stars, are associated with nucleonic matter at subsaturation densities arranged in regular shapes. Those complex phases, residing in a layer which is approximately 100-m thick, impact many features of neutron stars. Theoretical quantum-mechanical simulations of nuclear pasta are usually carried out in finite three-dimensional boxes assuming periodic boundary conditions. The resulting solutions are affected by spurious finite-size effects. To remove spurious finite-size effects, it is convenient to employ twist-averaged boundary conditions (TABC) used in condensed matter, nuclear matter, and lattice quantum chromodynamics applications. In this work, we study the effectivenessmore » of TABC in the context of pasta phase simulations within nuclear density functional theory. We demonstrated that by applying TABC reliable results can be obtained from calculations performed in relatively small volumes. By studying various contributions to the total energy, we gain insights into pasta phases in mid-density range. Future applications will include the TABC extension of the adaptive multiresolution 3D Hartree-Fock solver and Hartree-Fock-Bogoliubov TABC applications to superfluid pasta phases and complex nucleonic topologies as in fission.« less

Non-Born-Oppenheimer self-consistent field calculations with cubic scaling

NASA Astrophysics Data System (ADS)

Moncada, Félix; Posada, Edwin; Flores-Moreno, Roberto; Reyes, Andrés

2012-05-01

An efficient nuclear molecular orbital methodology is presented. This approach combines an auxiliary density functional theory for electrons (ADFT) and a localized Hartree product (LHP) representation for the nuclear wave function. A series of test calculations conducted on small molecules exposed that energy and geometry errors introduced by the use of ADFT and LHP approximations are small and comparable to those obtained by the use of electronic ADFT. In addition, sample calculations performed on (HF)n chains disclosed that the combined ADFT/LHP approach scales cubically with system size (n) as opposed to the quartic scaling of Hartree-Fock/LHP or DFT/LHP methods. Even for medium size molecules the improved scaling of the ADFT/LHP approach resulted in speedups of at least 5x with respect to Hartree-Fock/LHP calculations. The ADFT/LHP method opens up the possibility of studying nuclear quantum effects on large size systems that otherwise would be impractical.

Theoretical X-ray production cross sections at incident photon energies across Li (i=1-3) absorption edges of Br

NASA Astrophysics Data System (ADS)

Puri, Sanjiv

2015-08-01

The X-ray production (XRP) cross sections, σLk (k = l, η, α, β6, β1, β3, β4, β9,10, γ1,5, γ2,3) have been evaluated at incident photon energies across the Li(i=1-3) absorption edge energies of 35Br using theoretical data sets of different physical parameters, namely, the Li(i=1-3) sub-shell the X-ray emission rates based on the Dirac-Fock (DF) model, the fluorescence and Coster Kronig yields based on the Dirac-Hartree-Slater (DHS) model, and two sets of the photoionisation cross sections based on the relativistic Hartree-Fock-Slater (RHFS) model and the Dirac-Fock (DF) model, in order to highlight the importance of electron exchange effects at photon energies in vicinity of absorption edge energies.

Two-parameter partially correlated ground-state electron density of some light spherical atoms from Hartree-Fock theory with nonintegral nuclear charge

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cordero, Nicolas A.; March, Norman H.; Alonso, Julio A.

2007-05-15

Partially correlated ground-state electron densities for some spherical light atoms are calculated, into which nonrelativistic ionization potentials represent essential input data. The nuclear cusp condition of Kato is satisfied precisely. The basic theoretical starting point, however, is Hartree-Fock (HF) theory for the N electrons under consideration but with nonintegral nuclear charge Z{sup '} slightly different from the atomic number Z (=N). This HF density is scaled with a parameter {lambda}, near to unity, to preserve normalization. Finally, some tests are performed on the densities for the atoms Ne and Ar, as well as for Be and Mg.

Theoretical L-shell Coster-Kronig energies 11 or equal to z or equal to 103

NASA Technical Reports Server (NTRS)

Chen, M. H.; Crasemann, B.; Huang, K. N.; Aoyagi, M.; Mark, H.

1976-01-01

Relativistic relaxed-orbital calculations of L-shell Coster-Kronig transition energies have been performed for all possible transitions in atoms with atomic numbers. Hartree-Fock-Slater wave functions served as zeroth-order eigenfunctions to compute the expectation of the total Hamiltonian. A first-order approximation to the local approximation was thus included. Quantum-electrodynamic corrections were made. Each transition energy was computed as the difference between results of separate self-consistent-field calculations for the initial, singly ionized state and the final two-hole state. The following quantities are listed: total transition energy, 'electric' (Dirac-Hartree-Fock-Slater) contribution, magnetic and retardation contributions, and contributions due to vacuum polarization and self energy.

Multiconfiguration Dirac-Hartree-Fock calculations of energy levels and radiative rates of Fe VII

NASA Astrophysics Data System (ADS)

Li, Yang; Xu, Xiaokai; Li, Bowen; Jönsson, Per; Chen, Ximeng

2018-06-01

Detailed calculations are performed for 134 fine-structure levels of the 3p63d2, 3p63d4s, 3p53d3 and 3p63d4p configurations in Fe VII using the multiconfiguration Dirac-Hartree-Fock (MCDHF) and relativistic configuration interaction (RCI) methods. Important electron correlation effects are systematically accounted for through active space (AS) expansions. Our results compare well with experimental measurements, emphasizing the importance of a careful treatment of electron correlation, and provide some missing data in the NIST atomic database. The data obtained are expected to be useful in astrophysical applications, particularly for the research of the solar coronal plasma.

Accuracy of Hartree-Fock wave functions for electron-H/sub 2/ scattering calculations

DOE Office of Scientific and Technical Information (OSTI.GOV)

Feldt, A.N.

1988-05-01

Recent papers on electron-N/sub 2/ scattering by Rumble, Stevens, and Truhlar (J. Phys. B 17, 3151 (1984)) and Weatherford, Brown, and Temkin (Phys. Rev. A 35, 4561 (1987)) have suggested that Hartree-Fock (HF) wave functions may not be accurate for calculating potentials for use in studying electron-molecule collisions. A comparison of results for electron-H/sub 2/ scattering using both correlated and HF wave functions is presented. It is found that for both elastic and inelastic collisions and for all energies considered (up to 10 eV) the HF wave functions yield results in excellent agreement with those obtained from the more accuratemore » wave functions.« less

Parallel implementation of Hartree-Fock and density functional theory analytical second derivatives

NASA Astrophysics Data System (ADS)

Baker, Jon; Wolinski, Krzysztof; Malagoli, Massimo; Pulay, Peter

2004-01-01

We present an efficient, parallel implementation for the calculation of Hartree-Fock and density functional theory analytical Hessian (force constant, nuclear second derivative) matrices. These are important for the determination of harmonic vibrational frequencies, and to classify stationary points on potential energy surfaces. Our program is designed for modest parallelism (4-16 CPUs) as exemplified by our standard eight-processor QuantumCube™. We can routinely handle systems with up to 100+ atoms and 1000+ basis functions using under 0.5 GB of RAM memory per CPU. Timings are presented for several systems, ranging in size from aspirin (C9H8O4) to nickel octaethylporphyrin (C36H44N4Ni).

On the physical interpretation of the nuclear molecular orbital energy.

PubMed

Charry, Jorge; Pedraza-González, Laura; Reyes, Andrés

2017-06-07

Recently, several groups have extended and implemented molecular orbital (MO) schemes to simultaneously obtain wave functions for electrons and selected nuclei. Many of these schemes employ an extended Hartree-Fock approach as a first step to find approximate electron-nuclear wave functions and energies. Numerous studies conducted with these extended MO methodologies have explored various effects of quantum nuclei on physical and chemical properties. However, to the best of our knowledge no physical interpretation has been assigned to the nuclear molecular orbital energy (NMOE) resulting after solving extended Hartree-Fock equations. This study confirms that the NMOE is directly related to the molecular electrostatic potential at the position of the nucleus.

An efficient implementation of semi-numerical computation of the Hartree-Fock exchange on the Intel Phi processor

NASA Astrophysics Data System (ADS)

Liu, Fenglai; Kong, Jing

2018-07-01

Unique technical challenges and their solutions for implementing semi-numerical Hartree-Fock exchange on the Phil Processor are discussed, especially concerning the single- instruction-multiple-data type of processing and small cache size. Benchmark calculations on a series of buckyball molecules with various Gaussian basis sets on a Phi processor and a six-core CPU show that the Phi processor provides as much as 12 times of speedup with large basis sets compared with the conventional four-center electron repulsion integration approach performed on the CPU. The accuracy of the semi-numerical scheme is also evaluated and found to be comparable to that of the resolution-of-identity approach.

Asymptotic behavior and interpretation of virtual states: The effects of confinement and of basis sets

NASA Astrophysics Data System (ADS)

Boffi, Nicholas M.; Jain, Manish; Natan, Amir

2016-02-01

A real-space high order finite difference method is used to analyze the effect of spherical domain size on the Hartree-Fock (and density functional theory) virtual eigenstates. We show the domain size dependence of both positive and negative virtual eigenvalues of the Hartree-Fock equations for small molecules. We demonstrate that positive states behave like a particle in spherical well and show how they approach zero. For the negative eigenstates, we show that large domains are needed to get the correct eigenvalues. We compare our results to those of Gaussian basis sets and draw some conclusions for real-space, basis-sets, and plane-waves calculations.

Assessment of Orbital-Optimized MP2.5 for Thermochemistry and Kinetics: Dramatic Failures of Standard Perturbation Theory Approaches for Aromatic Bond Dissociation Energies and Barrier Heights of Radical Reactions.

PubMed

Soydaş, Emine; Bozkaya, Uğur

2015-04-14

An assessment of orbital-optimized MP2.5 (OMP2.5) [ Bozkaya, U.; Sherrill, C. D. J. Chem. Phys. 2014, 141, 204105 ] for thermochemistry and kinetics is presented. The OMP2.5 method is applied to closed- and open-shell reaction energies, barrier heights, and aromatic bond dissociation energies. The performance of OMP2.5 is compared with that of the MP2, OMP2, MP2.5, MP3, OMP3, CCSD, and CCSD(T) methods. For most of the test sets, the OMP2.5 method performs better than MP2.5 and CCSD, and provides accurate results. For barrier heights of radical reactions and aromatic bond dissociation energies OMP2.5-MP2.5, OMP2-MP2, and OMP3-MP3 differences become obvious. Especially, for aromatic bond dissociation energies, standard perturbation theory (MP) approaches dramatically fail, providing mean absolute errors (MAEs) of 22.5 (MP2), 17.7 (MP2.5), and 12.8 (MP3) kcal mol(-1), while the MAE values of the orbital-optimized counterparts are 2.7, 2.4, and 2.4 kcal mol(-1), respectively. Hence, there are 5-8-folds reductions in errors when optimized orbitals are employed. Our results demonstrate that standard MP approaches dramatically fail when the reference wave function suffers from the spin-contamination problem. On the other hand, the OMP2.5 method can reduce spin-contamination in the unrestricted Hartree-Fock (UHF) initial guess orbitals. For overall evaluation, we conclude that the OMP2.5 method is very helpful not only for challenging open-shell systems and transition-states but also for closed-shell molecules. Hence, one may prefer OMP2.5 over MP2.5 and CCSD as an O(N(6)) method, where N is the number of basis functions, for thermochemistry and kinetics. The cost of the OMP2.5 method is comparable with that of CCSD for energy computations. However, for analytic gradient computations, the OMP2.5 method is only half as expensive as CCSD.

Equilibration in the time-dependent Hartree-Fock approach probed with the Wigner distribution function

DOE Office of Scientific and Technical Information (OSTI.GOV)

Loebl, N.; Maruhn, J. A.; Reinhard, P.-G.

2011-09-15

By calculating the Wigner distribution function in the reaction plane, we are able to probe the phase-space behavior in the time-dependent Hartree-Fock scheme during a heavy-ion collision in a consistent framework. Various expectation values of operators are calculated by evaluating the corresponding integrals over the Wigner function. In this approach, it is straightforward to define and analyze quantities even locally. We compare the Wigner distribution function with the smoothed Husimi distribution function. Different reaction scenarios are presented by analyzing central and noncentral {sup 16}O +{sup 16}O and {sup 96}Zr +{sup 132}Sn collisions. Although we observe strong dissipation in the timemore » evolution of global observables, there is no evidence for complete equilibration in the local analysis of the Wigner function. Because the initial phase-space volumes of the fragments barely merge and mean values of the observables are conserved in fusion reactions over thousands of fm/c, we conclude that the time-dependent Hartree-Fock method provides a good description of the early stage of a heavy-ion collision but does not provide a mechanism to change the phase-space structure in a dramatic way necessary to obtain complete equilibration.« less

The properties of nuclear matter with lattice NN potential in relativistic Brueckner-Hartree-Fock theory

PubMed Central

Hu, Jinniu; Toki, Hiroshi; Shen, Hong

2016-01-01

We study the properties of nuclear matter with lattice nucleon-nucleon (NN) potential in the relativistic Brueckner-Hartree-Fock (RBHF) theory. To use this potential in such a microscopic many-body theory, we firstly have to construct a one-boson-exchange potential (OBEP) based on the latest lattice NN potential. Three mesons, pion, σ meson, and ω meson, are considered. Their coupling constants and cut-off momenta are determined by fitting the on-shell behaviors and phase shifts of the lattice force, respectively. Therefore, we obtain two parameter sets of the OBEP potential (named as LOBEP1 and LOBEP2) with these two fitting ways. We calculate the properties of symmetric and pure neutron matter with LOBEP1 and LOBEP2. In non-relativistic Brueckner-Hartree-Fock case, the binding energies of symmetric nuclear matter are around −3 and −5 MeV at saturation density, while it becomes −8 and −12 MeV in relativistic framework with 1S0, 3S1, and 3D1 channels using our two parameter sets. For the pure neutron matter, the equations of state in non-relativistic and relativistic cases are very similar due to only consideration 1S0 channel with isospin T = 1 case. PMID:27752124

The properties of nuclear matter with lattice NN potential in relativistic Brueckner-Hartree-Fock theory.

PubMed

Hu, Jinniu; Toki, Hiroshi; Shen, Hong

2016-10-18

We study the properties of nuclear matter with lattice nucleon-nucleon (NN) potential in the relativistic Brueckner-Hartree-Fock (RBHF) theory. To use this potential in such a microscopic many-body theory, we firstly have to construct a one-boson-exchange potential (OBEP) based on the latest lattice NN potential. Three mesons, pion, σ meson, and ω meson, are considered. Their coupling constants and cut-off momenta are determined by fitting the on-shell behaviors and phase shifts of the lattice force, respectively. Therefore, we obtain two parameter sets of the OBEP potential (named as LOBEP1 and LOBEP2) with these two fitting ways. We calculate the properties of symmetric and pure neutron matter with LOBEP1 and LOBEP2. In non-relativistic Brueckner-Hartree-Fock case, the binding energies of symmetric nuclear matter are around -3 and -5 MeV at saturation density, while it becomes -8 and -12 MeV in relativistic framework with 1 S 0 , 3 S 1 , and 3 D 1 channels using our two parameter sets. For the pure neutron matter, the equations of state in non-relativistic and relativistic cases are very similar due to only consideration 1 S 0 channel with isospin T = 1 case.

Orbital dependent functionals: An atom projector augmented wave method implementation

NASA Astrophysics Data System (ADS)

Xu, Xiao

This thesis explores the formulation and numerical implementation of orbital dependent exchange-correlation functionals within electronic structure calculations. These orbital-dependent exchange-correlation functionals have recently received renewed attention as a means to improve the physical representation of electron interactions within electronic structure calculations. In particular, electron self-interaction terms can be avoided. In this thesis, an orbital-dependent functional is considered in the context of Hartree-Fock (HF) theory as well as the Optimized Effective Potential (OEP) method and the approximate OEP method developed by Krieger, Li, and Iafrate, known as the KLI approximation. In this thesis, the Fock exchange term is used as a simple well-defined example of an orbital-dependent functional. The Projected Augmented Wave (PAW) method developed by P. E. Blochl has proven to be accurate and efficient for electronic structure calculations for local and semi-local functions because of its accurate evaluation of interaction integrals by controlling multiple moments. We have extended the PAW method to treat orbital-dependent functionals in Hartree-Fock theory and the Optimized Effective Potential method, particularly in the KLI approximation. In the course of study we develop a frozen-core orbital approximation that accurately treats the core electron contributions for above three methods. The main part of the thesis focuses on the treatment of spherical atoms. We have investigated the behavior of PAW-Hartree Fock and PAW-KLI basis, projector, and pseudopotential functions for several elements throughout the periodic table. We have also extended the formalism to the treatment of solids in a plane wave basis and implemented PWPAW-KLI code, which will appear in future publications.

Theoretical X-ray production cross sections at incident photon energies across L{sub i} (i=1-3) absorption edges of Br

DOE Office of Scientific and Technical Information (OSTI.GOV)

Puri, Sanjiv

The X-ray production (XRP) cross sections, σ{sub Lk} (k = l, η, α, β{sub 6}, β{sub 1}, β{sub 3}, β{sub 4}, β{sub 9,10}, γ{sub 1,5}, γ{sub 2,3}) have been evaluated at incident photon energies across the L{sub i}(i=1-3) absorption edge energies of {sub 35}Br using theoretical data sets of different physical parameters, namely, the L{sub i}(i=1-3) sub-shell the X-ray emission rates based on the Dirac-Fock (DF) model, the fluorescence and Coster Kronig yields based on the Dirac-Hartree-Slater (DHS) model, and two sets of the photoionisation cross sections based on the relativistic Hartree-Fock-Slater (RHFS) model and the Dirac-Fock (DF) model, inmore » order to highlight the importance of electron exchange effects at photon energies in vicinity of absorption edge energies.« less

Relativistic Brueckner-Hartree-Fock theory for neutron drops

NASA Astrophysics Data System (ADS)

Shen, Shihang; Liang, Haozhao; Meng, Jie; Ring, Peter; Zhang, Shuangquan

2018-05-01

Neutron drops confined in an external field are studied in the framework of relativistic Brueckner-Hartree-Fock theory using the bare nucleon-nucleon interaction. The ground-state energies and radii of neutron drops with even numbers from N =4 to N =50 are calculated and compared with results obtained from other nonrelativistic ab initio calculations and from relativistic density functional theory. Special attention has been paid to the magic numbers and to the subshell closures. The single-particle energies are investigated and the monopole effect of the tensor force on the evolutions of the spin-orbit and the pseudospin-orbit splittings is discussed. The results provide interesting insights into neutron-rich systems and can form an important guide for future density functionals.

Constrained Hartree-Fock Theory and Study of Deformed Structures of Closed Shell Nuclei

NASA Astrophysics Data System (ADS)

Praharaj, Choudhury

2016-03-01

We have studied some N or Z = 50 nuclei in a microscopic model with effective interaction in a reasonably large shell model space. Excitation of particles across 50 shell closure leads to well-deformed excited prolate configurations. The potential energy surfaces of nuclei are studied using Hartree-Fock theory with quadrupole constraint to explore the various deformed configurations of N = 50 nuclei 82Ge , 84Se and 86Kr . Energy spectra are calculated from various intrinsic states using Peierls-Yoccoz angular momentum projection technique. Results of spectra and electromagnetic moments and transitions will be presented for N = 50 nuclei and for Z = 50 114Sn nucleus. Supported by Grant No SB/S2/HEP-06/2013 of DST.

Computational Nuclear Physics and Post Hartree-Fock Methods

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lietz, Justin; Sam, Novario; Hjorth-Jensen, M.

We present a computational approach to infinite nuclear matter employing Hartree-Fock theory, many-body perturbation theory and coupled cluster theory. These lectures are closely linked with those of chapters 9, 10 and 11 and serve as input for the correlation functions employed in Monte Carlo calculations in chapter 9, the in-medium similarity renormalization group theory of dense fermionic systems of chapter 10 and the Green's function approach in chapter 11. We provide extensive code examples and benchmark calculations, allowing thereby an eventual reader to start writing her/his own codes. We start with an object-oriented serial code and end with discussions onmore » strategies for porting the code to present and planned high-performance computing facilities.« less

All-electron molecular Dirac-Hartree-Fock calculations - The group IV tetrahydrides CH4, SiH4, GeH4, SnH4, and PbH4

NASA Technical Reports Server (NTRS)

Dyall, Kenneth G.; Taylor, Peter R.; Faegri, Knut, Jr.; Partridge, Harry

1991-01-01

A basis-set-expansion Dirac-Hartree-Fock program for molecules is described. Bond lengths and harmonic frequencies are presented for the ground states of the group 4 tetrahydrides, CH4, SiH4, GeH4, SnH4, and PbH4. The results are compared with relativistic effective core potential (RECP) calculations, first-order perturbation theory (PT) calculations and with experimental data. The bond lengths are well predicted by first-order perturbation theory for all molecules, but none of the RECP's considered provides a consistent prediction. Perturbation theory overestimates the relativistic correction to the harmonic frequencies; the RECP calculations underestimate the correction.

All-electron molecular Dirac-Hartree-Fock calculations: The group 4 tetrahydrides CH4, SiH4, GeH4, SnH4 and PbH4

NASA Technical Reports Server (NTRS)

Dyall, Kenneth G.; Taylor, Peter R.; Faegri, Knut, Jr.; Partridge, Harry

1990-01-01

A basis-set-expansion Dirac-Hartree-Fock program for molecules is described. Bond lengths and harmonic frequencies are presented for the ground states of the group 4 tetrahydrides, CH4, SiH4, GeH4, SnH4, and PbH4. The results are compared with relativistic effective core potential (RECP) calculations, first-order perturbation theory (PT) calculations and with experimental data. The bond lengths are well predicted by first-order perturbation theory for all molecules, but non of the RECP's considered provides a consistent prediction. Perturbation theory overestimates the relativistic correction to the harmonic frequencies; the RECP calculations underestimate the correction.

Near Hartree-Fock quality GTO basis sets for the second-row atoms

NASA Technical Reports Server (NTRS)

Partridge, Harry

1987-01-01

Energy optimized, near Hartree-Fock quality Gaussian basis sets ranging in size from (17s12p) to (20s15p) are presented for the ground states of the second-row atoms for Na(2P), Na(+), Na(-), Mg(3P), P(-), S(-), and Cl(-). In addition, optimized supplementary functions are given for the ground state basis sets to describe the negative ions, and the excited Na(2P) and Mg(3P) atomic states. The ratios of successive orbital exponents describing the inner part of the 1s and 2p orbitals are found to be nearly independent of both nuclear charge and basis set size. This provides a method of obtaining good starting estimates for other basis set optimizations.

Interacting Electrons in Graphene: Fermi Velocity Renormalization and Optical Response

NASA Astrophysics Data System (ADS)

Stauber, T.; Parida, P.; Trushin, M.; Ulybyshev, M. V.; Boyda, D. L.; Schliemann, J.

2017-06-01

We have developed a Hartree-Fock theory for electrons on a honeycomb lattice aiming to solve a long-standing problem of the Fermi velocity renormalization in graphene. Our model employs no fitting parameters (like an unknown band cutoff) but relies on a topological invariant (crystal structure function) that makes the Hartree-Fock sublattice spinor independent of the electron-electron interaction. Agreement with the experimental data is obtained assuming static self-screening including local field effects. As an application of the model, we derive an explicit expression for the optical conductivity and discuss the renormalization of the Drude weight. The optical conductivity is also obtained via precise quantum Monte Carlo calculations which compares well to our mean-field approach.

New quantum number for the many-electron Dirac-Coulomb Hamiltonian

NASA Astrophysics Data System (ADS)

Komorovsky, Stanislav; Repisky, Michal; Bučinský, Lukáš

2016-11-01

By breaking the spin symmetry in the relativistic domain, a powerful tool in physical sciences was lost. In this work, we examine an alternative of spin symmetry for systems described by the many-electron Dirac-Coulomb Hamiltonian. We show that the square of many-electron operator K+, defined as a sum of individual single-electron time-reversal (TR) operators, is a linear Hermitian operator which commutes with the Dirac-Coulomb Hamiltonian in a finite Fock subspace. In contrast to the square of a standard unitary many-electron TR operator K , the K+2 has a rich eigenspectrum having potential to substitute spin symmetry in the relativistic domain. We demonstrate that K+ is connected to K through an exponential mapping, in the same way as spin operators are mapped to the spin rotational group. Consequently, we call K+ the generator of the many-electron TR symmetry. By diagonalizing the operator K+2 in the basis of Kramers-restricted Slater determinants, we introduce the relativistic variant of configuration state functions (CSF), denoted as Kramers CSF. A new quantum number associated with K+2 has potential to be used in many areas, for instance, (a) to design effective spin Hamiltonians for electron spin resonance spectroscopy of heavy-element containing systems; (b) to increase efficiency of methods for the solution of many-electron problems in relativistic computational chemistry and physics; (c) to define Kramers contamination in unrestricted density functional and Hartree-Fock theory as a relativistic analog of the spin contamination in the nonrelativistic domain.

Three-dimensional hole transport in nickel oxide by alloying with MgO or ZnO

NASA Astrophysics Data System (ADS)

Alidoust, Nima; Carter, Emily A.

2015-11-01

It has been shown previously that the movement of a hole in nickel oxide is confined to two dimensions, along a single ferromagnetic plane. Such confinement may hamper hole transport when NiO is used as a p-type transparent conductor in various solar energy conversion technologies. Here, we use the small polaron model, along with unrestricted Hartree-Fock and complete active space self-consistent field calculations to show that forming substitutional MxNi1-xO alloys with M = Mg or Zn reduces the barrier for movement of a hole away from the ferromagnetic plane to which it is confined. Such reduction occurs for hole transfer alongside one or two M ions that have been substituted for Ni ions. Furthermore, the Mg and Zn ions do not trap holes on O sites in their vicinity, and NiO's transparency is preserved upon forming the alloys. Thus, forming MxNi1-xO alloys with M = Mg or Zn may enhance NiO's potential as a p-type transparent conducting oxide, by disrupting the two-dimensional confinement of holes in pure NiO.

Construction of the Fock Matrix on a Grid-Based Molecular Orbital Basis Using GPGPUs.

PubMed

Losilla, Sergio A; Watson, Mark A; Aspuru-Guzik, Alán; Sundholm, Dage

2015-05-12

We present a GPGPU implementation of the construction of the Fock matrix in the molecular orbital basis using the fully numerical, grid-based bubbles representation. For a test set of molecules containing up to 90 electrons, the total Hartree-Fock energies obtained from reference GTO-based calculations are reproduced within 10(-4) Eh to 10(-8) Eh for most of the molecules studied. Despite the very large number of arithmetic operations involved, the high performance obtained made the calculations possible on a single Nvidia Tesla K40 GPGPU card.

Hartree-Fock mass formulas and extrapolation to new mass data

NASA Astrophysics Data System (ADS)

Goriely, S.; Samyn, M.; Heenen, P.-H.; Pearson, J. M.; Tondeur, F.

2002-08-01

The two previously published Hartree-Fock (HF) mass formulas, HFBCS-1 and HFB-1 (HF-Bogoliubov), are shown to be in poor agreement with new Audi-Wapstra mass data. The problem lies first with the prescription adopted for the cutoff of the single-particle spectrum used with the δ-function pairing force, and second with the Wigner term. We find an optimal mass fit if the spectrum is cut off both above EF+15 MeV and below EF-15 MeV, EF being the Fermi energy of the nucleus in question. In addition to the Wigner term of the form VW exp(-λ|N-Z|/A) already included in the two earlier HF mass formulas, we find that a second Wigner term linear in |N-Z| leads to a significant improvement in lighter nuclei. These two features are incorporated into our new Hartree-Fock-Bogoliubov model, which leads to much improved extrapolations. The 18 parameters of the model are fitted to the 2135 measured masses for N,Z>=8 with an rms error of 0.674 MeV. With this parameter set a complete mass table, labeled HFB-2, has been constructed, going from one drip line to the other, up to Z=120. The new pairing-cutoff prescription favored by the new mass data leads to weaker neutron-shell gaps in neutron-rich nuclei.

A multiconfigurational time-dependent Hartree-Fock method for excited electronic states. I. General formalism and application to open-shell states.

PubMed

Miranda, R P; Fisher, A J; Stella, L; Horsfield, A P

2011-06-28

The solution of the time-dependent Schrödinger equation for systems of interacting electrons is generally a prohibitive task, for which approximate methods are necessary. Popular approaches, such as the time-dependent Hartree-Fock (TDHF) approximation and time-dependent density functional theory (TDDFT), are essentially single-configurational schemes. TDHF is by construction incapable of fully accounting for the excited character of the electronic states involved in many physical processes of interest; TDDFT, although exact in principle, is limited by the currently available exchange-correlation functionals. On the other hand, multiconfigurational methods, such as the multiconfigurational time-dependent Hartree-Fock (MCTDHF) approach, provide an accurate description of the excited states and can be systematically improved. However, the computational cost becomes prohibitive as the number of degrees of freedom increases, and thus, at present, the MCTDHF method is only practical for few-electron systems. In this work, we propose an alternative approach which effectively establishes a compromise between efficiency and accuracy, by retaining the smallest possible number of configurations that catches the essential features of the electronic wavefunction. Based on a time-dependent variational principle, we derive the MCTDHF working equation for a multiconfigurational expansion with fixed coefficients and specialise to the case of general open-shell states, which are relevant for many physical processes of interest.

Breit interaction contribution to parity violating potentials in chiral molecules containing light nuclei.

PubMed

Berger, Robert

2008-10-21

The importance of the Breit interaction for an accurate prediction of parity violating energy differences between enantiomers is studied within electroweak quantum chemical frameworks. Besides two-electron orbit-orbit and spin-spin coupling contributions, the Breit interaction gives rise to the spin-other-orbit coupling term of the Breit-Pauli Hamiltonian. The present numerical study demonstrates that neglect of this latter term leads in hydrogen peroxide (H(2)O(2)) to relative deviations in the parity violating potential (V(pv)) by about 10%, whereas further relativistic corrections accounted for within a four-component Dirac-Hartree-Fock-Coulomb (DHFC) framework remain smaller, below 5%. Thus, the main source of discrepancy between previous one-component based (coupled perturbed) Hartree-Fock (HF) and four-component Dirac-Hartree-Fock results for parity violating potentials in H(2)O(2) is the neglect of the Breit contribution in DHFC. In heavier homologs of hydrogen peroxide the relative contribution of the spin-other-orbit coupling term to V(pv) decreases with increasing nuclear charge, whereas other relativistic effects become increasingly important. As shown for the H(2)X(2) (X = O,S,Se,Te,Po) series of molecules and for CHBrClF, to a good approximation these other relativistic influences on V(pv) can be accounted for in one-component based HF calculations with the help of relativistic enhancement factors proposed earlier in the theory of atomic parity violation.

Computational studies of molecular charge transfer complexes of heterocyclic 4-methylepyridine-2-azomethine-p-benzene derivatives with picric acid and m-dinitrobenzene.

PubMed

Al-Harbi, L M; El-Mossalamy, E H; Obaid, A Y; Al-Jedaani, A H

2014-01-01

Charge transfer complexes of substituted aryl Schiff bases as donors with picric acid and m-dinitrobenzene as acceptors were investigated by using computational analysis calculated by Configuration Interaction Singles Hartree-Fock (CIS-HF) at standard 6-31G∗ basis set and Time-Dependent Density-Functional Theory (TD-DFT) levels of theory at standard 6-31G∗∗ basis set, infrared spectra, visible and nuclear magnetic resonance spectra are investigated. The optimized geometries and vibrational frequencies were evaluated. The energy and oscillator strength were calculated by Configuration Interaction Singles Hartree-Fock method (CIS-HF) and the Time-Dependent Density-Functional Theory (TD-DFT) results. Electronic properties, such as HOMO and LUMO energies and band gaps of CTCs set, were studied by the Time-Dependent density functional theory with Becke-Lee-Young-Parr (B3LYP) composite exchange correlation functional and by Configuration Interaction Singles Hartree-Fock method (CIS-HF). The ionization potential Ip and electron affinity EA were calculated by PM3, HF and DFT methods. The columbic force was calculated theoretically by using (CIS-HF and TD-DFT) methods. This study confirms that the theoretical calculation of vibrational frequencies for (aryl Schiff bases--(m-dinitrobenzene and picric acid)) complexes are quite useful for the vibrational assignment and for predicting new vibrational frequencies. Copyright © 2013 Elsevier B.V. All rights reserved.

Interpretation of the silver L X-ray spectrum

NASA Technical Reports Server (NTRS)

Chen, M. H.; Crasemann, B.; Aoyagi, M.; Mark, H.

1977-01-01

Silver L X-ray energies were calculated using theoretical binding energies from relaxed orbital relativistic Hartree-Fock-Slater calculations. Theoretical X-ray energies are compared with experimental results.

Roothaan-Hartree-Fock ground-state atomic wave functions: Slater-type orbital expansions and expectation values for Z = 2-54

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bunge, C.F.; Barrientos, J.A.; Bunge, A.V.

1993-01-01

Roothaan-Hartree-Fock orbitals expressed in a Slater-type basis are reported for the ground states of He through Xe. Energy accuracy ranges between 8 and 10 significant figures, reducing by between 21 and 2,770 times the energy errors of the previous such compilation (E. Clementi and C. Roetti, Atomic Data and Nuclear Data Tables 14, 177, 1974). For each atom, the total energy, kinetic energy, potential energy, virial ratio, electron density at the nucleus, and the Kato cusp are given together with radial expectation values [l angle]r[sup n][r angle] with n from [minus]3 to 2 for each orbital, orbital energies, and orbitalmore » expansion coefficients. 29 refs., 1 tab.« less

Vibrational spectroscopic investigation of p-, m- and o-nitrobenzonitrile by using Hartree-Fock and density functional theory

NASA Astrophysics Data System (ADS)

Sert, Y.; Ucun, F.

2013-08-01

In the present work, the theoretical vibrational spectra of p-, m- and o-nitrobenzonitrile molecules have been analyzed. The harmonic vibrational frequencies and geometric parameters (bond lengths and bond angles) of these molecules have been calculated using ab initio Hartree-Fock and density functional theory methods with 6-311++G(d,p) basis set by Gaussian 03 W, for the first time. Assignments of the vibrational frequencies have been performed by potential energy distribution by using VEDA 4 program. The optimized geometric parameters and harmonic vibrational frequencies have been compared with the corresponding experimental data and seen to be in a good agreement with each other. Also, the highest occupied molecular orbital and lowest unoccupied molecular orbital energies have been obtained.

Time-Dependent Hartree-Fock Approach to Nuclear Pasta at Finite Temperature

NASA Astrophysics Data System (ADS)

Schuetrumpf, B.; Klatt, M. A.; Iida, K.; Maruhn, J. A.; Mecke, K.; Reinhard, P.-G.

2013-03-01

We present simulations of neutron-rich matter at subnuclear densities, like supernova matter, with the time-dependent Hartree-Fock approximation at temperatures of several MeV. The initial state consists of α particles randomly distributed in space that have a Maxwell-Boltzmann distribution in momentum space. Adding a neutron background initialized with Fermi distributed plane waves the calculations reflect a reasonable approximation of astrophysical matter. This matter evolves into spherical, rod-like, and slab-like shapes and mixtures thereof. The simulations employ a full Skyrme interaction in a periodic three-dimensional grid. By an improved morphological analysis based on Minkowski functionals, all eight pasta shapes can be uniquely identified by the sign of only two valuations, namely the Euler characteristic and the integral mean curvature.

Molecular structure and vibrational spectra of three substituted 4-thioflavones by density functional theory and ab initio Hartree-Fock calculations

NASA Astrophysics Data System (ADS)

Li, Xiao-Hong; Liu, Xiang-Ru; Zhang, Xian-Zhou

2011-01-01

The vibrational frequencies of three substituted 4-thioflavones in the ground state have been calculated using the Hartree-Fock and density functional method (B3LYP) with 6-31G* and 6-31+G** basis sets. The structural analysis shows that there exists H-bonding in the selected compounds and the hydrogen bond lengths increase with the augment of the conjugate parameters of the substituent group on the benzene ring. A complete vibrational assignment aided by the theoretical harmonic wavenumber analysis was proposed. The theoretical spectrograms for FT-IR spectra of the title compounds have been constructed. In addition, it is noted that the selected compounds show significant activity against Shigella flexniri. Several electronic properties and thermodynamic parameters were also calculated.

Angular distribution of photoelectrons from atomic oxygen, nitrogen and carbon. [in upper atmosphere

NASA Technical Reports Server (NTRS)

Manson, S. J.; Kennedy, D. J.; Starace, A. F.; Dill, D.

1974-01-01

The angular distributions of photoelectrons from atomic oxygen, nitrogen, and carbon are calculated. Both Hartree-Fock and Hartree-Slater (Herman-Skillman) wave functions are used for oxygen, and the agreement is excellent; thus only Hartree-Slater functions are used for carbon and nitrogen. The pitch-angle distribution of photoelectrons is discussed, and it is shown that previous approximations of energy-independent isotropic or sin squared theta distributions are at odds with the authors' results, which vary with energy. This variation with energy is discussed, as is the reliability of these calculations.

Mouvements collectifs de grandes amplitudes dans les noyaux : une approche microscopique

NASA Astrophysics Data System (ADS)

Giannoni, M.-J.

Various aspects of the adiabatic limit of the time-dependent Hartree-Fock approximation are studied. This formalism is a mean field theory for nuclear collective motion which provides microscopical foundations to the successful phenomenological collective models, and whose validity is not restricted to small amplitude phenomena. Emphasis is put on the classical Hamiltonian-like structure of the dynamical equations. Several limiting cases of the general formalism are considered : Random Phase Approximation, Nuclear Hydrodynamics, case of a single collective variable. Applications to low-lying vibrational modes are described. Results are discussed in terms of sum rules. A quantitative comparison between self-consistent and Inglis cranking mass parameters is made. Important dynamical corrections to the Hartree-Fock ground state are expected for soft nuclei. On étudie divers aspects de l'approximation de Hartree-Fock dépendant du temps à la limite adiabatique. Ce formalisme est une théorie de champ moyen adaptée à la description de phénomènes collectifs dans les noyaux, et dont le domaine de validité n'est pas limité aux mouvements de faibles amplitudes ; d'autre part il permet, grâce à l'approximation adiabatique, de comprendre en termes microscopiques les modèles collectifs purement phénoménologiques. La structure Hamiltonienne classique des équations de mouvement, est étudiée en détail. On considère plusieurs cas limites du formalisme général : approximation des phases au hasard (RPA), limite hydrodynamique, réduction à une seule variable collective. Dans le cadre de ce dernier cas limite, on calcule les paramètres de masse pour les modes vibrationnels quadrupolaires de plusieurs noyaux. Les résultats sont discutés en termes de règle de somme. On compare les paramètres de masse autocohérents aux paramètres de masse d'Inglis. Le formalisme conduit à d'importantes corrections, d'origine dynamique, à l'état fondamental de Hartree-Fock pour des noyaux mous.

A density matrix-based method for the linear-scaling calculation of dynamic second- and third-order properties at the Hartree-Fock and Kohn-Sham density functional theory levels.

PubMed

Kussmann, Jörg; Ochsenfeld, Christian

2007-11-28

A density matrix-based time-dependent self-consistent field (D-TDSCF) method for the calculation of dynamic polarizabilities and first hyperpolarizabilities using the Hartree-Fock and Kohn-Sham density functional theory approaches is presented. The D-TDSCF method allows us to reduce the asymptotic scaling behavior of the computational effort from cubic to linear for systems with a nonvanishing band gap. The linear scaling is achieved by combining a density matrix-based reformulation of the TDSCF equations with linear-scaling schemes for the formation of Fock- or Kohn-Sham-type matrices. In our reformulation only potentially linear-scaling matrices enter the formulation and efficient sparse algebra routines can be employed. Furthermore, the corresponding formulas for the first hyperpolarizabilities are given in terms of zeroth- and first-order one-particle reduced density matrices according to Wigner's (2n+1) rule. The scaling behavior of our method is illustrated for first exemplary calculations with systems of up to 1011 atoms and 8899 basis functions.

Dispersion correction derived from first principles for density functional theory and Hartree-Fock theory.

PubMed

Guidez, Emilie B; Gordon, Mark S

2015-03-12

The modeling of dispersion interactions in density functional theory (DFT) is commonly performed using an energy correction that involves empirically fitted parameters for all atom pairs of the system investigated. In this study, the first-principles-derived dispersion energy from the effective fragment potential (EFP) method is implemented for the density functional theory (DFT-D(EFP)) and Hartree-Fock (HF-D(EFP)) energies. Overall, DFT-D(EFP) performs similarly to the semiempirical DFT-D corrections for the test cases investigated in this work. HF-D(EFP) tends to underestimate binding energies and overestimate intermolecular equilibrium distances, relative to coupled cluster theory, most likely due to incomplete accounting for electron correlation. Overall, this first-principles dispersion correction yields results that are in good agreement with coupled-cluster calculations at a low computational cost.

All-electron molecular Dirac-Hartree-Fock calculations - Properties of the group IV monoxides GeO, SnO, and PbO

NASA Technical Reports Server (NTRS)

Dyall, Kenneth G.

1993-01-01

Dirac-Hartree-Fock calculations have been carried out on the ground states of the group IV monoxides GeO, SnO and PbO. Geometries, dipole moments and infrared data are presented. For comparison, nonrelativistic, first-order perturbation and relativistic effective core potential calculations have also been carried out. Where appropriate the results are compared with the experimental data and previous calculations. Spin-orbit effects are of great importance for PbO, where first-order perturbation theory including only the mass-velocity and Darwin terms is inadequate to predict the relativistic corrections to the properties. The relativistic effective core potential results show a larger deviation from the all-electron values than for the hydrides, and confirm the conclusions drawn on the basis of the hydride calculations.

All-electron molecular Dirac-Hartree-Fock calculations: Properties of the group IV monoxides GeO, SnO and PbO

NASA Technical Reports Server (NTRS)

Dyall, Kenneth G.

1991-01-01

Dirac-Hartree-Fock calculations have been carried out on the ground states of the group IV monoxides GeO, SnO and PbO. Geometries, dipole moments and infrared data are presented. For comparison, nonrelativistic, first-order perturbation and relativistic effective core potential calculations have also been carried out. Where appropriate the results are compared with the experimental data and previous calculations. Spin-orbit effects are of great importance for PbO, where first-order perturbation theory including only the mass-velocity and Darwin terms is inadequate to predict the relativistic corrections to the properties. The relativistic effective core potential results show a larger deviation from the all-electron values than for the hydrides, and confirm the conclusions drawn on the basis of the hydride calculations.

Hartree-Fock calculation of the differential photoionization cross sections of small Li clusters

DOE Office of Scientific and Technical Information (OSTI.GOV)

Galitskiy, S. A.; Artemyev, A. N.; Jänkälä, K.

2015-01-21

Cross sections and angular distribution parameters for the single-photon ionization of all electron orbitals of Li{sub 2−8} are systematically computed in a broad interval of the photoelectron kinetic energies for the energetically most stable geometry of each cluster. Calculations of the partial photoelectron continuum waves in clusters are carried out by the single center method within the Hartree-Fock approximation. We study photoionization cross sections per one electron and analyze in some details general trends in the photoionization of inner and outer shells with respect to the size and geometry of a cluster. The present differential cross sections computed for Li{submore » 2} are in a good agreement with the available theoretical data, whereas those computed for Li{sub 3−8} clusters can be considered as theoretical predictions.« less

Self-consistent Hartree-Fock RPA calculations in 208Pb

NASA Astrophysics Data System (ADS)

Taqi, Ali H.; Ali, Mohammed S.

2018-01-01

The nuclear structure of 208Pb is studied in the framework of the self-consistent random phase approximation (SCRPA). The Hartree-Fock mean field and single particle states are used to implement a completely SCRPA with Skyrme-type interactions. The Hamiltonian is diagonalised within a model space using five Skyrme parameter sets, namely LNS, SkI3, SkO, SkP and SLy4. In view of the huge number of the existing Skyrme-force parameterizations, the question remains which of them provide the best description of data. The approach attempts to accurately describe the structure of the spherical even-even nucleus 208Pb. To illustrate our approach, we compared the binding energy, charge density distribution, excitation energy levels scheme with the available experimental data. Moreover, we calculated isoscalar and isovector monopole, dipole, and quadrupole transition densities and strength functions.

A long-range-corrected density functional that performs well for both ground-state properties and time-dependent density functional theory excitation energies, including charge-transfer excited states.

PubMed

Rohrdanz, Mary A; Martins, Katie M; Herbert, John M

2009-02-07

We introduce a hybrid density functional that asymptotically incorporates full Hartree-Fock exchange, based on the long-range-corrected exchange-hole model of Henderson et al. [J. Chem. Phys. 128, 194105 (2008)]. The performance of this functional, for ground-state properties and for vertical excitation energies within time-dependent density functional theory, is systematically evaluated, and optimal values are determined for the range-separation parameter, omega, and for the fraction of short-range Hartree-Fock exchange. We denote the new functional as LRC-omegaPBEh, since it reduces to the standard PBEh hybrid functional (also known as PBE0 or PBE1PBE) for a certain choice of its two parameters. Upon optimization of these parameters against a set of ground- and excited-state benchmarks, the LRC-omegaPBEh functional fulfills three important requirements: (i) It outperforms the PBEh hybrid functional for ground-state atomization energies and reaction barrier heights; (ii) it yields statistical errors comparable to PBEh for valence excitation energies in both small and medium-sized molecules; and (iii) its performance for charge-transfer excitations is comparable to its performance for valence excitations. LRC-omegaPBEh, with the parameters determined herein, is the first density functional that satisfies all three criteria. Notably, short-range Hartree-Fock exchange appears to be necessary in order to obtain accurate ground-state properties and vertical excitation energies using the same value of omega.

A finite difference Hartree-Fock program for atoms and diatomic molecules

NASA Astrophysics Data System (ADS)

Kobus, Jacek

2013-03-01

The newest version of the two-dimensional finite difference Hartree-Fock program for atoms and diatomic molecules is presented. This is an updated and extended version of the program published in this journal in 1996. It can be used to obtain reference, Hartree-Fock limit values of total energies and multipole moments for a wide range of diatomic molecules and their ions in order to calibrate existing and develop new basis sets, calculate (hyper)polarizabilities (αzz, βzzz, γzzzz, Az,zz, Bzz,zz) of atoms, homonuclear and heteronuclear diatomic molecules and their ions via the finite field method, perform DFT-type calculations using LDA or B88 exchange functionals and LYP or VWN correlations ones or the self-consistent multiplicative constant method, perform one-particle calculations with (smooth) Coulomb and Krammers-Henneberger potentials and take account of finite nucleus models. The program is easy to install and compile (tarball+configure+make) and can be used to perform calculations within double- or quadruple-precision arithmetic. Catalogue identifier: ADEB_v2_0 Program summary URL:http://cpc.cs.qub.ac.uk/summaries/ADEB_v2_0.html Program obtainable from: CPC Program Library, Queen's University, Belfast, N. Ireland Licensing provisions: GNU General Public License version 2 No. of lines in distributed program, including test data, etc.: 171196 No. of bytes in distributed program, including test data, etc.: 9481802 Distribution format: tar.gz Programming language: Fortran 77, C. Computer: any 32- or 64-bit platform. Operating system: Unix/Linux. RAM: Case dependent, from few MB to many GB Classification: 16.1. Catalogue identifier of previous version: ADEB_v1_0 Journal reference of previous version: Comput. Phys. Comm. 98(1996)346 Does the new version supersede the previous version?: Yes Nature of problem: The program finds virtually exact solutions of the Hartree-Fock and density functional theory type equations for atoms, diatomic molecules and their ions. The lowest energy eigenstates of a given irreducible representation and spin can be obtained. The program can be used to perform one-particle calculations with (smooth) Coulomb and Krammers-Henneberger potentials and also DFT-type calculations using LDA or B88 exchange functionals and LYP or VWN correlations ones or the self-consistent multiplicative constant method. Solution method: Single-particle two-dimensional numerical functions (orbitals) are used to construct an antisymmetric many-electron wave function of the restricted open-shell Hartree-Fock model. The orbitals are obtained by solving the Hartree-Fock equations as coupled two-dimensional second-order (elliptic) partial differential equations (PDEs). The Coulomb and exchange potentials are obtained as solutions of the corresponding Poisson equations. The PDEs are discretized by the eighth-order central difference stencil on a two-dimensional single grid, and the resulting large and sparse system of linear equations is solved by the (multicolour) successive overrelaxation ((MC)SOR) method. The self-consistent-field iterations are interwoven with the (MC)SOR ones and orbital energies and normalization factors are used to monitor the convergence. The accuracy of solutions depends mainly on the grid and the system under consideration, which means that within double precision arithmetic one can obtain orbitals and energies having up to 12 significant figures. If more accurate results are needed, quadruple-precision floating-point arithmetic can be used. Reasons for new version: Additional features, many modifications and corrections, improved convergence rate, overhauled code and documentation. Summary of revisions: see ChangeLog found in tar.gz archive Restrictions: The present version of the program is restricted to 60 orbitals. The maximum grid size is determined at compilation time. Unusual features: The program uses two C routines for allocating and deallocating memory. Several BLAS (Basic Linear Algebra System) routines are emulated by the program. When possible they should be replaced by their library equivalents. Additional comments: automake and autoconf tools are required to build and compile the program; checked with f77, gfortran and ifort compilers Running time: Very case dependent - from a few CPU seconds for the H2 defined on a small grid up to several weeks for the Hartree-Fock-limit calculations for 40-50 electron molecules.

AB Initio Study of the Structure and Spectroscopic Properties of Halogenated Thioperoxy Radicals

NASA Technical Reports Server (NTRS)

Munoz, Luis A.; Binning, R. C., Jr.; Weiner, Brad R.; Ishikawa, Yasuyuki

1997-01-01

Thioperoxy (XSO or XOS) radicals exist in a variety of chemical environments, and they have as a consequence drawn some interest. HSO, an important species in the chemistry of the troposphere, has been examined both experimentally. The halogenated (X = F, Cl or Br) peroxy species and isovalent thioperoxy species have been studied less, but they too are potentially interesting because oxidized sulfur species and halogen sources are present in the atmosphere. Learning the fate of XSO and XOS radicals is important to understanding the atmospheric oxidation chemistry of sulfur compounds. Of these, FSO and ClSO are particularly interesting because they have been directly detected spectroscopically. Recent studies in our laboratory on the photochemistry of thionyl halides (X2SO; where X = F or Cl) have suggested new ways to generate XSO species. The laser-induced photodissociation of thionyl fluoride, F2SO, at 193 nm and thionyl chloride, ClSO, at 248 nm is characterized by a radical mechanism, X2SO -> XSO + X. The structure of FSO has been characterized experimentally by Endo et cd. employing microwave spectroscopy. Using the unrestricted Hartree-Fock (UHF) self-consistent field (SCF) method, Sakai and Morokuma computed the electronic structure of the ground (sup 2)A" and the first excited (sup 2)A' states of FSO. Electron correlation was not taken into account in their study. In a laser photodissociation experiment, Huber et al. identified ClSO mass spectromctrically. ClSO has also been detected in low temperature matrices by EPR and in the gas phase by far IR laser magnetic resonance. Although the structure of FSO is known in detail, the only study, experimental or theoretical, of CISO has been an ab initio HFSCF study by Hinchliffe. Electron correlation corrections were also excluded from this study. In order to better understand the isomerization and dissociation dynamics of the radical species, we have performed ab initio correlated studies of the potential energy surfaces (PES) of ClSO and its isomer ClOS at the QCISD(T)/6-31 G* level of theory. For FSO and FOS, more extensive QCISD/6-31 1G(2df) calculations have been possible, and the results are summarized here.

Neutral-atom electron binding energies from relaxed-orbital relativistic Hartree-Fock-Slater calculations for Z between 2 and 106

NASA Technical Reports Server (NTRS)

Huang, K.-N.; Aoyagi, M.; Mark, H.; Chen, M. H.; Crasemann, B.

1976-01-01

Electron binding energies in neutral atoms have been calculated relativistically, with the requirement of complete relaxation. Hartree-Fock-Slater wave functions served as zeroth-order eigenfunctions to compute the expectation of the total Hamiltonian. A first-order correction to the local approximation was thus included. Quantum-electrodynamic corrections were made. For all elements with atomic numbers ranging from 2 to 106, the following quantities are listed: total energies, electron kinetic energies, electron-nucleus potential energies, electron-electron potential energies consisting of electrostatic and Breit interaction (magnetic and retardation) terms, and vacuum polarization energies. Binding energies including relaxation are listed for all electrons in all atoms over the indicated range of atomic numbers. A self-energy correction is included for the 1s, 2s, and 2p(1/2) levels. Results for selected atoms are compared with energies calculated by other methods and with experimental values.

Theoretical dissociation energies for ionic molecules

NASA Technical Reports Server (NTRS)

Langhoff, S. R.; Bauschlicher, C. W., Jr.; Partridge, H.

1986-01-01

Ab initio calculations at the self-consistent-field and singles plus doubles configuration-interaction level are used to determine accurate spectroscopic parameters for most of the alkali and alkaline-earth fluorides, chlorides, oxides, sulfides, hydroxides, and isocyanides. Numerical Hartree-Fock (NHF) calculations are performed on selected systems to ensure that the extended Slater basis sets employed for the diatomic systems are near the Hartree-Fock limit. Extended Gaussian basis sets of at least triple-zeta plus double polarization equality are employed for the triatomic system. With this model, correlation effects are relatively small, but invariably increase the theoretical dissociation energies. The importance of correlating the electrons on both the anion and the metal is discussed. The theoretical dissociation energies are critically compared with the literature to rule out disparate experimental values. Theoretical (sup 2)Pi - (sup 2)Sigma (sup +) energy separations are presented for the alkali oxides and sulfides.

LoFEx - A local framework for calculating excitation energies: Illustrations using RI-CC2 linear response theory.

PubMed

Baudin, Pablo; Kristensen, Kasper

2016-06-14

We present a local framework for the calculation of coupled cluster excitation energies of large molecules (LoFEx). The method utilizes time-dependent Hartree-Fock information about the transitions of interest through the concept of natural transition orbitals (NTOs). The NTOs are used in combination with localized occupied and virtual Hartree-Fock orbitals to generate a reduced excitation orbital space (XOS) specific to each transition where a standard coupled cluster calculation is carried out. Each XOS is optimized to ensure that the excitation energies are determined to a predefined precision. We apply LoFEx in combination with the RI-CC2 model to calculate the lowest excitation energies of a set of medium-sized organic molecules. The results demonstrate the black-box nature of the LoFEx approach and show that significant computational savings can be gained without affecting the accuracy of CC2 excitation energies.

Optimized auxiliary basis sets for density fitted post-Hartree-Fock calculations of lanthanide containing molecules

NASA Astrophysics Data System (ADS)

Chmela, Jiří; Harding, Michael E.

2018-06-01

Optimised auxiliary basis sets for lanthanide atoms (Ce to Lu) for four basis sets of the Karlsruhe error-balanced segmented contracted def2 - series (SVP, TZVP, TZVPP and QZVPP) are reported. These auxiliary basis sets enable the use of the resolution-of-the-identity (RI) approximation in post Hartree-Fock methods - as for example, second-order perturbation theory (MP2) and coupled cluster (CC) theory. The auxiliary basis sets are tested on an enlarged set of about a hundred molecules where the test criterion is the size of the RI error in MP2 calculations. Our tests also show that the same auxiliary basis sets can be used together with different effective core potentials. With these auxiliary basis set calculations of MP2 and CC quality can now be performed efficiently on medium-sized molecules containing lanthanides.

a HARTREE-FOCK Nuclear Mass Table

NASA Astrophysics Data System (ADS)

Goriely, S.; Tondeur, F.; Pearson, J. M.

2001-03-01

We present the first complete nuclear mass table, HFBCS-1, to be based on the Hartree-Fock-BCS method. The force used, MSk7, is a 10-parameter Skyrme force, along with a 4-parameter δ-function pairing force and a 2-parameter phenomenological Wigner term. Our tabulation presents 9200 nuclei, including all those lying between the drip lines over the range Z, N≥8 and Z≤120. The root-mean-square error of our fit to the 1888 nuclei in this range for which measured masses are given in the 1995 Audi-Wapstra compilation is 0.738 MeV. In addition to the calculated masses, we show the calculated neutron- and proton-separation energies, and beta-decay energies. We also give for each nucleus in the table the calculated values for the deformation parameters and deformation energy (with axial and left-right symmetry assumed), and for the charge radius.

X-ray production cross sections at incident photon energies across the M{sub i} (i=1-5) edges of {sub 90}Th

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kaur, Rajnish; Shehla,; Kumar, Anil

2015-08-28

The X-ray production cross sections for the M{sub k} (k= ξ, δ, α, β, ζ, γ, m{sub 1}, m{sub 2}) groups of X-rays have been evaluated at incident photon energies across the M{sub i} (i =1-5) edges of {sub 90}Th using the relativistic Hartree-Fock-Slater model based photoionisation cross sections and recently reported values of the M-shell X-ray emission rates, fluorescence and Coster Kronig yields. Further, the energies of the prominent (M{sub i}-S{sub j}) (S{sub j}=N{sub j}, O{sub j} and i =1-3, j =1-7) resonant Raman scattered (RRS) peaks at different incident photon energies have also been evaluated using the neutral-atommore » electron binding energies (E{sub sj}) based on the relaxed orbital relativistic Hartree-Fock-Slater model.« less

Optimal plane-wave Hartree-Fock states for many-fermion systems

DOE Office of Scientific and Technical Information (OSTI.GOV)

de Llano, M.; Plastino, A.; Zabolitzky, J.G.

1979-12-01

The possibility of taking plane-wave orbitals of a Hartree-Fock determinant to fill k space differently from the ''normal'' Fermi sphere is investigated for several two-body potentials including the ''homework'' v/sub 0/, v/sub 1/, and v/sub 2/ - aken from the Reid nucleon-nucleon force - as well as a sum-of-Gaussians potential chosen to fit the deuteron binding and size. A random-search and random-walk numerical algorithm shows that, provided the potential strengths are made large enough, a single-shell ''abnormal'' occupation is always found to be lower in energy than the normal one if sufficient attraction is present in the two-body interaction. Nomore » abnormal occupation is possible for, among other pair interactions, the electron or charged-boson fluid, the repulsive square barrier, and a common form of the He-He interaction.« less

Modeling molecule-plasmon interactions using quantized radiation fields within time-dependent electronic structure theory

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nascimento, Daniel R.; DePrince, A. Eugene, E-mail: deprince@chem.fsu.edu

2015-12-07

We present a combined cavity quantum electrodynamics/ab initio electronic structure approach for simulating plasmon-molecule interactions in the time domain. The simple Jaynes-Cummings-type model Hamiltonian typically utilized in such simulations is replaced with one in which the molecular component of the coupled system is treated in a fully ab initio way, resulting in a computationally efficient description of general plasmon-molecule interactions. Mutual polarization effects are easily incorporated within a standard ground-state Hartree-Fock computation, and time-dependent simulations carry the same formal computational scaling as real-time time-dependent Hartree-Fock theory. As a proof of principle, we apply this generalized method to the emergence ofmore » a Fano-like resonance in coupled molecule-plasmon systems; this feature is quite sensitive to the nanoparticle-molecule separation and the orientation of the molecule relative to the polarization of the external electric field.« less

Axial deformed solution of the Skyrme-Hartree-Fock-Bogolyubov equations using the transformed harmonic oscillator Basis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Perez, R. Navarro; Schunck, N.; Lasseri, R.

2017-03-09

HFBTHO is a physics computer code that is used to model the structure of the nucleus. It is an implementation of the nuclear energy Density Functional Theory (DFT), where the energy of the nucleus is obtained by integration over space of some phenomenological energy density, which is itself a functional of the neutron and proton densities. In HFBTHO, the energy density derives either from the zero-range Dkyrme or the finite-range Gogny effective two-body interaction between nucleons. Nuclear superfluidity is treated at the Hartree-Fock-Bogoliubov (HFB) approximation, and axial-symmetry of the nuclear shape is assumed. This version is the 3rd release ofmore » the program; the two previous versions were published in Computer Physics Communications [1,2]. The previous version was released at LLNL under GPL 3 Open Source License and was given release code LLNL-CODE-573953.« less

Assessing the role of Hartree-Fock exchange, correlation energy and long range corrections in evaluating ionization potential, and electron affinity in density functional theory.

PubMed

Vikramaditya, Talapunur; Lin, Shiang-Tai

2017-06-05

Accurate determination of ionization potentials (IPs), electron affinities (EAs), fundamental gaps (FGs), and HOMO, LUMO energy levels of organic molecules play an important role in modeling and predicting the efficiencies of organic photovoltaics, OLEDs etc. In this work, we investigate the effects of Hartree Fock (HF) Exchange, correlation energy, and long range corrections in predicting IP and EA in Hybrid Functionals. We observe increase in percentage of HF exchange results in increase of IPs and decrease in EAs. Contrary to the general expectations inclusion of both HF exchange and correlation energy (from the second order perturbation theory MP2) leads to poor prediction. Range separated Hybrid Functionals are found to be more reliable among various DFT Functionals investigated. DFT Functionals predict accurate IPs whereas post HF methods predict accurate EAs. © 2017 Wiley Periodicals, Inc. © 2017 Wiley Periodicals, Inc.

Time-dependent Hartree-Fock approach to nuclear ``pasta'' at finite temperature

NASA Astrophysics Data System (ADS)

Schuetrumpf, B.; Klatt, M. A.; Iida, K.; Maruhn, J. A.; Mecke, K.; Reinhard, P.-G.

2013-05-01

We present simulations of neutron-rich matter at subnuclear densities, like supernova matter, with the time-dependent Hartree-Fock approximation at temperatures of several MeV. The initial state consists of α particles randomly distributed in space that have a Maxwell-Boltzmann distribution in momentum space. Adding a neutron background initialized with Fermi distributed plane waves the calculations reflect a reasonable approximation of astrophysical matter. This matter evolves into spherical, rod-like, and slab-like shapes and mixtures thereof. The simulations employ a full Skyrme interaction in a periodic three-dimensional grid. By an improved morphological analysis based on Minkowski functionals, all eight pasta shapes can be uniquely identified by the sign of only two valuations, namely the Euler characteristic and the integral mean curvature. In addition, we propose the variance in the cell density distribution as a measure to distinguish pasta matter from uniform matter.

Compton scattering study of electron momentum distribution in lithium fluoride using 662 keV gamma radiations

NASA Astrophysics Data System (ADS)

Vijayakumar, R.; Shivaramu; Ramamurthy, N.; Ford, M. J.

2008-12-01

Here we report the first ever 137Cs Compton spectroscopy study of lithium fluoride. The spherical average Compton profiles of lithium fluoride are deduced from Compton scattering measurements on poly crystalline sample at gamma ray energy of 662 keV. To compare the experimental data, we have computed the spherical average Compton profiles using self-consistent Hartree-Fock wave functions employed on linear combination of atomic orbital (HF-LCAO) approximation. The directional Compton profiles and their anisotropic effects are also calculated using the same HF-LCAO approximation. The experimental spherical average profiles are found to be in good agreement with the corresponding HF-LCAO calculations and in qualitative agreement with Hartree-Fock free atom values. The present experimental isotropic and calculated directional profiles are also compared with the available experimental isotropic and directional Compton profiles using 59.54 and 159 keV γ-rays.

Polyatomic molecular Dirac-Hartree-Fock calculations with Gaussian basis sets

NASA Technical Reports Server (NTRS)

Dyall, Kenneth G.; Faegri, Knut, Jr.; Taylor, Peter R.

1990-01-01

Numerical methods have been used successfully in atomic Dirac-Hartree-Fock (DHF) calculations for many years. Some DHF calculations using numerical methods have been done on diatomic molecules, but while these serve a useful purpose for calibration, the computational effort in extending this approach to polyatomic molecules is prohibitive. An alternative more in line with traditional quantum chemistry is to use an analytical basis set expansion of the wave function. This approach fell into disrepute in the early 1980's due to problems with variational collapse and intruder states, but has recently been put on firm theoretical foundations. In particular, the problems of variational collapse are well understood, and prescriptions for avoiding the most serious failures have been developed. Consequently, it is now possible to develop reliable molecular programs using basis set methods. This paper describes such a program and reports results of test calculations to demonstrate the convergence and stability of the method.

Generalization of the Hartree-Fock approach to collision processes

NASA Astrophysics Data System (ADS)

Hahn, Yukap

1997-06-01

The conventional Hartree and Hartree-Fock approaches for bound states are generalized to treat atomic collision processes. All the single-particle orbitals, for both bound and scattering states, are determined simultaneously by requiring full self-consistency. This generalization is achieved by introducing two Ansäauttze: (a) the weak asymptotic boundary condition, which maintains the correct scattering energy and target orbitals with correct number of nodes, and (b) square integrable amputated scattering functions to generate self-consistent field (SCF) potentials for the target orbitals. The exact initial target and final-state asymptotic wave functions are not required and thus need not be specified a priori, as they are determined simultaneously by the SCF iterations. To check the asymptotic behavior of the solution, the theory is applied to elastic electron-hydrogen scattering at low energies. The solution is found to be stable and the weak asymptotic condition is sufficient to produce the correct scattering amplitudes. The SCF potential for the target orbital shows the strong penetration by the projectile electron during the collision, but the exchange term tends to restore the original form. Potential applicabilities of this extension are discussed, including the treatment of ionization and shake-off processes.

Linear-scaling implementation of molecular response theory in self-consistent field electronic-structure theory.

PubMed

Coriani, Sonia; Høst, Stinne; Jansík, Branislav; Thøgersen, Lea; Olsen, Jeppe; Jørgensen, Poul; Reine, Simen; Pawłowski, Filip; Helgaker, Trygve; Sałek, Paweł

2007-04-21

A linear-scaling implementation of Hartree-Fock and Kohn-Sham self-consistent field theories for the calculation of frequency-dependent molecular response properties and excitation energies is presented, based on a nonredundant exponential parametrization of the one-electron density matrix in the atomic-orbital basis, avoiding the use of canonical orbitals. The response equations are solved iteratively, by an atomic-orbital subspace method equivalent to that of molecular-orbital theory. Important features of the subspace method are the use of paired trial vectors (to preserve the algebraic structure of the response equations), a nondiagonal preconditioner (for rapid convergence), and the generation of good initial guesses (for robust solution). As a result, the performance of the iterative method is the same as in canonical molecular-orbital theory, with five to ten iterations needed for convergence. As in traditional direct Hartree-Fock and Kohn-Sham theories, the calculations are dominated by the construction of the effective Fock/Kohn-Sham matrix, once in each iteration. Linear complexity is achieved by using sparse-matrix algebra, as illustrated in calculations of excitation energies and frequency-dependent polarizabilities of polyalanine peptides containing up to 1400 atoms.

Measurement of Kα and Kβ fluorescence cross sections for elements in the range 44<=Z<=68 at 59.5 keV

NASA Astrophysics Data System (ADS)

Budak, G.; Karabulut, A.; Demir, L.; Sahin, Y.

1999-09-01

The Kα and Kβ x-ray fluorescence cross sections have been measured for elements in the range 44<=Z<=68 at an excitation energy of 59.5-keV γ ray from 241Am radioisotope with a Si(Li) detector. A reasonable agreement is found between the present experimental results and the theoretically calculated values based on photoionization cross sections by Scofield using Hartree-Slater and Hartree-Fock central potential theory.

Physics in Screening Environments

NASA Astrophysics Data System (ADS)

Certik, Ondrej

In the current study, we investigated atoms in screening environments like plasmas. It is common practice to extract physical data, such as temperature and electron densities, from plasma experiments. We present results that address inherent computational difficulties that arise when the screening approach is extended to include the interaction between the atomic electrons. We show that there may arise an ambiguity in the interpretation of physical properties, such as temperature and charge density, from experimental data due to the opposing effects of electron-nucleus screening and electron-electron screening. The focus of the work, however, is on the resolution of inherent computational challenges that appear in the computation of two-particle matrix elements. Those enter already at the Hartree-Fock level. Furthermore, as examples of post Hartree-Fock calculations, we show second-order Green's function results and many body perturbation theory results of second order. A self-contained derivation of all necessary equations has been included. The accuracy of the implementation of the method is established by comparing standard unscreened results for various atoms and molecules against literature for Hartree-Fock as well as Green's function and many body perturbation theory. The main results of the thesis are presented in the chapter called Screened Results, where the behavior of several atomic systems depending on electron-electron and electron-nucleus Debye screening was studied. The computer code that we have developed has been made available for anybody to use. Finally, we present and discuss results obtained for screened interactions. We also examine thoroughly the computational details of the calculations and particular implementations of the method.

Computational Prediction of Kinetic Rate Constants

DTIC Science & Technology

2009-02-01

best experimental estimates are in kcal/mol. RMcdoo l> Uil. . 1 -.In 1 1 II. lei ,. »rrsnn • emu rtvm . « snfi. !>ii K.IIHlMi’ \\i . St"WTi H...straightforward extensions the HF energy and gradient expressions. For example, the energy and the gradient HF-DFT ’ dE designated as E r-IIF DF1 and...8217’ Coulomb Electron Electron «P Hartr » . pBecke-LYP I ^Hartree-Fock \\7 n ’ Exchange correlation \\H ’ r llarlree-Fock Contract

Toward a muon-specific electronic structure theory: effective electronic Hartree-Fock equations for muonic molecules.

PubMed

Rayka, Milad; Goli, Mohammad; Shahbazian, Shant

2018-02-07

An effective set of Hartree-Fock (HF) equations are derived for electrons of muonic systems, i.e., molecules containing a positively charged muon, conceiving the muon as a quantum oscillator, which are completely equivalent to the usual two-component HF equations used to derive stationary states of the muonic molecules. In these effective equations, a non-Coulombic potential is added to the orthodox coulomb and exchange potential energy terms, which describes the interaction of the muon and the electrons effectively and is optimized during the self-consistent field cycles. While in the two-component HF equations a muon is treated as a quantum particle, in the effective HF equations it is absorbed into the effective potential and practically transformed into an effective potential field experienced by electrons. The explicit form of the effective potential depends on the nature of muon's vibrations and is derivable from the basis set used to expand the muonic spatial orbital. The resulting effective Hartree-Fock equations are implemented computationally and used successfully, as a proof of concept, in a series of muonic molecules containing all atoms from the second and third rows of the Periodic Table. To solve the algebraic version of the equations muon-specific Gaussian basis sets are designed for both muon and surrounding electrons and it is demonstrated that the optimized exponents are quite distinct from those derived for the hydrogen isotopes. The developed effective HF theory is quite general and in principle can be used for any muonic system while it is the starting point for a general effective electronic structure theory that incorporates various types of quantum correlations into the muonic systems beyond the HF equations.

Influence of the plasma environment on atomic structure using an ion-sphere model

NASA Astrophysics Data System (ADS)

Belkhiri, Madeny; Fontes, Christopher J.; Poirier, Michel

2015-09-01

Plasma environment effects on atomic structure are analyzed using various atomic structure codes. To monitor the effect of high free-electron density or low temperatures, Fermi-Dirac and Maxwell-Boltzmann statistics are compared. After a discussion of the implementation of the Fermi-Dirac approach within the ion-sphere model, several applications are considered. In order to check the consistency of the modifications brought here to extant codes, calculations have been performed using the Los Alamos Cowan Atomic Structure (cats) code in its Hartree-Fock or Hartree-Fock-Slater form and the parametric potential Flexible Atomic Code (fac). The ground-state energy shifts due to the plasma effects for the six most ionized aluminum ions have been calculated using the fac and cats codes and fairly agree. For the intercombination resonance line in Fe22 +, the plasma effect within the uniform electron gas model results in a positive shift that agrees with the multiconfiguration Dirac-Fock value of B. Saha and S. Fritzsche [J. Phys. B 40, 259 (2007), 10.1088/0953-4075/40/2/002]. Last, the present model is compared to experimental data in titanium measured on the terawatt Astra facility and provides values for electron temperature and density in agreement with the maria code.

Photoionization of Atoms and Molecules using a Configuration-Average Distorted-Wave Method

NASA Astrophysics Data System (ADS)

Pindzola, M. S.; Balance, C. P.; Loch, S. D.; Ludlow, J. A.

2011-05-01

A configuration-average distorted-wave method is applied to calculate the photoionization cross section for the outer subshells of the C atom and the C2 diatomic molecule. Comparisions are made with previous R-matrix and Hartree- Fock distorted-wave calculations.

Spiral magnetism in the single-band Hubbard model: the Hartree-Fock and slave-boson approaches.

PubMed

Igoshev, P A; Timirgazin, M A; Gilmutdinov, V F; Arzhnikov, A K; Irkhin, V Yu

2015-11-11

The ground-state magnetic phase diagram is investigated within the single-band Hubbard model for square and different cubic lattices. The results of employing the generalized non-correlated mean-field (Hartree-Fock) approximation and generalized slave-boson approach by Kotliar and Ruckenstein with correlation effects included are compared. We take into account commensurate ferromagnetic, antiferromagnetic, and incommensurate (spiral) magnetic phases, as well as phase separation into magnetic phases of different types, which was often lacking in previous investigations. It is found that the spiral states and especially ferromagnetism are generally strongly suppressed up to non-realistically large Hubbard U by the correlation effects if nesting is absent and van Hove singularities are well away from the paramagnetic phase Fermi level. The magnetic phase separation plays an important role in the formation of magnetic states, the corresponding phase regions being especially wide in the vicinity of half-filling. The details of non-collinear and collinear magnetic ordering for different cubic lattices are discussed.

Ab initio effective core potentials including relativistic effects and their application to the electronic structure calculations of heavy atoms and molecules

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lee, Y.S.

1977-11-01

The effects of the 4f shell of electrons and the relativity of valence electrons are compared. The effect of 4f shell (lanthanide contraction) is estimated from the numerical Hartree-Fock (HF) calculations of pseudo-atoms corresponding to Hf, Re, Au, Hg, Tl, Pb and Bi without 4f electrons and with atomic numbers reduced by 14. The relativistic effect estimated from the numerical Dirac-Hartree-Fock (DHF) calculations of those atoms is comparable in the magnitude with that of the 4f shell of electrons. Both are larger for 6s than for 5d or 6p electrons. The various relativistic effects on valence electrons are discussed inmore » detail to determine the proper level of the approximation for the valence electron calculations of systems with heavy elements. An effective core potential system has been developed for heavy atoms in which relativistic effects are included in the effective potentials.« less

Automatic Differentiation in Quantum Chemistry with Applications to Fully Variational Hartree-Fock.

PubMed

Tamayo-Mendoza, Teresa; Kreisbeck, Christoph; Lindh, Roland; Aspuru-Guzik, Alán

2018-05-23

Automatic differentiation (AD) is a powerful tool that allows calculating derivatives of implemented algorithms with respect to all of their parameters up to machine precision, without the need to explicitly add any additional functions. Thus, AD has great potential in quantum chemistry, where gradients are omnipresent but also difficult to obtain, and researchers typically spend a considerable amount of time finding suitable analytical forms when implementing derivatives. Here, we demonstrate that AD can be used to compute gradients with respect to any parameter throughout a complete quantum chemistry method. We present DiffiQult , a Hartree-Fock implementation, entirely differentiated with the use of AD tools. DiffiQult is a software package written in plain Python with minimal deviation from standard code which illustrates the capability of AD to save human effort and time in implementations of exact gradients in quantum chemistry. We leverage the obtained gradients to optimize the parameters of one-particle basis sets in the context of the floating Gaussian framework.

Big Data Meets Quantum Chemistry Approximations: The Δ-Machine Learning Approach.

PubMed

Ramakrishnan, Raghunathan; Dral, Pavlo O; Rupp, Matthias; von Lilienfeld, O Anatole

2015-05-12

Chemically accurate and comprehensive studies of the virtual space of all possible molecules are severely limited by the computational cost of quantum chemistry. We introduce a composite strategy that adds machine learning corrections to computationally inexpensive approximate legacy quantum methods. After training, highly accurate predictions of enthalpies, free energies, entropies, and electron correlation energies are possible, for significantly larger molecular sets than used for training. For thermochemical properties of up to 16k isomers of C7H10O2 we present numerical evidence that chemical accuracy can be reached. We also predict electron correlation energy in post Hartree-Fock methods, at the computational cost of Hartree-Fock, and we establish a qualitative relationship between molecular entropy and electron correlation. The transferability of our approach is demonstrated, using semiempirical quantum chemistry and machine learning models trained on 1 and 10% of 134k organic molecules, to reproduce enthalpies of all remaining molecules at density functional theory level of accuracy.

Optimized norm-conserving Hartree-Fock pseudopotentials for plane-wave calculations

NASA Astrophysics Data System (ADS)

Al-Saidi, W. A.; Walter, E. J.; Rappe, A. M.

2008-02-01

We report Hartree-Fock (HF)-based pseudopotentials suitable for plane-wave calculations. Unlike typical effective core potentials, the present pseudopotentials are finite at the origin and exhibit rapid convergence in a plane-wave basis; the optimized pseudopotential method [A. M. Rappe , Phys. Rev. B 41, 1227 (1990)] improves plane-wave convergence. Norm-conserving HF pseudopotentials are found to develop long-range non-Coulombic behavior which does not decay faster than 1/r , and is nonlocal. This behavior, which stems from the nonlocality of the exchange potential, is remedied using a recently developed self-consistent procedure [J. R. Trail and R. J. Needs, J. Chem. Phys. 122, 014112 (2005)]. The resulting pseudopotentials slightly violate the norm conservation of the core charge. We calculated several atomic properties using these pseudopotentials, and the results are in good agreement with all-electron HF values. The dissociation energies, equilibrium bond lengths, and frequencies of vibration of several dimers obtained with these HF pseudopotentials and plane waves are also in good agreement with all-electron results.

Analytic energy gradient of projected Hartree-Fock within projection after variation

NASA Astrophysics Data System (ADS)

Uejima, Motoyuki; Ten-no, Seiichiro

2017-03-01

We develop a geometrical optimization technique for the projection-after-variation (PAV) scheme of the recently refined projected Hartree-Fock (PHF) as a fast alternative to the variation-after-projection (VAP) approach for optimizing the structures of molecules/clusters in symmetry-adapted electronic states at the mean-field computational cost. PHF handles the nondynamic correlation effects by restoring the symmetry of a broken-symmetry single reference wavefunction and moreover enables a black-box treatment of orbital selections. Using HF orbitals instead of PHF orbitals, our approach saves the computational cost for the orbital optimization, avoiding the convergence problem that sometimes emerges in the VAP scheme. We show that PAV-PHF provides geometries comparable to those of the complete active space self-consistent field and VAP-PHF for the tested systems, namely, CH2, O3, and the [Cu2O2 ] 2 + core, where nondynamic correlation is abundant. The proposed approach is useful for large systems mainly dominated by nondynamic correlation to find stable structures in many symmetry-adapted states.

Modified Hartree-Fock-Bogoliubov theory at finite temperature

NASA Astrophysics Data System (ADS)

Dinh Dang, Nguyen; Arima, Akito

2003-07-01

The modified Hartree-Fock-Bogoliubov (MHFB) theory at finite temperature is derived, which conserves the unitarity relation of the particle-density matrix. This is achieved by constructing a modified-quasiparticle-density matrix, where the fluctuation of the quasiparticle number is microscopically built in. This matrix can be directly obtained from the usual quasiparticle-density matrix by applying the secondary Bogoliubov transformation, which includes the quasiparticle-occupation number. It is shown that, in the limit of constant pairing parameter, the MHFB theory yields the previously obtained modified BCS (MBCS) equations. It is also proved that the modified quasiparticle-random-phase approximation, which is based on the MBCS quasiparticle excitations, conserves the Ikeda sum rule. The numerical calculations of the pairing gap, heat capacity, level density, and level-density parameter within the MBCS theory are carried out for 120Sn. The results show that the superfluid-normal phase transition is completely washed out. The applicability of the MBCS up to a temperature as high as T˜5 MeV is analyzed in detail.

Positive semidefinite tensor factorizations of the two-electron integral matrix for low-scaling ab initio electronic structure.

PubMed

Hoy, Erik P; Mazziotti, David A

2015-08-14

Tensor factorization of the 2-electron integral matrix is a well-known technique for reducing the computational scaling of ab initio electronic structure methods toward that of Hartree-Fock and density functional theories. The simplest factorization that maintains the positive semidefinite character of the 2-electron integral matrix is the Cholesky factorization. In this paper, we introduce a family of positive semidefinite factorizations that generalize the Cholesky factorization. Using an implementation of the factorization within the parametric 2-RDM method [D. A. Mazziotti, Phys. Rev. Lett. 101, 253002 (2008)], we study several inorganic molecules, alkane chains, and potential energy curves and find that this generalized factorization retains the accuracy and size extensivity of the Cholesky factorization, even in the presence of multi-reference correlation. The generalized family of positive semidefinite factorizations has potential applications to low-scaling ab initio electronic structure methods that treat electron correlation with a computational cost approaching that of the Hartree-Fock method or density functional theory.

Influence of the plasma environment on atomic structure using an ion-sphere model

DOE PAGES

Belkhiri, Madeny Jean; Fontes, Christopher John; Poirier, Michel

2015-09-03

Plasma environment effects on atomic structure are analyzed using various atomic structure codes. To monitor the effect of high free-electron density or low temperatures, Fermi-Dirac and Maxwell-Boltzmann statistics are compared. After a discussion of the implementation of the Fermi-Dirac approach within the ion-sphere model, several applications are considered. In order to check the consistency of the modifications brought here to extant codes, calculations have been performed using the Los Alamos Cowan Atomic Structure (cats) code in its Hartree-Fock or Hartree-Fock-Slater form and the parametric potential Flexible Atomic Code (fac). The ground-state energy shifts due to the plasma effects for themore » six most ionized aluminum ions have been calculated using the fac and cats codes and fairly agree. For the intercombination resonance line in Fe 22+, the plasma effect within the uniform electron gas model results in a positive shift that agrees with the MCDF value of B. Saha et al.« less

Influence of the plasma environment on atomic structure using an ion-sphere model

DOE Office of Scientific and Technical Information (OSTI.GOV)

Belkhiri, Madeny Jean; Fontes, Christopher John; Poirier, Michel

Plasma environment effects on atomic structure are analyzed using various atomic structure codes. To monitor the effect of high free-electron density or low temperatures, Fermi-Dirac and Maxwell-Boltzmann statistics are compared. After a discussion of the implementation of the Fermi-Dirac approach within the ion-sphere model, several applications are considered. In order to check the consistency of the modifications brought here to extant codes, calculations have been performed using the Los Alamos Cowan Atomic Structure (cats) code in its Hartree-Fock or Hartree-Fock-Slater form and the parametric potential Flexible Atomic Code (fac). The ground-state energy shifts due to the plasma effects for themore » six most ionized aluminum ions have been calculated using the fac and cats codes and fairly agree. For the intercombination resonance line in Fe 22+, the plasma effect within the uniform electron gas model results in a positive shift that agrees with the MCDF value of B. Saha et al.« less

Spin Hartree-Fock approach to studying quantum Heisenberg antiferromagnets in low dimensions

NASA Astrophysics Data System (ADS)

Werth, A.; Kopietz, P.; Tsyplyatyev, O.

2018-05-01

We construct a new mean-field theory for a quantum (spin-1/2) Heisenberg antiferromagnet in one (1D) and two (2D) dimensions using a Hartree-Fock decoupling of the four-point correlation functions. We show that the solution to the self-consistency equations based on two-point correlation functions does not produce any unphysical finite-temperature phase transition, in accord with the Mermin-Wagner theorem, unlike the common approach based on the mean-field equation for the order parameter. The next-neighbor spin-spin correlation functions, calculated within this approach, reproduce closely the strong renormalization by quantum fluctuations obtained via a Bethe ansatz in 1D and a small renormalization of the classical antiferromagnetic state in 2D. The heat capacity approximates with reasonable accuracy the full Bethe ansatz result at all temperatures in 1D. In 2D, we obtain a reduction of the peak height in the heat capacity at a finite temperature that is accessible by high-order 1 /T expansions.

Microscopic optical model potential based on a Dirac Brueckner Hartree Fock approach and the relevant uncertainty analysis

NASA Astrophysics Data System (ADS)

Xu, Ruirui; Ma, Zhongyu; Muether, Herbert; van Dalen, E. N. E.; Liu, Tinjin; Zhang, Yue; Zhang, Zhi; Tian, Yuan

2017-09-01

A relativistic microscopic optical model potential, named CTOM, for nucleon-nucleus scattering is investigated in the framework of Dirac-Brueckner-Hartree-Fock approach. The microscopic feature of CTOM is guaranteed through rigorously adopting the isospin dependent DBHF calculation within the subtracted T matrix scheme. In order to verify its prediction power, a global study n, p+ A scattering are carried out. The predicted scattering observables coincide with experimental data within a good accuracy over a broad range of targets and a large region of energies only with two free items, namely the free-range factor t in the applied improved local density approximation and minor adjustments of the scalar and vector potentials in the low-density region. In addition, to estimate the uncertainty of the theoretical results, the deterministic simple least square approach is preliminarily employed to derive the covariance of predicted angular distributions, which is also briefly contained in this paper.

Hartree-Fock implementation using a Laguerre-based wave function for the ground state and correlation energies of two-electron atoms.

PubMed

King, Andrew W; Baskerville, Adam L; Cox, Hazel

2018-03-13

An implementation of the Hartree-Fock (HF) method using a Laguerre-based wave function is described and used to accurately study the ground state of two-electron atoms in the fixed nucleus approximation, and by comparison with fully correlated (FC) energies, used to determine accurate electron correlation energies. A variational parameter A is included in the wave function and is shown to rapidly increase the convergence of the energy. The one-electron integrals are solved by series solution and an analytical form is found for the two-electron integrals. This methodology is used to produce accurate wave functions, energies and expectation values for the helium isoelectronic sequence, including at low nuclear charge just prior to electron detachment. Additionally, the critical nuclear charge for binding two electrons within the HF approach is calculated and determined to be Z HF C =1.031 177 528.This article is part of the theme issue 'Modern theoretical chemistry'. © 2018 The Author(s).

Quantum supercharger library: hyper-parallelism of the Hartree-Fock method.

PubMed

Fernandes, Kyle D; Renison, C Alicia; Naidoo, Kevin J

2015-07-05

We present here a set of algorithms that completely rewrites the Hartree-Fock (HF) computations common to many legacy electronic structure packages (such as GAMESS-US, GAMESS-UK, and NWChem) into a massively parallel compute scheme that takes advantage of hardware accelerators such as Graphical Processing Units (GPUs). The HF compute algorithm is core to a library of routines that we name the Quantum Supercharger Library (QSL). We briefly evaluate the QSL's performance and report that it accelerates a HF 6-31G Self-Consistent Field (SCF) computation by up to 20 times for medium sized molecules (such as a buckyball) when compared with mature Central Processing Unit algorithms available in the legacy codes in regular use by researchers. It achieves this acceleration by massive parallelization of the one- and two-electron integrals and optimization of the SCF and Direct Inversion in the Iterative Subspace routines through the use of GPU linear algebra libraries. © 2015 Wiley Periodicals, Inc. © 2015 Wiley Periodicals, Inc.

Toroidal high-spin isomers in the nucleus 304120

NASA Astrophysics Data System (ADS)

Staszczak, A.; Wong, Cheuk-Yin; Kosior, A.

2017-05-01

Background: Strongly deformed oblate superheavy nuclei form an intriguing region where the toroidal nuclear structures may bifurcate from the oblate spheroidal shape. The bifurcation may be facilitated when the nucleus is endowed with a large angular moment about the symmetry axis with I =Iz . The toroidal high-K isomeric states at their local energy minima can be theoretically predicted using the cranked self-consistent Skyrme-Hartree-Fock method. Purpose: We use the cranked Skyrme-Hartree-Fock method to predict the properties of the toroidal high-spin isomers in the superheavy nucleus 120304184. Method: Our method consists of three steps: First, we use the deformation-constrained Skyrme-Hartree-Fock-Bogoliubov approach to search for the nuclear density distributions with toroidal shapes. Next, using these toroidal distributions as starting configurations, we apply an additional cranking constraint of a large angular momentum I =Iz about the symmetry z axis and search for the energy minima of the system as a function of the deformation. In the last step, if a local energy minimum with I =Iz is found, we perform at this point the cranked symmetry- and deformation-unconstrained Skyrme-Hartree-Fock calculations to locate a stable toroidal high-spin isomeric state in free convergence. Results: We have theoretically located two toroidal high-spin isomeric states of 120304184 with an angular momentum I =Iz=81 ℏ (proton 2p-2h, neutron 4p-4h excitation) and I =Iz=208 ℏ (proton 5p-5h, neutron 8p-8h) at the quadrupole moment deformations Q20=-297.7 b and Q20=-300.8 b with energies 79.2 and 101.6 MeV above the spherical ground state, respectively. The nuclear density distributions of the toroidal high-spin isomers 120304184(Iz=81 ℏ and 208 ℏ ) have the maximum density close to the nuclear matter density, 0.16 fm-3, and a torus major to minor radius aspect ratio R /d =3.25 . Conclusions: We demonstrate that aligned angular momenta of Iz=81 ℏ and 208 ℏ arising from multiparticle-multihole excitations in the toroidal system of 120304184 can lead to high-spin isomeric states, even though the toroidal shape of 120304184 without spin is unstable. Toroidal energy minima without spin may be possible for superheavy nuclei with higher atomic numbers, Z ≳122 , as reported previously [7 A. Staszczak and C. Y. Wong, Acta Phys. Pol. B 40, 753 (2008)].

Toroidal high-spin isomers in the nucleus 120 304

DOE PAGES

Staszczak, A.; Wong, Cheuk-Yin; Kosior, A.

2017-05-22

Strongly deformed oblate superheavy nuclei form an intriguing region where the toroidal nuclear structures may bifurcate from the oblate spheroidal shape. The bifurcation may be facilitated when the nucleus is endowed with a large angular moment about the symmetry axis withmore » $$I=I_{z}$$. The toroidal high-$K$ isomeric states at their local energy minima can be theoretically predicted using the cranked self-consistent Skyrme-Hartree-Fock method. We use the cranked Skyrme-Hartree-Fock method to predict the properties of the toroidal high-spin isomers in the superheavy nucleus $$^{304}{120}_{184}$$. This method consists of three steps: first, we use the deformation-constrained Skyrme-Hartree-Fock-Bogoliubov approach to search for the nuclear density distributions with toroidal shapes. Next, using these toroidal distributions as starting configurations we apply an additional cranking constraint of a large angular momentum $$I=I_{z}$$ about the symmetry $z$-axis and search for the energy minima of the system as a function of the deformation. In the last step, if a local energy minimum with $$I=I_{z}$$ is found, we perform at this point the cranked symmetry- and deformation-unconstrained Skyrme-Hartree-Fock calculations to locate a stable toroidal high-spin isomeric state in free convergence. Furthemore, we have theoretically located two toroidal high-spin isomeric states of $$^{304}{120}_{184}$$ with an angular momentum $I$=$$I_z$$=81$$\\hbar$$ (proton 2p-2h, neutron 4p-4h excitation) and $I$=$$I_z$$=208$$\\hbar$$ (proton 5p-5h, neutron 8p-8h) at the quadrupole moment deformations $$Q_{20}=-297.7$$~b and $$Q_{20}=-300.8$$~b with energies 79.2 MeV and 101.6 MeV above the spherical ground state, respectively. The nuclear density distributions of the toroidal high-spin isomers $$^{304}{120}_{184}(I_z$$=81$$\\hbar$$ and 208$$\\hbar$$) have the maximum density close to the nuclear matter density, 0.16 fm$$^{-3}$$, and a torus major to minor radius aspect ratio $R/d=3.25$. Here, we demonstrate that aligned angular momenta of $$I_z$$=81$$\\hbar$$ and 208$$\\hbar$$ arising from multi-particle-multi-hole excitations in the toroidal system of $$^{304}{120}_{184}$$ can lead to high-spin isomeric states, even though the toroidal shape of $$^{304}120_{184}$$ without spin is unstable. Toroidal energy minima without spin may be possible for superheavy nuclei with higher atomic numbers, $$Z\\gtrsim$$122, as reported previously [A. Staszczak and C. Y. Wong,Acta Phys. Pol. B 40 , 753 (2008)].« less

Different equation-of-motion coupled cluster methods with different reference functions: The formyl radical

NASA Astrophysics Data System (ADS)

Kuś, Tomasz; Bartlett, Rodney J.

2008-09-01

The doublet and quartet excited states of the formyl radical have been studied by the equation-of-motion (EOM) coupled cluster (CC) method. The Sz spin-conserving singles and doubles (EOM-EE-CCSD) and singles, doubles, and triples (EOM-EE-CCSDT) approaches, as well as the spin-flipped singles and doubles (EOM-SF-CCSD) method have been applied, subject to unrestricted Hartree-Fock (HF), restricted open-shell HF, and quasirestricted HF references. The structural parameters, vertical and adiabatic excitation energies, and harmonic vibrational frequencies have been calculated. The issue of the reference function choice for the spin-flipped (SF) method and its impact on the results has been discussed using the experimental data and theoretical results available. The results show that if the appropriate reference function is chosen so that target states differ from the reference by only single excitations, then EOM-EE-CCSD and EOM-SF-CCSD methods give a very good description of the excited states. For the states that have a non-negligible contribution of the doubly excited configurations one is able to use the SF method with such a reference function, that in most cases the performance of the EOM-SF-CCSD method is better than that of the EOM-EE-CCSD approach.

COMPARATIVE DOCKING STUDIES OF THE BINDING OF POLYCYCLIC AROMATIC HYDROCARBONS TO THE ESTROGEN RECEPTOR

EPA Science Inventory

The interactions of several PAHs, and some of their possible metabolites, with the ligand binding domain of the estrogen receptor have been examined using molecular docking and quantum mechanical methods. The geometries of the PAHs were optimized at the Hartree-Fock level and the...

Accuracy of electron densities obtained via Koopmans-compliant hybrid functionals

NASA Astrophysics Data System (ADS)

Elmaslmane, A. R.; Wetherell, J.; Hodgson, M. J. P.; McKenna, K. P.; Godby, R. W.

2018-04-01

We evaluate the accuracy of electron densities and quasiparticle energy gaps given by hybrid functionals by directly comparing these to the exact quantities obtained from solving the many-electron Schrödinger equation. We determine the admixture of Hartree-Fock exchange to approximate exchange-correlation in our hybrid functional via one of several physically justified constraints, including the generalized Koopmans' theorem. We find that hybrid functionals yield strikingly accurate electron densities and gaps in both exchange-dominated and correlated systems. We also discuss the role of the screened Fock operator in the success of hybrid functionals.

Ab initio calculation of hyperfine splitting constants of molecules

NASA Astrophysics Data System (ADS)

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

1980-08-01

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

Semiempirical and DFT Investigations of the Dissociation of Alkyl Halides

ERIC Educational Resources Information Center

Waas, Jack R.

2006-01-01

Enthalpy changes corresponding to the gas phase heats of dissociation of 12 organic halides were calculated using two semiempirical methods, the Hartree-Fock method, and two DFT methods. These calculated values were compared to experimental values where possible. All five methods agreed generally with the expected empirically known trends in the…

Global hybrids from the semiclassical atom theory satisfying the local density linear response.

PubMed

Fabiano, Eduardo; Constantin, Lucian A; Cortona, Pietro; Della Sala, Fabio

2015-01-13

We propose global hybrid approximations of the exchange-correlation (XC) energy functional which reproduce well the modified fourth-order gradient expansion of the exchange energy in the semiclassical limit of many-electron neutral atoms and recover the full local density approximation (LDA) linear response. These XC functionals represent the hybrid versions of the APBE functional [Phys. Rev. Lett. 2011, 106, 186406] yet employing an additional correlation functional which uses the localization concept of the correlation energy density to improve the compatibility with the Hartree-Fock exchange as well as the coupling-constant-resolved XC potential energy. Broad energetic and structural testing, including thermochemistry and geometry, transition metal complexes, noncovalent interactions, gold clusters and small gold-molecule interfaces, as well as an analysis of the hybrid parameters, show that our construction is quite robust. In particular, our testing shows that the resulting hybrid, including 20% of Hartree-Fock exchange and named hAPBE, performs remarkably well for a broad palette of systems and properties, being generally better than popular hybrids (PBE0 and B3LYP). Semiempirical dispersion corrections are also provided.

A multireference perturbation method using non-orthogonal Hartree-Fock determinants for ground and excited states

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yost, Shane R.; Kowalczyk, Tim; Van Voorhis, Troy, E-mail: tvan@mit.edu

2013-11-07

In this article we propose the ΔSCF(2) framework, a multireference strategy based on second-order perturbation theory, for ground and excited electronic states. Unlike the complete active space family of methods, ΔSCF(2) employs a set of self-consistent Hartree-Fock determinants, also known as ΔSCF states. Each ΔSCF electronic state is modified by a first-order correction from Møller-Plesset perturbation theory and used to construct a Hamiltonian in a configuration interactions like framework. We present formulas for the resulting matrix elements between nonorthogonal states that scale as N{sub occ}{sup 2}N{sub virt}{sup 3}. Unlike most active space methods, ΔSCF(2) treats the ground and excited statemore » determinants even-handedly. We apply ΔSCF(2) to the H{sub 2}, hydrogen fluoride, and H{sub 4} systems and show that the method provides accurate descriptions of ground- and excited-state potential energy surfaces with no single active space containing more than 10 ΔSCF states.« less

Linear-scaling method for calculating nuclear magnetic resonance chemical shifts using gauge-including atomic orbitals within Hartree-Fock and density-functional theory.

PubMed

Kussmann, Jörg; Ochsenfeld, Christian

2007-08-07

Details of a new density matrix-based formulation for calculating nuclear magnetic resonance chemical shifts at both Hartree-Fock and density functional theory levels are presented. For systems with a nonvanishing highest occupied molecular orbital-lowest unoccupied molecular orbital gap, the method allows us to reduce the asymptotic scaling order of the computational effort from cubic to linear, so that molecular systems with 1000 and more atoms can be tackled with today's computers. The key feature is a reformulation of the coupled-perturbed self-consistent field (CPSCF) theory in terms of the one-particle density matrix (D-CPSCF), which avoids entirely the use of canonical MOs. By means of a direct solution for the required perturbed density matrices and the adaptation of linear-scaling integral contraction schemes, the overall scaling of the computational effort is reduced to linear. A particular focus of our formulation is to ensure numerical stability when sparse-algebra routines are used to obtain an overall linear-scaling behavior.

Holomorphic Hartree-Fock Theory: The Nature of Two-Electron Problems.

PubMed

Burton, Hugh G A; Gross, Mark; Thom, Alex J W

2018-02-13

We explore the existence and behavior of holomorphic restricted Hartree-Fock (h-RHF) solutions for two-electron problems. Through algebraic geometry, the exact number of solutions with n basis functions is rigorously identified as 1 / 2 (3 n - 1), proving that states must exist for all molecular geometries. A detailed study on the h-RHF states of HZ (STO-3G) then demonstrates both the conservation of holomorphic solutions as geometry or atomic charges are varied and the emergence of complex h-RHF solutions at coalescence points. Using catastrophe theory, the nature of these coalescence points is described, highlighting the influence of molecular symmetry. The h-RHF states of HHeH 2+ and HHeH (STO-3G) are then compared, illustrating the isomorphism between systems with two electrons and two electron holes. Finally, we explore the h-RHF states of ethene (STO-3G) by considering the π electrons as a two-electron problem and employ NOCI to identify a crossing of the lowest energy singlet and triplet states at the perpendicular geometry.

Configuration-constrained cranking Hartree-Fock pairing calculations for sidebands of nuclei

NASA Astrophysics Data System (ADS)

Liang, W. Y.; Jiao, C. F.; Wu, Q.; Fu, X. M.; Xu, F. R.

2015-12-01

Background: Nuclear collective rotations have been successfully described by the cranking Hartree-Fock-Bogoliubov (HFB) model. However, for rotational sidebands which are built on intrinsic excited configurations, it may not be easy to find converged cranking HFB solutions. The nonconservation of the particle number in the BCS pairing is another shortcoming. To improve the pairing treatment, a particle-number-conserving (PNC) pairing method was suggested. But the existing PNC calculations were performed within a phenomenological one-body potential (e.g., Nilsson or Woods-Saxon) in which one has to deal the double-counting problem. Purpose: The present work aims at an improved description of nuclear rotations, particularly for the rotations of excited configurations, i.e., sidebands. Methods: We developed a configuration-constrained cranking Skyrme Hartree-Fock (SHF) calculation with the pairing correlation treated by the PNC method. The PNC pairing takes the philosophy of the shell model which diagonalizes the Hamiltonian in a truncated model space. The cranked deformed SHF basis provides a small but efficient model space for the PNC diagonalization. Results: We have applied the present method to the calculations of collective rotations of hafnium isotopes for both ground-state bands and sidebands, reproducing well experimental observations. The first up-bendings observed in the yrast bands of the hafnium isotopes are reproduced, and the second up-bendings are predicted. Calculations for rotational bands built on broken-pair excited configurations agree well with experimental data. The band-mixing between two Kπ=6+ bands observed in 176Hf and the K purity of the 178Hf rotational state built on the famous 31 yr Kπ=16+ isomer are discussed. Conclusions: The developed configuration-constrained cranking calculation has been proved to be a powerful tool to describe both the yrast bands and sidebands of deformed nuclei. The analyses of rotational moments of inertia help to understand the structures of nuclei, including rotational alignments, configurations, and competitions between collective and single-particle excitations.

Studies of the electron density in the highest occupied molecular orbitals of PH 3, PF 3 and P(CH 3) 3 by electron momentum spectroscopy and Hartree-Fock, MRSD-CI and DFT calculations

NASA Astrophysics Data System (ADS)

Rolke, J.; Brion, C. E.

1996-06-01

The spherically averaged momentum profiles for the highest occupied molecular orbitals of PF 3 and P(CH 3) 3 have been obtained by electron momentum spectroscopy. The measurements provide a stringent test of basis set effects and the quality of ab-initio methods in the description of these larger molecular systems. As in previous work on the methyl-substituted amines, intuitive arguments fail to predict the correct amount of s- and p-type contributions to the momentum profile while delocalized molecular orbital concepts provide a more adequate description of the HOMOs. The experimental momentum profiles have been compared with theoretical momentum profiles calculated at the level of the target Hartree-Fock approximation with a range of basis sets. New Hartree-Fock calculations are also presented for the HOMO of PH 3 and compared to previously published experimental and theoretical momentum profiles. The experimental momentum profiles have further been compared to calculations at the level of the target Kohn-Sham approximation using density functional theory with the local density approximation and also with gradient corrected (non-local) exchange correlation potentials. In addition, total energies and dipole moments have been calculated for all three molecules by the various theoretical methods and compared to experimental values. Calculated 'density difference maps' show the regions where the HOMO momentum and position electron densities of PF 3 and P(CH 3) 3 change relative to the corresponding HOMO density of PH 3. The results suggest that methyl groups have an electron-attracting effect (relative to H) on the HOMO charge density in trimethyl phosphines. These conclusions are supported by a consideration of dipole moments and the 31P NMR chemical shifts for PH 3, PF 3 and P(CH 3) 3.

Wave-function-based approach to quasiparticle bands: Insight into the electronic structure of c-ZnS

NASA Astrophysics Data System (ADS)

Stoyanova, A.; Hozoi, L.; Fulde, P.; Stoll, H.

2011-05-01

Ab initio wave-function-based methods are employed for the study of quasiparticle energy bands of zinc-blende ZnS, with focus on the Zn 3d “semicore” states. The relative energies of these states with respect to the top of the S 3p valence bands appear to be poorly described as compared to experimental values not only within the local density approximation (LDA), but also when many-body corrections within the GW approximation are applied to the LDA or LDA + U mean-field solutions [T. Miyake, P. Zhang, M. L. Cohen, and S. G. Louie, Phys. Rev. BPRBMDO1098-012110.1103/PhysRevB.74.245213 74, 245213 (2006)]. In the present study, we show that for the accurate description of the Zn 3d states a correlation treatment based on wave-function methods is needed. Our study rests on a local Hamiltonian approach which rigorously describes the short-range polarization and charge redistribution effects around an extra hole or electron placed into the valence respective conduction bands of semiconductors and insulators. The method also facilitates the computation of electron correlation effects beyond relaxation and polarization. The electron correlation treatment is performed on finite clusters cut off the infinite system. The formalism makes use of localized Wannier functions and embedding potentials derived explicitly from prior periodic Hartree-Fock calculations. The on-site and nearest-neighbor charge relaxation lead to corrections of several eV to the Hartree-Fock band energies and gap. Corrections due to long-range polarization are of the order of 1.0 eV. The dispersion of the Hartree-Fock bands is only slightly affected by electron correlations. We find the Zn 3d “semicore” states to lie ~9.0 eV below the top of the S 3p valence bands, in very good agreement with values from valence-band x-ray photoemission.

Average Nuclear Potentials from Selfconsistent Semiclassical Calculations

NASA Astrophysics Data System (ADS)

Bartel, J.

1999-03-01

Using the selfconsistent semiclassical Extended Thomas-Fermi (ETF) method up to 4th order in connection with Skyrme forces it is demonstrated that the neutron and proton average potentials obtained using the semiclassical functionals τ (ETF)[ρ] and vec {J}(ETF)[ρ] reproduce the corresponding Hartree-Fock fields extremely well, except for shell oscillations in the nuclear center.

Direct mapping between exchange potentials of Hartree-Fock and Kohn-Sham schemes as origin of orbital proximity

NASA Astrophysics Data System (ADS)

Cinal, M.

2010-01-01

It is found that for closed-l-shell atoms, the exact local exchange potential vx(r) calculated in the exchange-only Kohn-Sham (KS) scheme of the density functional theory (DFT) is very well represented within the region of every atomic shell by each of the suitably shifted potentials obtained with the nonlocal Fock exchange operator for the individual Hartree-Fock (HF) orbitals belonging to this shell. This newly revealed property is not related to the well-known steplike shell structure in the response part of vx(r), but it results from specific relations satisfied by the HF orbital exchange potentials. These relations explain the outstanding proximity of the occupied HF and exchange-only KS orbitals as well as the high quality of the Krieger-Li-Iafrate and localized HF (or, equivalently, common-energy-denominator) approximations to the DFT exchange potential vx(r). Another highly accurate representation of vx(r) is given by the continuous piecewise function built of shell-specific exchange potentials, each defined as the weighted average of the shifted orbital exchange potentials corresponding to a given shell. The constant shifts added to the HF orbital exchange potentials, to map them onto vx(r), are nearly equal to the differences between the energies of the corresponding KS and HF orbitals. It is discussed why these differences are positive and grow when the respective orbital energies become lower for inner orbitals.

Equation-of-motion coupled-cluster method for ionised states with spin-orbit coupling using open-shell reference wavefunction

NASA Astrophysics Data System (ADS)

Wang, Zhifan; Wang, Fan

2018-04-01

The equation-of-motion coupled-cluster method for ionised states at the singles and doubles level (EOM-IP-CCSD) with spin-orbit coupling (SOC) included in post-Hartree-Fock (HF) steps is extended to spatially non-degenerate open-shell systems such as high spin states of s1, p3, σ1 or π2 configuration in this work. Pseudopotentials are employed to treat relativistic effects and spin-unrestricted scalar relativistic HF determinant is adopted as reference in calculations. Symmetry is not exploited in the implementation since both time-reversal and spatial symmetry is broken due to SOC. IPs with the EOM-IP-CCSD approach are those from the 3Σ1- states for high spin state of π2 configuration, while the ground state is the 3Σ0- state. When removing an electron from the high spin state of p3 configuration, only the 3P2 state can be reached. The open-shell EOM-IP-CCSD approach with SOC was employed in calculating IPs of some open-shell atoms with s1 configuration, diatomic molecules with π2 configuration and SOC splitting of the ionised π1 state, as well as IPs of VA atoms with p3 configuration. Our results demonstrate that this approach can be applied to ionised states of spatially non-degenerate open-shell states containing heavy elements with reasonable accuracy.

M sub shell X-ray emission cross section measurements for Pt, Au, Hg, Pb, Th and U at 8 and 10 keV synchrotron photons

NASA Astrophysics Data System (ADS)

Kaur, Gurpreet; Gupta, Sheenu; Tiwari, M. K.; Mittal, Raj

2014-02-01

M sub shell X-ray emission cross sections of Pt, Au, Hg, Pb, Th and U at 8 and 10 keV photon energies have been determined with linearly polarized photon beam from Indus-2 synchrotron source. The measured cross sections have been reported for the first time and were used to check the available theoretical Dirac-Hartree-Slater (DHS) and Dirac-Fock (DF) values reported in literature and also the presently derived Non Relativistic Hartree-Slater (NRHS), DF and DHS values for Mξ, Mδ, Mα, Mβ, Mγ, Mm1 and Mm2 group of X-rays.

VizieR Online Data Catalog: Energy levels & transition rates for F-like ions (Si+, 2016)

NASA Astrophysics Data System (ADS)

Si, R.; Li, S.; Guo, X. L.; Chen, Z. B.; Brage, T.; Jonsson, P.; Wang, K.; Yan, J.; Chen, C. Y.; Zou, Y. M.

2017-01-01

For the multiconfiguration Dirac-Hartree-Fock (MCDHF) calculation we use the latest version of the GRASP2K code (Jonsson+ 2013CoPhC.184.2197J), while the many-body perturbation theory (MBPT) calculation is performed using the Flexible Atomic Code (FAC; Gu 2008CaJPh..86..675G). (2 data files).

The trust-region self-consistent field method in Kohn-Sham density-functional theory.

PubMed

Thøgersen, Lea; Olsen, Jeppe; Köhn, Andreas; Jørgensen, Poul; Sałek, Paweł; Helgaker, Trygve

2005-08-15

The trust-region self-consistent field (TRSCF) method is extended to the optimization of the Kohn-Sham energy. In the TRSCF method, both the Roothaan-Hall step and the density-subspace minimization step are replaced by trust-region optimizations of local approximations to the Kohn-Sham energy, leading to a controlled, monotonic convergence towards the optimized energy. Previously the TRSCF method has been developed for optimization of the Hartree-Fock energy, which is a simple quadratic function in the density matrix. However, since the Kohn-Sham energy is a nonquadratic function of the density matrix, the local energy functions must be generalized for use with the Kohn-Sham model. Such a generalization, which contains the Hartree-Fock model as a special case, is presented here. For comparison, a rederivation of the popular direct inversion in the iterative subspace (DIIS) algorithm is performed, demonstrating that the DIIS method may be viewed as a quasi-Newton method, explaining its fast local convergence. In the global region the convergence behavior of DIIS is less predictable. The related energy DIIS technique is also discussed and shown to be inappropriate for the optimization of the Kohn-Sham energy.

Molecular wave function and effective adiabatic potentials calculated by extended multi-configuration time-dependent Hartree-Fock method

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kato, Tsuyoshi; Ide, Yoshihiro; Yamanouchi, Kaoru

We first calculate the ground-state molecular wave function of 1D model H{sub 2} molecule by solving the coupled equations of motion formulated in the extended multi-configuration time-dependent Hartree-Fock (MCTDHF) method by the imaginary time propagation. From the comparisons with the results obtained by the Born-Huang (BH) expansion method as well as with the exact wave function, we observe that the memory size required in the extended MCTDHF method is about two orders of magnitude smaller than in the BH expansion method to achieve the same accuracy for the total energy. Second, in order to provide a theoretical means to understandmore » dynamical behavior of the wave function, we propose to define effective adiabatic potential functions and compare them with the conventional adiabatic electronic potentials, although the notion of the adiabatic potentials is not used in the extended MCTDHF approach. From the comparison, we conclude that by calculating the effective potentials we may be able to predict the energy differences among electronic states even for a time-dependent system, e.g., time-dependent excitation energies, which would be difficult to be estimated within the BH expansion approach.« less

Description of plasmon-like band in silver clusters: the importance of the long-range Hartree-Fock exchange in time-dependent density-functional theory simulations.

PubMed

Rabilloud, Franck

2014-10-14

Absorption spectra of Ag20 and Ag55(q) (q = +1, -3) nanoclusters are investigated in the framework of the time-dependent density functional theory in order to analyse the role of the d electrons in plasmon-like band of silver clusters. The description of the plasmon-like band from calculations using density functionals containing an amount of Hartree-Fock exchange at long range, namely, hybrid and range-separated hybrid (RSH) density functionals, is in good agreement with the classical interpretation of the plasmon-like structure as a collective excitation of valence s-electrons. In contrast, using local or semi-local exchange functionals (generalized gradient approximations (GGAs) or meta-GGAs) leads to a strong overestimation of the role of d electrons in the plasmon-like band. The semi-local asymptotically corrected model potentials also describe the plasmon as mainly associated to d electrons, though calculated spectra are in fairly good agreement with those calculated using the RSH scheme. Our analysis shows that a portion of non-local exchange modifies the description of the plasmon-like band.

Higher order alchemical derivatives from coupled perturbed self-consistent field theory.

PubMed

Lesiuk, Michał; Balawender, Robert; Zachara, Janusz

2012-01-21

We present an analytical approach to treat higher order derivatives of Hartree-Fock (HF) and Kohn-Sham (KS) density functional theory energy in the Born-Oppenheimer approximation with respect to the nuclear charge distribution (so-called alchemical derivatives). Modified coupled perturbed self-consistent field theory is used to calculate molecular systems response to the applied perturbation. Working equations for the second and the third derivatives of HF/KS energy are derived. Similarly, analytical forms of the first and second derivatives of orbital energies are reported. The second derivative of Kohn-Sham energy and up to the third derivative of Hartree-Fock energy with respect to the nuclear charge distribution were calculated. Some issues of practical calculations, in particular the dependence of the basis set and Becke weighting functions on the perturbation, are considered. For selected series of isoelectronic molecules values of available alchemical derivatives were computed and Taylor series expansion was used to predict energies of the "surrounding" molecules. Predicted values of energies are in unexpectedly good agreement with the ones computed using HF/KS methods. Presented method allows one to predict orbital energies with the error less than 1% or even smaller for valence orbitals. © 2012 American Institute of Physics

Efficient method of evaluation for Gaussian Hartree-Fock exchange operator for Gau-PBE functional

NASA Astrophysics Data System (ADS)

Song, Jong-Won; Hirao, Kimihiko

2015-07-01

We previously developed an efficient screened hybrid functional called Gaussian-Perdew-Burke-Ernzerhof (Gau-PBE) [Song et al., J. Chem. Phys. 135, 071103 (2011)] for large molecules and extended systems, which is characterized by the usage of a Gaussian function as a modified Coulomb potential for the Hartree-Fock (HF) exchange. We found that the adoption of a Gaussian HF exchange operator considerably decreases the calculation time cost of periodic systems while improving the reproducibility of the bandgaps of semiconductors. We present a distance-based screening scheme here that is tailored for the Gaussian HF exchange integral that utilizes multipole expansion for the Gaussian two-electron integrals. We found a new multipole screening scheme helps to save the time cost for the HF exchange integration by efficiently decreasing the number of integrals of, specifically, the near field region without incurring substantial changes in total energy. In our assessment on the periodic systems of seven semiconductors, the Gau-PBE hybrid functional with a new screening scheme has 1.56 times the time cost of a pure functional while the previous Gau-PBE was 1.84 times and HSE06 was 3.34 times.

Nuclear Pasta at Finite Temperature with the Time-Dependent Hartree-Fock Approach

NASA Astrophysics Data System (ADS)

Schuetrumpf, B.; Klatt, M. A.; Iida, K.; Maruhn, J. A.; Mecke, K.; Reinhard, P.-G.

2016-01-01

We present simulations of neutron-rich matter at sub-nuclear densities, like supernova matter. With the time-dependent Hartree-Fock approximation we can study the evolution of the system at temperatures of several MeV employing a full Skyrme interaction in a periodic three-dimensional grid [1]. The initial state consists of α particles randomly distributed in space that have a Maxwell-Boltzmann distribution in momentum space. Adding a neutron background initialized with Fermi distributed plane waves the calculations reflect a reasonable approximation of astrophysical matter. The matter evolves into spherical, rod-like, connected rod-like and slab-like shapes. Further we observe gyroid-like structures, discussed e.g. in [2], which are formed spontaneously choosing a certain value of the simulation box length. The ρ-T-map of pasta shapes is basically consistent with the phase diagrams obtained from QMD calculations [3]. By an improved topological analysis based on Minkowski functionals [4], all observed pasta shapes can be uniquely identified by only two valuations, namely the Euler characteristic and the integral mean curvature. In addition we propose the variance in the cell-density distribution as a measure to distinguish pasta matter from uniform matter.

Bubble nuclei within the self-consistent Hartree-Fock mean field plus pairing approach

NASA Astrophysics Data System (ADS)

Phuc, L. Tan; Hung, N. Quang; Dang, N. Dinh

2018-02-01

The depletion of the nuclear density at its center, called the nuclear bubble, is studied within the Skyrme Hartree-Fock mean field consistently incorporating the superfluid pairing. The latter is obtained within the finite-temperature Bardeen-Cooper-Schrieffer theory and within the approach using the exact pairing. The numerical calculations are carried out for 22O and 34Si nuclei, whose bubble structures, caused by a very low occupancy of the 2 s1 /2 level, were previously predicted at T =0 . Among 24 Skyrme interactions under consideration, the MSk3 is the only one which reproduces the experimentally measured occupancy of the 2 s1 /2 proton level as well as the binding energy, and consequently produces the most pronounced bubble structure in 34Si. As compared to the approaches employing the same BSk14 interaction, our approach with exact pairing predicts a pairing effect which is stronger in 22O and weaker in 34Si. The increase in temperature depletes the bubble structure and completely washes it out when the temperature reaches a critical value, at which the factor measuring the depletion of the nucleon density vanishes.

Efficient method of evaluation for Gaussian Hartree-Fock exchange operator for Gau-PBE functional

DOE Office of Scientific and Technical Information (OSTI.GOV)

Song, Jong-Won; Hirao, Kimihiko, E-mail: hirao@riken.jp

2015-07-14

We previously developed an efficient screened hybrid functional called Gaussian-Perdew–Burke–Ernzerhof (Gau-PBE) [Song et al., J. Chem. Phys. 135, 071103 (2011)] for large molecules and extended systems, which is characterized by the usage of a Gaussian function as a modified Coulomb potential for the Hartree-Fock (HF) exchange. We found that the adoption of a Gaussian HF exchange operator considerably decreases the calculation time cost of periodic systems while improving the reproducibility of the bandgaps of semiconductors. We present a distance-based screening scheme here that is tailored for the Gaussian HF exchange integral that utilizes multipole expansion for the Gaussian two-electron integrals.more » We found a new multipole screening scheme helps to save the time cost for the HF exchange integration by efficiently decreasing the number of integrals of, specifically, the near field region without incurring substantial changes in total energy. In our assessment on the periodic systems of seven semiconductors, the Gau-PBE hybrid functional with a new screening scheme has 1.56 times the time cost of a pure functional while the previous Gau-PBE was 1.84 times and HSE06 was 3.34 times.« less

Axially deformed solution of the Skyrme-Hartree-Fock-Bogolyubov equations using the transformed harmonic oscillator basis (III) HFBTHO (v3.00): A new version of the program

NASA Astrophysics Data System (ADS)

Perez, R. Navarro; Schunck, N.; Lasseri, R.-D.; Zhang, C.; Sarich, J.

2017-11-01

We describe the new version 3.00 of the code HFBTHO that solves the nuclear Hartree-Fock (HF) or Hartree-Fock-Bogolyubov (HFB) problem by using the cylindrical transformed deformed harmonic oscillator basis. In the new version, we have implemented the following features: (i) the full Gogny force in both particle-hole and particle-particle channels, (ii) the calculation of the nuclear collective inertia at the perturbative cranking approximation, (iii) the calculation of fission fragment charge, mass and deformations based on the determination of the neck, (iv) the regularization of zero-range pairing forces, (v) the calculation of localization functions, (vi) a MPI interface for large-scale mass table calculations. Program Files doi:http://dx.doi.org/10.17632/c5g2f92by3.1 Licensing provisions: GPL v3 Programming language: FORTRAN-95 Journal reference of previous version: M.V. Stoitsov, N. Schunck, M. Kortelainen, N. Michel, H. Nam, E. Olsen, J. Sarich, and S. Wild, Comput. Phys. Commun. 184 (2013). Does the new version supersede the previous one: Yes Summary of revisions: 1. the Gogny force in both particle-hole and particle-particle channels was implemented; 2. the nuclear collective inertia at the perturbative cranking approximation was implemented; 3. fission fragment charge, mass and deformations were implemented based on the determination of the position of the neck between nascent fragments; 4. the regularization method of zero-range pairing forces was implemented; 5. the localization functions of the HFB solution were implemented; 6. a MPI interface for large-scale mass table calculations was implemented. Nature of problem:HFBTHO is a physics computer code that is used to model the structure of the nucleus. It is an implementation of the energy density functional (EDF) approach to atomic nuclei, where the energy of the nucleus is obtained by integration over space of some phenomenological energy density, which is itself a functional of the neutron and proton intrinsic densities. In the present version of HFBTHO, the energy density derives either from the zero-range Skyrme or the finite-range Gogny effective two-body interaction between nucleons. Nuclear super-fluidity is treated at the Hartree-Fock-Bogolyubov (HFB) approximation. Constraints on the nuclear shape allows probing the potential energy surface of the nucleus as needed e.g., for the description of shape isomers or fission. The implementation of a local scale transformation of the single-particle basis in which the HFB solutions are expanded provide a tool to properly compute the structure of weakly-bound nuclei. Solution method: The program uses the axial Transformed Harmonic Oscillator (THO) single-particle basis to expand quasiparticle wave functions. It iteratively diagonalizes the Hartree-Fock-Bogolyubov Hamiltonian based on generalized Skyrme-like energy densities and zero-range pairing interactions or the finite-range Gogny force until a self-consistent solution is found. A previous version of the program was presented in M.V. Stoitsov, N. Schunck, M. Kortelainen, N. Michel, H. Nam, E. Olsen, J. Sarich, and S. Wild, Comput. Phys. Commun. 184 (2013) 1592-1604 with much of the formalism presented in the original paper M.V. Stoitsov, J. Dobaczewski, W. Nazarewicz, P. Ring, Comput. Phys. Commun. 167 (2005) 43-63. Additional comments: The user must have access to (i) the LAPACK subroutines DSYEEVR, DSYEVD, DSYTRF and DSYTRI, and their dependencies, which compute eigenvalues and eigenfunctions of real symmetric matrices, (ii) the LAPACK subroutines DGETRI and DGETRF, which invert arbitrary real matrices, and (iii) the BLAS routines DCOPY, DSCAL, DGEMM and DGEMV for double-precision linear algebra (or provide another set of subroutines that can perform such tasks). The BLAS and LAPACK subroutines can be obtained from the Netlib Repository at the University of Tennessee, Knoxville: http://netlib2.cs.utk.edu/.

SU-E-I-43: Photoelectric Cross Section Revisited

DOE Office of Scientific and Technical Information (OSTI.GOV)

Haga, A; Nakagawa, K; Kotoku, J

2015-06-15

Purpose: The importance of the precision in photoelectric cross-section value increases for recent developed technology such as dual energy computed tomography, in which some reconstruction algorithms require the energy dependence of the photo-absorption in each material composition of human being. In this study, we revisited the photoelectric cross-section calculation by self-consistent relativistic Hartree-Fock (HF) atomic model and compared with that widely distributed as “XCOM database” in National Institute of Standards and Technology, which was evaluated with localdensity approximation for electron-exchange (Fock)z potential. Methods: The photoelectric cross section can be calculated with the electron wave functions in initial atomic state (boundmore » electron) and final continuum state (photoelectron). These electron states were constructed based on the selfconsistent HF calculation, where the repulsive Coulomb potential from the electron charge distribution (Hartree term) and the electron exchange potential with full electromagnetic interaction (Fock term) were included for the electron-electron interaction. The photoelectric cross sections were evaluated for He (Z=2), Be (Z=4), C (Z=6), O (Z=8), and Ne (Z=10) in energy range of 10keV to 1MeV. The Result was compared with XCOM database. Results: The difference of the photoelectric cross section between the present calculation and XCOM database was 8% at a maximum (in 10keV for Be). The agreement tends to be better as the atomic number increases. The contribution from each atomic shell has a considerable discrepancy with XCOM database except for K-shell. However, because the photoelectric cross section arising from K-shell is dominant, the net photoelectric cross section was almost insensitive to the different handling in Fock potential. Conclusion: The photoelectric cross-section program has been developed based on the fully self-consistent relativistic HF atomic model. Due to small effect on the Fock potential for K-shell electrons, the difference from XCOM database was limited: 1% to 8% for low-Z elements in 10keV-1MeV energy ranges. This work was partly supported by the JSPS Core-to-Core Program (No. 23003)« less

Exact exchange potential evaluated from occupied Kohn-Sham and Hartree-Fock solutions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cinal, M.; Holas, A.

2011-06-15

The reported algorithm determines the exact exchange potential v{sub x} in an iterative way using energy shifts (ESs) and orbital shifts (OSs) obtained with finite-difference formulas from the solutions (occupied orbitals and their energies) of the Hartree-Fock-like equation and the Kohn-Sham-like equation, the former used for the initial approximation to v{sub x} and the latter for increments of ES and OS due to subsequent changes of v{sub x}. Thus, the need for solution of the differential equations for OSs, used by Kuemmel and Perdew [Phys. Rev. Lett. 90, 043004 (2003)], is bypassed. The iterated exchange potential, expressed in terms ofmore » ESs and OSs, is improved by modifying ESs at odd iteration steps and OSs at even steps. The modification formulas are related to the optimized-effective-potential equation (satisfied at convergence) written as the condition of vanishing density shift (DS). They are obtained, respectively, by enforcing its satisfaction through corrections to approximate OSs and by determining the optimal ESs that minimize the DS norm. The proposed method, successfully tested for several closed-(sub)shell atoms, from Be to Kr, within the density functional theory exchange-only approximation, proves highly efficient. The calculations using the pseudospectral method for representing orbitals give iterative sequences of approximate exchange potentials (starting with the Krieger-Li-Iafrate approximation) that rapidly approach the exact v{sub x} so that, for Ne, Ar, and Zn, the corresponding DS norm becomes less than 10{sup -6} after 13, 13, and 9 iteration steps for a given electron density. In self-consistent density calculations, orbital energies of 10{sup -4} hartree accuracy are obtained for these atoms after, respectively, 9, 12, and 12 density iteration steps, each involving just two steps of v{sub x} iteration, while the accuracy limit of 10{sup -6} to 10{sup -7} hartree is reached after 20 density iterations.« less

Exact exchange potential evaluated from occupied Kohn-Sham and Hartree-Fock solutions

NASA Astrophysics Data System (ADS)

Cinal, M.; Holas, A.

2011-06-01

The reported algorithm determines the exact exchange potential vx in an iterative way using energy shifts (ESs) and orbital shifts (OSs) obtained with finite-difference formulas from the solutions (occupied orbitals and their energies) of the Hartree-Fock-like equation and the Kohn-Sham-like equation, the former used for the initial approximation to vx and the latter for increments of ES and OS due to subsequent changes of vx. Thus, the need for solution of the differential equations for OSs, used by Kümmel and Perdew [Phys. Rev. Lett.PRLTAO0031-900710.1103/PhysRevLett.90.043004 90, 043004 (2003)], is bypassed. The iterated exchange potential, expressed in terms of ESs and OSs, is improved by modifying ESs at odd iteration steps and OSs at even steps. The modification formulas are related to the optimized-effective-potential equation (satisfied at convergence) written as the condition of vanishing density shift (DS). They are obtained, respectively, by enforcing its satisfaction through corrections to approximate OSs and by determining the optimal ESs that minimize the DS norm. The proposed method, successfully tested for several closed-(sub)shell atoms, from Be to Kr, within the density functional theory exchange-only approximation, proves highly efficient. The calculations using the pseudospectral method for representing orbitals give iterative sequences of approximate exchange potentials (starting with the Krieger-Li-Iafrate approximation) that rapidly approach the exact vx so that, for Ne, Ar, and Zn, the corresponding DS norm becomes less than 10-6 after 13, 13, and 9 iteration steps for a given electron density. In self-consistent density calculations, orbital energies of 10-4 hartree accuracy are obtained for these atoms after, respectively, 9, 12, and 12 density iteration steps, each involving just two steps of vx iteration, while the accuracy limit of 10-6 to 10-7 hartree is reached after 20 density iterations.

Testing the single-state dominance hypothesis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Álvarez-Rodríguez, R.; Moreno, O.; Moya de Guerra, E.

2013-12-30

We present a theoretical analysis of the single-state dominance hypothesis for the two-neutrino double-beta decay process. The theoretical framework is a proton-neutron QRPA based on a deformed Hartree-Fock mean field with BCS pairing correlations. We focus on the decays of {sup 100}Mo, {sup 116}Cd and {sup 128}Te. We do not find clear evidences for single-state dominance within the present approach.

Electronic Structure and Absorption Spectra of Sodium 2-Hydroxy-5-({2-Methoxy-4[(4-Sulfophenyl)Diazenyl]Phenyl}Diazenyl)Benzoate

NASA Astrophysics Data System (ADS)

Almodarresiyeh, H. A.; Shahab, S. N.; Zelenkovsky, V. M.; Agabekov, V. E.

2014-03-01

The electronic structure and geometry of the synthesized azodye sodium 2-hydroxy-5-({2-methoxy-4[(4-sulfophenyl) diazenyl]phenyl}diazenyl)benzoate (M12) were calculated theoretically by an ab initio Hartree-Fock method in basis set 6-31G. The nature of absorption bands in the visible and near-UV spectral regions was interpreted.

Dynamical description of the fission process using the TD-BCS theory

DOE Office of Scientific and Technical Information (OSTI.GOV)

Scamps, Guillaume, E-mail: scamps@nucl.phys.tohoku.ac.jp; Simenel, Cédric; Lacroix, Denis

2015-10-15

The description of fission remains a challenge for nuclear microscopic theories. The time-dependent Hartree-Fock approach with BCS pairing is applied to study the last stage of the fission process. A good agreement is found for the one-body observables: the total kinetic energy and the average mass asymmetry. The non-physical dependence of two-body observables with the initial shape is discussed.

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

PubMed

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

2015-04-21

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

Calculation of UV, IR, and NMR Spectra of Diethyl 2,2'-[(1,1'-Biphenyl)-4,4'-Diylbis(Azanediyl)]Diacetate

NASA Astrophysics Data System (ADS)

Almodarresiyeh, H. A.; Shahab, S. N.; Zelenkovsky, V. M.; Ariko, N. G.; Filippovich, L. N.; Agabekov, V. E.

2014-03-01

The new substance diethyl 2,2'-[(1,1'-biphenyl)-4,4'-diylbis(azanediyl)]diacetate (M13) was modeled using the Hartree-Fock and density functional theory methods and then synthesized. The electronic absorption spectrum of M13 in dimethylformamide solution was calculated. The UV, IR, and NMR spectra of M13 were presented.

A minimal multiconfigurational technique.

PubMed

Fernández Rico, J; Paniagua, M; GarcíA De La Vega, J M; Fernández-Alonso, J I; Fantucci, P

1986-04-01

A direct minimization method previously presented by the authors is applied here to biconfigurational wave functions. A very moderate increasing in the time by iteration with respect to the one-determinant calculation and good convergence properties have been found. So qualitatively correct studies on singlet systems with strong biradical character can be performed with a cost similar to that required by Hartree-Fock calculations. Copyright © 1986 John Wiley & Sons, Inc.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ünlü, Hilmi, E-mail: hunlu@itu.edu.tr

We propose a non-orthogonal sp{sup 3} hybrid bond orbital model to determine the electronic properties of semiconductor heterostructures. The model considers the non-orthogonality of sp{sup 3} hybrid states of nearest neighboring adjacent atoms using the intra-atomic Coulomb interactions corrected Hartree-Fock atomic energies and metallic contribution to calculate the valence band width energies of group IV elemental and group III-V and II-VI compound semiconductors without any adjustable parameter.

Hartree-Fock study of the Anderson metal-insulator transition in the presence of Coulomb interaction: Two types of mobility edges and their multifractal scaling exponents

NASA Astrophysics Data System (ADS)

Lee, Hyun-Jung; Kim, Ki-Seok

2018-04-01

We investigate the role of Coulomb interaction in the multifractality of Anderson metal-insulator transition, where the Coulomb interaction is treated within the Hartree-Fock approximation, but disorder effects are taken into account exactly. An innovative technical aspect in our simulation is to utilize the Ewald-sum technique, which allows us to introduce the long-range nature of the Coulomb interaction into Hartree-Fock self-consistent equations of order parameters more accurately. This numerical simulation reproduces the Altshuler-Aronov correction in a metallic state and the Efros-Shklovskii pseudogap in an insulating phase, where the density of states ρ (ω ) is evaluated in three dimensions. Approaching the quantum critical point of a metal-insulator transition from either the metallic or insulting phase, we find that the density of states is given by ρ (ω ) ˜|ω| 1 /2 , which determines one critical exponent of the McMillan-Shklovskii scaling theory. Our main result is to evaluate the eigenfunction multifractal scaling exponent αq, given by the Legendre transformation of the fractal dimension τq, which characterizes the scaling behavior of the inverse participation ratio with respect to the system size L . Our multifractal analysis leads us to identify two kinds of mobility edges, one of which occurs near the Fermi energy and the other of which appears at a high energy, where the density of states at the Fermi energy shows the Coulomb-gap feature. We observe that the multifractal exponent at the high-energy mobility edge remains to be almost identical to that of the Anderson localization transition in the absence of Coulomb interactions. On the other hand, we find that the multifractal exponent near the Fermi energy is more enhanced than that at the high-energy mobility edge, suspected to result from interaction effects. However, both the multifractal exponents do not change even if the strength of the Coulomb interaction varies. We also show that the multifractality singular spectrum can be classified into two categories, confirming the appearance of two types of mobility edges.

Immediate estimation of correlation energy for molecular systems from the partial charges on atoms in the molecule

NASA Astrophysics Data System (ADS)

Kristyán, Sándor

1997-11-01

In the author's previous work (Chem. Phys. Lett. 247 (1995) 101 and Chem. Phys. Lett. 256 (1996) 229) a simple quasi-linear relationship was introduced between the number of electrons, N, participating in any molecular system and the correlation energy: -0.035 ( N - 1) > Ecorr[hartree] > - 0.045( N -1). This relationship was developed to estimate more accurately correlation energy immediately in ab initio calculations by using the partial charges of atoms in the molecule, easily obtained after Hartree-Fock self-consistent field (HF-SCF) calculations. The method is compared to the well-known B3LYP, MP2, CCSD and G2M methods. Correlation energy estimations for negatively (-1) charged atomic ions are also reported.

Many-body expansion of the Fock matrix in the fragment molecular orbital method

NASA Astrophysics Data System (ADS)

Fedorov, Dmitri G.; Kitaura, Kazuo

2017-09-01

A many-body expansion of the Fock matrix in the fragment molecular orbital method is derived up to three-body terms for restricted Hartree-Fock and density functional theory in the atomic orbital basis and compared to the expansion in the basis of fragment molecular orbitals (MOs). The physical nature of many-body corrections is revealed in terms of charge transfer terms. An improvement of the fragment MO expansion is proposed by adding exchange to the embedding. The accuracy of all developed methods is demonstrated in comparison to unfragmented results for polyalanines, a water cluster, Trp-cage (PDB: 1L2Y) and crambin (PDB: 1CRN) proteins, a zeolite cluster, a Si nano-wire, and a boron nitride ribbon. The physical nature of metallicity is discussed, and it is shown what kinds of metallic systems can be treated by fragment-based methods. The density of states is calculated for a fully closed and a partially open nano-ring of boron nitride with a diameter of 105 nm.

The generator coordinate Dirac-Fock method for open-shell atomic systems

NASA Astrophysics Data System (ADS)

Malli, Gulzari L.; Ishikawa, Yasuyuki

1998-11-01

Recently we developed generator coordinate Dirac-Fock and Dirac-Fock-Breit methods for closed-shell systems assuming finite nucleus and have reported Dirac-Fock and Dirac-Fock-Breit energies for the atoms He through Nobelium (Z=102) [see Refs. Reference 10Reference 11Reference 12Reference 13]. In this paper, we generalize our earlier work on closed-shell systems and develop a generator coordinate Dirac-Fock method for open-shell systems. We present results for a number of representative open-shell heavy atoms (with nuclear charge Z>80) including the actinide and superheavy transactinide (with Z>103) atomic systems: Fr (Z=87), Ac (Z=89), and Lr (Z=103) to E113 (eka-thallium, Z=113). The high accuracy obtained in our open-shell Dirac-Fock calculations is similar to that of our closed-shell calculations, and we attribute it to the fact that the representation of the relativistic dynamics of an electron in a spherical ball finite nucleus near the origin in terms of our universal Gaussian basis set is as accurate as that provided by the numerical finite difference method. The DF SCF energies calculated by Desclaux [At. Data. Nucl. Data Tables 12, 311 (1973)] (apart from a typographic error for Fr pointed out here) are higher than those reported here for atoms of some of the superheavy transactinide elements by as much as 5 hartrees (136 eV). We believe that this is due to the use by Desclaux of much larger atomic masses than the currently accepted values for these elements.

Ab initio molecular orbital studies of the positive muon and muonium in 4-arylmethyleneamino-TEMPO derivatives

NASA Astrophysics Data System (ADS)

Briere, T. M.; Jeong, J.; Das, T. P.; Ohira, S.; Nagamine, K.

2000-08-01

The muon and muonium bonding sites of the 4-arylmethyleneamino-2,2,6,6-tetramethylpiperidin-1-yloxyl radical crystals with aryl groups consisting of biphenyl and 4-pyridyl were studied via ab initio Hartree-Fock theory. The hyperfine fields, including both intramolecular and intermolecular interactions, were calculated at the sites of interest and compared to zero field μSR results.

Non-expanded dispersion energies and damping functions for Ar 2 and Li 2

NASA Astrophysics Data System (ADS)

Knowles, Peter J.; Meath, William J.

1986-02-01

The non-expanded second-order dispersion energies and damping functions associated with the long-range dispersion energies varying as R-6, R-8and R-10 have been calculated for Ar 2 and Li 2 with the time-dependent Hartree-Fock method, using extended Gaussian basis sets. These results are used to discuss the difficulties associated with ab initio computations of these quantities.

The energy gap in a-Si 1 - xC g: H alloys

NASA Astrophysics Data System (ADS)

Valladares, Ariel A.; Valladares, Alexander; Enrique Sansores, L.; Nelis, Mary Ann Me

1997-02-01

The electronic structure of amorphous tetrahedral clusters of the type a-Si 1 - xC g: H are studied using the pseudopotential SCF Hartree-Fock approximation. The reduced energy gap isgiven by Egr( x) - 1 + 0.84 x for x ⩽ 0.5, whereas experimentally Egr( x) = 1 + 0.96 x. For x ⩾ 0.5 the dip in the gap value reported experimentally is verified.

Vibrational Spectral Studies of Gemfibrozil

NASA Astrophysics Data System (ADS)

Benitta, T. Asenath; Balendiran, G. K.; James, C.

2008-11-01

The Fourier Transform Raman and infrared spectra of the crystallized drug molecule 5-(2,5-Dimethylphenoxy)-2,2-dimethylpentanoic acid (Gemfibrozil) have been recorded and analyzed. Quantum chemical computational methods have been employed using Gaussian 03 software package based on Hartree Fock method for theoretically modeling the grown molecule. The optimized geometry and vibrational frequencies have been predicted. Observed vibrational modes have been assigned with the aid of normal coordinate analysis.

Toroidal high-spin isomers in light nuclei with N ≠ Z

NASA Astrophysics Data System (ADS)

Staszczak, A.; Wong, Cheuk-Yin

2015-11-01

The combined considerations of both the bulk liquid-drop-type behavior and the quantized aligned rotation with cranked Skyrme-Hartree-Fock approach revealed previously (Staszczak and Wong 2014 Phys. Lett. B 738 401) that even-even, N = Z, toroidal high-spin isomeric states have general occurrences for light nuclei with 28≤slant A≤slant 52. We find that in this mass region there are in addition N\

Molecular dynamics simulation of gas-phase ozone reactions with sabinene and benzene.

PubMed

Ridgway, H F; Mohan, B; Cui, X; Chua, K J; Islam, M R

2017-06-01

Gas-phase reactions of ozone (O 3 ) with volatile organic compounds were investigated both by experiment and molecular simulations. From our experiments, it was found ozone readily reacts with VOC pure components and reduces it effectively. By introducing ozone intermittently, the reaction between VOC and ozone is markedly enhanced. In order to understand the relationship between intermediate reactions and end products, ozone reaction with benzene and alicyclic monoterpene sabinene were simulated via a novel hybrid quantum mechanical/molecular mechanics (QM/MM) algorithm that forced repeated bimolecular collisions. Molecular orbital (MO) rearrangements (manifested as bond dissociation or formation), resulting from the collisions, were computed by semi-empirical unrestricted Hartree-Fock methods (e.g., RM1). A minimum of 975 collisions between ozone and targeted organic species were performed to generate a distribution of reaction products. Results indicated that benzene and sabinene reacted with ozone to produce a range of stable products and intermediates, including carbocations, ring-scission products, as well as peroxy (HO 2 and HO 3 ) and hydroxyl (OH) radicals. Among the stable sabinene products observed included formaldehyde and sabina-ketone, which have been experimentally demonstrated in gas-phase ozonation reactions. Among the benzene ozonation products detected composed of oxygen mono-substituted aromatic C 6 H 5 O, which may undergo further transformation or rearrangement to phenol, benzene oxide or 2,4-cyclohexadienone; a phenomenon which has been experimentally observed in vapor-phase photocatalytic ozonation reactions. Copyright © 2017 Elsevier Inc. All rights reserved.

Analytic gradient for second order Møller-Plesset perturbation theory with the polarizable continuum model based on the fragment molecular orbital method.

PubMed

Nagata, Takeshi; Fedorov, Dmitri G; Li, Hui; Kitaura, Kazuo

2012-05-28

A new energy expression is proposed for the fragment molecular orbital method interfaced with the polarizable continuum model (FMO/PCM). The solvation free energy is shown to be more accurate on a set of representative polypeptides with neutral and charged residues, in comparison to the original formulation at the same level of the many-body expansion of the electrostatic potential determining the apparent surface charges. The analytic first derivative of the energy with respect to nuclear coordinates is formulated at the second-order Møller-Plesset (MP2) perturbation theory level combined with PCM, for which we derived coupled perturbed Hartree-Fock equations. The accuracy of the analytic gradient is demonstrated on test calculations in comparison to numeric gradient. Geometry optimization of the small Trp-cage protein (PDB: 1L2Y) is performed with FMO/PCM/6-31(+)G(d) at the MP2 and restricted Hartree-Fock with empirical dispersion (RHF/D). The root mean square deviations between the FMO optimized and NMR experimental structure are found to be 0.414 and 0.426 Å for RHF/D and MP2, respectively. The details of the hydrogen bond network in the Trp-cage protein are revealed.

Multi-configuration Dirac-Hartree-Fock (MCDHF) calculations for Ni XXV

NASA Astrophysics Data System (ADS)

Singh, Narendra; Aggarwal, Sunny

2018-03-01

We present accurate 165 fine-structure energy levels related to the configurations 1s22s2, 1s22p2, 1s2nƖn‧l‧ (n = 2, n‧ = 2, 3, 4, 5, Ɩ = s,p Ɩ‧ = s, p, d, f, g) of Ni XXV which may be useful ion for astrophysical and fusion plasma. For the calculations of energy levels and radiative rates, we have used the multiconfiguration Dirac-Hartree-Fock (MCDHF) method employed in GRASP2K code. The calculations are carried out in the active space approximation with the inclusion of the Breit interaction, the finite nuclear size effect, and quantum electrodynamic corrections. The transition wavelengths, transition probabilities, line strengths, and absorption oscillator strengths are reported for electric dipole (E1), electric quadrupole (E2), magnetic dipole (M1), magnetic quadrupole (M2) transitions from the ground state. We have compared our calculated results with available theoretical and experimental data and good agreement is achieved. We predict new energy levels, oscillator strengths, line strengths and transition probabilities, where no other experimental or theoretical results are available. The present complete set of results should be of great help in line identification and the interpretation of spectra, as well as in the modelling and diagnostics of astrophysical and fusion plasmas.

Analytic gradient for second order Møller-Plesset perturbation theory with the polarizable continuum model based on the fragment molecular orbital method

NASA Astrophysics Data System (ADS)

Nagata, Takeshi; Fedorov, Dmitri G.; Li, Hui; Kitaura, Kazuo

2012-05-01

A new energy expression is proposed for the fragment molecular orbital method interfaced with the polarizable continuum model (FMO/PCM). The solvation free energy is shown to be more accurate on a set of representative polypeptides with neutral and charged residues, in comparison to the original formulation at the same level of the many-body expansion of the electrostatic potential determining the apparent surface charges. The analytic first derivative of the energy with respect to nuclear coordinates is formulated at the second-order Møller-Plesset (MP2) perturbation theory level combined with PCM, for which we derived coupled perturbed Hartree-Fock equations. The accuracy of the analytic gradient is demonstrated on test calculations in comparison to numeric gradient. Geometry optimization of the small Trp-cage protein (PDB: 1L2Y) is performed with FMO/PCM/6-31(+)G(d) at the MP2 and restricted Hartree-Fock with empirical dispersion (RHF/D). The root mean square deviations between the FMO optimized and NMR experimental structure are found to be 0.414 and 0.426 Å for RHF/D and MP2, respectively. The details of the hydrogen bond network in the Trp-cage protein are revealed.

Structure of Be9Λ and 10Be Λ Λ using the beyond-mean-field Skyrme-Hartree-Fock approach

NASA Astrophysics Data System (ADS)

Li, Wen-Ying; Cui, Ji-Wei; Zhou, Xian-Rong

2018-03-01

Based on the beyond-mean-field Skyrme-Hartree-Fock model, the up-to-date Skyrme-type N Λ interaction, SLL4, is used to investigate the properties of Be9Λ comprehensively. Energies of different configurations, such as 8Be⊗Λ [000 ] 1 /2+ , 8Be⊗Λ [110 ] 1 /2- , 8Be⊗Λ [101 ] 3 /2- , and 8Be⊗Λ [101 ] 1 /2- are given and used to study the effects of Λ occupying different orbitals. The calculated energy spectra, including both positive- and negative-parity levels, are given and compared to the experimental data. The observed positive-parity spin doublets (3 /2+,5 /2+ ) are successfully reproduced, but the energy difference needs further investigation. The two well-known band structures corresponding to the genuine hypernuclear states and the 9Be-analog states are also obtained and compared with the observed ones. The shrinkage effect of Λ occupying Λ [000 ] 1 /2+ is investigated through the density distributions of nuclear core. And finally, the E 2 transition rates are given and compared with the observed data and with the results of the hypernuclear particle-rotor model. Properties of 10Be Λ Λ are also studied to show the completeness of this current model.

Tensor force effect on the evolution of single-particle energies in some isotopic chains in the relativistic Hartree-Fock approximation

NASA Astrophysics Data System (ADS)

López-Quelle, M.; Marcos, S.; Niembro, R.; Savushkin, L. N.

2018-03-01

Within a nonlinear relativistic Hartree-Fock approximation combined with the BCS method, we study the effect of the nucleon-nucleon tensor force of the π-exchange potential on the spin- and pseudospin-orbit doublets along the Ca and Sn isotopic chains. We show how the self-consistent tensor force effect modifies the splitting of both kinds of doublets in an interdependent form, leading, quite generally, to opposite effects in the accomplishment of the spin and pseudospin symmetries (the one is restored, the other one deteriorates and vice versa). The ordering of the single-particle energy levels is crucial to this respect. Also, we observe a mutual dependence on the evolution of the shell closure gap Z = 50 and the energy band outside the core, along the Sn chain, as due to the tensor force. In fact, when the shell gap is quenched the outside energy band is enlarged, and vice versa. A reduction of the strength of the pion tensor force with respect to its experimental value from the nucleon-nucleon scattering is needed to get results closer to the experiment. Pairing correlations act to some extent in the opposite direction of the tensor term of the one-pion-exchange force.

Long-range corrected density functional theory with accelerated Hartree-Fock exchange integration using a two-Gaussian operator [LC-ωPBE(2Gau)].

PubMed

Song, Jong-Won; Hirao, Kimihiko

2015-10-14

Since the advent of hybrid functional in 1993, it has become a main quantum chemical tool for the calculation of energies and properties of molecular systems. Following the introduction of long-range corrected hybrid scheme for density functional theory a decade later, the applicability of the hybrid functional has been further amplified due to the resulting increased performance on orbital energy, excitation energy, non-linear optical property, barrier height, and so on. Nevertheless, the high cost associated with the evaluation of Hartree-Fock (HF) exchange integrals remains a bottleneck for the broader and more active applications of hybrid functionals to large molecular and periodic systems. Here, we propose a very simple yet efficient method for the computation of long-range corrected hybrid scheme. It uses a modified two-Gaussian attenuating operator instead of the error function for the long-range HF exchange integral. As a result, the two-Gaussian HF operator, which mimics the shape of the error function operator, reduces computational time dramatically (e.g., about 14 times acceleration in C diamond calculation using periodic boundary condition) and enables lower scaling with system size, while maintaining the improved features of the long-range corrected density functional theory.

Hartree-Fock treatment of Fermi polarons using the Lee-Low-Pine transformation

NASA Astrophysics Data System (ADS)

Kain, Ben; Ling, Hong Y.

2017-09-01

We consider the Fermi polaron problem at zero temperature, where a single impurity interacts with noninteracting host fermions. We approach the problem starting with a Fröhlich-like Hamiltonian where the impurity is described with canonical position and momentum operators. We apply the Lee-Low-Pine (LLP) transformation to change the fermionic Fröhlich Hamiltonian into the fermionic LLP Hamiltonian, which describes a many-body system containing host fermions only. We adapt the self-consistent Hartree-Fock (HF) approach, first proposed by Edwards, to the fermionic LLP Hamiltonian in which a pair of host fermions with momenta k and k' interact with a potential proportional to k .k' . We apply the HF theory, which has the advantage of not restricting the number of particle-hole pairs, to repulsive Fermi polarons in one dimension. When the impurity and host fermion masses are equal our variational ansatz, where HF orbitals are expanded in terms of free-particle states, produces results in excellent agreement with McGuire's exact analytical results based on the Bethe ansatz. This work raises the prospect of using the HF ansatz and its time-dependent generalization as building blocks for developing all-coupling theories for both equilibrium and nonequilibrium Fermi polarons in higher dimensions.

Generalization of the Kohn-Sham system that can represent arbitrary one-electron density matrices

DOE PAGES

Hubertus J. J. van Dam

2016-04-27

Density functional theory is currently the most widely applied method in electronic structure theory. The Kohn-Sham method, based on a fictitious system of noninteracting particles, is the workhorse of the theory. The particular form of the Kohn-Sham wave function admits only idempotent one-electron density matrices whereas wave functions of correlated electrons in post-Hartree-Fock methods invariably have fractional occupation numbers. Here we show that by generalizing the orbital concept and introducing a suitable dot product as well as a probability density, a noninteracting system can be chosen that can represent the one-electron density matrix of any system, even one with fractionalmore » occupation numbers. This fictitious system ensures that the exact electron density is accessible within density functional theory. It can also serve as the basis for reduced density matrix functional theory. Moreover, to aid the analysis of the results the orbitals may be assigned energies from a mean-field Hamiltonian. This produces energy levels that are akin to Hartree-Fock orbital energies such that conventional analyses based on Koopmans' theorem are available. Lastly, this system is convenient in formalisms that depend on creation and annihilation operators as they are trivially applied to single-determinant wave functions.« less

A minimal model for the structural energetics of VO2

NASA Astrophysics Data System (ADS)

Kim, Chanul; Marianetti, Chris; The Marianetti Group Team

Resolving the structural, magnetic, and electronic structure of VO2 from the first-principles of quantum mechanics is still a forefront problem despite decades of attention. Hybrid functionals have been shown to qualitatively ruin the structural energetics. While density functional theory (DFT) combined with cluster extensions of dynamical mean-field theory (DMFT) have demonstrated promising results in terms of the electronic properties, structural phase stability has not yet been addressed. In order to capture the basic physics of the structural transition, we propose a minimal model of VO2 based on the one dimensional Peierls-Hubbard model and parameterize this based on DFT calculations of VO2. The total energy versus dimerization in the minimal mode is then solved numerically exactly using density matrix renormalization group (DMRG) and compared to the Hartree-Fock solution. We demonstrate that the Hartree-Fock solution exhibits the same pathologies as DFT+U, and spin density functional theory for that matter, while the DMRG solution is consistent with experimental observation. Our results demonstrate the critical role of non-locality in the total energy, and this will need to be accounted for to obtain a complete description of VO2 from first-principles. The authors acknowledge support from FAME, one of six centers of STARnet, a Semiconductor Research Corporation program sponsored by MARCO and DARPA.

Combining density functional and incremental post-Hartree-Fock approaches for van der Waals dominated adsorbate-surface interactions: Ag{sub 2}/graphene

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lara-Castells, María Pilar de, E-mail: Pilar.deLara.Castells@csic.es; Mitrushchenkov, Alexander O.; Stoll, Hermann

2015-09-14

A combined density functional (DFT) and incremental post-Hartree-Fock (post-HF) approach, proven earlier to calculate He-surface potential energy surfaces [de Lara-Castells et al., J. Chem. Phys. 141, 151102 (2014)], is applied to describe the van der Waals dominated Ag{sub 2}/graphene interaction. It extends the dispersionless density functional theory developed by Pernal et al. [Phys. Rev. Lett. 103, 263201 (2009)] by including periodic boundary conditions while the dispersion is parametrized via the method of increments [H. Stoll, J. Chem. Phys. 97, 8449 (1992)]. Starting with the elementary cluster unit of the target surface (benzene), continuing through the realistic cluster model (coronene), andmore » ending with the periodic model of the extended system, modern ab initio methodologies for intermolecular interactions as well as state-of-the-art van der Waals-corrected density functional-based approaches are put together both to assess the accuracy of the composite scheme and to better characterize the Ag{sub 2}/graphene interaction. The present work illustrates how the combination of DFT and post-HF perspectives may be efficient to design simple and reliable ab initio-based schemes in extended systems for surface science applications.« less

Effect of Hartree-Fock exact exchange on intramolecular magnetic coupling constants of organic diradicals

NASA Astrophysics Data System (ADS)

Cho, Daeheum; Ko, Kyoung Chul; Ikabata, Yasuhiro; Wakayama, Kazufumi; Yoshikawa, Takeshi; Nakai, Hiromi; Lee, Jin Yong

2015-01-01

The intramolecular magnetic coupling constant (J) of diradical systems linked with five- or six-membered aromatic rings was calculated to obtain the scaling factor (experimental J/calculated J ratio) for various density functional theory (DFT) functionals. Scaling factors of group A (PBE, TPSSh, B3LYP, B97-1, X3LYP, PBE0, and BH&HLYP) and B (M06-L, M06, M06-2X, and M06-HF) were shown to decrease as the amount of Hartree-Fock exact exchange (HFx) increases, in other words, overestimation of calculated J becomes more severe as the HFx increases. We further investigated the effect of HFx fraction of DFT functional on J value, spin contamination, and spin density distributions by comparing the B3LYP analogues containing different amount of HFx. It was revealed that spin contamination and spin densities at each atom increases as the HFx increases. Above all, newly developed BLYP-5 functional, which has 5% of HFx, was found to have the scaling factor of 1.029, indicating that calculated J values are very close to that of experimental values without scaling. BLYP-5 has potential to be utilized for accurate evaluation of intramolecular magnetic coupling constant (J) of diradicals linked by five- or six-membered aromatic ring couplers.

Effect of Hartree-Fock exact exchange on intramolecular magnetic coupling constants of organic diradicals.

PubMed

Cho, Daeheum; Ko, Kyoung Chul; Ikabata, Yasuhiro; Wakayama, Kazufumi; Yoshikawa, Takeshi; Nakai, Hiromi; Lee, Jin Yong

2015-01-14

The intramolecular magnetic coupling constant (J) of diradical systems linked with five- or six-membered aromatic rings was calculated to obtain the scaling factor (experimental J/calculated J ratio) for various density functional theory (DFT) functionals. Scaling factors of group A (PBE, TPSSh, B3LYP, B97-1, X3LYP, PBE0, and BH&HLYP) and B (M06-L, M06, M06-2X, and M06-HF) were shown to decrease as the amount of Hartree-Fock exact exchange (HFx) increases, in other words, overestimation of calculated J becomes more severe as the HFx increases. We further investigated the effect of HFx fraction of DFT functional on J value, spin contamination, and spin density distributions by comparing the B3LYP analogues containing different amount of HFx. It was revealed that spin contamination and spin densities at each atom increases as the HFx increases. Above all, newly developed BLYP-5 functional, which has 5% of HFx, was found to have the scaling factor of 1.029, indicating that calculated J values are very close to that of experimental values without scaling. BLYP-5 has potential to be utilized for accurate evaluation of intramolecular magnetic coupling constant (J) of diradicals linked by five- or six-membered aromatic ring couplers.

Ab initio Hartree-Fock and density functional theory investigations on the conformational stability, molecular structure and vibrational spectra of 5-chloro-3-(2-(4-methylpiperazin-1-yl)-2-oxoethyl)benzo[d]thiazol-2(3H)-one drug molecule.

PubMed

Taşal, Erol; Kumalar, Mustafa

2012-09-01

In this work, the experimental and theoretical spectra of 5-chloro-3-(2-(4-methylpiperazin-1-yl)-2-oxoethyl)benzo[d]thiazol-2(3H)-one molecule (abbreviated as 5CMOT) are studied. The molecular geometry and vibrational frequencies are calculated in the ground state of molecule using ab initio Hartree-Fock (HF) and Density Function Theory (DFT) methods with 6-311++G(d,p), 6-31G++(d,p), 6-31G(d,p), 6-31G(d) and 6-31G basis sets. Three staggered stable conformers were observed on the torsional potential energy surfaces. The complete assignments were performed on the basis of the total energy distribution (TED) of the vibrational modes calculated. The comparison of the theoretical and experimental geometries of the title compound indicated that the X-ray parameters fairly well agree with the theoretically obtained values for the most stable conformer. The theoretical results showed an excellent agreement with the experimental values. The calculated HOMO and LUMO energies show that the charge transfer occurs within the molecule. Copyright © 2012 Elsevier B.V. All rights reserved.

Rayleigh scattering of x-ray and γ-ray by 1s and 2s electrons in ions and neutral atoms

NASA Astrophysics Data System (ADS)

Costescu, A.; Karim, K.; Moldovan, M.; Spanulescu, S.; Stoica, C.

2011-02-01

Using the Coulomb-Green function method and considering the nonrelativistic limit for the two-photon S-matrix element, the right nonrelativistic 2s Rayleigh scattering amplitudes are obtained. Our result takes into account all multipoles, retardation and relativistic kinematics contributions, and the old dipole approximation result of Costescu [1] is retrieved as a limit case. The total photoeffect cross-section which is related to the imaginary part of the Rayleigh forward scattering amplitude through the optical theorem is also obtained. Our Coulombian formulae are used in the more realistic case of elastic scattering of photons by bound 1s and 2s electrons in ions and neutral atoms. Screening effects are considered in the independent particle approximation through the Hartree-Fock method. The effective charge Zeff is obtained by fitting the Hartree-Fock charge distribution by a Coulombian one. Good agreement (within 10%) is found when comparing the numerical predictions given by our nonrelativistic formulae with the full relativistic numerical results of Kissel [2] in the case of elastic scattering of photons by 1s and 2s electrons and Scofield [3] in the case of K-shell and 2s subshell photoionization for neutral atoms with 18 <= Z <= 92 and photon energies ω <= αZm.

Fingerprints of spin-orbital polarons and of their disorder in the photoemission spectra of doped Mott insulators with orbital degeneracy

NASA Astrophysics Data System (ADS)

Avella, Adolfo; Oleś, Andrzej M.; Horsch, Peter

2018-04-01

We explore the effects of disordered charged defects on the electronic excitations observed in the photoemission spectra of doped transition metal oxides in the Mott insulating regime by the example of the R1 -xCaxVO3 perovskites, where R = La, ⋯, Lu. A fundamental characteristic of these vanadium d2 compounds with partly filled t2 g valence orbitals is the persistence of spin and orbital order up to high doping, in contrast to the loss of magnetic order in high-Tc cuprates at low defect concentration. We study the disordered electronic structure of such doped Mott-Hubbard insulators within the unrestricted Hartree-Fock approximation and, as a result, manage to explain the spectral features that occur in photoemission and inverse photoemission. In particular, (i) the atomic multiplet excitations in the inverse photoemission spectra and the various defect-related states and satellites are qualitatively well reproduced, (ii) a robust Mott gap survives up to large doping, and (iii) we show that the defect states inside the Mott gap develop a soft gap at the Fermi energy. The soft defect-states gap, which separates the highest occupied from the lowest unoccupied states, can be characterized by a shape and a scale parameter extracted from a Weibull statistical sampling of the density of states near the chemical potential. These parameters provide a criterion and a comprehensive schematization for the insulator-metal transition in disordered systems. Our results provide clear indications that doped holes are bound to charged defects and form small spin-orbital polarons whose internal kinetic energy is responsible for the opening of the soft defect-states gap. We show that this kinetic gap survives disorder fluctuations of defects and is amplified by the long-range electron-electron interactions, whereas we observe a Coulomb singularity in the atomic limit. The small size of spin-orbital polarons is inferred by an analysis of the inverse participation ratio and by means of a complementary many-body polaron theory, which yields a similar robust spin and orbital order as the Hartree-Fock approximation. Using realistic parameters for the vanadium perovskite La1 -xCaxVO3 , we show that its soft gap is reproduced as well as the marginal doping dependence of the position of the chemical potential relative to the center of the lower Hubbard band. The present theory uncovers also the reasons why the d1→d0 satellite excitations, which directly probe the effect of the random defect fields on the polaron state, are not well resolved in the available experimental photoemission spectra for La1 -xCaxVO3 .

Electron-electron interaction and spin-orbit coupling in InAs/AlSb heterostructures with a two-dimensional electron gas

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gavrilenko, V. I.; Krishtopenko, S. S., E-mail: ds_a-teens@mail.ru; Goiran, M.

2011-01-15

The effect of electron-electron interaction on the spectrum of two-dimensional electron states in InAs/AlSb (001) heterostructures with a GaSb cap layer with one filled size-quantization subband. The energy spectrum of two-dimensional electrons is calculated in the Hartree and Hartree-Fock approximations. It is shown that the exchange interaction decreasing the electron energy in subbands increases the energy gap between subbands and the spin-orbit splitting of the spectrum in the entire region of electron concentrations, at which only the lower size-quantization band is filled. The nonlinear dependence of the Rashba splitting constant at the Fermi wave vector on the concentration of two-dimensionalmore » electrons is demonstrated.« less

Quantum chemical approach for positron annihilation spectra of atoms and molecules beyond plane-wave approximation

NASA Astrophysics Data System (ADS)

Ikabata, Yasuhiro; Aiba, Risa; Iwanade, Toru; Nishizawa, Hiroaki; Wang, Feng; Nakai, Hiromi

2018-05-01

We report theoretical calculations of positron-electron annihilation spectra of noble gas atoms and small molecules using the nuclear orbital plus molecular orbital method. Instead of a nuclear wavefunction, the positronic wavefunction is obtained as the solution of the coupled Hartree-Fock or Kohn-Sham equation for a positron and the electrons. The molecular field is included in the positronic Fock operator, which allows an appropriate treatment of the positron-molecule repulsion. The present treatment succeeds in reproducing the Doppler shift, i.e., full width at half maximum (FWHM) of experimentally measured annihilation (γ-ray) spectra for molecules with a mean absolute error less than 10%. The numerical results indicate that the interpretation of the FWHM in terms of a specific molecular orbital is not appropriate.

A calculation for radial expectation values of helium like actinide ions (Z=89-93)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ürer, G., E-mail: gurer@sakarya.edu.tr; Arslan, M., E-mail: murat.arslan4@ogr.sakarya.edu.tr; Balkaya, E., E-mail: eda.balkaya@ogr.sakarya.edu.tr

2016-03-25

Radial expectation values, , for helium like actinides (Z{sub Ac}=89, Z{sub Th}=90, Z{sub Pa}=91, Z{sub U}=92, and Z{sub Np}=93) are reported using the Multiconfiguration Hartree-Fock (MCHF) within the framework Breit-Pauli corrections. Atomic data as energy levels, wavelengths, weighted oscillator strengths, and transition probabilities for allowed and forbidden transitions need these calculations. The obtained results are compared available works.

Calculation of longitudinal polarizability and second hyperpolarizability of polyacetylene with the coupled perturbed Hartree-Fock/Kohn-Sham scheme: Where it is shown how finite oligomer chains tend to the infinite periodic polymer

NASA Astrophysics Data System (ADS)

Lacivita, Valentina; Rèrat, Michel; Orlando, Roberto; Ferrero, Mauro; Dovesi, Roberto

2012-03-01

The longitudinal polarizability, αxx, and second hyperpolarizability, γxxxx, of polyacetylene are evaluated by using the coupled perturbed Hartree-Fock/Kohn-Sham (HF/KS) scheme as implemented in the periodic CRYSTAL code and a split valence type basis set. Four different density functionals, namely local density approximation (LDA) (pure local), Perdew-Becke-Ernzerhof (PBE) (gradient corrected), PBE0, and B3LYP (hybrid), and the Hartree-Fock Hamiltonian are compared. It is shown that very tight computational conditions must be used to obtain well converged results, especially for γxxxx, that is, very sensitive to the number of k points in reciprocal space when the band gap is small (as for LDA and PBE), and to the extension of summations of the exact exchange series (HF and hybrids). The band gap in LDA is only 0.01 eV: at least 300 k points are required to obtain well converged total energy and equilibrium geometry, and 1200 for well converged optical properties. Also, the exchange series convergence is related to the band gap. The PBE0 band gap is as small as 1.4 eV and the exchange summation must extend to about 130 Å from the origin cell. Total energy, band gap, equilibrium geometry, polarizability, and second hyperpolarizability of oligomers -(C2H2)m-, with m up to 50 (202 atoms), and of the polymer have been compared. It turns out that oligomers of that length provide an extremely poor representation of the infinite chain polarizability and hyperpolarizability when the gap is smaller than 0.2 eV (that is, for LDA and PBE). Huge differences are observed on αxx and γxxxx of the polymer when different functionals are used, that is in connection to the well-known density functional theory (DFT) overshoot, reported in the literature about short oligomers: for the infinite model the ratio between LDA (or PBE) and HF becomes even more dramatic (about 500 for αxx and 1010 for γxxxx). On the basis of previous systematic comparisons of results obtained with various approaches including DFT, HF, Moller-Plesset (MP2) and coupled cluster for finite chains, we can argue that, for the infinite chain, the present HF results are the most reliable.

Adaptive multi-resolution 3D Hartree-Fock-Bogoliubov solver for nuclear structure

NASA Astrophysics Data System (ADS)

Pei, J. C.; Fann, G. I.; Harrison, R. J.; Nazarewicz, W.; Shi, Yue; Thornton, S.

2014-08-01

Background: Complex many-body systems, such as triaxial and reflection-asymmetric nuclei, weakly bound halo states, cluster configurations, nuclear fragments produced in heavy-ion fusion reactions, cold Fermi gases, and pasta phases in neutron star crust, are all characterized by large sizes and complex topologies in which many geometrical symmetries characteristic of ground-state configurations are broken. A tool of choice to study such complex forms of matter is an adaptive multi-resolution wavelet analysis. This method has generated much excitement since it provides a common framework linking many diversified methodologies across different fields, including signal processing, data compression, harmonic analysis and operator theory, fractals, and quantum field theory. Purpose: To describe complex superfluid many-fermion systems, we introduce an adaptive pseudospectral method for solving self-consistent equations of nuclear density functional theory in three dimensions, without symmetry restrictions. Methods: The numerical method is based on the multi-resolution and computational harmonic analysis techniques with a multi-wavelet basis. The application of state-of-the-art parallel programming techniques include sophisticated object-oriented templates which parse the high-level code into distributed parallel tasks with a multi-thread task queue scheduler for each multi-core node. The internode communications are asynchronous. The algorithm is variational and is capable of solving coupled complex-geometric systems of equations adaptively, with functional and boundary constraints, in a finite spatial domain of very large size, limited by existing parallel computer memory. For smooth functions, user-defined finite precision is guaranteed. Results: The new adaptive multi-resolution Hartree-Fock-Bogoliubov (HFB) solver madness-hfb is benchmarked against a two-dimensional coordinate-space solver hfb-ax that is based on the B-spline technique and a three-dimensional solver hfodd that is based on the harmonic-oscillator basis expansion. Several examples are considered, including the self-consistent HFB problem for spin-polarized trapped cold fermions and the Skyrme-Hartree-Fock (+BCS) problem for triaxial deformed nuclei. Conclusions: The new madness-hfb framework has many attractive features when applied to nuclear and atomic problems involving many-particle superfluid systems. Of particular interest are weakly bound nuclear configurations close to particle drip lines, strongly elongated and dinuclear configurations such as those present in fission and heavy-ion fusion, and exotic pasta phases that appear in neutron star crust.

Covariant density functional theory: predictive power and first attempts of a microscopic derivation

NASA Astrophysics Data System (ADS)

Ring, Peter

2018-05-01

We discuss systematic global investigations with modern covariant density functionals. The number of their phenomenological parameters can be reduced considerable by using microscopic input from ab-initio calculations in nuclear matter. The size of the tensor force is still an open problem. Therefore we use the first full relativistic Brueckner-Hartree-Fock calculations in finite nuclear systems in order to study properties of such functionals, which cannot be obtained from nuclear matter calculations.

High spin states of 72-74Kr

NASA Astrophysics Data System (ADS)

Kaushik, M.; Kumawat, M.; Singh, U. K.; Saxena, G.

2018-05-01

A theoretical investigation has made on the structure of high spin states of 72-74Kr within the framework of cranked Hartree-Fock-Bogoliubov (CHFB) theory employing a pairing + quadrupole + hexadecapole model interaction. Dependence of shape with the spin, excitation energy, alignment of proton as well as neutron 0g9/2 orbital along with backbending phenomenon are discussed upto a high spin J = 26. We found reasonable agreement with the experimental values and other theoretical calculations.

Roothaan's approach to solve the Hartree-Fock equations for atoms confined by soft walls: Basis set with correct asymptotic behavior.

PubMed

Rodriguez-Bautista, Mariano; Díaz-García, Cecilia; Navarrete-López, Alejandra M; Vargas, Rubicelia; Garza, Jorge

2015-07-21

In this report, we use a new basis set for Hartree-Fock calculations related to many-electron atoms confined by soft walls. One- and two-electron integrals were programmed in a code based in parallel programming techniques. The results obtained with this proposal for hydrogen and helium atoms were contrasted with other proposals to study just one and two electron confined atoms, where we have reproduced or improved the results previously reported. Usually, an atom enclosed by hard walls has been used as a model to study confinement effects on orbital energies, the main conclusion reached by this model is that orbital energies always go up when the confinement radius is reduced. However, such an observation is not necessarily valid for atoms confined by penetrable walls. The main reason behind this result is that for atoms with large polarizability, like beryllium or potassium, external orbitals are delocalized when the confinement is imposed and consequently, the internal orbitals behave as if they were in an ionized atom. Naturally, the shell structure of these atoms is modified drastically when they are confined. The delocalization was an argument proposed for atoms confined by hard walls, but it was never verified. In this work, the confinement imposed by soft walls allows to analyze the delocalization concept in many-electron atoms.

Dielectronic satellite spectra of hydrogen-like titanium (Ti XXII)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bitter, M.; von Goeler, S.; Cohen, S.

High resolution spectra of the Ly ..cap alpha../sub 1/ and Ly ..cap alpha../sub 2/ lines of hydrogenlike titanium, TiXXII, and the associated dielectronic satellites which are due to transitions 1snl-2pnl with n greater than or equal to 2, have been observed from tokamak discharges with auxiliary ion cyclotron heating (ICRH) with central electron temperatures of 2 keV and central electron densities of 8 x 10/sup 13/ cm/sup -3/ on the Princeton Large Torus (PLT). The data have been used for a detailed comparison with theoretical predictions based on the Z - expansion method and Hartree - Fock calculations. The resultsmore » obtained with the Z - expansion method are in excellent agreement with the observed spectral data except for minor discrepancies between the theoretical and experimental wavelengths of 0.0003 A for the n = 2 satellites and of 0.0001 A for the separation of the Ly ..cap alpha../sub 1/ and Ly ..cap alpha../sub 2/ lines. Very good agreement with the experimental data is also obtained for the results from the Hartree - Fock calculations though somewhat larger discrepancies (approx. = 0.0009 A) exist between experimental and theoretical wavelengths which are systematically too small. The observed spectra are used for diagnosis of the central ion and electron temperatures of the PLT discharges and for a measurement of the dielectronic recombination rate coefficient of TiXXII.« less

Improvement of one-nucleon removal and total reaction cross sections in the Liège intranuclear-cascade model using Hartree-Fock-Bogoliubov calculations

NASA Astrophysics Data System (ADS)

Rodríguez-Sánchez, Jose Luis; David, Jean-Christophe; Mancusi, Davide; Boudard, Alain; Cugnon, Joseph; Leray, Sylvie

2017-11-01

The prediction of one-nucleon-removal cross sections by the Liège intranuclear-cascade model has been improved using a refined description of the matter and energy densities in the nuclear surface. Hartree-Fock-Bogoliubov calculations with the Skyrme interaction are used to obtain a more realistic description of the radial-density distributions of protons and neutrons, as well as the excitation-energy uncorrelation at the nuclear surface due to quantum effects and short-range correlations. The results are compared with experimental data covering a large range of nuclei, from carbon to uranium, and projectile kinetic energies. We find that the new approach is in good agreement with experimental data of one-nucleon-removal cross sections covering a broad range in nuclei and energies. The new ingredients also improve the description of total reaction cross sections induced by protons at low energies, the production cross sections of heaviest residues close to the projectile, and the triple-differential cross sections for one-proton removal. However, other observables such as quadruple-differential cross sections of coincident protons do not present any sizable sensitivity to the new approach. Finally, the model is also tested for light-ion-induced reactions. It is shown that the new parameters can give a reasonable description of the nucleus-nucleus total reaction cross sections at high energies.

Roothaan’s approach to solve the Hartree-Fock equations for atoms confined by soft walls: Basis set with correct asymptotic behavior

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rodriguez-Bautista, Mariano; Díaz-García, Cecilia; Navarrete-López, Alejandra M.

2015-07-21

In this report, we use a new basis set for Hartree-Fock calculations related to many-electron atoms confined by soft walls. One- and two-electron integrals were programmed in a code based in parallel programming techniques. The results obtained with this proposal for hydrogen and helium atoms were contrasted with other proposals to study just one and two electron confined atoms, where we have reproduced or improved the results previously reported. Usually, an atom enclosed by hard walls has been used as a model to study confinement effects on orbital energies, the main conclusion reached by this model is that orbital energiesmore » always go up when the confinement radius is reduced. However, such an observation is not necessarily valid for atoms confined by penetrable walls. The main reason behind this result is that for atoms with large polarizability, like beryllium or potassium, external orbitals are delocalized when the confinement is imposed and consequently, the internal orbitals behave as if they were in an ionized atom. Naturally, the shell structure of these atoms is modified drastically when they are confined. The delocalization was an argument proposed for atoms confined by hard walls, but it was never verified. In this work, the confinement imposed by soft walls allows to analyze the delocalization concept in many-electron atoms.« less

Scaled Hartree-Fock force field calculations for organothallium compounds: Normal-mode analysis for TlCH sub 3 Tl(CH sub 3 ) sub 2 sup + , Tl(CH sub 3 ) sub 3 , Tl(CH sub 3 ) sub 2 Br, and Tl(CH sub 3 ) sub 4 sup minus

DOE Office of Scientific and Technical Information (OSTI.GOV)

Schwerdtfeger, P.; Bowmaker, G.A.; Boyd, P.D.W.

1990-02-01

In a recent paper we presented Hartree-Fock (HF) calculations for aliphatic organothallium compounds. The diagonal HF force constants obtained from a Fletcher-Powell geometry optimization are now used for a normal-mode analysis of TlCH{sub 3}, Tl(CH{sub 3}){sub 2}{sup +}, Tl(CH{sub 3}){sub 3}, Tl(CH{sub 3}){sub 2}Br, and Tl(CH{sub 3}){sub 4}{sup {minus}}. In order to calculate frequencies comparable to experimental values, the HF force field has been scaled by using scaling factors obtained from experimental infrared and Raman measurements on Tl(CH{sub 3}){sub 2}{sup +} and TlBr. The vibrational spectra of Tl(CH{sub 3}){sub 2}{sup +} were remeasured (infrared and Raman) in order to obtainmore » an accurate force field. Predictions are made for the vibrational spectrum of the as yet undetected TlCH{sub 3} molecule. Experimental infrared and Raman results for Tl(CH{sub 3}){sub 3} compare reasonably well with our calculated frequencies. Relativistic and correlation effects are analyzed for the vibrational frequencies of Tl(CH{sub 3}){sub 2}{sup +}.« less

Nonadiabatic electron wavepacket dynamics behind molecular autoionization

NASA Astrophysics Data System (ADS)

Matsuoka, Takahide; Takatsuka, Kazuo

2018-01-01

A theoretical method for real-time dynamics of nonadiabatic reorganization of electronic configurations in molecules is developed, with dual aim that the intramolecular electron dynamics can be probed by means of direct and/or indirect photoionizations and that the physical origins behind photoionization signals attained in the time domain can be identified in terms of the language of time-dependent quantum chemistry. In doing so, we first formulate and implement a new computational scheme for nonadiabatic electron dynamics associated with molecular ionization, which well fits in the general theory of nonadiabatic electron dynamics. In this method, the total nonadiabatic electron wavepackets are propagated in time directly with complex natural orbitals without referring to Hartree-Fock molecular orbitals, and the amount of electron flux from a molecular region leading to ionization is evaluated in terms of the relevant complex natural orbitals. In the second half of this paper, we apply the method to electron dynamics in the elementary processes consisting of the Auger decay to demonstrate the methodological significance. An illustrative example is taken from an Auger decay starting from the 2a1 orbital hole-state of H2O+. The roles of nuclear momentum (kinetic) couplings in electronic-state mixing during the decay process are analyzed in terms of complex natural orbitals, which are schematically represented in the conventional language of molecular symmetry of the Hartree-Fock orbitals.

Recent advances in PC-Linux systems for electronic structure computations by optimized compilers and numerical libraries.

PubMed

Yu, Jen-Shiang K; Yu, Chin-Hui

2002-01-01

One of the most frequently used packages for electronic structure research, GAUSSIAN 98, is compiled on Linux systems with various hardware configurations, including AMD Athlon (with the "Thunderbird" core), AthlonMP, and AthlonXP (with the "Palomino" core) systems as well as the Intel Pentium 4 (with the "Willamette" core) machines. The default PGI FORTRAN compiler (pgf77) and the Intel FORTRAN compiler (ifc) are respectively employed with different architectural optimization options to compile GAUSSIAN 98 and test the performance improvement. In addition to the BLAS library included in revision A.11 of this package, the Automatically Tuned Linear Algebra Software (ATLAS) library is linked against the binary executables to improve the performance. Various Hartree-Fock, density-functional theories, and the MP2 calculations are done for benchmarking purposes. It is found that the combination of ifc with ATLAS library gives the best performance for GAUSSIAN 98 on all of these PC-Linux computers, including AMD and Intel CPUs. Even on AMD systems, the Intel FORTRAN compiler invariably produces binaries with better performance than pgf77. The enhancement provided by the ATLAS library is more significant for post-Hartree-Fock calculations. The performance on one single CPU is potentially as good as that on an Alpha 21264A workstation or an SGI supercomputer. The floating-point marks by SpecFP2000 have similar trends to the results of GAUSSIAN 98 package.

Molecular structure, vibrational spectra, AIM, HOMO-LUMO, NBO, UV, first order hyperpolarizability, analysis of 3-thiophenecarboxylic acid monomer and dimer by Hartree-Fock and density functional theory

NASA Astrophysics Data System (ADS)

Issaoui, Noureddine; Ghalla, Houcine; Muthu, S.; Flakus, H. T.; Oujia, Brahim

2015-02-01

In this work, the molecular structure, harmonic vibrational frequencies, UV, NBO and AIM of 3-thiophenecarboxilic acid (abbreviated as 3-TCA) monomer and dimer has been investigated. The FT-IR and FT-Raman spectra were recorded. The ground-state molecular geometry and vibrational frequencies have been calculated by using the Hartree-Fock (HF) and density functional theory (DFT)/B3LYP methods and 6-311++G(d,p) as a basis set. The fundamental vibrations were assigned on the basis of the total energy distribution (TED) of the vibrational modes, calculated with VEDA program. Comparison of the observed fundamental vibrational frequencies of 3-TCA with calculated results by HF and DFT methods indicates that B3LYP is better to HF method for molecular vibrational problems. The difference between the observed and scaled wavenumber values is very small. The theoretically predicted FT-IR and FT-Raman spectra of the title compound have been constructed. A study on the Mulliken atomic charges, the electronic properties were performed by time-dependent DFT (TD-DFT) approach, frontier molecular orbitals (HOMO-LUMO), molecular electrostatic potential (MEP) and thermodynamic properties have been performed. The electric dipole moment (μ) and the first hyperpolarizability (β) values of the investigated molecule have been also computed.

Molecular structure, vibrational spectra, AIM, HOMO-LUMO, NBO, UV, first order hyperpolarizability, analysis of 3-thiophenecarboxylic acid monomer and dimer by Hartree-Fock and density functional theory.

PubMed

Issaoui, Noureddine; Ghalla, Houcine; Muthu, S; Flakus, H T; Oujia, Brahim

2015-02-05

In this work, the molecular structure, harmonic vibrational frequencies, UV, NBO and AIM of 3-thiophenecarboxilic acid (abbreviated as 3-TCA) monomer and dimer has been investigated. The FT-IR and FT-Raman spectra were recorded. The ground-state molecular geometry and vibrational frequencies have been calculated by using the Hartree-Fock (HF) and density functional theory (DFT)/B3LYP methods and 6-311++G(d,p) as a basis set. The fundamental vibrations were assigned on the basis of the total energy distribution (TED) of the vibrational modes, calculated with VEDA program. Comparison of the observed fundamental vibrational frequencies of 3-TCA with calculated results by HF and DFT methods indicates that B3LYP is better to HF method for molecular vibrational problems. The difference between the observed and scaled wavenumber values is very small. The theoretically predicted FT-IR and FT-Raman spectra of the title compound have been constructed. A study on the Mulliken atomic charges, the electronic properties were performed by time-dependent DFT (TD-DFT) approach, frontier molecular orbitals (HOMO-LUMO), molecular electrostatic potential (MEP) and thermodynamic properties have been performed. The electric dipole moment (μ) and the first hyperpolarizability (β) values of the investigated molecule have been also computed. Copyright © 2014 Elsevier B.V. All rights reserved.

Formal expressions and corresponding expansions for the exact Kohn-Sham exchange potential

NASA Astrophysics Data System (ADS)

Bulat, Felipe A.; Levy, Mel

2009-11-01

Formal expressions and their corresponding expansions in terms of Kohn-Sham (KS) orbitals are deduced for the exchange potential vx(r) . After an alternative derivation of the basic optimized effective potential integrodifferential equations is given through a Hartree-Fock adiabatic connection perturbation theory, we present an exact infinite expansion for vx(r) that is particularly simple in structure. It contains the very same occupied-virtual quantities that appear in the well-known optimized effective potential integral equation, but in this new expression vx(r) is isolated on one side of the equation. An orbital-energy modified Slater potential is its leading term which gives encouraging numerical results. Along different lines, while the earlier Krieger-Li-Iafrate approximation truncates completely the necessary first-order perturbation orbitals, we observe that the improved localized Hartree-Fock (LHF) potential, or common energy denominator potential (CEDA), or effective local potential (ELP), incorporates the part of each first-order orbital that consists of the occupied KS orbitals. With this in mind, the exact correction to the LHF, CEDA, or ELP potential (they are all equivalent) is deduced and displayed in terms of the virtual portions of the first-order orbitals. We close by observing that the newly derived exact formal expressions and corresponding expansions apply as well for obtaining the correlation potential from an orbital-dependent correlation energy functional.

Nonadiabatic Dynamics for Electrons at Second-Order: Real-Time TDDFT and OSCF2.

PubMed

Nguyen, Triet S; Parkhill, John

2015-07-14

We develop a new model to simulate nonradiative relaxation and dephasing by combining real-time Hartree-Fock and density functional theory (DFT) with our recent open-systems theory of electronic dynamics. The approach has some key advantages: it has been systematically derived and properly relaxes noninteracting electrons to a Fermi-Dirac distribution. This paper combines the new dissipation theory with an atomistic, all-electron quantum chemistry code and an atom-centered model of the thermal environment. The environment is represented nonempirically and is dependent on molecular structure in a nonlocal way. A production quality, O(N(3)) closed-shell implementation of our theory applicable to realistic molecular systems is presented, including timing information. This scaling implies that the added cost of our nonadiabatic relaxation model, time-dependent open self-consistent field at second order (OSCF2), is computationally inexpensive, relative to adiabatic propagation of real-time time-dependent Hartree-Fock (TDHF) or time-dependent density functional theory (TDDFT). Details of the implementation and numerical algorithm, including factorization and efficiency, are discussed. We demonstrate that OSCF2 approaches the stationary self-consistent field (SCF) ground state when the gap is large relative to k(b)T. The code is used to calculate linear-response spectra including the effects of bath dynamics. Finally, we show how our theory of finite-temperature relaxation can be used to correct ground-state DFT calculations.

Alternative derivation of an exchange-only density-functional optimized effective potential

DOE Office of Scientific and Technical Information (OSTI.GOV)

Joubert, D. P.

2007-10-15

An alternative derivation of the exchange-only density-functional optimized effective potential equation is given. It is shown that the localized Hartree-Fock-common energy denominator Green's function approximation (LHF-CEDA) for the density-functional exchange potential proposed independently by Della Sala and Goerling [J. Chem. Phys. 115, 5718 (2001)] and Gritsenko and Baerends [Phys. Rev. A 64, 42506 (2001)] can be derived as an approximation to the OEP exchange potential in a similar way that the KLI approximation [Phys. Rev. A 45, 5453 (1992)] was derived. An exact expression for the correction term to the LHF-CEDA approximation can thus be found. The correction term canmore » be expressed in terms of the first-order perturbation-theory many-electron wave function shift when the Kohn-Sham Hamiltonian is subjected to a perturbation equal to the difference between the density-functional exchange potential and the Hartree-Fock nonlocal potential, expressed in terms of the Kohn-Sham orbitals. An explicit calculation shows that the density weighted mean of the correction term is zero, confirming that the LHF-CEDA approximation can be interpreted as a mean-field approximation. The corrected LHF-CEDA equation and the optimized effective potential equation are shown to be identical, with information distributed differently between terms in the equations. For a finite system the correction term falls off at least as fast as 1/r{sup 4} for large r.« less

Alternative derivation of an exchange-only density-functional optimized effective potential

NASA Astrophysics Data System (ADS)

Joubert, D. P.

2007-10-01

An alternative derivation of the exchange-only density-functional optimized effective potential equation is given. It is shown that the localized Hartree-Fock common energy denominator Green’s function approximation (LHF-CEDA) for the density-functional exchange potential proposed independently by Della Sala and Görling [J. Chem. Phys. 115, 5718 (2001)] and Gritsenko and Baerends [Phys. Rev. A 64, 42506 (2001)] can be derived as an approximation to the OEP exchange potential in a similar way that the KLI approximation [Phys. Rev. A 45, 5453 (1992)] was derived. An exact expression for the correction term to the LHF-CEDA approximation can thus be found. The correction term can be expressed in terms of the first-order perturbation-theory many-electron wave function shift when the Kohn-Sham Hamiltonian is subjected to a perturbation equal to the difference between the density-functional exchange potential and the Hartree-Fock nonlocal potential, expressed in terms of the Kohn-Sham orbitals. An explicit calculation shows that the density weighted mean of the correction term is zero, confirming that the LHF-CEDA approximation can be interpreted as a mean-field approximation. The corrected LHF-CEDA equation and the optimized effective potential equation are shown to be identical, with information distributed differently between terms in the equations. For a finite system the correction term falls off at least as fast as 1/r4 for large r .

Incoherent vs. coherent behavior in the normal state of copper oxide superconductors

NASA Technical Reports Server (NTRS)

Tesanovic, Zlatko

1991-01-01

The self-consistent quantum fluctuations around the mean-field Hartree-Fock state of the Hubbard model provide a very good description of the ground state and low temperature properties of a 2-D itinerant antiferromagnet. Very good agreement with numerical calculations and experimental data is obtained by including the one- and two-loop spin wave corrections to various physical quantities. In particular, the destruction of the long-range order above the Neel temperature can be understood as a spontaneous generation of a length-scale epsilon(T), which should be identified as the spin correlation length. For finite doping, the question of the Hartree-Fock starting point becomes a more complex one since an extra hole tends to self-trap in antiferromagnetic background. Such quantum defects in an underlying antiferromagnetic state can be spin-bags or vortex-like structures and tend to suppress the long-range order. If motion of the holes occurs on a time-scale shorter than the one associated with the motion of these quantum defects of a spin background, one obtains several important empirical features of the normal state of CuO superconductors like linear T-dependence of resistivity, the cusp in the tunneling density of states, etc. As opposed to a familiar Fermi-liquid behavior, the phenomenology of the above system is dominated by a large incoherent piece of a single hole propagator, resulting in many unusual normal state properties.

The effect of basis set and exchange-correlation functional on time-dependent density functional theory calculations within the Tamm-Dancoff approximation of the x-ray emission spectroscopy of transition metal complexes.

PubMed

Roper, Ian P E; Besley, Nicholas A

2016-03-21

The simulation of X-ray emission spectra of transition metal complexes with time-dependent density functional theory (TDDFT) is investigated. X-ray emission spectra can be computed within TDDFT in conjunction with the Tamm-Dancoff approximation by using a reference determinant with a vacancy in the relevant core orbital, and these calculations can be performed using the frozen orbital approximation or with the relaxation of the orbitals of the intermediate core-ionised state included. Both standard exchange-correlation functionals and functionals specifically designed for X-ray emission spectroscopy are studied, and it is shown that the computed spectral band profiles are sensitive to the exchange-correlation functional used. The computed intensities of the spectral bands can be rationalised by considering the metal p orbital character of the valence molecular orbitals. To compute X-ray emission spectra with the correct energy scale allowing a direct comparison with experiment requires the relaxation of the core-ionised state to be included and the use of specifically designed functionals with increased amounts of Hartree-Fock exchange in conjunction with high quality basis sets. A range-corrected functional with increased Hartree-Fock exchange in the short range provides transition energies close to experiment and spectral band profiles that have a similar accuracy to those from standard functionals.

An ab initio time-dependent Hartree Fock study of solvent effects on the polarizability and second hyperpolarizability of polyacetylene chains within the polarizable continuum model

NASA Astrophysics Data System (ADS)

Champagne, Benoı̂t; Mennucci, Benedetta; Cossi, Maurizio; Cammi, Roberto; Tomasi, Jacopo

1998-11-01

The solvent effects upon the longitudinal polarizability ( αL) and second hyperpolarizability ( γL) of small all-trans polyacetylene (PA) chains ranging from C 2H 4 to C 10H 12 have been evaluated at the time-dependent Hartree-Fock (TDHF) level within the framework of the polarizable continuum model. The solvent effects, which correspond to the solvent-induced modifications of the solute properties, result in large increases of the linear and nonlinear responses even for solvents with low dielectric constants. When the dielectric constant is increased, the αL values tend to saturate at values 30%-40% larger than in vacuo, whereas for γL it ranges from 100% to 400% depending upon the nonlinear optical process and the length of the PA chain. These solvent-induced αL and γL enhancements can partially be accounted for by the corresponding decrease of the energy of the lowest optically-allowed electronic excitation. The geometrical parameters of the ground state of the PA chains are almost unaffected by the solvent. This shows that the solvent effects are mainly of electronic nature. In addition, the local field factors, which relate the macroscopic or Maxwell field to the field experienced by the solute, tend towards unity with increasing chain length for the longitudinal PA axis.

Effects of compositional defects on small polaron hopping in micas.

PubMed

Rosso, Kevin M; Ilton, Eugene S

2005-06-22

Hartree-Fock calculations and electron transfer (ET) theory were used to model the effects of compositional defects on ET in the brucite-like octahedral sheet of mica. ET was modeled as an Fe(IIIII) valence interchange reaction across shared octahedral edges of the M2-M2 iron sublattice. The model entails the hopping of localized electrons and small polaron behavior. Hartree-Fock calculations indicate that substitution of F for structural OH bridges increases the reorganization energy lambda, decreases the electronic coupling matrix element V(AB), and thereby substantially decreases the hopping rate. The lambda increase arises from modification of the metal-ligand bond force constants, and the V(AB) decrease arises from reduction of superexchange interaction through anion bridges. Deprotonation of an OH bridge, consistent with a possible mechanism of maintaining charge neutrality during net oxidation, yields a net increase in the ET rate. Although substitution of Al or Mg for Fe in M1 sites distorts the structure of adjacent Fe-occupied M2 sites, the distortion has little net impact on ET rates through these M2 sites. Hence the main effect of Al or Mg substitution for Fe, should it occur in the M2 sublattice, is to block ET pathways. Collectively, these findings pave the way for larger-scale oxidation/reduction models to be constructed for realistic, compositionally diverse micas.

Stopping power and range calculations in human tissues by using the Hartree-Fock-Roothaan wave functions

NASA Astrophysics Data System (ADS)

Usta, Metin; Tufan, Mustafa Çağatay

2017-11-01

The object of this work is to present the consequences for the stopping power and range values of some human tissues at energies ranging from 1 MeV to 1 GeV and 1-500 MeV, respectively. The considered human tissues are lung, intestine, skin, larynx, breast, bladder, prostate and ovary. In this work, the stopping power is calculated by considering the number of velocity-dependent effective charge and effective mean excitation energies of the target material. We used the Hartree-Fock-Roothaan (HFR) atomic wave function to determine the charge density and the continuous slowing down approximation (CSDA) method for the calculation of the proton range. Electronic stopping power values of tissues results have been compared with the ICRU 44, 46 reports, SRIM, Janni and CasP data over the percent error rate. Range values relate to tissues have compared the range results with the SRIM, FLUKA and Geant4 data. For electronic stopping power results, ICRU, SRIM and Janni's data indicated the best fit with our values at 1-50, 50-250 MeV and 250 MeV-1 GeV, respectively. For range results, the best accordance with the calculated values have been found the SRIM data and the error level is less than 10% in proton therapy. However, greater 30% errors were observed in the 250 MeV and over energies.

Solution of the Skyrme-Hartree-Fock-Bogolyubov equations in the Cartesian deformed harmonic-oscillator basis. (IV) HFODD (v2.08i): a new version of the program

NASA Astrophysics Data System (ADS)

Dobaczewski, J.; Olbratowski, P.

2004-04-01

We describe the new version (v2.08i) of the code HFODD which solves the nuclear Skyrme-Hartree-Fock or Skyrme-Hartree-Fock-Bogolyubov problem by using the Cartesian deformed harmonic-oscillator basis. In the new version, all symmetries can be broken, which allows for calculations with angular frequency and angular momentum tilted with respect to the mass distribution. The new version contains an interface to the LAPACK subroutine ZHPEVX. Program summaryTitle of the program:HFODD (v2.08i) Catalogue number: ADTO Program obtainable from: CPC Program Library, Queen's University of Belfast, N. Ireland Program summary URL:http://cpc.cs.qub.ac.uk/summaries/ADTO Reference in CPC for earlier version of program: J. Dobaczewski and J. Dudek, Comput. Phys. Commun. 131 (2000) 164 (v1.75r) Catalogue number of previous version: ADML Licensing provisions: none Does the new version supersede the previous one: yes Computers on which the program has been tested: SG Power Challenge L, Pentium-II, Pentium-III, AMD-Athlon Operating systems: UNIX, LINUX, Windows-2000 Programming language used: FORTRAN-77 and FORTRAN-90 Memory required to execute with typical data: 10 Mwords No. of bits in a word: The code is written in single-precision for the use on a 64-bit processor. The compiler option -r8 or +autodblpad (or equivalent) has to be used to promote all real and complex single-precision floating-point items to double precision when the code is used on a 32-bit machine. Has the code been vectorised?: Yes No. of bytes in distributed program, including test data, etc.: 265352 No. of lines in distributed program: 52656 Distribution format: tar gzip file Nature of physical problem: The nuclear mean-field and an analysis of its symmetries in realistic cases are the main ingredients of a description of nuclear states. Within the Local Density Approximation, or for a zero-range velocity-dependent Skyrme interaction, the nuclear mean-field is local and velocity dependent. The locality allows for an effective and fast solution of the self-consistent Hartree-Fock equations, even for heavy nuclei, and for various nucleonic (n-particle n-hole) configurations, deformations, excitation energies, or angular momenta. Similar Local Density Approximation in the particle-particle channel, which is equivalent to using a zero-range interaction, allows for a simple implementation of pairing effects within the Hartree-Fock-Bogolyubov method. Method of solution: The program uses the Cartesian harmonic oscillator basis to expand single-particle or single-quasiparticle wave functions of neutrons and protons interacting by means of the Skyrme effective interaction and zero-range pairing interaction. The expansion coefficients are determined by the iterative diagonalization of the mean field Hamiltonians or Routhians which depend non-linearly on the local neutron and proton densities. Suitable constraints are used to obtain states corresponding to a given configuration, deformation or angular momentum. The method of solution has been presented in: J. Dobaczewski, J. Dudek, Comput. Phys. Commun. 102 (1997) 166. Summary of revisions:Two insignificant errors have been corrected. Breaking of all the three plane-reflection symmetries has been implemented. Breaking of all the three time-reversal×plane-reflection symmetries has been implemented. Conservation of parity with simultaneously broken simplex has been implemented. Tilted-axis cranking has been implemented. Cranking with isovector angular frequency has been implemented. Quadratic constraint on tilted angular momentum has been added. Constraint on the vector product of angular frequency and angular momentum has been added. Calculation of surface multipole moments has been added. Constraints on surface multipole moments have been added. Calculation of magnetic moments has been added. Calculation of multipole and surface multipole moments in the center-of-mass reference frame has been added. Calculation of multipole, surface multipole, and magnetic moments in the principal-axes (intrinsic) reference frame has been added. Calculation of angular momenta in the center-of-mass and principal-axes reference frames has been added. New single-particle observables for a diabatic blocking have been added. Solution of the Hartree-Fock-Bogolyubov equations has been implemented. Non-standard spin-orbit energy density has been implemented. Non-standard center-of-mass corrections have been implemented. Definition of the time-odd terms through the Landau parameters has been implemented. Definition of Skyrme forces taken from the literature now includes the force parameters as well as the value of the nucleon mass and the treatment of tensor, spin-orbit, and center-of-mass terms specific to the given force. Interface to the LAPACK subroutine ZHPEVX has been implemented. Computer memory management has been improved by implementing the memory-allocation features available within FORTRAN-90. Restrictions on the complexity of the problem: The main restriction is the CPU time required for calculations of heavy deformed nuclei and for a given precision required. Pairing correlations are only included for even-even nuclei and conserved simplex symmetry. Typical running time: One Hartree-Fock iteration for the superdeformed, rotating, parity conserving state of 15266Dy 86 takes about six seconds on the AMD-Athlon 1600+ processor. Starting from the Woods-Saxon wave functions, about fifty iterations are required to obtain the energy converged within the precision of about 0.1 keV. In case when every value of the angular velocity is converged separately, the complete superdeformed band with precisely determined dynamical moments J(2) can be obtained within forty minutes of CPU on the AMD-Athlon 1600+ processor. This time can be often reduced by a factor of three when a self-consistent solution for a given rotational frequency is used as a starting point for a neighboring rotational frequency. Unusual features of the program: The user must have an access to the NAGLIB subroutine F02AXE, or to the LAPACK subroutines ZHPEV or ZHPEVX, which diagonalize complex hermitian matrices, or provide another subroutine which can perform such a task. The LAPACK subroutines ZHPEV and ZHPEVX can be obtained from the Netlib Repository at University of Tennessee, Knoxville: http://netlib2.cs.utk.edu/cgi-bin/netlibfiles.pl?filename=/lapack/complex16/zhpev.f and http://netlib2.cs.utk.edu/cgi-bin/netlibfiles.pl?filename=/lapack/complex16/zhpevx.f respectively.

A Fortran 90 Hartree-Fock program for one-dimensional periodic π-conjugated systems using Pariser-Parr-Pople model

NASA Astrophysics Data System (ADS)

Kondayya, Gundra; Shukla, Alok

2012-03-01

Pariser-Parr-Pople (P-P-P) model Hamiltonian is employed frequently to study the electronic structure and optical properties of π-conjugated systems. In this paper we describe a Fortran 90 computer program which uses the P-P-P model Hamiltonian to solve the Hartree-Fock (HF) equation for infinitely long, one-dimensional, periodic, π-electron systems. The code is capable of computing the band structure, as also the linear optical absorption spectrum, by using the tight-binding and the HF methods. Furthermore, using our program the user can solve the HF equation in the presence of a finite external electric field, thereby, allowing the simulation of gated systems. We apply our code to compute various properties of polymers such as trans-polyacetylene, poly- para-phenylene, and armchair and zigzag graphene nanoribbons, in the infinite length limit. Program summaryProgram title: ppp_bulk.x Catalogue identifier: AEKW_v1_0 Program summary URL:http://cpc.cs.qub.ac.uk/summaries/AEKW_v1_0.html Program obtainable from: CPC Program Library, Queen's University, Belfast, N. Ireland Licensing provisions: Standard CPC licence, http://cpc.cs.qub.ac.uk/licence/licence.html No. of lines in distributed program, including test data, etc.: 87 464 No. of bytes in distributed program, including test data, etc.: 2 046 933 Distribution format: tar.gz Programming language: Fortran 90 Computer: PCs and workstations Operating system: Linux, Code was developed and tested on various recent versions of 64-bit Fedora including Fedora 14 (kernel version 2.6.35.12-90). Classification: 7.3 External routines: This program needs to link with LAPACK/BLAS libraries compiled with the same compiler as the program. For the Intel Fortran Compiler we used the ACML library version 4.4.0, while for the gfortran compiler we used the libraries supplied with the Fedora distribution. Nature of problem: The electronic structure of one-dimensional periodic π-conjugated systems is an intense area of research at present because of the tremendous interest in the physics of conjugated polymers and graphene nanoribbons. The computer program described in this paper provides an efficient way of solving the Hartree-Fock equations for such systems within the P-P-P model. In addition to the Bloch orbitals, band structure, and the density of states, the program can also compute quantities such as the linear absorption spectrum, and the electro-absorption spectrum of these systems. Solution method: For a one-dimensional periodic π-conjugated system lying in the xy-plane, the single-particle Bloch orbitals are expressed as linear combinations of p-orbitals of individual atoms. Then using various parameters defining the P-P-P Hamiltonian, the Hartree-Fock equations are set up as a matrix eigenvalue problem in the k-space. Thereby, its solutions are obtained in a self-consistent manner, using the iterative diagonalizing technique at several k points. The band structure and the corresponding Bloch orbitals thus obtained are used to perform a variety of calculations such as the density of states, linear optical absorption spectrum, electro-absorption spectrum, etc. Running time: Most of the examples provided take only a few seconds to run. For a large system, however, depending on the system size, the run time may be a few minutes to a few hours.

Hybrid density functional study of organic magnetic crystals: bi-metallic CrIII cyanides and rhombohedral C60

NASA Astrophysics Data System (ADS)

Chan, J. A.; Montanari, B.; Chan, W. L.; Harrison, N. M.

Periodic hybrid-exchange density functional theory calculations have been used to investigate the magnetic properties of two classes of organic magnets, namely the bi-metallic CrIII cyanides and the polymerized rhombohedral C60 fullerenes (Rh-C60). For the systems KMII[CrIII(CN)6] with M II=V, Mn, Ni and CrIII[CrIII(CN)6], the magnetic ordering energies, Mulliken populations, and spin density plots are reported for the optimized geometries. The qualitative nature of the magnetic coupling mechanism is consistent with that observed in previous unrestricted Hartree-Fock calculations, but the coupling energies computed here are significantly higher. The increased coupling is found to be a result of both changes in the geometry and the electronic structure resulting from the more reliable treatment of electronic exchange and correlation effects. The existence of long-range coupling between local spin moments is investigated in three different defective Rh-C60 structures: (i) a previously proposed prototype structure, where an atom is removed from the C60 cage; (ii) a related structure in which vacancies in nearby cages are brought closer together in pairs; and (iii) a structure where the intra-fullerene bond between the two inter-fullerene bonds is broken spontaneously after applying isotropic pressure to one layer of the Rh-C60 structure. All of these structures are characterized by low flat spin polarized bands at the Fermi edge and localized spin moments around the defects, but no evidence of long-range magnetic coupling is found.

Magnetic susceptibilities of actinide 3d-metal intermetallic compounds

DOE Office of Scientific and Technical Information (OSTI.GOV)

Muniz, R.B.; d'Albuquerque e Castro, J.; Troper, A.

1988-04-15

We have numerically calculated the magnetic susceptibilities which appear in the Hartree--Fock instability criterion for actinide 3d transition-metal intermetallic compounds. This calculation is based on a previous tight-binding description of these actinide-based compounds (A. Troper and A. A. Gomes, Phys. Rev. B 34, 6487 (1986)). The parameters of the calculation, which starts from simple tight-binding d and f bands are (i) occupation numbers, (ii) ratio of d-f hybridization to d bandwidth, and (iii) electron-electron Coulomb-type interactions.

Computation of energy states of hydrogenic quantum dot with two-electrons

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yakar, Y., E-mail: yuyakar@yahoo.com; Özmen, A., E-mail: aozmen@selcuk.edu.tr; Çakır, B., E-mail: bcakir@selcuk.edu.tr

2016-03-25

In this study we have investigated the electronic structure of the hydrogenic quantum dot with two electrons inside an impenetrable potential surface. The energy eigenvalues and wavefunctions of the ground and excited states of spherical quantum dot have been calculated by using the Quantum Genetic Algorithm (QGA) and Hartree-Fock Roothaan (HFR) method, and the energies are investigated as a function of dot radius. The results show that as dot radius increases, the energy of quantum dot decreases.

Continuous opacity from Ne^-

NASA Astrophysics Data System (ADS)

John, T. L.

1996-04-01

Free-free absorption coefficients of the negative neon ion are calculated by the phase-shift approximation based on multiconfiguration Hartree-Fock continuum wave functions. These wave functions accurately account for electron-neon correlation and polarization, and yield scattering cross-sections in excellent agreement with the latest experimental values. The coefficients are expected to give the best current estimates of Ne^- continuous absorption. We find that Ne^- makes only a small contribution (less than 0.3 per cent) to stellar opacities, including hydrogen-deficient stars with enhanced Ne abundances.

An Extension of the Krieger-Li-Iafrate Approximation to the Optimized-Effective-Potential Method

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wilson, B.G.

1999-11-11

The Krieger-Li-Iafrate approximation can be expressed as the zeroth order result of an unstable iterative method for solving the integral equation form of the optimized-effective-potential method. By pre-conditioning the iterate a first order correction can be obtained which recovers the bulk of quantal oscillations missing in the zeroth order approximation. A comparison of calculated total energies are given with Krieger-Li-Iafrate, Local Density Functional, and Hyper-Hartree-Fock results for non-relativistic atoms and ions.

Trial densities for the extended Thomas-Fermi model

NASA Astrophysics Data System (ADS)

Yu, An; Jimin, Hu

1996-02-01

A new and simplified form of nuclear densities is proposed for the extended Thomas-Fermi method (ETF) and applied to calculate the ground-state properties of several spherical nuclei, with results comparable or even better than other conventional density profiles. With the expectation value method (EVM) for microscopic corrections we checked our new densities for spherical nuclei. The binding energies of ground states almost reproduce the Hartree-Fock (HF) calculations exactly. Further applications to nuclei far away from the β-stability line are discussed.

International Conference on Quantum Chemical Calculations of NMR and EPR Parameters Held in Castle Smolenice, Slovak Republic on September 14-18 1998

DTIC Science & Technology

1998-10-21

site. The electric-field- induced linear shift is also observed in the hyperfine splitting of nuclear quadrupole resonance ( NQR ) spectrum of a nucleus...located at a noncentrosymmetric site in a molecule or in crystal lattice. Thus, the linear electric field effect on the ESR and NQR hyperfine splitting...the electric field effects on ESR and NQR hyperfine couplings. Theoretical methods to calculate the electric field effects within Hartree-Fock

Semiclassical perturbation Stark widths of singly charged argon spectral lines

NASA Astrophysics Data System (ADS)

Hamdi, Rafik; Ben Nessib, Nabil; Sahal-Bréchot, Sylvie; Dimitrijević, Milan S.

2018-03-01

Using a semiclassical perturbation approach with the impact approximation, Stark widths for singly charged argon (Ar II) spectral lines have been calculated. Energy levels and oscillator strengths needed for this calculation have been determined using the Hartree-Fock method with relativistic corrections. Our Stark widths are compared with experimental results for 178 spectral lines. Our results may be of interest not only for laboratory plasma, lasers and technological plasmas but also for white dwarfs and A- and B-type stars.

Photoionization cross sections for atomic chlorine using an open-shell random phase approximation

NASA Technical Reports Server (NTRS)

Starace, A. F.; Armstrong, L., Jr.

1975-01-01

The use of the Random Phase Approximation with Exchange (RPAE) for calculating partial and total photoionization cross sections and photoelectron angular distributions for open shell atoms is examined for atomic chlorine. Whereas the RPAE corrections in argon (Z=18) are large, it is found that those in chlorine (Z=17) are much smaller due to geometric factors. Hartree-Fock calculations with and without core relaxation are also presented. Sizable deviations from the close coupling results of Conneely are also found.

Theoretical description of the 2A/double prime/ and 2A/prime/ states of the peroxyformyl radical. [for air pollution and Mars atmospheric studies

NASA Technical Reports Server (NTRS)

Winter, N. W.; Goddard, W. A., III; Bender, C. F.

1975-01-01

Simple orbital ideas are used to describe the lowest two states of the peroxyformyl radical, and ab initio Hartree-Fock calculations in these states are reported. It is found that both states may be formed exothermically by association of O2 and HCO in their ground states; however, the excited state may decompose readily to OH and CO2. The possible role of such processes in oxidation of aldelydes is discussed.

Adaptation of the projector-augmented-wave formalism to the treatment of orbital-dependent exchange-correlation functionals

NASA Astrophysics Data System (ADS)

Xu, Xiao; Holzwarth, N. A. W.

2011-10-01

This paper presents the formulation and numerical implementation of a self-consistent treatment of orbital-dependent exchange-correlation functionals within the projector-augmented-wave method of Blöchl [Phys. Rev. BPRBMDO1098-012110.1103/PhysRevB.50.17953 50, 17953 (1994)] for electronic structure calculations. The methodology is illustrated with binding energy curves for C in the diamond structure and LiF in the rock salt structure, by comparing results from the Hartree-Fock (HF) formalism and the optimized effective potential formalism in the so-called KLI approximation [Krieger, Li, and Iafrate, Phys. Rev. APLRAAN1050-294710.1103/PhysRevA.45.101 45, 101 (1992)] with those of the local density approximation. While the work here uses pure Fock exchange only, the formalism can be extended to treat orbital-dependent functionals more generally.

The positronium and the dipositronium in a Hartree-Fock approximation of quantum electrodynamics

NASA Astrophysics Data System (ADS)

Sok, Jérémy

2016-02-01

The Bogoliubov-Dirac-Fock (BDF) model is a no-photon approximation of quantum electrodynamics. It allows to study relativistic electrons in interaction with the Dirac sea. A state is fully characterized by its one-body density matrix, an infinite rank non-negative projector. We prove the existence of the para-positronium, the bound state of an electron and a positron with antiparallel spins, in the BDF model represented by a critical point of the energy functional in the absence of an external field. We also prove the existence of the dipositronium, a molecule made of two electrons and two positrons that also appears as a critical point. More generally, for any half integer j ∈ 1/2 + Z + , we prove the existence of a critical point of the energy functional made of 2j + 1 electrons and 2j + 1 positrons.

Theoretical investigation of gas-surface interactions

NASA Technical Reports Server (NTRS)

Dyall, Kenneth G.

1990-01-01

A Dirac-Hartree-Fock code was developed for polyatomic molecules. The program uses integrals over symmetry-adapted real spherical harmonic Gaussian basis functions generated by a modification of the MOLECULE integrals program. A single Gaussian function is used for the nuclear charge distribution, to ensure proper boundary conditions at the nuclei. The Gaussian primitive functions are chosen to satisfy the kinetic balance condition. However, contracted functions which do not necessarily satisfy this condition may be used. The Fock matrix is constructed in the scalar basis and transformed to a jj-coupled 2-spinor basis before diagonalization. The program was tested against numerical results for atoms with a Gaussian nucleus and diatomic molecules with point nuclei. The energies converge on the numerical values as the basis set size is increased. Full use of molecular symmetry (restricted to D sub 2h and subgroups) is yet to be implemented.

Solution of the Skyrme-Hartree-Fock-Bogolyubov equations in the Cartesian deformed harmonic-oscillator basis.. (VI) HFODD (v2.40h): A new version of the program

NASA Astrophysics Data System (ADS)

Dobaczewski, J.; Satuła, W.; Carlsson, B. G.; Engel, J.; Olbratowski, P.; Powałowski, P.; Sadziak, M.; Sarich, J.; Schunck, N.; Staszczak, A.; Stoitsov, M.; Zalewski, M.; Zduńczuk, H.

2009-11-01

We describe the new version (v2.40h) of the code HFODD which solves the nuclear Skyrme-Hartree-Fock or Skyrme-Hartree-Fock-Bogolyubov problem by using the Cartesian deformed harmonic-oscillator basis. In the new version, we have implemented: (i) projection on good angular momentum (for the Hartree-Fock states), (ii) calculation of the GCM kernels, (iii) calculation of matrix elements of the Yukawa interaction, (iv) the BCS solutions for state-dependent pairing gaps, (v) the HFB solutions for broken simplex symmetry, (vi) calculation of Bohr deformation parameters, (vii) constraints on the Schiff moments and scalar multipole moments, (viii) the DT2h transformations and rotations of wave functions, (ix) quasiparticle blocking for the HFB solutions in odd and odd-odd nuclei, (x) the Broyden method to accelerate the convergence, (xi) the Lipkin-Nogami method to treat pairing correlations, (xii) the exact Coulomb exchange term, (xiii) several utility options, and we have corrected three insignificant errors. New version program summaryProgram title: HFODD (v2.40h) Catalogue identifier: ADFL_v2_2 Program summary URL:http://cpc.cs.qub.ac.uk/summaries/ADFL_v2_2.html Program obtainable from: CPC Program Library, Queen's University, Belfast, N. Ireland Licensing provisions: Standard CPC licence, http://cpc.cs.qub.ac.uk/licence/licence.html No. of lines in distributed program, including test data, etc.: 79 618 No. of bytes in distributed program, including test data, etc.: 372 548 Distribution format: tar.gz Programming language: FORTRAN-77 and Fortran-90 Computer: Pentium-III, AMD-Athlon, AMD-Opteron Operating system: UNIX, LINUX, Windows XP Has the code been vectorised or parallelized?: Yes, vectorised RAM: 10 Mwords Word size: The code is written in single-precision for use on a 64-bit processor. The compiler option -r8 or +autodblpad (or equivalent) has to be used to promote all real and complex single-precision floating-point items to double precision when the code is used on a 32-bit machine. Classification: 17.22 Catalogue identifier of previous version: ADFL_v2_1 Journal reference of previous version: Comput. Phys. Commun. 167 (2005) 214 External routines: Lapack (http://www.netlib.org/lapack/), Blas (http://www.netlib.org), linpack (http://www.netlib/linpack/) Does the new version supersede the previous version?: Yes Nature of problem: The nuclear mean-field and an analysis of its symmetries in realistic cases are the main ingredients of a description of nuclear states. Within the Local Density Approximation, or for a zero-range velocity-dependent Skyrme interaction, the nuclear mean-field is local and velocity dependent. The locality allows for an effective and fast solution of the self-consistent Hartree-Fock equations, even for heavy nuclei, and for various nucleonic (n-particle n-hole) configurations, deformations, excitation energies, or angular momenta. Similar Local Density Approximation in the particle-particle channel, which is equivalent to using a zero-range interaction, allows for a simple implementation of pairing effects within the Hartree-Fock-Bogolyubov method. Solution method: The program uses the Cartesian harmonic oscillator basis to expand single-particle or single-quasiparticle wave functions of neutrons and protons interacting by means of the Skyrme effective interaction and zero-range pairing interaction. The expansion coefficients are determined by the iterative diagonalization of the mean field Hamiltonians or Routhians which depend non-linearly on the local neutron and proton densities. Suitable constraints are used to obtain states corresponding to a given configuration, deformation or angular momentum. The method of solution has been presented in [1]. Summary of revisions: Projection on good angular momentum (for the Hartree-Fock states) has been implemented. Calculation of the GCM kernels has been implemented. Calculation of matrix elements of the Yukawa interaction has been implemented. The BCS solutions for state-dependent pairing gaps have been implemented. The HFB solutions for broken simplex symmetry have been implemented. Calculation of Bohr deformation parameters has been implemented. Constraints on the Schiff moments and scalar multipole moments have been implemented. The DT2h transformations and rotations of wave functions have been implemented. The quasiparticle blocking for the HFB solutions in odd and odd-odd nuclei has been implemented. The Broyden method to accelerate the convergence has been implemented. The Lipkin-Nogami method to treat pairing correlations has been implemented. The exact Coulomb exchange term has been implemented. Several utility options have been implemented. Three insignificant errors have been corrected. Restrictions: The main restriction is the CPU time required for calculations of heavy deformed nuclei and for a given precision required. Unusual features: The user must have access to an implementation of the BLAS (Basic Linear Algebra Subroutines), the NAGLIB subroutine F02AXE, or LAPACK subroutines ZHPEV, ZHPEVX, or ZHEEVR, which diagonalize complex Hermitian matrices, and the LINPACK subroutines ZGEDI and ZGECO, which invert arbitrary complex matrices and calculate determinants or provide another set of subroutines that can perform such a tasks. The LAPACK and LINPACK subroutines and an unoptimized version of the BLAS can be obtained from the Netlib Repository at the University of Tennessee, Knoxville: http://www.netlib.org/. Running time: One Hartree-Fock iteration for the superdeformed, rotating, parity conserving state of 15266Dy86 takes about six seconds on the AMD-Athlon 1600+ processor. Starting from the Woods-Saxon wave functions, about fifty iterations are required to obtain the energy converged within the precision of about 0.1 keV. In the case where every value of the angular velocity is converged separately, the complete superdeformed band with precisely determined dynamical moments J (2) can be obtained in forty minutes of CPU time on the AMD-Athlon 1600+ processor. This time can be often reduced by a factor of three when a self-consistent solution for a given rotational frequency is used as a starting point for a neighboring rotational frequency. References: J. Dobaczewski, J. Dudek, Comput. Phys. Commun. 102 (1997) 166.

Importance of dispersion and electron correlation in ab initio protein folding.

PubMed

He, Xiao; Fusti-Molnar, Laszlo; Cui, Guanglei; Merz, Kenneth M

2009-04-16

Dispersion is well-known to be important in biological systems, but the effect of electron correlation in such systems remains unclear. In order to assess the relationship between the structure of a protein and its electron correlation energy, we employed both full system Hartree-Fock (HF) and second-order Møller-Plesset perturbation (MP2) calculations in conjunction with the Polarizable Continuum Model (PCM) on the native structures of two proteins and their corresponding computer-generated decoy sets. Because of the expense of the MP2 calculation, we have utilized the fragment molecular orbital method (FMO) in this study. We show that the sum of the Hartree-Fock (HF) energy and force field (LJ6)-derived dispersion energy (HF + LJ6) is well correlated with the energies obtained using second-order Møller-Plesset perturbation (MP2) theory. In one of the two examples studied, the correlation energy as well as the empirical dispersive energy term was able to discriminate between native and decoy structures. On the other hand, for the second protein we studied, neither the correlation energy nor dispersion energy showed discrimination capabilities; however, the ab initio MP2 energy and the HF+LJ6 both ranked the native structure correctly. Furthermore, when we randomly scrambled the Lennard-Jones parameters, the correlation between the MP2 energy and the sum of the HF energy and dispersive energy (HF+LJ6) significantly drops, which indicates that the choice of Lennard-Jones parameters is important.

Low-lying electric-dipole strengths of Ca, Ni, and Sn isotopes imprinted on total reaction cross sections

NASA Astrophysics Data System (ADS)

Horiuchi, W.; Hatakeyama, S.; Ebata, S.; Suzuki, Y.

2017-08-01

Low-lying electric-dipole (E 1 ) strength of a neutron-rich nucleus contains information on neutron-skin thickness, deformation, and shell evolution. We discuss the possibility of making use of total reaction cross sections on 40Ca, 120Sn, and 208Pb targets to probe the E 1 strength of neutron-rich Ca, Ni, and Sn isotopes. They exhibit large enhancement of the E 1 strength at neutron number N >28 , 50, and 82, respectively, due to a change of the single-particle orbits near the Fermi surface participating in the transitions. The density distributions and the electric-multipole strength functions of those isotopes are calculated by the Hartree-Fock+BCS and the canonical-basis-time-dependent-Hartree-Fock-Bogoliubov methods, respectively, using three kinds of Skyrme-type effective interaction. The nuclear and Coulomb breakup processes are respectively described with the Glauber model and the equivalent photon method in which the effect of finite-charge distribution is taken into account. The three Skyrme interactions give different results for the total reaction cross sections because of different Coulomb breakup contributions. The contribution of the low-lying E 1 strength is amplified when the low-incident energy is chosen. With an appropriate choice of the incident energy and target nucleus, the total reaction cross section can be complementary to the Coulomb excitation for analyzing the low-lying E 1 strength of unstable nuclei.

Theoretical study of the NMR chemical shift of Xe in supercritical condition.

PubMed

Lacerda, Evanildo G; Sauer, Stephan P A; Mikkelsen, Kurt V; Coutinho, Kaline; Canuto, Sylvio

2018-02-20

In this work we investigate the level of theory necessary for reproducing the non-linear variation of the 129 Xe nuclear magnetic resonance (NMR) chemical shift with the density of Xe in supercritical conditions. In detail we study how the 129 Xe chemical shift depends under supercritical conditions on electron correlation, relativistic and many-body effects. The latter are included using a sequential-QM/MM methodology, in which a classical MD simulation is performed first and the chemical shift is then obtained as an average of quantum calculations of 250 MD snapshots conformations carried out for Xe n clusters (n = 2 - 8 depending on the density). The analysis of the relativistic effects is made at the level of 4-component Hartree-Fock calculations (4c-HF) and electron correlation effects are considered using second order Møller-Plesset perturbation theory (MP2). To simplify the calculations of the relativistic and electron correlation effects we adopted an additive scheme, where the calculations on the Xe n clusters are carried out at the non-relativistic Hartree-Fock (HF) level, while electron correlation and relativistic corrections are added for all the pairs of Xe atoms in the clusters. Using this approach we obtain very good agreement with the experimental data, showing that the chemical shift of 129 Xe in supercritical conditions is very well described by cluster calculations at the HF level, with small contributions from relativistic and electron correlation effects.

Efficient exact-exchange time-dependent density-functional theory methods and their relation to time-dependent Hartree-Fock.

PubMed

Hesselmann, Andreas; Görling, Andreas

2011-01-21

A recently introduced time-dependent exact-exchange (TDEXX) method, i.e., a response method based on time-dependent density-functional theory that treats the frequency-dependent exchange kernel exactly, is reformulated. In the reformulated version of the TDEXX method electronic excitation energies can be calculated by solving a linear generalized eigenvalue problem while in the original version of the TDEXX method a laborious frequency iteration is required in the calculation of each excitation energy. The lowest eigenvalues of the new TDEXX eigenvalue equation corresponding to the lowest excitation energies can be efficiently obtained by, e.g., a version of the Davidson algorithm appropriate for generalized eigenvalue problems. Alternatively, with the help of a series expansion of the new TDEXX eigenvalue equation, standard eigensolvers for large regular eigenvalue problems, e.g., the standard Davidson algorithm, can be used to efficiently calculate the lowest excitation energies. With the help of the series expansion as well, the relation between the TDEXX method and time-dependent Hartree-Fock is analyzed. Several ways to take into account correlation in addition to the exact treatment of exchange in the TDEXX method are discussed, e.g., a scaling of the Kohn-Sham eigenvalues, the inclusion of (semi)local approximate correlation potentials, or hybrids of the exact-exchange kernel with kernels within the adiabatic local density approximation. The lowest lying excitations of the molecules ethylene, acetaldehyde, and pyridine are considered as examples.

Structure factors for tunneling ionization rates of molecules: General Hartree-Fock-based integral representation

NASA Astrophysics Data System (ADS)

Madsen, Lars Bojer; Jensen, Frank; Dnestryan, Andrey I.; Tolstikhin, Oleg I.

2017-07-01

In the leading-order approximation of the weak-field asymptotic theory (WFAT), the dependence of the tunneling ionization rate of a molecule in an electric field on its orientation with respect to the field is determined by the structure factor of the ionizing molecular orbital. The WFAT yields an expression for the structure factor in terms of a local property of the orbital in the asymptotic region. However, in general quantum chemistry approaches molecular orbitals are expanded in a Gaussian basis which does not reproduce their asymptotic behavior correctly. This hinders the application of the WFAT to polyatomic molecules, which are attracting increasing interest in strong-field physics. Recently, an integral-equation approach to the WFAT for tunneling ionization of one electron from an arbitrary potential has been developed. The structure factor is expressed in an integral form as a matrix element involving the ionizing orbital. The integral is not sensitive to the asymptotic behavior of the orbital, which resolves the difficulty mentioned above. Here, we extend the integral representation for the structure factor to many-electron systems treated within the Hartree-Fock method and show how it can be implemented on the basis of standard quantum chemistry software packages. We validate the methodology by considering noble-gas atoms and the CO molecule, for which accurate structure factors exist in the literature. We also present benchmark results for CO2 and for NH3 in the pyramidal and planar geometries.

Green Rust Reduction of Chromium Part 2: Comparison of Heterogeneous and Homogeneous Chromate Reduction

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wander, Matthew C.; Schoonen, Martin A.

White and green rusts are the active chemical reagents of buried scrap iron pollutant remediation. In this work, a comparison of the initial electron-transfer step for the reduction of CrO{sub 4}{sup -2} by Fe{sub (aq)}{sup 2+} and Fe(OH){sub 2}(s) is presented. Using hybrid density functional theory and Hartree-Fock cluster calculations for the aqueous reaction, the rate constant for the homogeneous reduction of chromium by ferrous iron was determined to be 5 x 10{sup -2} M{sup -1} s{sup -1} for the initial electron transfer. Using a combination of Hartree-Fock slab and cluster calculations for the heterogeneous reaction, the initial electron transfermore » for the heterogeneous reduction of chromium by ferrous iron was determined to be 1 x 10{sup 2} s{sup -1}. The difference in rates is driven by the respective free energies of reaction: 33.4 vs -653.2 kJ/mol. This computational result is apparently the opposite of what has been observed experimentally, but further analysis suggests that these results are fully convergent with experiment. The experimental heterogeneous rate is limited by surface passivation from slow intersheet electron transfer, while the aqueous reaction may be an autocatalytic heterogeneous reaction involving the iron oxyhydroxide product. As a result, it is possible to produce a clear model of the pollutant reduction reaction sequence for these two reactants.« less

Quantum treatment of protons with the reduced explicitly correlated Hartree-Fock approach

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sirjoosingh, Andrew; Pak, Michael V.; Brorsen, Kurt R.

2015-06-07

The nuclear-electronic orbital (NEO) approach treats select nuclei quantum mechanically on the same level as the electrons and includes nonadiabatic effects between the electrons and the quantum nuclei. The practical implementation of this approach is challenging due to the significance of electron-nucleus dynamical correlation. Herein, we present a general extension of the previously developed reduced NEO explicitly correlated Hartree-Fock (RXCHF) approach, in which only select electronic orbitals are explicitly correlated to each quantum nuclear orbital via Gaussian-type geminal functions. Approximations of the electronic exchange between the geminal-coupled electronic orbitals and the other electronic orbitals are also explored. This general approachmore » enables computationally tractable yet accurate calculations on molecular systems with quantum protons. The RXCHF method is applied to the hydrogen cyanide (HCN) and FHF{sup −} systems, where the proton and all electrons are treated quantum mechanically. For the HCN system, only the two electronic orbitals associated with the CH covalent bond are geminal-coupled to the proton orbital. For the FHF{sup −} system, only the four electronic orbitals associated with the two FH covalent bonds are geminal-coupled to the proton orbital. For both systems, the RXCHF method produces qualitatively accurate nuclear densities, in contrast to mean field-based NEO approaches. The development and implementation of the RXCHF method provide the framework to perform calculations on systems such as proton-coupled electron transfer reactions, where electron-proton nonadiabatic effects are important.« less

Calculation of longitudinal polarizability and second hyperpolarizability of polyacetylene with the coupled perturbed Hartree-Fock/Kohn-Sham scheme: where it is shown how finite oligomer chains tend to the infinite periodic polymer.

PubMed

Lacivita, Valentina; Rèrat, Michel; Orlando, Roberto; Ferrero, Mauro; Dovesi, Roberto

2012-03-21

The longitudinal polarizability, α(xx), and second hyperpolarizability, γ(xxxx), of polyacetylene are evaluated by using the coupled perturbed Hartree-Fock/Kohn-Sham (HF/KS) scheme as implemented in the periodic CRYSTAL code and a split valence type basis set. Four different density functionals, namely local density approximation (LDA) (pure local), Perdew-Becke-Ernzerhof (PBE) (gradient corrected), PBE0, and B3LYP (hybrid), and the Hartree-Fock Hamiltonian are compared. It is shown that very tight computational conditions must be used to obtain well converged results, especially for γ(xxxx), that is, very sensitive to the number of k(->) points in reciprocal space when the band gap is small (as for LDA and PBE), and to the extension of summations of the exact exchange series (HF and hybrids). The band gap in LDA is only 0.01 eV: at least 300 k(->) points are required to obtain well converged total energy and equilibrium geometry, and 1200 for well converged optical properties. Also, the exchange series convergence is related to the band gap. The PBE0 band gap is as small as 1.4 eV and the exchange summation must extend to about 130 Å from the origin cell. Total energy, band gap, equilibrium geometry, polarizability, and second hyperpolarizability of oligomers -(C(2)H(2))(m)-, with m up to 50 (202 atoms), and of the polymer have been compared. It turns out that oligomers of that length provide an extremely poor representation of the infinite chain polarizability and hyperpolarizability when the gap is smaller than 0.2 eV (that is, for LDA and PBE). Huge differences are observed on α(xx) and γ(xxxx) of the polymer when different functionals are used, that is in connection to the well-known density functional theory (DFT) overshoot, reported in the literature about short oligomers: for the infinite model the ratio between LDA (or PBE) and HF becomes even more dramatic (about 500 for α(xx) and 10(10) for γ(xxxx)). On the basis of previous systematic comparisons of results obtained with various approaches including DFT, HF, Moller-Plesset (MP2) and coupled cluster for finite chains, we can argue that, for the infinite chain, the present HF results are the most reliable. © 2012 American Institute of Physics

Nondynamical correlation energy in model molecular systems

NASA Astrophysics Data System (ADS)

Chojnacki, Henryk

The hypersurfaces for the deprotonation processes have been studied at the nonempirical level for H3O+, NH+4, PH+4, and H3S+ cations within their correlation consistent basis set. The potential energy curves were calculated and nondynamical correlation energies analyzed. We have found that the restricted Hartree-Fock wavefunction leads to the improper dissociation limit and, in the three latest cases requires multireference description. We conclude that these systems may be treated as a good models for interpretation of the proton transfer mechanism as well as for testing one-determinantal or multireference cases.

Radiative lifetimes, branching fractions, and oscillator strengths of some levels in Be I

NASA Astrophysics Data System (ADS)

Wang, Xinghao; Quinet, Pascal; Li, Qiu; Yu, Qi; Li, Yongfan; Wang, Qian; Gong, Yimin; Dai, Zhenwen

2018-06-01

Radiative lifetimes of five levels in Be I lying in the energy range 64,506.45-71,160.52 cm-1 were measured by the time-resolved laser-induced fluorescence technique. These new data, together with previously measured radiative lifetimes and two reliable calculated lifetimes, were combined with branching fractions obtained from pseudo-relativistic Hartree-Fock calculations to deduce semi-empirical transition probabilities and oscillator strengths for 90 Be I spectral lines involving upper levels ranging from 42,565.35 to 72,251.27 cm-1.

Polariton biexciton transitions in a ZnSe-based microcavity

NASA Astrophysics Data System (ADS)

Neukirch, U.; Bolton, S. R.; Fromer, N. A.; Sham, L. J.; Chemla, D. S.

2000-06-01

The optical third-order nonlinearity of a ZnSe-based microcavity is investigated by the pump-and-probe method. In the specially designed non-monolithic sample the biexciton binding energy exceeds all damping constants and the normal-mode splitting between exciton and cavity photon. For counter-circular polarized beams the nonlinear response exhibits strong oscillatory structures in the spectral vicinity of the polariton-biexciton transition. Comparison to model calculations shows that in this case the coherent nonlinearity is completely dominated by biexciton-exciton interactions beyond the Hartree-Fock approximation.

Elongation cutoff technique armed with quantum fast multipole method for linear scaling.

PubMed

Korchowiec, Jacek; Lewandowski, Jakub; Makowski, Marcin; Gu, Feng Long; Aoki, Yuriko

2009-11-30

A linear-scaling implementation of the elongation cutoff technique (ELG/C) that speeds up Hartree-Fock (HF) self-consistent field calculations is presented. The cutoff method avoids the known bottleneck of the conventional HF scheme, that is, diagonalization, because it operates within the low dimension subspace of the whole atomic orbital space. The efficiency of ELG/C is illustrated for two model systems. The obtained results indicate that the ELG/C is a very efficient sparse matrix algebra scheme. Copyright 2009 Wiley Periodicals, Inc.

Level Energies, Oscillator Strengths and Lifetimes for Transitions in Pb IV

DOE Office of Scientific and Technical Information (OSTI.GOV)

Colon, C.; Alonso-Medina, A.; Zanon, A.

2008-10-22

Oscillator strengths for several lines of astrophysical interest arising from some configurations and some levels radiative lifetimes of Pb IV have been calculated. These values were obtained in intermediate coupling (IC) and using ab initio relativistic Hartree-Fock calculations. We use for the IC calculations the standard method of least square fitting of experimental energy levels by means of computer codes from Cowan. Transition Probabilities and oscillator strengths obtained, although in general agreement with the rare experimental data, do present some noticeable discrepancies that are studied in the text.

Theoretical studies of possible toroidal high-spin isomers in the light-mass region

DOE PAGES

Staszczak, A.; Wong, Cheuk-Yin

2016-05-11

We review our theoretical knowledge of possible toroidal high-spin isomers in the light mass region in 28≤A≤52 obtained previously in cranked Skyrme-Hartree-Fock calculations. We report additional toroidal high-spin isomers in 56Ni with I=114ℏ and 140ℏ, which follow the same (multi-particle) (multi-hole) systematics as other toroidal high-spin isomers. We examine the production of these exotic nuclei by fusion of various projectiles on 20Ne or 28Si as an active target in time-projection-chamber (TPC) experiments.

Computational Study of the Adsorption of Dimethyl Methylphosphonate (DMMP) on the (010) Surface of Anatase TiO2 With and Without Faceting

DTIC Science & Technology

2009-12-05

surface area of anatase nanocrystals [6] and to be es- pecially active in photocatalysis [7]. Recent work by Dzwigaj et al. [8] has clearly shown that the...two-fold-coordinated (O2c) sites can also be involved in hydrogen bond (H-bond) formation. The effects, on the structure of the (100) and other...To reduce the computational cost , geometry optimization was done at the restricted Hartree Fock (RHF) level. This has previously been shown [36,37

On the semiclassical treatment of hot nuclear systems

NASA Astrophysics Data System (ADS)

Bartel, J.; Brack, M.; Guet, C.; Håkansson, H.-B.

1984-05-01

We discuss two different semiclassical approaches for calculating properties of hot nuclei and compare them to Hartree-Fock calculations using the same effective interaction. Good agreement is found for the entropy and the root-mean square radii as functions of the excitation energy. For a realistic Skyrme force we evaluate the temperature dependence of the free surface, curvature and constant energy coefficients of the liquid drop model, considering a plane interface of condensed symmetric nuclear matter in thermodynamical equilibrium with a nucleon gas. Present address: ASEA-PFBC AB, S-61220 Finspong, Sweden.

Hydrogen atom abstraction from aldehydes - OH + H2CO and O + H2CO

NASA Technical Reports Server (NTRS)

Dupuis, M.; Lester, W. A., Jr.

1984-01-01

The essential features of the potential energy surfaces governing hydrogen abstraction from formaldehyde by oxygen atom and hydroxyl radical have been characterized with ab inito multiconfiguration Hartree-Fock (MCHF) and configuration interaction (CI) wave functions. The results are consistent with a very small activation energy for the OH + H2CO reaction, and an activation energy of a few kcal/mol for the O + H2CO reaction. In the transition state structure of both systems, the attacking oxygen atom is nearly collinear with the attacked CH bond.

Hole transport in pure and doped hematite

NASA Astrophysics Data System (ADS)

Liao, Peilin; Carter, Emily A.

2012-07-01

Hematite (α-Fe2O3) is a promising candidate for use in photovoltaic (PV) and photoelectrochemical devices. Its poor conductivity is one major drawback. Doping hematite either p-type or n-type greatly enhances its measured conductivity and is required for potential p-n junctions in PVs. Here, we study hole transport in pure and doped hematite using an electrostatically embedded cluster model with ab initio quantum mechanics (unrestricted Hartree-Fock theory). Consistent with previous work, the model suggests that hole hopping is via oxygen anions for pure hematite. The activation energy for hole mobility is predicted to be at least 0.1 eV higher than the activation energy for electron mobility, consistent with the trend observed in experiments. We examine four dopants—magnesium(II), nickel(II), copper(II), and manganese(II/III) in direct cation substitution sites—to gain insight into the mechanism by which conductivity is improved. The activation energies are used to assess qualitative effects of different dopants. The hole carriers are predicted to be attracted to O anions near the dopants. The magnitude of the trapping effect is similar among the four dopants in their +2 oxidation states. The multivalent character of Mn doping facilitates local hole transport around Mn centers via a low-barrier O-Mn-O pathway, which suggests that higher hole mobility can be achieved with increasing Mn doping concentration, especially when a network of these low-barrier pathways is produced. Our results suggest that the experimentally observed conductivity increase in Mg-, Ni-, and Cu-doped p-type hematite is mostly due to an increase in hole carriers rather than improved mobility, and that Mg-, Ni-, and Cu-doping perform similarly, while the conductivity of Mn-doped hematite might be significantly improved in the high doping concentration limit.

Theoretical hyperfine structures of 19F i and 17O i

NASA Astrophysics Data System (ADS)

Aourir, Nouria; Nemouchi, Messaoud; Godefroid, Michel; Jönsson, Per

2018-03-01

Multiconfiguration Hartree-Fock (MCHF) and multiconfiguration Dirac-Hartree-Fock (MCDHF) calculations are performed for the 2 p5P2o , 2 p4(3P ) 3 s 4P , 2 p4(3P ) 3 s 2P , and 2 p4(3P ) 3 p 4So states of 19F i to determine their hyperfine constants. Several computing strategies are considered to investigate electron correlation and relativistic effects. High-order correlation contributions are included in MCHF calculations based on single and double multireference expansions. The largest components of the single reference MCHF wave functions are selected to define the multireference (MR) sets. In this scheme, relativistic corrections are evaluated in the Breit-Pauli approximation. A similar strategy is used for the calculation of MCDHF relativistic wave functions and hyperfine parameters. While correlation and relativistic corrections are found to be rather small for the ground state, we highlight large relativistic effects on the hyperfine constant A3 /2 of 2 p4(3P ) 3 p 4So and, to a lesser extent, on A1 /2 of 2 p4(3P ) 3 s 4P . As expected for such a light system, electron correlation effects dominate over relativity in the calculation of the hyperfine interaction of all other levels considered. We also revisit the hyperfine constants of 2 p3(4S ) 3 s S5o and 2 p3(4S ) 3 p 5P in 17O using similar strategies. The results are found to be in excellent agreement with experiment.

A Hartree-Fock Application Using UPC++ and the New DArray Library

DOE PAGES

Ozog, David; Kamil, Amir; Zheng, Yili; ...

2016-07-21

The Hartree-Fock (HF) method is the fundamental first step for incorporating quantum mechanics into many-electron simulations of atoms and molecules, and it is an important component of computational chemistry toolkits like NWChem. The GTFock code is an HF implementation that, while it does not have all the features in NWChem, represents crucial algorithmic advances that reduce communication and improve load balance by doing an up-front static partitioning of tasks, followed by work stealing whenever necessary. To enable innovations in algorithms and exploit next generation exascale systems, it is crucial to support quantum chemistry codes using expressive and convenient programming modelsmore » and runtime systems that are also efficient and scalable. Here, this paper presents an HF implementation similar to GTFock using UPC++, a partitioned global address space model that includes flexible communication, asynchronous remote computation, and a powerful multidimensional array library. UPC++ offers runtime features that are useful for HF such as active messages, a rich calculus for array operations, hardware-supported fetch-and-add, and functions for ensuring asynchronous runtime progress. We present a new distributed array abstraction, DArray, that is convenient for the kinds of random-access array updates and linear algebra operations on block-distributed arrays with irregular data ownership. Finally, we analyze the performance of atomic fetch-and-add operations (relevant for load balancing) and runtime attentiveness, then compare various techniques and optimizations for each. Our optimized implementation of HF using UPC++ and the DArrays library shows up to 20% improvement over GTFock with Global Arrays at scales up to 24,000 cores.« less

Microscopically based energy density functionals for nuclei using the density matrix expansion: Implementation and pre-optimization

NASA Astrophysics Data System (ADS)

Stoitsov, M.; Kortelainen, M.; Bogner, S. K.; Duguet, T.; Furnstahl, R. J.; Gebremariam, B.; Schunck, N.

2010-11-01

In a recent series of articles, Gebremariam, Bogner, and Duguet derived a microscopically based nuclear energy density functional by applying the density matrix expansion (DME) to the Hartree-Fock energy obtained from chiral effective field theory two- and three-nucleon interactions. Owing to the structure of the chiral interactions, each coupling in the DME functional is given as the sum of a coupling constant arising from zero-range contact interactions and a coupling function of the density arising from the finite-range pion exchanges. Because the contact contributions have essentially the same structure as those entering empirical Skyrme functionals, a microscopically guided Skyrme phenomenology has been suggested in which the contact terms in the DME functional are released for optimization to finite-density observables to capture short-range correlation energy contributions from beyond Hartree-Fock. The present article is the first attempt to assess the ability of the newly suggested DME functional, which has a much richer set of density dependencies than traditional Skyrme functionals, to generate sensible and stable results for nuclear applications. The results of the first proof-of-principle calculations are given, and numerous practical issues related to the implementation of the new functional in existing Skyrme codes are discussed. Using a restricted singular value decomposition optimization procedure, it is found that the new DME functional gives numerically stable results and exhibits a small but systematic reduction of our test χ2 function compared to standard Skyrme functionals, thus justifying its suitability for future global optimizations and large-scale calculations.

The molecular structure and vibrational spectra of N-(2,2-diphenylacetyl)- N'-(naphthalen-1yl)-thiourea by Hartree-Fock and density functional methods

NASA Astrophysics Data System (ADS)

Arslan, Hakan; Mansuroglu, Demet Sezgin; VanDerveer, Don; Binzet, Gun

2009-04-01

N-(2,2-Diphenylacetyl)- N'-(naphthalen-1yl)-thiourea (PANT) has been synthesized and characterized by elemental analysis, IR spectroscopy and 1H NMR spectroscopy. The crystal and molecular structure of the title compound has been determined from single crystal X-ray diffraction data. It crystallizes in the triclinic space group P-1, Z = 2 with a = 10.284(2) Å, b = 10.790(2) Å, c = 11.305(2) Å, α = 64.92(3)°, β = 89.88(3)°, γ = 62.99(3)°, V = 983.7(3) Å 3 and Dcalc = 1.339 Mg/m 3. The molecular structure, vibrational frequencies and infrared intensities of PANT were calculated by the Hartree-Fock and density functional theory methods (BLYP and B3LYP) using the 6-31G* basis set. The calculated geometric parameters were compared to the corresponding X-ray structure of the title compound. We obtained 22 stable conformers for the title compound; however Conformer 1 is approximately 9.53 kcal/mol more stable than Conformer 22. The comparison of the theoretical and experimental geometry of the title compound shows that the X-ray parameters fairly well reproduce the geometry of Conformer 17. The harmonic vibrations computed for this compound by the B3LYP/6-31G* method are in good agreement with the observed IR spectral data. Theoretical vibrational spectra of the title compound were interpreted by means of PEDs using the VEDA 4 program. A general better performance of the investigated methods was calculated by PAVF 1.0 program.

A Hartree-Fock Application Using UPC++ and the New DArray Library

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ozog, David; Kamil, Amir; Zheng, Yili

The Hartree-Fock (HF) method is the fundamental first step for incorporating quantum mechanics into many-electron simulations of atoms and molecules, and it is an important component of computational chemistry toolkits like NWChem. The GTFock code is an HF implementation that, while it does not have all the features in NWChem, represents crucial algorithmic advances that reduce communication and improve load balance by doing an up-front static partitioning of tasks, followed by work stealing whenever necessary. To enable innovations in algorithms and exploit next generation exascale systems, it is crucial to support quantum chemistry codes using expressive and convenient programming modelsmore » and runtime systems that are also efficient and scalable. Here, this paper presents an HF implementation similar to GTFock using UPC++, a partitioned global address space model that includes flexible communication, asynchronous remote computation, and a powerful multidimensional array library. UPC++ offers runtime features that are useful for HF such as active messages, a rich calculus for array operations, hardware-supported fetch-and-add, and functions for ensuring asynchronous runtime progress. We present a new distributed array abstraction, DArray, that is convenient for the kinds of random-access array updates and linear algebra operations on block-distributed arrays with irregular data ownership. Finally, we analyze the performance of atomic fetch-and-add operations (relevant for load balancing) and runtime attentiveness, then compare various techniques and optimizations for each. Our optimized implementation of HF using UPC++ and the DArrays library shows up to 20% improvement over GTFock with Global Arrays at scales up to 24,000 cores.« less

On the photoisomerization of 5-hydroxytropolone: An ab initio and nuclear wave function study

NASA Astrophysics Data System (ADS)

Paz, Juan J.; Moreno, Miquel; Lluch, José M.

1997-10-01

In this paper we perform ab initio calculations for the stable conformations and the transition states for the isomerization processes in 5-hydroxytropolone in both the ground (S0) and first excited (S1) singlet electronic states. The Hartree-Fock self-consistent field (SCF) level and a complete active space SCF (CASSCF) level for S0 are considered, whereas the configuration interaction all single excitation method (CIS) and the CASSCF levels are used to deal with the S1 state. Energies are reevaluated at all levels through perturbation theory up to second order: Møller-Plesset for the Hartree-Fock and CIS methods, and the CASPT2 method for CAS results. The ab initio results are then used to perform different monodimensional fits to the potential energy surfaces in order to analyze the wave functions for the nuclear motions in both electronic states. Our best results predict that for the S0 state two stable conformers, syn and anti, can exist in thermal equilibrium. In accordance with experimental expectations the syn isomer is the most stable. As for the S1 state, and again in accord with experimental spectroscopical data, the order of stability reverses, the anti being the most stable. A more interesting result is that analysis of the nuclear wave functions shows an important syn-anti mixing in the S1 state that does not appear in S0. This result explains the appearance of syn-anti and anti-syn crossover transitions observed in the electronic spectra of 5-hydroxytropolone so that syn-anti reaction may take place through photoisomerization.

The adsorption of argon on ZnO at 77K

NASA Astrophysics Data System (ADS)

Marinelli, Francis; Grillet, Yves; Pellenq, Roland J.-M.

We have studied the adsorption of argon onto ZnO surfaces at 77K by means of quasiequilibrium adsorption volumetry coupled with high resolution microcalorimetry and Grand Canonical Monte-Carlo (GCMC) simulations. The adsorbate/surface adsorption potential function (PN type) used in the simulations, was determined on the basis of ab initio calculations (corrected for dispersion interactions). The first aspect of this work was to test the ability of a standard solid-state Hartree-Fock technique coupled with a perturbative semiempirical approach in deriving a reliable adsorption potential function. The dispersion part of the adsorbate/surface interatomic potential was derived by using perturbation theory-based equations while the repulsive and induction interactions were derived from periodic HartreeFock (CRYSTAL92) calculations. GCMC simulations based on this adsorption potential allow one to calculate adsorption isotherms and isosteric heat versus loading curves as well as singlet distribution functions at 77K for each type of ZnO (neutral and polar) faces. The combined analysis of the simulation data for all surfaces gives a good insight of the adsorption mechanism of argon onto ZnO surfaces at 77K in agreement with experiment. As far as neutral surfaces are concerned, it is shown that adsorption first takes place within the 'troughs' which cover ZnO neutral surfaces. At low chemical potentials, these semi-channels are preferential adsorption sites in which we could detect a nearly one-dimensional adsorbate freezing in a commensurate phase at 77K. The polar O faces are the most favourable surfaces for adsorption at higher chemical potentials.

Semiempirical UNO-CAS and UNO-CI: method and applications in nanoelectronics.

PubMed

Dral, Pavlo O; Clark, Timothy

2011-10-20

Unrestricted Natural Orbital-Complete Active Space Configuration Interaction, abbreviated as UNO-CAS, has been implemented for NDDO-based semiempirical molecular-orbital (MO) theory. A computationally more economic technique, UNO-CIS, in which we use a configuration interaction (CI) calculation with only single excitations (CIS) to calculate excited states, has also been implemented and tested. The class of techniques in which unrestricted natural orbitals (UNOs) are used as the reference for CI calculations is denoted UNO-CI. Semiempirical UNO-CI gives good results for the optical band gaps of organic semiconductors such as polyynes and polyacenes, which are promising materials for nanoelectronics. The results of these semiempirical UNO-CI techniques are generally in better agreement with experiment than those obtained with the corresponding conventional semiempirical CI methods and comparable to or better than those obtained with far more computationally expensive methods such as time-dependent density-functional theory. We also show that symmetry breaking in semiempirical UHF calculations is very useful for predicting the diradical character of organic compounds in the singlet spin state.

Density functional study of intramolecular ferromagnetic interaction through m-phenylene coupling unit (I): UBLYP, UB3LYP, and UHF calculations

NASA Astrophysics Data System (ADS)

Mitani, Masaki; Mori, Hiroki; Takano, Yu; Yamaki, Daisuke; Yoshioka, Yasunori; Yamaguchi, Kizashi

2000-09-01

Polyradicals comprised of m-phenylene-bridged organic radicals are well known as building blocks of organic ferromagnets, in which radical groups are connected with each other at the meta position in the benzene ring, and the parallel-spin configurations between radical sites are more stabilized than the antiparallel ones. Topological rules for spin alignments enable us to design organic high-spin dendrimers and polymers with the ferromagnetic ground states by linking various radical species through an m-phenylene unit. However, no systematic ab initio treatment of such spin dendrimers and magnetic polymers has been reported until now, though experimental studies on these materials have been performed extensively in the past ten years. As a first step to examine the possibilities of ferromagnetic dendrimers and polymers constructed of m-phenylene units with organic radicals, we report density functional and molecular orbital calculations of six m-phenylene biradical units with radical substituents and polycarbenes linked with an m-phenylene-type network. The relative stability between the spin states and spin density population are estimated by BLYP or B3LYP and Hartree-Fock calculations in order to clarify their utility for constructions of large spin denderimers and periodic magnetic polymers, which are final targets in this series of papers. It is shown that neutral polyradicals with an m-phenylene bridge are predicted as high-spin ground-state molecules by the computations, while m-phenylene-bridged ion-radical species formed by doping may have the low-spin ground states if zwitterionic configurations play significant roles to stabilize low-spin states. Ab initio computations also show an important role of conformations of polyradicals for stabilization of their high-spin states. The computational results are applied to molecular design of high-spin dendrimers and polymers. Implications of them are also discussed in relation to recent experimental results for high-spin organic molecules.

The nuclear electric quadrupole moment of antimony from the molecular method.

PubMed

Haiduke, Roberto L A; da Silva, Albérico B F; Visscher, Lucas

2006-08-14

Relativistic Dirac-Coulomb (DC) Hartree-Fock calculations are employed to obtain the analytic electric field gradient (EFG) on the antimony nucleus in the SbN, SbP, SbF, and SbCl molecules. The electronic correlation contribution to the EFGs is included with the DC-CCSD(T) and DC-CCSD-T approaches, also in the four-component framework, using a finite-difference method. The total EFG results, along with the experimental nuclear quadrupole coupling constants from microwave spectroscopy, allow to derive the nuclear quadrupole moments of (121)Sb and (123)Sb, respectively, as -543(11) and -692(14) mb.

Medium-heavy nuclei from nucleon-nucleon interactions in lattice QCD

NASA Astrophysics Data System (ADS)

Inoue, Takashi; Aoki, Sinya; Charron, Bruno; Doi, Takumi; Hatsuda, Tetsuo; Ikeda, Yoichi; Ishii, Noriyoshi; Murano, Keiko; Nemura, Hidekatsu; Sasaki, Kenji; HAL QCD Collaboration

2015-01-01

On the basis of the Brueckner-Hartree-Fock method with the nucleon-nucleon forces obtained from lattice QCD simulations, the properties of the medium-heavy doubly magic nuclei such as 16O and 40Ca are investigated. We found that those nuclei are bound for the pseudoscalar meson mass MPS≃470 MeV. The mass number dependence of the binding energies, single-particle spectra, and density distributions are qualitatively consistent with those expected from empirical data at the physical point, although these hypothetical nuclei at heavy quark mass have smaller binding energies than the real nuclei.

Screened hybrid density functionals for solid-state chemistry and physics.

PubMed

Janesko, Benjamin G; Henderson, Thomas M; Scuseria, Gustavo E

2009-01-21

Density functional theory incorporating hybrid exchange-correlation functionals has been extraordinarily successful in providing accurate, computationally tractable treatments of molecular properties. However, conventional hybrid functionals can be problematic for solids. Their nonlocal, Hartree-Fock-like exchange term decays slowly and incorporates unphysical features in metals and narrow-bandgap semiconductors. This article provides an overview of our group's work on designing hybrid functionals for solids. We focus on the Heyd-Scuseria-Ernzerhof screened hybrid functional [J. Chem. Phys. 2003, 118, 8207], its applications to the chemistry and physics of solids and surfaces, and our efforts to build upon its successes.

On the way to a microscopic derivation of covariant density functionals in nuclei

NASA Astrophysics Data System (ADS)

Ring, Peter

2018-02-01

Several methods are discussed to derive covariant density functionals from the microscopic input of bare nuclear forces. In a first step there are semi-microscopic functionals, which are fitted to ab-initio calculations of nuclear matter and depend in addition on very few phenomenological parameters. They are able to describe nuclear properties with the same precision as fully phenomenological functionals. In a second step we present first relativistic Brueckner-Hartree-Fock calculations in finite nuclei in order to study properties of such functionals, which cannot be obtained from nuclear matter calculations.

Assessment of interaction-strength interpolation formulas for gold and silver clusters

NASA Astrophysics Data System (ADS)

Giarrusso, Sara; Gori-Giorgi, Paola; Della Sala, Fabio; Fabiano, Eduardo

2018-04-01

The performance of functionals based on the idea of interpolating between the weak- and the strong-interaction limits the global adiabatic-connection integrand is carefully studied for the challenging case of noble-metal clusters. Different interpolation formulas are considered and various features of this approach are analyzed. It is found that these functionals, when used as a correlation correction to Hartree-Fock, are quite robust for the description of atomization energies, while performing less well for ionization potentials. Future directions that can be envisaged from this study and a previous one on main group chemistry are discussed.

Rotational and vibrational transitions for Li + H2 collisions

NASA Technical Reports Server (NTRS)

Choi, B. H.; Poe, R. T.; Tang, K. T.

1977-01-01

Close coupling calculations for integral and differential cross sections have been carried out for Li + H2 collisions with an ab initio Hartree-Fock potential energy surface. Rotational, vibrational, and vib-rotational excitation cross sections are reported at 0.4336 eV, 0.7 eV, and 0.8673 eV in the center of mass system. For pure rotational excitations, which dominate the inelastic scattering, coupling with vibrational states is not very important. For vibrational transitions, the influence of large multiquantum rotational transitions is far less than that found for Li(+) + H2 collisions.

Communication: An efficient approach to compute state-specific nuclear gradients for a generic state-averaged multi-configuration self consistent field wavefunction.

PubMed

Granovsky, Alexander A

2015-12-21

We present a new, very efficient semi-numerical approach for the computation of state-specific nuclear gradients of a generic state-averaged multi-configuration self consistent field wavefunction. Our approach eliminates the costly coupled-perturbed multi-configuration Hartree-Fock step as well as the associated integral transformation stage. The details of the implementation within the Firefly quantum chemistry package are discussed and several sample applications are given. The new approach is routinely applicable to geometry optimization of molecular systems with 1000+ basis functions using a standalone multi-core workstation.

Towards a formal definition of static and dynamic electronic correlations.

PubMed

Benavides-Riveros, Carlos L; Lathiotakis, Nektarios N; Marques, Miguel A L

2017-05-24

Some of the most spectacular failures of density-functional and Hartree-Fock theories are related to an incorrect description of the so-called static electron correlation. Motivated by recent progress in the N-representability problem of the one-body density matrix for pure states, we propose a method to quantify the static contribution to the electronic correlation. By studying several molecular systems we show that our proposal correlates well with our intuition of static and dynamic electron correlation. Our results bring out the paramount importance of the occupancy of the highest occupied natural spin-orbital in such quantification.

Effects of nitrogenous substituent groups on the benzene dication

NASA Astrophysics Data System (ADS)

Forgy, C. C.; Schlimgen, A. W.; Mazziotti, D. A.

2018-05-01

The benzene dication possesses a pentagonal-pyramidal structure with a hexacoordinated carbon. In contrast, halogenated benzene dications retain a similar structure to their parent molecules. In this work, we report on theoretical studies of the structures of the dications of benzene with nitrogenous substituents. We find that the nitrobenzene dication favours a near ideal pentagonal-pyramidal structure, while the aniline dication favours a flat, hexagonal structure. Reduced-density-matrices methods give predictions in agreement with available ab initio calculations and experiment. These results are also compared with those from the Hartree-Fock method and density functional theory.

Multiconfiguration calculations of electronic isotope shift factors in Al i

NASA Astrophysics Data System (ADS)

Filippin, Livio; Beerwerth, Randolf; Ekman, Jörgen; Fritzsche, Stephan; Godefroid, Michel; Jönsson, Per

2016-12-01

The present work reports results from systematic multiconfiguration Dirac-Hartree-Fock calculations of electronic isotope shift factors for a set of transitions between low-lying levels of neutral aluminium. These electronic quantities together with observed isotope shifts between different pairs of isotopes provide the changes in mean-square charge radii of the atomic nuclei. Two computational approaches are adopted for the estimation of the mass- and field-shift factors. Within these approaches, different models for electron correlation are explored in a systematic way to determine a reliable computational strategy and to estimate theoretical error bars of the isotope shift factors.

Communication: An efficient approach to compute state-specific nuclear gradients for a generic state-averaged multi-configuration self consistent field wavefunction

DOE Office of Scientific and Technical Information (OSTI.GOV)

Granovsky, Alexander A., E-mail: alex.granovsky@gmail.com

We present a new, very efficient semi-numerical approach for the computation of state-specific nuclear gradients of a generic state-averaged multi-configuration self consistent field wavefunction. Our approach eliminates the costly coupled-perturbed multi-configuration Hartree-Fock step as well as the associated integral transformation stage. The details of the implementation within the Firefly quantum chemistry package are discussed and several sample applications are given. The new approach is routinely applicable to geometry optimization of molecular systems with 1000+ basis functions using a standalone multi-core workstation.

Electron correlation within the relativistic no-pair approximation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Almoukhalalati, Adel; Saue, Trond, E-mail: trond.saue@irsamc.ups-tlse.fr; Knecht, Stefan

This paper addresses the definition of correlation energy within 4-component relativistic atomic and molecular calculations. In the nonrelativistic domain the correlation energy is defined as the difference between the exact eigenvalue of the electronic Hamiltonian and the Hartree-Fock energy. In practice, what is reported is the basis set correlation energy, where the “exact” value is provided by a full Configuration Interaction (CI) calculation with some specified one-particle basis. The extension of this definition to the relativistic domain is not straightforward since the corresponding electronic Hamiltonian, the Dirac-Coulomb Hamiltonian, has no bound solutions. Present-day relativistic calculations are carried out within themore » no-pair approximation, where the Dirac-Coulomb Hamiltonian is embedded by projectors eliminating the troublesome negative-energy solutions. Hartree-Fock calculations are carried out with the implicit use of such projectors and only positive-energy orbitals are retained at the correlated level, meaning that the Hartree-Fock projectors are frozen at the correlated level. We argue that the projection operators should be optimized also at the correlated level and that this is possible by full Multiconfigurational Self-Consistent Field (MCSCF) calculations, that is, MCSCF calculations using a no-pair full CI expansion, but including orbital relaxation from the negative-energy orbitals. We show by variational perturbation theory that the MCSCF correlation energy is a pure MP2-like correlation expression, whereas the corresponding CI correlation energy contains an additional relaxation term. We explore numerically our theoretical analysis by carrying out variational and perturbative calculations on the two-electron rare gas atoms with specially tailored basis sets. In particular, we show that the correlation energy obtained by the suggested MCSCF procedure is smaller than the no-pair full CI correlation energy, in accordance with the underlying minmax principle and our theoretical analysis. We also show that the relativistic correlation energy, obtained from no-pair full MCSCF calculations, scales at worst as X{sup −2} with respect to the cardinal number X of our correlation-consistent basis sets optimized for the two-electron atoms. This is better than the X{sup −1} scaling suggested by previous studies, but worse than the X{sup −3} scaling observed in the nonrelativistic domain. The well-known 1/Z- expansion in nonrelativistic atomic theory follows from coordinate scaling. We point out that coordinate scaling for consistency should be accompanied by velocity scaling. In the nonrelativistic domain this comes about automatically, whereas in the relativistic domain an explicit scaling of the speed of light is required. This in turn explains why the relativistic correlation energy to the lowest order is not independent of nuclear charge, in contrast to nonrelativistic theory.« less

Dispersion corrected hartree-fock and density functional theory for organic crystal structure prediction.

PubMed

Brandenburg, Jan Gerit; Grimme, Stefan

2014-01-01

We present and evaluate dispersion corrected Hartree-Fock (HF) and Density Functional Theory (DFT) based quantum chemical methods for organic crystal structure prediction. The necessity of correcting for missing long-range electron correlation, also known as van der Waals (vdW) interaction, is pointed out and some methodological issues such as inclusion of three-body dispersion terms are discussed. One of the most efficient and widely used methods is the semi-classical dispersion correction D3. Its applicability for the calculation of sublimation energies is investigated for the benchmark set X23 consisting of 23 small organic crystals. For PBE-D3 the mean absolute deviation (MAD) is below the estimated experimental uncertainty of 1.3 kcal/mol. For two larger π-systems, the equilibrium crystal geometry is investigated and very good agreement with experimental data is found. Since these calculations are carried out with huge plane-wave basis sets they are rather time consuming and routinely applicable only to systems with less than about 200 atoms in the unit cell. Aiming at crystal structure prediction, which involves screening of many structures, a pre-sorting with faster methods is mandatory. Small, atom-centered basis sets can speed up the computation significantly but they suffer greatly from basis set errors. We present the recently developed geometrical counterpoise correction gCP. It is a fast semi-empirical method which corrects for most of the inter- and intramolecular basis set superposition error. For HF calculations with nearly minimal basis sets, we additionally correct for short-range basis incompleteness. We combine all three terms in the HF-3c denoted scheme which performs very well for the X23 sublimation energies with an MAD of only 1.5 kcal/mol, which is close to the huge basis set DFT-D3 result.

The Dielectric Permittivity of Crystals in the Reduced Hartree-Fock Approximation

NASA Astrophysics Data System (ADS)

Cancès, Éric; Lewin, Mathieu

2010-07-01

In a recent article (Cancès et al. in Commun Math Phys 281:129-177, 2008), we have rigorously derived, by means of bulk limit arguments, a new variational model to describe the electronic ground state of insulating or semiconducting crystals in the presence of local defects. In this so-called reduced Hartree-Fock model, the ground state electronic density matrix is decomposed as {γ = γ^0_per + Q_{ν,\\varepsilon_F}}, where {γ^0_per} is the ground state density matrix of the host crystal and {Q_{ν,\\varepsilon_F}} the modification of the electronic density matrix generated by a modification ν of the nuclear charge of the host crystal, the Fermi level ɛ F being kept fixed. The purpose of the present article is twofold. First, we study in more detail the mathematical properties of the density matrix {Q_{ν,\\varepsilon_F}} (which is known to be a self-adjoint Hilbert-Schmidt operator on {L^2(mathbb{R}^3)}). We show in particular that if {int_{mathbb{R}^3} ν neq 0, Q_{ν,\\varepsilon_F}} is not trace-class. Moreover, the associated density of charge is not in {L^1(mathbb{R}^3)} if the crystal exhibits anisotropic dielectric properties. These results are obtained by analyzing, for a small defect ν, the linear and nonlinear terms of the resolvent expansion of {Q_{ν,\\varepsilon_F}}. Second, we show that, after an appropriate rescaling, the potential generated by the microscopic total charge (nuclear plus electronic contributions) of the crystal in the presence of the defect converges to a homogenized electrostatic potential solution to a Poisson equation involving the macroscopic dielectric permittivity of the crystal. This provides an alternative (and rigorous) derivation of the Adler-Wiser formula.

A poly-epoxy surface explored by Hartree-Fock ΔSCF simulations of C1s XPS spectra

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gavrielides, A.; Duguet, T., E-mail: thomas.duguet@ensiacet.fr, E-mail: Paul.Bagus@unt.edu; Esvan, J.

Whereas poly-epoxy polymers represent a class of materials with a wide range of applications, the structural disorder makes them difficult to model. In the present work, we use good experimental model samples in the sense that they are pure, fully polymerized, flat and smooth, defect-free, and suitable for ultrahigh vacuum x-ray photoelectron spectroscopy, XPS, experiments. In parallel, we perform Hartree-Fock, HF, calculations of the binding energies, BEs, of the C1s electrons in a model molecule composed of the two constituents of the poly-epoxy sample. These C1s BEs were determined using the HF ΔSCF method, which is known to yield accuratemore » values, especially for the shifts of the BEs, ΔBEs. We demonstrate the benefits of combining rigorous theory with careful XPS measurements in order to obtain correct assignments of the C1s XPS spectra of the polymer sample. Both the relative binding energies—by the ΔSCF method—and relative intensities—in the sudden approximation, SA, are calculated. It results in an excellent match with the experimental spectra. We are able to identify 9 different chemical environments under the C1s peak, where an exclusively experimental work would have found only 3 contributions. In addition, we observe that some contributions are localized at discrete binding energies, whereas others allow a much wider range because of the variation of their second neighbor bound polarization. Therefore, HF-ΔSCF simulations significantly increase the spectral resolution of XPS and thus offer a new avenue for the exploration of the surface of polymers.« less

A Hartree-Fock-Bogoliubov mass formula

NASA Astrophysics Data System (ADS)

Samyn, M.; Goriely, S.; Heenen, P.-H.; Pearson, J. M.; Tondeur, F.

2002-03-01

In order to have more reliable predictions of nuclear masses at the neutron drip line, we here go beyond the recent mass formula HFBCS-1 and present a new mass formula, HFB-1, based on the Hartree-Fock-Bogoliubov method. As with the HFBCS-1 mass formula, we use a 10-parameter Skyrme force along with a 4-parameter δ-function pairing force and a 2-parameter phenomenological Wigner term. However, with the original HFBCS-1 Skyrme force (MSk7), the rms error becomes unacceptably large and a new force fit is required. With the isoscalar and isovector effective masses constrained to be equal, the remaining 15 degrees of freedom are fitted to the masses of all the 1754 measured nuclei with A⩾16, | N- Z|>2 given in the 1995 Audi-Wapstra compilation. The rms error with respect to the masses of all the 1888 measured nuclei with Z, N⩾8 is 0.764 MeV. A complete mass table, HFB-1 (available on the Web), has been constructed, giving all nuclei lying between the two drip lines over the range Z, N⩾8 and Z⩽120. A comparison between HFB-1 and HFBCS-1 mass tables shows that the HFBCS model is a very good approximation of the HFB theory, in particular for masses, the extrapolated masses never differing by more than 2 MeV below Z⩽110. We also find that the behaviour of shell gaps far away from the region of beta stability does not depend on whether the HFBCS or HFB methods are used, in particular, no quenching of astrophysical interest arises from replacing the BCS method by the Bogoliubov method.

Stability conditions for exact-exchange Kohn-Sham methods and their relation to correlation energies from the adiabatic-connection fluctuation-dissipation theorem.

PubMed

Bleiziffer, Patrick; Schmidtel, Daniel; Görling, Andreas

2014-11-28

The occurrence of instabilities, in particular singlet-triplet and singlet-singlet instabilities, in the exact-exchange (EXX) Kohn-Sham method is investigated. Hessian matrices of the EXX electronic energy with respect to the expansion coefficients of the EXX effective Kohn-Sham potential in an auxiliary basis set are derived. The eigenvalues of these Hessian matrices determine whether or not instabilities are present. Similar as in the corresponding Hartree-Fock case instabilities in the EXX method are related to symmetry breaking of the Hamiltonian operator for the EXX orbitals. In the EXX methods symmetry breaking can easily be visualized by displaying the local multiplicative exchange potential. Examples (N2, O2, and the polyyne C10H2) for instabilities and symmetry breaking are discussed. The relation of the stability conditions for EXX methods to approaches calculating the Kohn-Sham correlation energy via the adiabatic-connection fluctuation-dissipation (ACFD) theorem is discussed. The existence or nonexistence of singlet-singlet instabilities in an EXX calculation is shown to indicate whether or not the frequency-integration in the evaluation of the correlation energy is singular in the EXX-ACFD method. This method calculates the Kohn-Sham correlation energy through the ACFD theorem theorem employing besides the Coulomb kernel also the full frequency-dependent exchange kernel and yields highly accurate electronic energies. For the case of singular frequency-integrands in the EXX-ACFD method a regularization is suggested. Finally, we present examples of molecular systems for which the self-consistent field procedure of the EXX as well as the Hartree-Fock method can converge to more than one local minimum depending on the initial conditions.

Effects of structural spin-orbit coupling in two dimensional electron and hole liquids

NASA Astrophysics Data System (ADS)

Chesi, Stefano

The recent interest in spin-dependent phenomena in semiconductor heterostructures motivates our detailed study of the structural spin-orbit coupling present in clean two-dimensional electron and hole liquids. Interesting polarization effects are produced in a system out of equilibrium, as when a finite current flows in the sample. In particular, the consequences of a lateral confinement creating a quasi one-dimensional wire are studied in detail, partially motivated by a recent experimental investigation of the point-contact transmission for two-dimensional holes. We also address the role of the electron-electron interaction in the presence of spin-orbit coupling, which has received little attention in the literature. We discuss the formulation of the Hartree-Fock approximation in the particular case of linear Rashba spin-orbit. We establish the form of the mean-field phase diagram in the homogeneous case, which shows a complex interplay between paramagnetic and ferromagnetic states. The latter can be polarized in the plane or in a transverse direction, and are characterized by a complex spin structure and nontrivial occupation. The generality of the Hartree-Fock method allows a simple treatment of the Pauli spin susceptibility, and the application to different forms of spin-orbit coupling. Correlation corrections can be obtained in an analytic form for particular asymptotic regimes. For linear Rashba spin-orbit we identified the relevance of the large spin-orbit limit, dominated by many-body effects, and explicitly treated the high density limit, in which the system is asymptotically noninteracting. As a special case, we derive a new exact formula for the polarization dependence of the ring-diagram correlation energy.

Electronic structure investigations of 4-aminophthal hydrazide by UV-visible, NMR spectral studies and HOMO-LUMO analysis by ab initio and DFT calculations.

PubMed

Sambathkumar, K; Jeyavijayan, S; Arivazhagan, M

2015-08-05

Combined experimental and theoretical studies were conducted on the molecular structure and vibrational spectra of 4-AminoPhthalhydrazide (APH). The FT-IR and FT-Raman spectra of APH were recorded in the solid phase. The molecular geometry and vibrational frequencies of APH in the ground state have been calculated by using the ab initio HF (Hartree-Fock) and density functional methods (B3LYP) invoking 6-311+G(d,p) basis set. The optimized geometric bond lengths and bond angles obtained by HF and B3LYP method show best agreement with the experimental values. Comparison of the observed fundamental vibrational frequencies of APH with calculated results by HF and density functional methods indicates that B3LYP is superior to the scaled Hartree-Fock approach for molecular vibrational problems. The difference between the observed and scaled wave number values of most of the fundamentals is very small. A detailed interpretation of the NMR spectra of APH was also reported. The theoretical spectrograms for infrared and Raman spectra of the title molecule have been constructed. UV-vis spectrum of the compound was recorded and the electronic properties, such as HOMO and LUMO energies, were performed by time dependent density functional theory (TD-DFT) approach. Finally the calculations results were applied to simulated infrared and Raman spectra of the title compound which show good agreement with observed spectra. And the temperature dependence of the thermodynamic properties of constant pressure (Cp), entropy (S) and enthalpy change (ΔH0→T) for APH were also determined. Copyright © 2015 Elsevier B.V. All rights reserved.

Koopmans' theorem in the Hartree-Fock method. General formulation

NASA Astrophysics Data System (ADS)

Plakhutin, Boris N.

2018-03-01

This work presents a general formulation of Koopmans' theorem (KT) in the Hartree-Fock (HF) method which is applicable to molecular and atomic systems with arbitrary orbital occupancies and total electronic spin including orbitally degenerate (OD) systems. The new formulation is based on the full set of variational conditions imposed upon the HF orbitals by the variational principle for the total energy and the conditions imposed by KT on the orbitals of an ionized electronic shell [B. N. Plakhutin and E. R. Davidson, J. Chem. Phys. 140, 014102 (2014)]. Based on these conditions, a general form of the restricted open-shell HF method is developed, whose eigenvalues (orbital energies) obey KT for the whole energy spectrum. Particular attention is paid to the treatment of OD systems, for which the new method gives a number of unexpected results. For example, the present method gives four different orbital energies for the triply degenerate atomic level 2p in the second row atoms B to F. Based on both KT conditions and a parallel treatment of atoms B to F within a limited configuration interaction approach, we prove that these four orbital energies, each of which is triply degenerate, are related via KT to the energies of different spin-dependent ionization and electron attachment processes (2p)N → (2p ) N ±1. A discussion is also presented of specific limitations of the validity of KT in the HF method which arise in OD systems. The practical applicability of the theory is verified by comparing KT estimates of the ionization potentials I2s and I2p for the second row open-shell atoms Li to F with the relevant experimental data.

Multiconfiguration Dirac-Hartree-Fock energy levels, oscillator strengths, transition probabilities, hyperfine constants and Landé g-factor of intermediate Rydberg series in neutral argon atom

NASA Astrophysics Data System (ADS)

Salah, Wa'el; Hassouneh, Ola

2017-04-01

We computed the energy levels, oscillator strengths f_{ij}, the radiative transition rates A_{ij}, the Landé g -factor, the magnetic dipole moment and the electric quadrupole hyperfine constants of the intermediate Rydberg series ns [k]J ( 4 ≤ n ≤ 6), nd [k]J (3 ≤ n ≤ 4), np [k]J (4 ≤ n ≤ 5) relative to the ground state 3p6 1S0 for neutral argon atom spectra. The values are obtained in the framework of the multiconfiguration Dirac-Hartree-Fock (MCDHF) approach. In this approach, Breit interaction, leading quantum electrodynamics (QED) effects and self-energy correction are taken into account. Moreover, these spectroscopic parameters have been calculated for many levels belonging to the configuration 3p54s, 3p55s, 3p56s, 3p53d, 3p54d, 3p54p, 3p55p as well as for transitions between levels 3p54s-3p54p, 3p54p-3p53d, 3p54p-3p55s, 3p55s-3p55p and 3p55p-3p56s. The large majority of the lines from the 4p-5s and 4p-3d, 5s-5p and 5p-6s transition arrays have been observed and the calculations are consistent with the J -file-sum rule. The obtained theoretical values are compared with previous experimental and theoretical data available in the literature. An overall satisfactory agreement is noticed allowing assessing the reliability of our data.

The nature of excess electrons in anatase and rutile from hybrid DFT and RPA.

PubMed

Spreafico, Clelia; VandeVondele, Joost

2014-12-21

The behavior of excess electrons in undoped and defect free bulk anatase and rutile TiO2 has been investigated by state-of-the-art electronic structure methods including hybrid density functional theory (DFT) and the random phase approximation (RPA). Consistent with experiment, charge trapping and polaron formation is observed in both anatase and rutile. The difference in the anisotropic shape of the polarons is characterized, confirming for anatase the large polaron picture. For anatase, where polaron formation energies are small, charge trapping is observed also with standard hybrid functionals, provided the simulation cell is sufficiently large (864 atoms) to accommodate the lattice relaxation. Even though hybrid orbitals are required as a starting point for RPA in this system, the obtained polaron formation energies are relatively insensitive to the amount of Hartree-Fock exchange employed. The difference in trapping energy between rutile and anatase can be obtained accurately with both hybrid functionals and RPA. Computed activation energies for polaron hopping and delocalization clearly show that anatase and rutile might have different charge transport mechanisms. In rutile, only hopping is likely, whereas in anatase hopping and delocalization are competing. Delocalization will result in conduction-band-like and thus enhanced transport. Anisotropic conduction, in agreement with experimental data, is observed, and results from the tendency to delocalize in the [001] direction in rutile and the (001) plane in anatase. For future work, our calculations serve as a benchmark and suggest RPA on top on hybrid orbitals (PBE0 with 30% Hartree-Fock exchange), as a suitable method to study the rich chemistry and physics of TiO2.

Solution of the Skyrme Hartree Fock Bogolyubov equations in the Cartesian deformed harmonic-oscillator basis. (V) HFODD(v2.08k)

NASA Astrophysics Data System (ADS)

Dobaczewski, J.; Olbratowski, P.

2005-05-01

We describe the new version (v2.08k) of the code HFODD which solves the nuclear Skyrme-Hartree-Fock or Skyrme-Hartree-Fock-Bogolyubov problem by using the Cartesian deformed harmonic-oscillator basis. Similarly as in the previous version (v2.08i), all symmetries can be broken, which allows for calculations with angular frequency and angular momentum tilted with respect to the mass distribution. In the new version, three minor errors have been corrected. New Version Program SummaryTitle of program: HFODD; version: 2.08k Catalogue number: ADVA Catalogue number of previous version: ADTO (Comput. Phys. Comm. 158 (2004) 158) Program summary URL:http://cpc.cs.qub.ac.uk/summaries/ADVA Program obtainable from: CPC Program Library, Queen's University of Belfast, N. Ireland Does the new version supersede the previous one: yes Computers on which this or another recent version has been tested: SG Power Challenge L, Pentium-II, Pentium-III, AMD-Athlon Operating systems under which the program has been tested: UNIX, LINUX, Windows-2000 Programming language used: Fortran Memory required to execute with typical data: 10M words No. of bits in a word: 64 No. of lines in distributed program, including test data, etc.: 52 631 No. of bytes in distributed program, including test data, etc.: 266 885 Distribution format:tar.gz Nature of physical problem: The nuclear mean-field and an analysis of its symmetries in realistic cases are the main ingredients of a description of nuclear states. Within the Local Density Approximation, or for a zero-range velocity-dependent Skyrme interaction, the nuclear mean-field is local and velocity dependent. The locality allows for an effective and fast solution of the self-consistent Hartree-Fock equations, even for heavy nuclei, and for various nucleonic ( n-particle n-hole) configurations, deformations, excitation energies, or angular momenta. Similar Local Density Approximation in the particle-particle channel, which is equivalent to using a zero-range interaction, allows for a simple implementation of pairing effects within the Hartree-Fock-Bogolyubov method. Solution method: The program uses the Cartesian harmonic-oscillator basis to expand single-particle or single-quasiparticle wave functions of neutrons and protons interacting by means of the Skyrme effective interaction and zero-range pairing interaction. The expansion coefficients are determined by the iterative diagonalization of the mean field Hamiltonians or Routhians which depend non-linearly on the local neutron and proton densities. Suitable constrains are used to obtain states corresponding to a given configuration, deformation or angular momentum. The method of solution has been presented in [J. Dobaczewski, J. Dudek, Comput. Phys. Comm. 102 (1997) 166]. Summary of revisions: 1. Incorrect value of the " t" force parameter for SLY5 has been corrected. 2. Opening of an empty file "FILREC" for IWRIRE=-1 has been removed. 3. Call to subroutine "OLSTOR" has been moved before that to "SPZERO". In this way, correct data transferred to "FLISIG", "FLISIM", "FLISIQ" or "FLISIZ" allow for a correct determination of the candidate states for diabatic blocking. These corrections pertain to the user interface of the code and do not affect results performed for forces other than SLY5. Restrictions on the complexity of the problem: The main restriction is the CPU time required for calculations of heavy deformed nuclei and for a given precision required. Pairing correlations are only included for even-even nuclei and conserved simplex symmetry. Unusual features: The user must have access to the NAGLIB subroutine F02AXE or to the LAPACK subroutines ZHPEV or ZHPEVX, which diagonalize complex Hermitian matrices, or provide another subroutine which can perform such a task. The LAPACK subroutines ZHPEV and ZHPEVX can be obtained from the Netlib Repository at University of Tennessee, Knoxville: http://netlib2.cs.utk.edu/cgi-bin/netlibfiles.pl?filename=/lapack/complex16/zhpev.f and http://netlib2.cs.utk.edu/cgi-bin/netlibfiles.pl?filename=/lapack/complex16/zhpevx.f, respectively. The code is written in single-precision for use on a 64-bit processor. The compiler option -r8 or +autodblpad (or equivalent) has to be used to promote all real and complex single-precision floating-point items to double precision when the code is used on a 32-bit machine. Typical running time: One Hartree-Fock iteration for the superdeformed, rotating, parity conserving state of 15266Dy 86 takes about six seconds on the AMD-Athlon 1600+ processor. Starting from the Woods-Saxon wave functions, about fifty iterations are required to obtain the energy converged within the precision of about 0.1 keV. In the case when every value of the angular velocity is converged separately, the complete superdeformed band with precisely determined dynamical moments J can be obtained within forty minutes of CPU on the AMD-Athlon 1600+ processor. This time can be often reduced by a factor of three when a self-consistent solution for a given rotational frequency is used as a starting point for a neighboring rotational frequency. Additional comments: The actual output files obtained during user's test runs may differ from those provided in the distribution file. The differences may occur because various compilers may produce different results in the following aspects: The initial Nilsson spectrum (the starting point of each run) is Kramers degenerate, and thus the diagonalization routine may return the degenerate states in arbitrary order and in arbitrary mixture. For an odd number of particles, one of these states becomes occupied, and the other one is left empty. Therefore, starting points of such runs can widely vary from compiler to compiler, and these differences cannot be controlled. For axial shapes, two quadrupole moments (with respect to two different axes) become very small and their values reflect only a numerical noise. However, depending on which of these two moments is smaller, the intrinsic-frame Euler axes will differ, most often by 180 degrees. Hence, signs of some moments and angular momenta may vary from compiler to compiler, and these differences cannot be controlled. These differences are insignificant. The final energies do not depend on them, although the intermediate results can.

Fast and accurate 3D tensor calculation of the Fock operator in a general basis

NASA Astrophysics Data System (ADS)

Khoromskaia, V.; Andrae, D.; Khoromskij, B. N.

2012-11-01

The present paper contributes to the construction of a “black-box” 3D solver for the Hartree-Fock equation by the grid-based tensor-structured methods. It focuses on the calculation of the Galerkin matrices for the Laplace and the nuclear potential operators by tensor operations using the generic set of basis functions with low separation rank, discretized on a fine N×N×N Cartesian grid. We prove the Ch2 error estimate in terms of mesh parameter, h=O(1/N), that allows to gain a guaranteed accuracy of the core Hamiltonian part in the Fock operator as h→0. However, the commonly used problem adapted basis functions have low regularity yielding a considerable increase of the constant C, hence, demanding a rather large grid-size N of about several tens of thousands to ensure the high resolution. Modern tensor-formatted arithmetics of complexity O(N), or even O(logN), practically relaxes the limitations on the grid-size. Our tensor-based approach allows to improve significantly the standard basis sets in quantum chemistry by including simple combinations of Slater-type, local finite element and other basis functions. Numerical experiments for moderate size organic molecules show efficiency and accuracy of grid-based calculations to the core Hamiltonian in the range of grid parameter N3˜1015.

Wavelets in electronic structure calculations

NASA Astrophysics Data System (ADS)

Modisette, Jason Perry

1997-09-01

Ab initio calculations of the electronic structure of bulk materials and large clusters are not possible on today's computers using current techniques. The storage and diagonalization of the Hamiltonian matrix are the limiting factors in both memory and execution time. The scaling of both quantities with problem size can be reduced by using approximate diagonalization or direct minimization of the total energy with respect to the density matrix in conjunction with a localized basis. Wavelet basis members are much more localized than conventional bases such as Gaussians or numerical atomic orbitals. This localization leads to sparse matrices of the operators that arise in SCF multi-electron calculations. We have investigated the construction of the one-electron Hamiltonian, and also the effective one- electron Hamiltonians that appear in density-functional and Hartree-Fock theories. We develop efficient methods for the generation of the kinetic energy and potential matrices, the Hartree and exchange potentials, and the local exchange-correlation potential of the LDA. Test calculations are performed on one-electron problems with a variety of potentials in one and three dimensions.

Low-energy proton induced M X-ray production cross sections for 70Yb, 81Tl and 82Pb

NASA Astrophysics Data System (ADS)

Shehla; Mandal, A.; Kumar, Ajay; Roy Chowdhury, M.; Puri, Sanjiv; Tribedi, L. C.

2018-07-01

The cross sections for production of Mk (k = Mξ, Mαβ, Mγ, Mm1) X-rays of 70Yb, 81Tl and 82Pb induced by 50-250 keV protons have been measured in the present work. The experimental cross sections have been compared with the earlier reported values and those calculated using the ionization cross sections based on the ECPSSR (Perturbed (P) stationary(S) state(S), incident ion energy (E) loss, Coulomb (C) deflection and relativistic (R) correction) model, the X-ray emission rates based on the Dirac-Fock model, the fluorescence and Coster-Kronig yields based on the Dirac-Hartree-Slater (DHS) model. In addition, the present measured proton induced X-ray production cross sections have also been compared with those calculated using the Dirac-Hartree-Slater (DHS) model based ionization cross sections and those based on the Plane wave Born Approximation (PWBA). The measured M X-ray production cross sections are, in general, found to be higher than the ECPSSR and DHS model based values and lower than the PWBA model based cross sections.

Sub-barrier fusion and transfers in the 40Ca + 58,64Ni systems

NASA Astrophysics Data System (ADS)

Bourgin, D.; Courtin, S.; Haas, F.; Goasduff, A.; Stefanini, A. M.; Montagnoli, G.; Montanari, D.; Corradi, L.; Huiming, J.; Scarlassara, F.; Fioretto, E.; Simenel, C.; Rowley, N.; Szilner, S.; Mijatović, T.

2016-05-01

Fusion cross sections have been measured in the 40Ca + 58Ni and 40Ca + 64Ni systems at energies around and below the Coulomb barrier. The 40Ca beam was delivered by the XTU Tandem accelerator of the Laboratori Nazionali di Legnaro and evaporation residues were measured at very forward angles with the LNL electrostatic beam deflector. Coupled-channels calculations were performed which highlight possible strong effects of neutron transfers on the fusion below the barrier in the 40Ca + 64Ni system. Microscopic time-dependent Hartree-Fock calculations have also been performed for both systems. Preliminary results are shown.

Pasta phases in core-collapse supernova matter

NASA Astrophysics Data System (ADS)

Pais, Helena; Chiacchiera, Silvia; Providência, Constança

2016-04-01

The pasta phase in core-collapse supernova matter (finite temperatures and fixed proton fractions) is studied within relativistic mean field models. Three different calculations are used for comparison, the Thomas-Fermi (TF), the Coexisting Phases (CP) and the Compressible Liquid Drop (CLD) approximations. The effects of including light clusters in nuclear matter and the densities at which the transitions between pasta configurations and to uniform matter occur are also investigated. The free energy and pressure, in the space of particle number densities and temperatures expected to cover the pasta region, are calculated. Finally, a comparison with a finite temperature Skyrme-Hartree-Fock calculation is drawn.

Critical Frequency in Nuclear Chiral Rotation

NASA Astrophysics Data System (ADS)

Olbratowski, P.; Dobaczewski, J.; Dudek, J.; Płóciennik, W.

2004-07-01

Self-consistent solutions for the so-called planar and chiral rotational bands in 132La are obtained for the first time within the Skyrme-Hartree-Fock cranking approach. It is suggested that the chiral rotation cannot exist below a certain critical frequency which under the approximations used is estimated as ℏωcrit≈0.5 0.6 MeV. However, the exact values of ℏωcrit may vary, to an extent, depending on the microscopic model used, in particular, through the pairing correlations and/or calculated equilibrium deformations. The existence of the critical frequency is explained in terms of a simple classical model of two gyroscopes coupled to a triaxial rigid body.

Parity-violating electric-dipole transitions in helium

NASA Technical Reports Server (NTRS)

Hiller, J.; Sucher, J.; Bhatia, A. K.; Feinberg, G.

1980-01-01

The paper examines parity-violating electric-dipole transitions in He in order to gain insight into the reliability of approximate calculations which are carried out for transitions in many-electron atoms. The contributions of the nearest-lying states are computed with a variety of wave functions, including very simple product wave functions, Hartree-Fock functions and Hylleraas-type wave functions with up to 84 parameters. It is found that values of the matrix elements of the parity-violating interaction can differ considerably from the values obtained from the good wave functions, even when these simple wave functions give accurate values for the matrix elements in question

Ab initio quantum chemical study of electron transfer in carboranes

NASA Astrophysics Data System (ADS)

Pati, Ranjit; Pineda, Andrew C.; Pandey, Ravindra; Karna, Shashi P.

2005-05-01

The electron transfer (ET) properties of 10- and 12-vertex carboranes are investigated by the ab initio Hartree-Fock method within the Marcus-Hush (MH) two-state model and the Koopman theorem (KT) approach. The calculated value of the ET coupling matrix element, VAB, is consistently higher in the KT approach than in the MH two-state model. For the carborane molecules functionalized by -CH 2 groups at C-vertices, VAB strongly depends on the relative orientation of the planes containing the terminal -CH 2 groups. The predicted conformation dependence of VAB offers a molecular mechanism to control ET between two active centers in molecular systems.

Experimental and theoretical debate on efficient second harmonic generation in Bis (Cinnamic acid): Hexamine cocrystal

NASA Astrophysics Data System (ADS)

Vijayalakshmi, S.; Kalyanaraman, S.; Ravindran, T. R.

2014-02-01

Second harmonic generation (SHG) in Bis (Cinnamic acid): Hexamine cocrystal was extensively analyzed through charge transfer (CT). The CT interactions through hydrogen bonding were well established with the aid of vibrational analysis and Natural Bond Orbital (NBO) analysis. The retentivity of coplanar nature of the cinnamic acid in the cocrystal was confirmed through UV-Visible spectroscopy and supported by Raman studies. Structural analysis indicated the quinoidal character of the given material presenting a high SHG efficiency. The first order hyperpolarizability value was calculated theoretically by density functional theory (DFT) and Hartree-Fock (HF) methods in support for the large value of SHG.

Accurate and Efficient Approximation to the Optimized Effective Potential for Exchange

NASA Astrophysics Data System (ADS)

Ryabinkin, Ilya G.; Kananenka, Alexei A.; Staroverov, Viktor N.

2013-07-01

We devise an efficient practical method for computing the Kohn-Sham exchange-correlation potential corresponding to a Hartree-Fock electron density. This potential is almost indistinguishable from the exact-exchange optimized effective potential (OEP) and, when used as an approximation to the OEP, is vastly better than all existing models. Using our method one can obtain unambiguous, nearly exact OEPs for any reasonable finite one-electron basis set at the same low cost as the Krieger-Li-Iafrate and Becke-Johnson potentials. For all practical purposes, this solves the long-standing problem of black-box construction of OEPs in exact-exchange calculations.

The Hartree-Fock calculation of the magnetic properties of molecular solutes

NASA Astrophysics Data System (ADS)

Cammi, R.

1998-08-01

In this paper we set the formal bases for the calculation of the magnetic susceptibility and of the nuclear magnetic shielding tensors for molecular solutes described within the framework of the polarizable continuum model (PCM). The theory has been developed at self-consistent field (SCF) level and adapted to be used within the framework of some of the computational procedures of larger use, i.e., the gauge invariant atomic orbital method (GIAO) and the continuous set gauge transformation method (CSGT). The numerical results relative to the magnetizabilities and chemical shielding of acetonitrile and nitrometane in various solvents computed with the PCM-CSGT method are also presented.

Nonequilibrium itinerant-electron magnetism: A time-dependent mean-field theory

NASA Astrophysics Data System (ADS)

Secchi, A.; Lichtenstein, A. I.; Katsnelson, M. I.

2016-08-01

We study the dynamical magnetic susceptibility of a strongly correlated electronic system in the presence of a time-dependent hopping field, deriving a generalized Bethe-Salpeter equation that is valid also out of equilibrium. Focusing on the single-orbital Hubbard model within the time-dependent Hartree-Fock approximation, we solve the equation in the nonequilibrium adiabatic regime, obtaining a closed expression for the transverse magnetic susceptibility. From this, we provide a rigorous definition of nonequilibrium (time-dependent) magnon frequencies and exchange parameters, expressed in terms of nonequilibrium single-electron Green's functions and self-energies. In the particular case of equilibrium, we recover previously known results.

Nuclear Symmetry Energy and the Breaking of the Isospin Symmetry: How Do They Reconcile with Each Other?

NASA Astrophysics Data System (ADS)

Roca-Maza, X.; Colò, G.; Sagawa, H.

2018-05-01

We analyze and propose a solution to the apparent inconsistency between our current knowledge of the equation of state of asymmetric nuclear matter, the energy of the isobaric analog state (IAS) in a heavy nucleus such as 208Pb, and the isospin symmetry breaking forces in the nuclear medium. This is achieved by performing state-of-the-art Hartree-Fock plus random phase approximation calculations of the IAS that include all isospin symmetry breaking contributions. To this aim, we propose a new effective interaction that is successful in reproducing the IAS excitation energy without compromising other properties of finite nuclei.

High-field instability of a field-induced triplon Bose-Einstein condensate

NASA Astrophysics Data System (ADS)

Rakhimov, Abdulla; Sherman, E. Ya.; Kim, Chul Koo

2010-01-01

We study properties of magnetic field-induced Bose-Einstein condensate of triplons as a function of temperature and the field within the Hartree-Fock-Bogoliubov approach including the anomalous density. We show that the magnetization is continuous across the transition, in agreement with the experiment. In sufficiently strong fields the condensate becomes unstable due to triplon-triplon repulsion. As a result, the system is characterized by two critical magnetic fields: one producing the condensate and the other destroying it. We show that nonparabolic triplon dispersion arising due to the gapped bare spectrum and the crystal structure has a strong influence on the phase diagram.

Restoring the Pauli principle in the random phase approximation ground state

NASA Astrophysics Data System (ADS)

Kosov, D. S.

2017-12-01

Random phase approximation ground state contains electronic configurations where two (and more) identical electrons can occupy the same molecular spin-orbital violating the Pauli exclusion principle. This overcounting of electronic configurations happens due to quasiboson approximation in the treatment of electron-hole pair operators. We describe the method to restore the Pauli principle in the RPA wavefunction. The proposed theory is illustrated by the calculations of molecular dipole moments and electronic kinetic energies. The Hartree-Fock based RPA, which is corrected for the Pauli principle, gives the results of comparable accuracy with Møller-Plesset second order perturbation theory and coupled-cluster singles and doubles method.

Nuclear Symmetry Energy and the Breaking of the Isospin Symmetry: How Do They Reconcile with Each Other?

PubMed

Roca-Maza, X; Colò, G; Sagawa, H

2018-05-18

We analyze and propose a solution to the apparent inconsistency between our current knowledge of the equation of state of asymmetric nuclear matter, the energy of the isobaric analog state (IAS) in a heavy nucleus such as ^{208}Pb, and the isospin symmetry breaking forces in the nuclear medium. This is achieved by performing state-of-the-art Hartree-Fock plus random phase approximation calculations of the IAS that include all isospin symmetry breaking contributions. To this aim, we propose a new effective interaction that is successful in reproducing the IAS excitation energy without compromising other properties of finite nuclei.

An efficient MPI/OpenMP parallelization of the Hartree–Fock–Roothaan method for the first generation of Intel® Xeon Phi™ processor architecture

DOE PAGES

Mironov, Vladimir; Moskovsky, Alexander; D’Mello, Michael; ...

2017-10-04

The Hartree-Fock (HF) method in the quantum chemistry package GAMESS represents one of the most irregular algorithms in computation today. Major steps in the calculation are the irregular computation of electron repulsion integrals (ERIs) and the building of the Fock matrix. These are the central components of the main Self Consistent Field (SCF) loop, the key hotspot in Electronic Structure (ES) codes. By threading the MPI ranks in the official release of the GAMESS code, we not only speed up the main SCF loop (4x to 6x for large systems), but also achieve a significant (>2x) reduction in the overallmore » memory footprint. These improvements are a direct consequence of memory access optimizations within the MPI ranks. We benchmark our implementation against the official release of the GAMESS code on the Intel R Xeon PhiTM supercomputer. Here, scaling numbers are reported on up to 7,680 cores on Intel Xeon Phi coprocessors.« less

Projector Augmented Wave formulation of orbital-dependent exchange-correlation functionals

NASA Astrophysics Data System (ADS)

Xu, Xiao; Holzwarth, N. A. W.

2012-02-01

The use of orbital-dependent exchange-correlation functionals within electronic structure calculations has recently received renewed attention for improving the accuracy of the calculations, especially correcting self-interaction errors. Since the Projector Augmented Wave (PAW) methodootnotetext P. Bl"ochl, Phys. Rev. B 50, 17953 (1994). is an efficient pseudopotential-like scheme which ensures accurate evaluation of all multipole moments of direct and exchange Coulomb integrals, it is a natural choice for implementing orbital-dependent formalisms. Using Fock exchange as an example of an orbital-dependent functional, we developed the formulation and numerical implementation of the approximate optimized effective potential formalism of Kreiger, Li, and Iafrate (KLI)ootnotetext J. B. Krieger, Y. Li, and G. J. Iafrate Phys. Rev. A 45, 101 (1992). within the PAW method, comparing results with the analogous Hartree-Fock treatment.ootnotetext Xiao Xu and N. A. W. Holzwarth, Phys. Rev. B 81, 245105 (2010); 84, 155113 (2011). Test results are presented for ground state properties of two well-known materials -- diamond and LiF. This formalism can be extended to treat orbital-dependent functionals more generally.

A Sparse Self-Consistent Field Algorithm and Its Parallel Implementation: Application to Density-Functional-Based Tight Binding.

PubMed

Scemama, Anthony; Renon, Nicolas; Rapacioli, Mathias

2014-06-10

We present an algorithm and its parallel implementation for solving a self-consistent problem as encountered in Hartree-Fock or density functional theory. The algorithm takes advantage of the sparsity of matrices through the use of local molecular orbitals. The implementation allows one to exploit efficiently modern symmetric multiprocessing (SMP) computer architectures. As a first application, the algorithm is used within the density-functional-based tight binding method, for which most of the computational time is spent in the linear algebra routines (diagonalization of the Fock/Kohn-Sham matrix). We show that with this algorithm (i) single point calculations on very large systems (millions of atoms) can be performed on large SMP machines, (ii) calculations involving intermediate size systems (1000-100 000 atoms) are also strongly accelerated and can run efficiently on standard servers, and (iii) the error on the total energy due to the use of a cutoff in the molecular orbital coefficients can be controlled such that it remains smaller than the SCF convergence criterion.

On the accurate theoretical determination of the static hyperpolarizability of trans-butadiene

NASA Astrophysics Data System (ADS)

Maroulis, George

1999-07-01

Finite-field many-body perturbation theory and coupled cluster calculations are reported for the static second dipole hyperpolarizability γαβγδ of trans-butadiene. A very large basis set of [9s6p4d1f/6s3p1d] size (336 contracted Gaussian-type functions) should lead to self-consistent field (SCF) values of near-Hartree-Fock quality. We report γxxxx=6.19, γxxxz=-0.44, γxxyy=3.42, γzzxx=2.07, γxyyz=-0.50, γxzzz=1.73, γyyyy=14.72, γyyzz=8.46, γzzzz=24.10 and γ¯=14.58 for 10-3×γαβγδ/e4a04Eh-3 at the experimental geometry (molecule on the xz plane with z as the main axis). γ¯=(14.6±0.4)×103e4a04Eh-3 should be a very reliable estimate of the Hartree-Fock limit of the mean hyperpolarizability. Keeping all other molecular geometry parameters constant, we find that near the Hartree-Fock limit the mean hyperpolarizability varies with the C=C bond length as 10-3×γ¯(RC=C)/e4a04Eh-3=14.93+31.78ΔR+30.88ΔR2-2.96ΔR3 and with the C-C bond length as 10-3×γ¯(RC-C)/e4a04Eh-3=14.93-7.20ΔR+3.04ΔR2, where ΔR/a0 is the displacement from the respective experimental value. The dependence of the components of γαβγδ on the molecular geometry parameters is not uniform. Electron correlation corrections have been calculated at various molecular geometries at the coupled-cluster single, double and perturbatively linked triple excitations level of theory for all independent components of γαβγδ. In absolute terms, electron correlation affects strongly the γzzzz, less strongly the γxxxx, and even less strongly the out-of-plane component γyyyy. The present analysis suggests a conservative estimate of (3.0±0.6)×103e4a04Eh-3 for the electron correlation correction to γ¯ at the experimental molecular geometry. Most of this value is appropriate to γzzzz. A static limit of γ¯=(17.6±1.0)×103e4a04Eh-3 is advanced (neglecting vibrational averaging). Even if a crude theoretical estimate of the dispersion of γ¯ at 1064 nm is added to this value, the result sets up an unambiguous claim to accord with the experimental value of (20.18±0.11)×103e4a04Eh-3 [D. P. Shelton, Phys. Rev. A 42, 2578 (1990)].

UNO DMRG CASCI calculations of effective exchange integrals for m-phenylene-bis-methylene spin clusters

NASA Astrophysics Data System (ADS)

Kawakami, Takashi; Sano, Shinsuke; Saito, Toru; Sharma, Sandeep; Shoji, Mitsuo; Yamada, Satoru; Takano, Yu; Yamanaka, Shusuke; Okumura, Mitsutaka; Nakajima, Takahito; Yamaguchi, Kizashi

2017-09-01

Theoretical examinations of the ferromagnetic coupling in the m-phenylene-bis-methylene molecule and its oligomer were carried out. These systems are good candidates for exchange-coupled systems to investigate strong electronic correlations. We studied effective exchange integrals (J), which indicated magnetic coupling between interacting spins in these species. First, theoretical calculations based on a broken-symmetry single-reference procedure, i.e. the UHF, UMP2, UMP4, UCCSD(T) and UB3LYP methods, were carried out with a GAUSSIAN program code under an SR wave function. From these results, the J value by the UHF method was largely positive because of the strong ferromagnetic spin polarisation effect. The J value by the UCCSD(T) and UB3LYP methods improved an overestimation problem by correcting the dynamical electronic correlation. Next, magnetic coupling among these spins was studied using the CAS-based method of the symmetry-adapted multireference methods procedure. Thus, the UNO DMRG CASCI (UNO, unrestricted natural orbital; DMRG, density matrix renormalised group; CASCI, complete active space configuration interaction) method was mainly employed with a combination of ORCA and BLOCK program codes. DMRG CASCI calculations in valence electron counting, which included all orbitals to full valence CI, provided the most reliable result, and support the UB3LYP method for extended systems.

Small Water Cluster Cations

NASA Astrophysics Data System (ADS)

Novakovskaya, Yu. V.; Stepanov, N. F.

Structures of water cluster cations (H_{2}O)^{+}_{n} with n ≤ 5 are optimized at the unrestricted Hartree-Fock level with the 4 - 31 + +G** basis set. Energetic characteristics of the cations are then estimated taking into account the second order perturbation corrections (MP2). After the electron detachment from a neutral cluster, the structure of the latter substantially changes, so that OH and H3O+ fragments can be distinguished in it. In some cations H3O+ is so strongly bonded to water molecules that it is reasonable to speak of the [H2n-1On-1]+ fragments. According to the position of OH, the structures form two groups. In one group, OH acts exclusively as the proton acceptor in H-bonds with water molecules, thus being terminal in the chain-like structures; in the other group it is directly bonded to H3O and, as a proton donor, forms an H-bond with water molecule. Cluster cations do not tend to dissociate into the fragments. However, an external influence of ≤ 0.4 eV is sufficient for the cations of the first group to dissociate into a free OH radical and a protonated cluster H+(H2O)n-1. Extrapolation of the calculated adiabatic ionization potentials of the water clusters to n → ∞ provides a value of 8.6 eV, which can be considered as an estimation of the electron work function of water. This value is close to the experimental photoelectric thresholds of amorphous ice (8.7 ± 0.1 eV) and water (9.39 ± 0.3 eV). Solvation of the electron lowers the value, and an energy of 7 eV can be sufficient for initiating conductivity. This prediction is in accord with the experiment: irradiating ice with ultraviolet light of the photon energy 6.5-6.8 eV initiates photoconductivity, and hydrogen peroxide and H3O+ ions are observed.

Static electric dipole polarizabilities of An(5+/6+) and AnO2 (+/2+) (An = U, Np, and Pu) ions.

PubMed

Parmar, Payal; Peterson, Kirk A; Clark, Aurora E

2014-12-21

The parallel components of static electric dipole polarizabilities have been calculated for the lowest lying spin-orbit states of the penta- and hexavalent oxidation states of the actinides (An) U, Np, and Pu, in both their atomic and molecular diyl ion forms (An(5+/6+) and AnO2 (+/2+)) using the numerical finite-field technique within a four-component relativistic framework. The four-component Dirac-Hartree-Fock method formed the reference for MP2 and CCSD(T) calculations, while multireference Fock space coupled-cluster (FSCC), intermediate Hamiltonian Fock space coupled-cluster (IH-FSCC) and Kramers restricted configuration interaction (KRCI) methods were used to incorporate additional electron correlation. It is observed that electron correlation has significant (∼5 a.u.(3)) impact upon the parallel component of the polarizabilities of the diyls. To the best of our knowledge, these quantities have not been previously reported and they can serve as reference values in the determination of various electronic and response properties (for example intermolecular forces, optical properties, etc.) relevant to the nuclear fuel cycle and material science applications. The highest quality numbers for the parallel components (αzz) of the polarizability for the lowest Ω levels corresponding to the ground electronic states are (in a.u.(3)) 44.15 and 41.17 for UO2 (+) and UO2 (2+), respectively, 45.64 and 41.42 for NpO2 (+) and NpO2 (2+), respectively, and 47.15 for the PuO2 (+) ion.

Interaction of the NO 3pπ (C {sup 2}Π) Rydberg state with RG (RG = Ne, Kr, and Xe): Potential energy surfaces and spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ershova, Olga V.; Besley, Nicholas A., E-mail: Nick.Besley@nottingham.ac.uk; Wright, Timothy G., E-mail: Tim.Wright@nottingham.ac.uk

2015-01-21

We present new potential energy surfaces for the interaction of NO(C {sup 2}Π) with each of Ne, Kr, and Xe. The potential energy surfaces have been calculated using second order Møller-Plesset perturbation theory, exploiting a procedure to converge the reference Hartree-Fock wavefunction for the excited states: the maximum overlap method. The bound rovibrational states obtained from the surfaces are used to simulate the electronic spectra and their appearance is in good agreement with available (2+1) REMPI spectra. We discuss the assignment and appearance of these spectra, comparing to that of NO-Ar.

Comment on "Generalization of the Kohn-Sham system that can represent arbitrary one-electron density matrices"

NASA Astrophysics Data System (ADS)

Piris, Mario; Pernal, Katarzyna

2017-10-01

van Dam [Phys. Rev. A 93, 052512 (2016), 10.1103/PhysRevA.93.052512] claims that the one-particle reduced density matrix (1RDM) of an interacting system can be represented by means of a single-determinant wave function of fictitious noninteracting particles. van Dam [Phys. Rev. A 93, 052512 (2016), 10.1103/PhysRevA.93.052512] introduced orbitals within a mean-field framework that produce energy levels similar to Hartree-Fock orbital energies, therefore he also claims that conventional analyses based on Koopmans' theorem are possible in 1RDM functional theory. In this Comment, we demonstrate that both claims are unfounded.

The Importance of Three-Body Interactions in Molecular Dynamics Simulations of Water with the Fragment Molecular Orbital Method

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pruitt, Spencer R.; Nakata, Hiroya; Nagata, Takeshi

2016-04-12

The analytic first derivative with respect to nuclear coordinates is formulated and implemented in the framework of the three-body fragment molecular orbital (FMO) method. The gradient has been derived and implemented for restricted Hartree-Fock, second-order Møller-Plesset perturbation, and density functional theories. The importance of the three-body fully analytic gradient is illustrated through the failure of the two-body FMO method during molecular dynamics simulations of a small water cluster. The parallel implementation of the fragment molecular orbital method, its parallel efficiency, and its scalability on the Blue Gene/Q architecture up to 262,144 CPU cores, are also discussed.

Configuration interaction in charge exchange spectra of tin and xenon

NASA Astrophysics Data System (ADS)

D'Arcy, R.; Morris, O.; Ohashi, H.; Suda, S.; Tanuma, H.; Fujioka, S.; Nishimura, H.; Nishihara, K.; Suzuki, C.; Kato, T.; Koike, F.; O'Sullivan, G.

2011-06-01

Charge-state-specific extreme ultraviolet spectra from both tin ions and xenon ions have been recorded at Tokyo Metropolitan University. The electron cyclotron resonance source spectra were produced from charge exchange collisions between the ions and rare gas target atoms. To identify unknown spectral lines of tin and xenon, atomic structure calculations were performed for Sn14+-Sn17+ and Xe16+-Xe20+ using the Hartree-Fock configuration interaction code of Cowan (1981 The Theory of Atomic Structure and Spectra (Berkeley, CA: University of California Press)). The energies of the capture states involved in the single-electron process that occurs in these slow collisions were estimated using the classical over-barrier model.

Calculation of total electron excitation cross-sections and partial electron ionization cross-sections for the elements. Ph.D. Thesis

NASA Technical Reports Server (NTRS)

Green, T. J.

1973-01-01

Computer programs were used to calculate the total electron excitation cross-section for atoms and the partial ionization cross-section. The approximations to the scattering amplitude used are as follows: (1) Born, Bethe, and Modified Bethe for non-exchange excitation; (2) Ochkur for exchange excitation; and (3) Coulomb-Born of non-exchange ionization. The amplitudes are related to the differential cross-sections which are integrated to give the total excitation (or partial ionization) cross-section for the collision. The atomic wave functions used are Hartree-Fock-Slater functions for bound states and the coulomb wave function for the continuum. The programs are presented and the results are examined.

Analytical W-He and H-He interatomic potentials for a W-H-He system

NASA Astrophysics Data System (ADS)

Li, Xiao-Chun; Shu, Xiaolin; Liu, Yi-Nan; Yu, Yi; Gao, F.; Lu, Guang-Hong

2012-07-01

We have constructed W-He and H-He analytical bond-order potentials for a W-H-He system. In combination with the previously self-developed W-H potential [X.-C. Li, X. Shu, Y.-N. Liu, F. Gao, G.-H. Lu, J. Nucl. Mater. 408 (2011) 12] and the Hartree-Fock-dispersion pair potential (Aziz-potential) for He-He interactions, we demonstrate that such potentials behave well for reproducing various properties of the W-H-He system such as defect formation energies, structural properties, and diffusion barriers. Such potentials can be employed to model both the He behaviours and the H-He synergetic effects in the W-H-He system.

One-range addition theorems for derivatives of Slater-type orbitals.

PubMed

Guseinov, Israfil

2004-06-01

Using addition theorems for STOs introduced by the author with the help of complete orthonormal sets of psi(alpha)-ETOs (Guseinov II (2003) J Mol Model 9:190-194), where alpha=1, 0, -1, -2, ..., a large number of one-range addition theorems for first and second derivatives of STOs are established. These addition theorems are especially useful for computation of multicenter-multielectron integrals over STOs that arise in the Hartree-Fock-Roothaan approximation and also in the Hylleraas function method, which play a significant role for the study of electronic structure and electron-nuclei interaction properties of atoms, molecules, and solids. The relationships obtained are valid for arbitrary quantum numbers, screening constants and location of STOs.

Ultrafast Processes in Atoms and Molecules: Integrated treatment of electronic and nuclear motion in ultrashort XUV pulses

DOE Office of Scientific and Technical Information (OSTI.GOV)

McCurdy, C. William

This project made use of Multiconfiguration Time-Dependent Hartree-Fock method developed earlier in the McCurdy group in a series of novel applications of the method to ultrafast spectroscopic processes. MCTDHF treats the dynamics of a molecule or atom under the influence of an external field in manner that has all electrons active. That property distinguishes this method from the more popular (and much less computationally demanding) approaches for treating the electron dynamics of atoms and molecules in fields, such as the time-dependent “Configuration Interaction Singles” approximation or approaches that limit the treatment to either one or two-electron models.

Low-rank factorization of electron integral tensors and its application in electronic structure theory

DOE PAGES

Peng, Bo; Kowalski, Karol

2017-01-25

In this paper, we apply reverse Cuthill-McKee (RCM) algorithm to transform two-electron integral tensors to their block diagonal forms. By further applying Cholesky decomposition (CD) on each of the diagonal blocks, we are able to represent the high-dimensional two-electron integral tensors in terms of permutation matrices and low-rank Cholesky vectors. This representation facilitates low-rank factorizations of high-dimensional tensor contractions in post-Hartree-Fock calculations. Finally, we discuss the second-order Møller-Plesset (MP2) method and the linear coupled-cluster model with doubles (L-CCD) as examples to demonstrate the efficiency of this technique in representing the two-electron integrals in a compact form.

Spin symmetry in the Dirac sea derived from the bare nucleon-nucleon interaction

NASA Astrophysics Data System (ADS)

Shen, Shihang; Liang, Haozhao; Meng, Jie; Ring, Peter; Zhang, Shuangquan

2018-06-01

The spin symmetry in the Dirac sea has been investigated with relativistic Brueckner-Hartree-Fock theory using the bare nucleon-nucleon interaction. Taking the nucleus 16O as an example and comparing the theoretical results with the data, the definition of the single-particle potential in the Dirac sea is studied in detail. It is found that if the single-particle states in the Dirac sea are treated as occupied states, the ground state properties are in better agreement with experimental data. Moreover, in this case, the spin symmetry in the Dirac sea is better conserved and it is more consistent with the findings using phenomenological relativistic density functionals.

Proposed software system for atomic-structure calculation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fischer, C.F.

1981-07-01

Atomic structure calculations are understood well enough that, at a routine level, an atomic structure software package can be developed. At the Atomic Physics Conference in Riga, 1978 L.V. Chernysheva and M.Y. Amusia of Leningrad University, presented a paper on Software for Atomic Calculations. Their system, called ATOM is based on the Hartree-Fock approximation and correlation is included within the framework of RPAE. Energy level calculations, transition probabilities, photo-ionization cross-sections, electron scattering cross-sections are some of the physical properties that can be evaluated by their system. The MCHF method, together with CI techniques and the Breit-Pauli approximation also provides amore » sound theoretical basis for atomic structure calculations.« less

A complex-polarization-propagator protocol for magneto-chiral axial dichroism and birefringence dispersion.

PubMed

Cukras, Janusz; Kauczor, Joanna; Norman, Patrick; Rizzo, Antonio; Rikken, Geert L J A; Coriani, Sonia

2016-05-21

A computational protocol for magneto-chiral dichroism and magneto-chiral birefringence dispersion is presented within the framework of damped response theory, also known as complex polarization propagator theory, at the level of time-dependent Hartree-Fock and time-dependent density functional theory. Magneto-chiral dichroism and magneto-chiral birefringence spectra in the (resonant) frequency region below the first ionization threshold of R-methyloxirane and l-alanine are presented and compared with the corresponding results obtained for both the electronic circular dichroism and the magnetic circular dichroism. The additional information content yielded by the magneto-chiral phenomena, as well as their potential experimental detectability for the selected species, is discussed.

Imidazole derivatives as angiotensin II AT1 receptor blockers: Benchmarks, drug-like calculations and quantitative structure-activity relationships modeling

NASA Astrophysics Data System (ADS)

Alloui, Mebarka; Belaidi, Salah; Othmani, Hasna; Jaidane, Nejm-Eddine; Hochlaf, Majdi

2018-03-01

We performed benchmark studies on the molecular geometry, electron properties and vibrational analysis of imidazole using semi-empirical, density functional theory and post Hartree-Fock methods. These studies validated the use of AM1 for the treatment of larger systems. Then, we treated the structural, physical and chemical relationships for a series of imidazole derivatives acting as angiotensin II AT1 receptor blockers using AM1. QSAR studies were done for these imidazole derivatives using a combination of various physicochemical descriptors. A multiple linear regression procedure was used to design the relationships between molecular descriptor and the activity of imidazole derivatives. Results validate the derived QSAR model.

Ab initio Hartree-Fock investigation of 1- H-pyrrolo[3,2- b]pyridine-3-yl acetic acid

NASA Astrophysics Data System (ADS)

Ramek, Michael; Tomić, Sanja

2001-09-01

The potential energy surface of 1- H-pyrrolo[3,2- b]pyridine-3-yl acetic acid has been investigated via RIIF/6-31G* calculations. The stationary points and reaction paths for syn orientation of the COOH group were determined and are compared with those of the derivatives of 3-indole acetic acid, which act as plant growth hormones. 1- H-pyrrolo[3,2- b]pyridine-3-yl acetic acid forms a kinetically stable conformer with a strong intramolecular hydrogen bond, in which the COOH group is in anti orientation. The influence of this hydrogen bond on bond lengths and vibration frequencies is described.

Equation of state for nucleonic matter and its quark mass dependence from the nuclear force in lattice QCD.

PubMed

Inoue, Takashi; Aoki, Sinya; Doi, Takumi; Hatsuda, Tetsuo; Ikeda, Yoichi; Ishii, Noriyoshi; Murano, Keiko; Nemura, Hidekatsu; Sasaki, Kenji

2013-09-13

Quark mass dependence of the equation of state (EOS) for nucleonic matter is investigated, on the basis of the Brueckner-Hartree-Fock method with the nucleon-nucleon interaction extracted from lattice QCD simulations. We observe saturation of nuclear matter at the lightest available quark mass corresponding to the pseudoscalar meson mass ≃469  MeV. Mass-radius relation of the neutron stars is also studied with the EOS for neutron-star matter from the same nuclear force in lattice QCD. We observe that the EOS becomes stiffer and thus the maximum mass of neutron star increases as the quark mass decreases toward the physical point.

The argon nuclear quadrupole moments

NASA Astrophysics Data System (ADS)

Sundholm, Dage; Pyykkö, Pekka

2018-07-01

New standard values -116(2) mb and 76(3) mb are suggested for the nuclear quadrupole moments (Q) of the 39Ar and 37Ar nuclei, respectively. The Q values were obtained by combining optical measurements of the quadrupole coupling constant (B or eqQ/h) of the 3s23p54s[3/2]2 (3Po) and 3s23p54p[5/2]3 (3De) states of argon with large scale numerical complete active space self-consistent field and restricted active space self-consistent field calculations of the electric field gradient at the nucleus (q) using the LUCAS code, which is a finite-element based multiconfiguration Hartree-Fock program for atomic structure calculations.

A spatially homogeneous and isotropic Einstein-Dirac cosmology

NASA Astrophysics Data System (ADS)

Finster, Felix; Hainzl, Christian

2011-04-01

We consider a spatially homogeneous and isotropic cosmological model where Dirac spinors are coupled to classical gravity. For the Dirac spinors we choose a Hartree-Fock ansatz where all one-particle wave functions are coherent and have the same momentum. If the scale function is large, the universe behaves like the classical Friedmann dust solution. If however the scale function is small, quantum effects lead to oscillations of the energy-momentum tensor. It is shown numerically and proven analytically that these quantum oscillations can prevent the formation of a big bang or big crunch singularity. The energy conditions are analyzed. We prove the existence of time-periodic solutions which go through an infinite number of expansion and contraction cycles.

Non-expanded dispersion and induction energies, and damping functions, for molecular interactions with application to HF-He

NASA Astrophysics Data System (ADS)

Knowles, Peter J.; Meath, William J.

The evaluation of second order non-expanded dispersion and induction energies, and the associated damping functions, for interactions involving molecules is discussed with emphasis placed on using the time-dependent coupled Hartree-Fock method. Results are given for the HF-He interaction for all individual partial wave non-expanded dispersion and induction energies varying asymptotically for large R through O(R-8) and O(R-10) respectively and for most of the individual dispersion energies varying as R-9 and R-10. They are used to illustrate various features of charge overlap effects and the damping functions for molecular interactions, which are considerably more complicated than for atom-atom interactions.

Double Photoionization of helium atom using Screening Potential Approach

NASA Astrophysics Data System (ADS)

Saha, Haripada

2014-05-01

The triple differential cross section for double Photoionization of helium atom will be investigated using our recently extended MCHF method. It is well known that electron correlation effects in both the initial and the final states are very important. To incorporate these effects we will use the multi-configuration Hartree-Fock method to account for electron correlation in the initial state. The electron correlation in the final state will be taken into account using the angle-dependent screening potential approximation. The triple differential cross section (TDCS) will be calculated for 20 eV photon energy, which has experimental results. Our results will be compared with available experimental and the theoretical observations.

Time-dependent variational approach in terms of squeezed coherent states: Implication to semi-classical approximation

NASA Technical Reports Server (NTRS)

Tsue, Yasuhiko

1994-01-01

A general framework for time-dependent variational approach in terms of squeezed coherent states is constructed with the aim of describing quantal systems by means of classical mechanics including higher order quantal effects with the aid of canonicity conditions developed in the time-dependent Hartree-Fock theory. The Maslov phase occurring in a semi-classical quantization rule is investigated in this framework. In the limit of a semi-classical approximation in this approach, it is definitely shown that the Maslov phase has a geometric nature analogous to the Berry phase. It is also indicated that this squeezed coherent state approach is a possible way to go beyond the usual WKB approximation.

The self-trapping transition in the non-half-filled strongly correlated extended Holstein-Hubbard model in two-dimensions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sankar, I. V., E-mail: ivshankar27@gmail.com; Chatterjee, Ashok, E-mail: ivshankar27@gmail.com

2014-04-24

The two-dimensional extended Holstein-Hubbard model (EHH) has been considered at strong correlation regime in the non-half-filled band case to understand the self-trapping transition of electrons in strongly correlated electron system. We have used the method of optimized canonical transformations to transform an EHH model into an effective extended Hubbard (EEH) model. In the strong on-site correlation limit an EH model can be transformed into a t-J model which is finally solved using Hartree-Fock approximation (HFA). We found that, for non-half-filled band case, the transition is abrupt in the adiabatic region whereas it is continuous in the anti-adiabatic region.

A reformulation of the coupled perturbed self-consistent field equations entirely within a local atomic orbital density matrix-based scheme

NASA Astrophysics Data System (ADS)

Ochsenfeld, Christian; Head-Gordon, Martin

1997-05-01

To exploit the exponential decay found in numerical studies for the density matrix and its derivative with respect to nuclear displacements, we reformulate the coupled perturbed self-consistent field (CPSCF) equations and a quadratically convergent SCF (QCSCF) method for Hartree-Fock and density functional theory within a local density matrix-based scheme. Our D-CPSCF (density matrix-based CPSCF) and D-QCSCF schemes open the way for exploiting sparsity and to achieve asymptotically linear scaling of computational complexity with molecular size ( M), in case of D-CPSCF for all O( M) derivative densities. Furthermore, these methods are even for small molecules strongly competitive to conventional algorithms.

Thermodynamic Properties of Low-Density {}^{132}Xe Gas in the Temperature Range 165-275 K

NASA Astrophysics Data System (ADS)

Akour, Abdulrahman

2018-01-01

The method of static fluctuation approximation was used to calculate selected thermodynamic properties (internal energy, entropy, energy capacity, and pressure) for xenon in a particularly low-temperature range (165-270 K) under different conditions. This integrated microscopic study started from an initial basic assumption as the main input. The basic assumption in this method was to replace the local field operator with its mean value, then numerically solve a closed set of nonlinear equations using an iterative method, considering the Hartree-Fock B2-type dispersion potential as the most appropriate potential for xenon. The results are in very good agreement with those of an ideal gas.

Delocalization of frontier orbitals induced red emission for heptazine based thermally activated delayed fluorescence molecule: First-principles study

NASA Astrophysics Data System (ADS)

Kang, Yongxiang; Zhao, Liyun; Leng, Jiancai

2018-04-01

Design of red organic emitting molecules with characteristic of thermally activated delayed fluorescence (TADF) remains a great challenge. Here, electronic and optical properties of a series of multi-branched TADF molecules have been investigated based on the newly-proposed optimal Hartree-Fock percentage method. Results show that, though enlarging the delocalization of HOMO and LUMO, the emission wavelength is redshift. The designed red TADF molecule possesses smaller reorganization energy than these for reported molecules. This indicates the non-radiative energy consumption of excited state is small and effective luminescence can be expected. Thus, a promising red thermally activated delayed fluorescence molecule is proposed.

Ab initio study on the formation of triiodide CT complex from the reaction of iodine with 2,3-diaminopyridine.

PubMed

Al-Hashimi, Nessreen A; Hussein, Yasser H A

2010-01-01

The charge transfer (CT) interaction between iodine and 2,3-diaminopyridine (DAPY) has been thoroughly investigated via theoretical calculations. A Hartree-Fock, 3-21G level of theory was used to optimize and calculate the Mullican charge distribution scheme as well as the vibrational frequencies of DAPY alone and both its CT complexes with one and two iodine molecules. A very good agreement was found between experiment and theory. New illustrations were concluded with a deep analysis and description for the vibrational frequencies of the formed CT complexes. The two-step CT complex formation mechanism published earlier was supported. Copyright 2009 Elsevier B.V. All rights reserved.

Matter distribution and spin-orbit force in spherical nuclei

NASA Astrophysics Data System (ADS)

Co', G.; Anguiano, M.; De Donno, V.; Lallena, A. M.

2018-03-01

We investigate the possibility that some nuclei show density distributions with a depletion in the center, a semibubble structure, by using a Hartree-Fock plus Bardeen-Cooper-Schrieffer approach. We separately study the proton, neutron, and matter distributions in 37 spherical nuclei mainly in the s -d shell region. We found a relation between the semibubble structure and the energy splitting of spin-orbit partner single particle levels. The presence of semibubble structure reduces this splitting, and we study its consequences on the excitation spectrum of the nuclei under investigation by using a quasiparticle random-phase-approximation approach. The excitation energies of the low-lying 4+ states can be related to the presence of semibubble structure in nuclei.

Structure and Electronic Properties of Nano-complex CCl4…Cr(AcacCl)3 on Evidence Derived from Vibrational Spectroscopy

NASA Astrophysics Data System (ADS)

Slabzhennikov, S. N.; Kuarton, L. A.; Ryabchenko, O. B.

In order to specify influence of intermolecular interaction on IR spectrum of interacting species, an investigation of a process CCl4 + Cr(AcacCl)3 → CCl4…Cr(AcacCl)3 has been performed by means of Hartree-Fock-Roothaan method in MIDI basis set with p- and d- polarization functions. An estimation of intermolecular interaction in geometrical parameters, electron density function both between interacting particles and inside themselves, frequencies and intensities of normal modes has been carried out. Chemical bonds with the most significant shifts of characteristics under formation of nano-complex CCl4…Cr(AcacCl)3 have been noted.

Low-rank factorization of electron integral tensors and its application in electronic structure theory

DOE Office of Scientific and Technical Information (OSTI.GOV)

Peng, Bo; Kowalski, Karol

In this paper, we apply reverse Cuthill-McKee (RCM) algorithm to transform two-electron integral tensors to their block diagonal forms. By further applying Cholesky decomposition (CD) on each of the diagonal blocks, we are able to represent the high-dimensional two-electron integral tensors in terms of permutation matrices and low-rank Cholesky vectors. This representation facilitates low-rank factorizations of high-dimensional tensor contractions in post-Hartree-Fock calculations. Finally, we discuss the second-order Møller-Plesset (MP2) method and the linear coupled-cluster model with doubles (L-CCD) as examples to demonstrate the efficiency of this technique in representing the two-electron integrals in a compact form.

Multiple mobility edges in a 1D Aubry chain with Hubbard interaction in presence of electric field: Controlled electron transport

NASA Astrophysics Data System (ADS)

Saha, Srilekha; Maiti, Santanu K.; Karmakar, S. N.

2016-09-01

Electronic behavior of a 1D Aubry chain with Hubbard interaction is critically analyzed in presence of electric field. Multiple energy bands are generated as a result of Hubbard correlation and Aubry potential, and, within these bands localized states are developed under the application of electric field. Within a tight-binding framework we compute electronic transmission probability and average density of states using Green's function approach where the interaction parameter is treated under Hartree-Fock mean field scheme. From our analysis we find that selective transmission can be obtained by tuning injecting electron energy, and thus, the present model can be utilized as a controlled switching device.

Microwave spectrum and structure of bicyclo /1.1.1/ pentanone and comparison with several theoretical structures

NASA Technical Reports Server (NTRS)

Mcrae, Glenn A.; Cohen, Edward A.; Sponsler, Michael B.; Dougherty, Dennis A.

1986-01-01

The microwave spectra of five isotopic species of bicyclo (1.1.1) pentanone have been investigated. The rotational constants along with various centrifugal distortion constants for each species have been determined. From the rotational constants, a complete r(s) structure has been determined for the heavy atoms. Analysis of Stark effect measurements has shown the dipole moment to be along the a principal inertial axis with a magnitude of 3.164 (5) D. These results are compared with those obtained by four current theoretical methods: molecular mechanics (MM2), MNDO, and Hartree-Fock ab initio theory with STO-3G and 3-21G basis sets.

Direct Quantum Dynamics Using Grid-Based Wave Function Propagation and Machine-Learned Potential Energy Surfaces.

PubMed

Richings, Gareth W; Habershon, Scott

2017-09-12

We describe a method for performing nuclear quantum dynamics calculations using standard, grid-based algorithms, including the multiconfiguration time-dependent Hartree (MCTDH) method, where the potential energy surface (PES) is calculated "on-the-fly". The method of Gaussian process regression (GPR) is used to construct a global representation of the PES using values of the energy at points distributed in molecular configuration space during the course of the wavepacket propagation. We demonstrate this direct dynamics approach for both an analytical PES function describing 3-dimensional proton transfer dynamics in malonaldehyde and for 2- and 6-dimensional quantum dynamics simulations of proton transfer in salicylaldimine. In the case of salicylaldimine we also perform calculations in which the PES is constructed using Hartree-Fock calculations through an interface to an ab initio electronic structure code. In all cases, the results of the quantum dynamics simulations are in excellent agreement with previous simulations of both systems yet do not require prior fitting of a PES at any stage. Our approach (implemented in a development version of the Quantics package) opens a route to performing accurate quantum dynamics simulations via wave function propagation of many-dimensional molecular systems in a direct and efficient manner.

L i ( i = 1-3) subshell X-ray production cross sections and fluorescence yields for some elements with 56 ⩽ Z ⩽ 68 at 22.6 keV

NASA Astrophysics Data System (ADS)

Chauhan, Yogeshwar; Tiwari, M. K.; Puri, Sanjiv

2008-01-01

The L k ( k = l, α, β 1,4, β 3,6, β 2,15,9,10,7, γ 1,5 and γ 2,3,4) X-ray production (XRP) cross sections have been measured for six elements with 56 ⩽ Z ⩽ 68 at 22.6 keV incident photon energy using the EDXRF spectrometer. The incident photon intensity, detector efficiency and geometrical factors have been determined from the K X-ray yields emitted from elemental targets with 22 ⩽ Z ⩽ 42 in the same geometrical setup and from knowledge of the K XRP cross sections. The L 1 and L 2 subshell fluorescence yields have been deduced from the present measured L k XRP cross sections using the relativistic Hartree-Fock-Slater (HFS) model based photoionization cross sections. The present deduced ω1 (exp) values have been found to be, on an average, higher by 15% and 20% than those based on the Dirac-Hartree-Slater (DHS) model and the semi-empirical values compiled by Krause, respectively, for elements with 60 ⩽ Z ⩽ 68.

M ξ, M αβ, M γ and M m X-ray production cross-sections for elements with 71⩽ z⩽92 at 5.96 keV photon energy

NASA Astrophysics Data System (ADS)

Sharma, Manju; Sharma, Veena; Kumar, Sanjeev; Puri, S.; Singh, Nirmal

2006-11-01

The M ξ, M αβ, M γ and M m X-ray production (XRP) cross-sections have been measured for the elements with 71⩽ Z⩽92 at 5.96 keV incident photon energy satisfying EM1< Einc< EL3, where EM1(L3) is the M 1(L 3) subshell binding energy. These XRP cross-sections have been calculated using photoionization cross-sections based on the relativistic Dirac-Hartree-Slater (RDHS) model with three sets of X-ray emission rates, fluorescence, Coster-Kronig and super Coster-Kronig yields based on (i) the non-relativistic Hartree-Slater (NRHS) potential model, (ii) the RDHS model and (iii) the relativistic Dirac-Fock (RDF) model. For the third set, the M i ( i=1-5) subshell fluorescence yields have been calculated using the RDF model-based X-ray emission rates and total widths reevaluated to incorporate the RDF model-based radiative widths. The measured cross-sections have been compared with the calculated values to check the applicability of the physical parameters based on different models.

A single-electron picture based on the multiconfiguration time-dependent Hartree-Fock method: application to the anisotropic ionization and subsequent high-harmonic generation of the CO molecule

NASA Astrophysics Data System (ADS)

Ohmura, S.; Kato, T.; Oyamada, T.; Koseki, S.; Ohmura, H.; Kono, H.

2018-02-01

The mechanisms of anisotropic near-IR tunnel ionization and high-order harmonic generation (HHG) in a CO molecule are theoretically investigated by using the multiconfiguration time-dependent Hartree-Fock (MCTDHF) method developed for the simulation of multielectron dynamics of molecules. The multielectron dynamics obtained by numerically solving the equations of motion (EOMs) in the MCTDHF method is converted to a single orbital picture in the natural orbital representation where the first-order reduced density matrix is diagonalized. The ionization through each natural orbital is examined and the process of HHG is classified into different optical paths designated by a combinations of initial, intermediate and final natural orbitals. The EOMs for natural spin-orbitals are also derived within the framework of the MCTDHF, which maintains the first-order reduced density matrix to be a diagonal one throughout the time propagation of a many-electron wave function. The orbital dependent, time-dependent effective potentials that govern the dynamics of respective time-dependent natural orbitals are deduced from the derived EOMs, of which the temporal variation can be used to interpret the motion of the electron density associated with each natural spin-orbital. The roles of the orbital shape, multiorbital ionization, linear Stark effect and multielectron interaction in the ionization and HHG of a CO molecule are revealed by the effective potentials obtained. When the laser electric field points to the nucleus O from C, tunnel ionization from the C atom side is enhanced; a hump structure originating from multielectron interaction is then formed on the top of the field-induced distorted barrier of the HOMO effective potential. This hump formation, responsible for the directional anisotropy of tunnel ionization, restrains the influence of the linear Stark effect on the energy shifts of bound states.

Etats excites en couche interne de haut spin de neon hautement ionise

NASA Astrophysics Data System (ADS)

Lapierre, Alain

En plus d'être observés lors de plusieurs phénomènes d'interactions multi- électroniques et multi-atomiques, la description des états excités en couche interne est un test sensible à celle de la corrélation électronique. Suivant une spectroscopie faisceau- lame effectuée antérieurement des régions spectrales de l'ultraviolet et du visible (1800-5300 Å) de néon à 10 MeV, des raies spectrales (d'émission) satellites de celles des transitions hydrogéniques (l = n - 1) et l < n - 1, n = 6 - n' = 7, n = 7 - n' = 8 et n = 8 - n' = 9 du néon lithiumoïde (Ne VIII) sont assignées à l'aide de calculs Hartree-Fock, à des transitions de mêmes nombres quantiques principaux entre des états quadruplet dont le cœur est excité en 1s2s 3S. Quelques raies sont assignées à des transitions entre des niveaux n = 3 pour le Ne VI, VII et IX. Par la suite, les transitions quadruplet, quintuplet et sextuplet n = 2 - n' = 3 et n = 2 - n' = 4 du néon lithiumoïde, bérylliumoïde (Ne VII) et boroïde (Ne VI), respectivement, ont été investiguées par spectroscopie faisceau-lame dans la région spectrale des XUV (60-125 Å). Ces investigations sont supportées par des calculs Hartree-Fock et des régressions linéaires sur les séquences isoélectroniques, effectués en parallèle. Des mesures de la durée de vie moyenne de termes n = 3 ont été réalisées et plusieurs raies sont nouvellement identifiées à des transitions de Ne VI à IX.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Malli, Gulzari L., E-mail: malli@sfu.ca

Our ab initio all-electron fully relativistic Dirac-Fock (DF) and nonrelativistic Hartree-Fock (NR) calculations for seaborgium isocarbonyl SgOC predict atomization energy (AE) of 13.04 and 11.05 eV, respectively. However, the corresponding DF and NR atomization energies for the seaborgium carbonyl SgCO are predicted as 12.75 and 12.45 eV, respectively. This is the first such result in Chemistry where an isocarbonyl (and especially for a system of superheavy element Sg) is predicted to be more stable at the DF level of theory than the corresponding carbonyl. The predicted energy for the formation of the carbonyl SgCO at the relativistic DF and NRmore » levels of theory is -54.90 and -50.95 kJ /mol, whereas the corresponding energy of formation of the isocarbonyl SgOC is -64.44 and -18.64 kJ/mol, respectively. Ours are the first results of relativistic effects for isomerization and atomization energies of the superheavy seaborgium isocarbonyl SgOC and its isomer SgCO.The formation of isocarbonyl SgOC, should be favored over the carbonyl isomer SgCO in the first step of the reaction Sg+CO →SgOC.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Malli, Gulzari L.

Our ab initio all-electron fully relativistic Dirac-Fock (DF) and nonrelativistic Hartree-Fock (NR) calculations for seaborgium isocarbonyl SgOC predict atomization energy (AE) of 13.04 and 11.05 eV, respectively. However, the corresponding DF and NR atomization energies for the seaborgium carbonyl SgCO are predicted as 12.75 and 12.45 eV, respectively. This is the first such result in Chemistry where an isocarbonyl (and especially for a system of superheavy element Sg) is predicted to be more stable at the DF level of theory than the corresponding carbonyl. The predicted energy for the formation of the carbonyl SgCO at the relativistic DF and NRmore » levels of theory is -54.90 and -50.95 kJ /mol, whereas the corresponding energy of formation of the isocarbonyl SgOC is -64.44 and -18.64 kJ/mol, respectively. Ours are the first results of relativistic effects for isomerization and atomization energies of the superheavy seaborgium isocarbonyl SgOC and its isomer SgCO. Lastly, the formation of isocarbonyl SgOC, should be favored over the carbonyl isomer SgCO in the first step of the reaction Sg+CO →SgOC.« less

Static electric dipole polarizabilities of tri- and tetravalent U, Np, and Pu ions.

PubMed

Parmar, Payal; Peterson, Kirk A; Clark, Aurora E

2013-11-21

High-quality static electric dipole polarizabilities have been determined for the ground states of the hard-sphere cations of U, Np, and Pu in the III and IV oxidation states. The polarizabilities have been calculated using the numerical finite field technique in a four-component relativistic framework. Methods including Fock-space coupled cluster (FSCC) and Kramers-restricted configuration interaction (KRCI) have been performed in order to account for electron correlation effects. Comparisons between polarizabilities calculated using Dirac-Hartree-Fock (DHF), FSCC, and KRCI methods have been made using both triple- and quadruple-ζ basis sets for U(4+). In addition to the ground state, this study also reports the polarizability data for the first two excited states of U(3+/4+), Np(3+/4+), and Pu(3+/4+) ions at different levels of theory. The values reported in this work are the most accurate to date calculations for the dipole polarizabilities of the hard-sphere tri- and tetravalent actinide ions and may serve as reference values, aiding in the calculation of various electronic and response properties (for example, intermolecular forces, optical properties, etc.) relevant to the nuclear fuel cycle and material science applications.

The vibrational spectroscopic studies and molecular property analysis of L-Phenylalanine using quantum chemical method

NASA Astrophysics Data System (ADS)

Borah, Mukunda Madhab; Devi, Th. Gomti

2017-05-01

In the present work, L-phenylalanine is studied using the experimental and theoretical methods. The spectral characterization of the molecule has been done using Raman, FTIR, Hartee-Fock(HF), density functional theory (DFT) and vibrational energy distribution analysis (VEDA) calculation. The optimization of the molecule has been studied using basis set HF/6-31G(d,p) and B3LYP/6-31G(d,p) for Hartree Fock and density functional theory calculation. The complete vibrational assignment of the molecule in monomer and dimer states have been attempted. The potential energy distribution and normal mode analysis are also carried out to determine the contributions of bond oscillators in each normal mode. The molecular geometry, HOMO-LUMO energy gap, molecular hardness (η), ionization energy (IE), electron affinity (EA), total energy and dipole moment were determined from the calculated data. The observed experimental and the scaled theoretical results are compared and found to be in good agreement. The vibrational assignment of molecule in different dimer states has also been done using SERS data and better correlated Raman peaks are observed as compare to normal Raman technique.

Relativistic interpretation of the nature of the nuclear tensor force

NASA Astrophysics Data System (ADS)

Zong, Yao-Yao; Sun, Bao-Yuan

2018-02-01

The spin-dependent nature of the nuclear tensor force is studied in detail within the relativistic Hartree-Fock approach. The relativistic formalism for the tensor force is supplemented with an additional Lorentz-invariant tensor formalism in the σ-scalar channel, so as to take into account almost fully the nature of the tensor force brought about by the Fock diagrams in realistic nuclei. Specifically, the tensor sum rules are tested for the spin and pseudo-spin partners with and without nodes, to further understand the nature of the tensor force within the relativistic model. It is shown that the interference between the two components of nucleon spinors causes distinct violations of the tensor sum rules in realistic nuclei, mainly due to the opposite signs on the κ quantities of the upper and lower components, as well as the nodal difference. However, the sum rules can be precisely reproduced if the same radial wave functions are taken for the spin/pseudo-spin partners in addition to neglecting the lower/upper components, revealing clearly the nature of the tensor force. Supported by National Natural Science Foundation of China (11375076, 11675065) and the Fundamental Research Funds for the Central Universities (lzujbky-2016-30)

Zn Coordination Chemistry:  Development of Benchmark Suites for Geometries, Dipole Moments, and Bond Dissociation Energies and Their Use To Test and Validate Density Functionals and Molecular Orbital Theory.

PubMed

Amin, Elizabeth A; Truhlar, Donald G

2008-01-01

We present nonrelativistic and relativistic benchmark databases (obtained by coupled cluster calculations) of 10 Zn-ligand bond distances, 8 dipole moments, and 12 bond dissociation energies in Zn coordination compounds with O, S, NH3, H2O, OH, SCH3, and H ligands. These are used to test the predictions of 39 density functionals, Hartree-Fock theory, and seven more approximate molecular orbital theories. In the nonrelativisitic case, the M05-2X, B97-2, and mPW1PW functionals emerge as the most accurate ones for this test data, with unitless balanced mean unsigned errors (BMUEs) of 0.33, 0.38, and 0.43, respectively. The best local functionals (i.e., functionals with no Hartree-Fock exchange) are M06-L and τ-HCTH with BMUEs of 0.54 and 0.60, respectively. The popular B3LYP functional has a BMUE of 0.51, only slightly better than the value of 0.54 for the best local functional, which is less expensive. Hartree-Fock theory itself has a BMUE of 1.22. The M05-2X functional has a mean unsigned error of 0.008 Å for bond lengths, 0.19 D for dipole moments, and 4.30 kcal/mol for bond energies. The X3LYP functional has a smaller mean unsigned error (0.007 Å) for bond lengths but has mean unsigned errors of 0.43 D for dipole moments and 5.6 kcal/mol for bond energies. The M06-2X functional has a smaller mean unsigned error (3.3 kcal/mol) for bond energies but has mean unsigned errors of 0.017 Å for bond lengths and 0.37 D for dipole moments. The best of the semiempirical molecular orbital theories are PM3 and PM6, with BMUEs of 1.96 and 2.02, respectively. The ten most accurate functionals from the nonrelativistic benchmark analysis are then tested in relativistic calculations against new benchmarks obtained with coupled-cluster calculations and a relativistic effective core potential, resulting in M05-2X (BMUE = 0.895), PW6B95 (BMUE = 0.90), and B97-2 (BMUE = 0.93) as the top three functionals. We find significant relativistic effects (∼0.01 Å in bond lengths, ∼0.2 D in dipole moments, and ∼4 kcal/mol in Zn-ligand bond energies) that cannot be neglected for accurate modeling, but the same density functionals that do well in all-electron nonrelativistic calculations do well with relativistic effective core potentials. Although most tests are carried out with augmented polarized triple-ζ basis sets, we also carried out some tests with an augmented polarized double-ζ basis set, and we found, on average, that with the smaller basis set DFT has no loss in accuracy for dipole moments and only ∼10% less accurate bond lengths.

Sum-over-states density functional perturbation theory: Prediction of reliable 13C, 15N, and 17O nuclear magnetic resonance chemical shifts

NASA Astrophysics Data System (ADS)

Olsson, Lars; Cremer, Dieter

1996-11-01

Sum-over-states density functional perturbation theory (SOS-DFPT) has been used to calculate 13C, 15N, and 17O NMR chemical shifts of 20 molecules, for which accurate experimental gas-phase values are available. Compared to Hartree-Fock (HF), SOS-DFPT leads to improved chemical shift values and approaches the degree of accuracy obtained with second order Møller-Plesset perturbation theory (MP2). This is particularly true in the case of 15N chemical shifts where SOS-DFPT performs even better than MP2. Additional improvements of SOS-DFPT chemical shifts can be obtained by empirically correcting diamagnetic and paramagnetic contributions to compensate for deficiencies which are typical of DFT.

Atomic Decay Data for Modeling K Lines of Iron Peak and Light Odd-Z Elements*

NASA Technical Reports Server (NTRS)

Palmeri, P.; Quinet, P.; Mendoza, C.; Bautista, M. A.; Garcia, J.; Witthoeft, M. C.; Kallman, T. R.

2012-01-01

Complete data sets of level energies, transition wavelengths, A-values, radiative and Auger widths and fluorescence yields for K-vacancy levels of the F, Na, P, Cl, K, Sc, Ti, V, Cr, Mn, Co, Cu and Zn isonuclear sequences have been computed by a Hartree-Fock method that includes relativistic corrections as implemented in Cowan's atomic structure computer suite. The atomic parameters for more than 3 million fine-structure K lines have been determined. Ions with electron number N greater than 9 are treated for the first time, and detailed comparisons with available measurements and theoretical data for ions with N less than or equal to 9 are carried out in order to estimate reliable accuracy ratings.

Atomic electron energies including relativistic effects and quantum electrodynamic corrections

NASA Technical Reports Server (NTRS)

Aoyagi, M.; Chen, M. H.; Crasemann, B.; Huang, K. N.; Mark, H.

1977-01-01

Atomic electron energies have been calculated relativistically. Hartree-Fock-Slater wave functions served as zeroth-order eigenfunctions to compute the expectation of the total Hamiltonian. A first order correction to the local approximation was thus included. Quantum-electrodynamic corrections were made. For all orbitals in all atoms with 2 less than or equal to Z less than or equal to 106, the following quantities are listed: total energies, electron kinetic energies, electron-nucleus potential energies, electron-electron potential energies consisting of electrostatic and Breit interaction (magnetic and retardation) terms, and vacuum polarization energies. These results will serve for detailed comparison of calculations based on other approaches. The magnitude of quantum electrodynamic corrections is exhibited quantitatively for each state.

Microscopic Modeling of Intersubband Optical Processes in Type II Semiconductor Quantum Wells: Linear Absorption

NASA Technical Reports Server (NTRS)

Li, Jian-Zhong; Kolokolov, Kanstantin I.; Ning, Cun-Zheng

2003-01-01

Linear absorption spectra arising from intersubband transitions in semiconductor quantum well heterostructures are analyzed using quantum kinetic theory by treating correlations to the first order within Hartree-Fock approximation. The resulting intersubband semiconductor Bloch equations take into account extrinsic dephasing contributions, carrier-longitudinal optical phonon interaction and carrier-interface roughness interaction which is considered with Ando s theory. As input for resonance lineshape calculation, a spurious-states-free 8-band kp Hamiltonian is used, in conjunction with the envelop function approximation, to compute self-consistently the energy subband structure of electrons in type II InAs/AlSb single quantum well structures. We demonstrate the interplay of nonparabolicity and many-body effects in the mid-infrared frequency range for such heterostructures.

Short-range correlations in carbon-12, oxygen-16, and neon-20: Intrinsic properties

NASA Technical Reports Server (NTRS)

Braley, R. C.; Ford, W. F.; Becker, R. L.; Patterson, M. R.

1972-01-01

The Brueckner-Hartree-Fock (BHF) method has been applied to nuclei whose intrinsic structure is nonspherical. Reaction matrix elements were calculated as functions of starting energy for the Hamada-Johnston interaction using the Pauli operator appropriate to O-16 and a shifted oscillator spectrum for virtual excited states. Binding energies, single particle energies, radii, and shape deformations of the intrinsic state, in ordinary as well as renormalized BHF, are discussed and compared with previous HF studies and with experiment when possible. Results are presented for C-12, 0-16 and Ne-20. It is found that the binding energies and radii are too small, but that separation energies are well reproduced when the renormalized theory is used.

Energy-consistent small-core pseudopotentials for 3d-transition metals adapted to quantum Monte Carlo calculations.

PubMed

Burkatzki, M; Filippi, Claudia; Dolg, M

2008-10-28

We extend our recently published set of energy-consistent scalar-relativistic Hartree-Fock pseudopotentials by the 3d-transition metal elements, scandium through zinc. The pseudopotentials do not exhibit a singularity at the nucleus and are therefore suitable for quantum Monte Carlo (QMC) calculations. The pseudopotentials and the accompanying basis sets (VnZ with n=T,Q) are given in standard Gaussian representation and their parameter sets are presented. Coupled cluster, configuration interaction, and QMC studies are carried out for the scandium and titanium atoms and their oxides, demonstrating the good performance of the pseudopotentials. Even though the choice of pseudopotential form is motivated by QMC, these pseudopotentials can also be employed in other quantum chemical approaches.

Mass, radius and composition of the outer crust of nonaccreting cold neutron stars

NASA Astrophysics Data System (ADS)

Hempel, Matthias; Schaffner-Bielich, Jürgen

2008-01-01

The properties and composition of the outer crust of nonaccreting cold neutron stars are studied by applying the model of Baym, Pethick and Sutherland, which was extended by including higher order corrections of the atomic binding, screening, exchange and zero-point energy. The most recent experimental nuclear data from the atomic mass table of Audi, Wapstra and Thibault from 2003 are used. Extrapolation to the drip line is utilized by various state-of-the-art theoretical nuclear models (finite range droplet, relativistic nuclear field and non-relativistic Skyrme Hartree Fock parameterizations). The different nuclear models are compared with respect to the mass and radius of the outer crust for different neutron star configurations and the nuclear compositions of the outer crust.

Theoretical analysis for the specific heat and thermal parameters of solid C60

NASA Astrophysics Data System (ADS)

Soto, J. R.; Calles, A.; Castro, J. J.

1997-08-01

We present the results of a theoretical analysis for the thermal parameters and phonon contribution to the specific heat in solid C60. The phonon contribution to the specific heat is calculated through the solution of the corresponding dynamical matrix, for different points in the Brillouin zone, and the construccion of the partial and generalized phonon density of states. The force constants are obtained from a first principle calculation, using a SCF Hartree-Fock wave function from the Gaussian 92 program. The thermal parameters reported are the effective temperatures and vibrational amplitudes as a function of temperature. Using this model we present a parametization scheme in order to reproduce the general behaviour of the experimental specific heat for these materials.

Quanty4RIXS: a program for crystal field multiplet calculations of RIXS and RIXS-MCD spectra using Quanty.

PubMed

Zimmermann, Patric; Green, Robert J; Haverkort, Maurits W; de Groot, Frank M F

2018-05-01

Some initial instructions for the Quanty4RIXS program written in MATLAB ® are provided. The program assists in the calculation of 1s 2p RIXS and 1s 2p RIXS-MCD spectra using Quanty. Furthermore, 1s XAS and 2p 3d RIXS calculations in different symmetries can also be performed. It includes the Hartree-Fock values for the Slater integrals and spin-orbit interactions for several 3d transition metal ions that are required to create the .lua scripts containing all necessary parameters and quantum mechanical definitions for the calculations. The program can be used free of charge and is designed to allow for further adjustments of the scripts. open access.

Theory of inhomogeneous quantum systems. III. Variational wave functions for Fermi fluids

NASA Astrophysics Data System (ADS)

Krotscheck, E.

1985-04-01

We develop a general variational theory for inhomogeneous Fermi systems such as the electron gas in a metal surface, the surface of liquid 3He, or simple models of heavy nuclei. The ground-state wave function is expressed in terms of two-body correlations, a one-body attenuation factor, and a model-system Slater determinant. Massive partial summations of cluster expansions are performed by means of Born-Green-Yvon and hypernetted-chain techniques. An optimal single-particle basis is generated by a generalized Hartree-Fock equation in which the two-body correlations screen the bare interparticle interaction. The optimization of the pair correlations leads to a state-averaged random-phase-approximation equation and a strictly microscopic determination of the particle-hole interaction.

Length-dependence of intramolecular electron transfer in σ-bonded rigid molecular rods: an ab initio molecular orbital study

NASA Astrophysics Data System (ADS)

Pati, Ranjit; Karna, Shashi P.

2002-01-01

The dependence of electron transfer (ET) coupling element, VAB, on the length of rigid-rod-like systems consisting of bicyclo[1.1.1]pentane (BCP), cubane (CUB), and bicyclo[2.2.2]octane (BCO) monomers, has been investigated with the use of ab initio Hartree-Fock (HF) method employing Marcus-Hush two-state (TS) model. The value of VAB decreases exponentially with increase in the number of the cage units of the σ-bonded molecules. The calculated decay constant, β, shows good agreement with previously reported data. For molecular length⩾15 Å, the value of VAB becomes negligibly small, suggesting complete suppression of the through bond direct tunneling contribution to ET process.

Spectra for the reemission of attosecond and shorter electromagnetic pulses by multielectron atoms

NASA Astrophysics Data System (ADS)

Makarov, D. N.; Matveev, V. I.

2017-08-01

Based on the analytical solution of the Schrödinger equation, we have considered the reemission of attosecond and shorter electromagnetic pulses by multielectron atoms in the sudden perturbation approximation. We have developed a technique of calculating the spectra for the reemission of attosecond and shorter electromagnetic pulses by neutral multielectron atoms with nuclear charges from 1 to 92. The results are presented in the form of analytical formulas dependent on several coefficients and screening parameters tabulated for all of the atoms whose electron densities are described by the well-known Dirac-Hartree-Fock-Slater model. As examples we have calculated the spectra for the reemission by lithium, carbon, calcium, and iron atoms for two types of incident pulse: Gaussian and "sombrero."

New Critical Compilations of Atomic Transition Probabilities for Neutral and Singly Ionized Carbon, Nitrogen, and Iron

NASA Technical Reports Server (NTRS)

Wiese, Wolfgang L.; Fuhr, J. R.

2006-01-01

We have undertaken new critical assessments and tabulations of the transition probabilities of important lines of these spectra. For Fe I and Fe II, we have carried out a complete re-assessment and update, and we have relied almost exclusively on the literature of the last 15 years. Our updates for C I, C II and N I, N II primarily address the persistent lower transitions as well as a greatly expanded number of forbidden lines (M1, M2, and E2). For these transitions, sophisticated multiconfiguration Hartree-Fock (MCHF) calculations have been recently carried out, which have yielded data considerably improved and often appreciably different from our 1996 NIST compilation.

Two-photon excitation cross-section in light and intermediate atoms

NASA Technical Reports Server (NTRS)

Omidvar, K.

1980-01-01

The method of explicit summation over the intermediate states is used along with LS coupling to derive an expression for two-photon absorption cross section in light and intermediate atoms in terms of integrals over radial wave functions. Two selection rules, one exact and one approximate, are also derived. In evaluating the radial integrals, for low-lying levels, the Hartree-Fock wave functions, and for high-lying levels, hydrogenic wave functions obtained by the quantum defect method are used. A relationship between the cross section and the oscillator strengths is derived. Cross sections due to selected transitions in nitrogen, oxygen, and chlorine are given. The expression for the cross section is useful in calculating the two-photon absorption in light and intermediate atoms.

Two-photon excitation cross section in light and intermediate atoms in frozen-core LS-coupling approximation

NASA Technical Reports Server (NTRS)

Omidvar, K.

1980-01-01

Using the method of explicit summation over the intermediate states two-photon absorption cross sections in light and intermediate atoms based on the simplistic frozen-core approximation and LS coupling have been formulated. Formulas for the cross section in terms of integrals over radial wave functions are given. Two selection rules, one exact and one approximate, valid within the stated approximations are derived. The formulas are applied to two-photon absorptions in nitrogen, oxygen, and chlorine. In evaluating the radial integrals, for low-lying levels, the Hartree-Fock wave functions, and for high-lying levels, hydrogenic wave functions obtained by the quantum-defect method have been used. A relationship between the cross section and the oscillator strengths is derived.

Compton profiles and electronic properties of TiB{sub 2}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bhatt, Samir, E-mail: sameerbhatt011@gmail.com; Suthar, K. K.; Ahuja, B. L.

In this paper, we report the experimental Compton profile (CP) of TiB{sub 2} using high energy {sup 137}Cs γ-rays Compton spectrometer. To interpret the experimental momentum density, we have calculated the CPs using Hartree-Fock (HF), density functional theory (DFT) and hybridization of DFT and HF within linear combination of atomic orbitals. The theoretical profile with generalized gradient approximation is found to be relatively in better agreement with the experimental profile. A sharp valley in density of states and hence the pseudogap near the Fermi energy is attributed to hybridization of Ti-3d and B-2p states and almost reverse trend of energymore » bands below and above the Fermi energy.« less

Electronic properties of Laves phase ZrFe{sub 2} using Compton spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bhatt, Samir, E-mail: sameerbhatto11@gmail.com; Kumar, Kishor; Ahuja, B. L.

First-ever experimental Compton profile of Laves phase ZrFe{sub 2}, using indigenous 20 Ci {sup 137}Cs Compton spectrometer, is presented. To analyze the experimental electron momentum density, we have deduced the theoretical Compton profiles using density functional theory (DFT) and hybridization of DFT and Hartree-Fock scheme within linear combination of atomic orbitals (LCAO) method. The energy bands and density of states are also calculated using LCAO prescription. The theoretical profile based on local density approximation gives a better agreement with the experimental profile than other reported schemes. The present investigations validate the inclusion of correlation potential of Perdew-Zunger in predicting themore » electronic properties of ZrFe{sub 2}.« less

Final Scientific/Technical Report: Breakthrough Design and Implementation of Many-Body Theories for Electron Correlation

DOE Office of Scientific and Technical Information (OSTI.GOV)

So Hirata

2012-01-03

This report discusses the following highlights of the project: (1) grid-based Hartree-Fock equation solver; (2) explicitly correlated coupled-cluster and perturbation methods; (3) anharmonic vibrational frequencies and vibrationally averaged NMR and structural parameters of FHF; (4) anharmonic vibrational frequencies and vibrationally averaged structures of hydrocarbon combustion species; (5) anharmonic vibrational analysis of the guanine-cytosine base pair; (6) the nature of the Born-Oppenheimer approximation; (7) Polymers and solids Brillouin-zone downsampling - the modulo MP2 method; (8) explicitly correlated MP2 for extended systems; (9) fast correlated method for molecular crystals - solid formic acid; and (10) fast correlated method for molecular crystals -more » solid hydrogen fluoride.« less

Electron momentum density and band structure calculations of α- and β-GeTe

NASA Astrophysics Data System (ADS)

Vadkhiya, Laxman; Arora, Gunjan; Rathor, Ashish; Ahuja, B. L.

2011-12-01

We have measured isotropic experimental Compton profile of α-GeTe by employing high energy (662 keV) γ-radiation from a 137Cs isotope. To compare our experiment, we have also computed energy bands, density of states, electron momentum densities and Compton profiles of α- and β-phases of GeTe using the linear combination of atomic orbitals method. The electron momentum density is found to play a major role in understanding the topology of bands in the vicinity of the Fermi level. It is seen that the density functional theory (DFT) with generalised gradient approximation is relatively in better agreement with the experiment than the local density approximation and hybrid Hartree-Fock/DFT.

Hybrid and Constrained Resolution-of-Identity Techniques for Coulomb Integrals.

PubMed

Duchemin, Ivan; Li, Jing; Blase, Xavier

2017-03-14

The introduction of auxiliary bases to approximate molecular orbital products has paved the way to significant savings in the evaluation of four-center two-electron Coulomb integrals. We present a generalized dual space strategy that sheds a new light on variants over the standard density and Coulomb-fitting schemes, including the possibility of introducing minimization constraints. We improve in particular the charge- or multipole-preserving strategies introduced respectively by Baerends and Van Alsenoy that we compare to a simple scheme where the Coulomb metric is used for lowest angular momentum auxiliary orbitals only. We explore the merits of these approaches on the basis of extensive Hartree-Fock and MP2 calculations over a standard set of medium size molecules.

Natural chemical shielding analysis of nuclear magnetic resonance shielding tensors from gauge-including atomic orbital calculations

NASA Astrophysics Data System (ADS)

Bohmann, Jonathan A.; Weinhold, Frank; Farrar, Thomas C.

1997-07-01

Nuclear magnetic shielding tensors computed by the gauge including atomic orbital (GIAO) method in the Hartree-Fock self-consistent-field (HF-SCF) framework are partitioned into magnetic contributions from chemical bonds and lone pairs by means of natural chemical shielding (NCS) analysis, an extension of natural bond orbital (NBO) analysis. NCS analysis complements the description provided by alternative localized orbital methods by directly calculating chemical shieldings due to delocalized features in the electronic structure, such as bond conjugation and hyperconjugation. Examples of NCS tensor decomposition are reported for CH4, CO, and H2CO, for which a graphical mnemonic due to Cornwell is used to illustrate the effect of hyperconjugative delocalization on the carbon shielding.

Electronic and magnetic structure of KNiF3 perovskite

NASA Astrophysics Data System (ADS)

Ricart, J. M.; Dovesi, R.; Roetti, C.; Saunders, V. R.

1995-07-01

The ground-state electronic structure of the ferromagnetic and antiferromagnetic phases of KNiF3 has been investigated using the ab initio periodic Hartree-Fock approach. The system is a wide-gap insulator. The antiferromagnetic phase is correctly predicted to be more stable than the ferromagnetic phase (0.031 eV per Ni pair at the experimental geometry). The energy difference between these phases is shown to obey a d-12 (d is the shortest Ni-Ni distance) power law, as suggested in the literature. The superexchange interaction turns out to be additive with respect to the number of Ni-Ni neighbors, as assumed in model spin Hamiltonians. Elastic properties, charge, and spin-density maps, and density of states plots are reported.

Efficient two-component relativistic method for large systems

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nakai, Hiromi; Research Institute for Science and Engineering, Waseda University, Tokyo 169-8555; CREST, Japan Science and Technology Agency, 4-1-8 Honcho, Kawaguchi, Saitama 332-0012

This paper reviews a series of theoretical studies to develop efficient two-component (2c) relativistic method for large systems by the author’s group. The basic theory is the infinite-order Douglas-Kroll-Hess (IODKH) method for many-electron Dirac-Coulomb Hamiltonian. The local unitary transformation (LUT) scheme can effectively produce the 2c relativistic Hamiltonian, and the divide-and-conquer (DC) method can achieve linear-scaling of Hartree-Fock and electron correlation methods. The frozen core potential (FCP) theoretically connects model potential calculations with the all-electron ones. The accompanying coordinate expansion with a transfer recurrence relation (ACE-TRR) scheme accelerates the computations of electron repulsion integrals with high angular momenta and longmore » contractions.« less

Exotic superconducting states in the extended attractive Hubbard model.

PubMed

Nayak, Swagatam; Kumar, Sanjeev

2018-04-04

We show that the extended attractive Hubbard model on a square lattice allows for a variety of superconducting phases, including exotic mixed-symmetry phases with [Formula: see text] and [Formula: see text] symmetries, and a novel [Formula: see text] state. The calculations are performed within the Hartree-Fock Bardeen-Cooper-Schrieffer framework. The ground states of the mean-field Hamiltonian are obtained via a minimization scheme that relaxes the symmetry constraints on the superconducting solutions, hence allowing for a mixing of s-, p- and d-wave order parameters. The results are obtained within the assumption of uniform-density states. Our results show that extended attractive Hubbard model can serve as an effective model for investigating properties of exotic superconductors.

Vibrational analysis and quantum chemical calculations of 2,2‧-bipyridine Zinc(II) halide complexes

NASA Astrophysics Data System (ADS)

Ozel, Aysen E.; Kecel, Serda; Akyuz, Sevim

2007-05-01

In this study the molecular structure and vibrational spectra of Zn(2,2'-bipyridine)X 2 (X = Cl and Br) complexes were studied in their ground states by computational vibrational study and scaled quantum mechanical (SQM) analysis. The geometry optimization, vibrational wavenumber and intensity calculations of free and coordinated 2,2'-bipyridine were carried out with the Gaussian03 program package by using Hartree-Fock (HF) and Density Functional Theory (DFT) with B3LYP functional and 6-31G (d,p) basis set. The total energy distributions (TED) of the vibrational modes were calculated by using Scaled Quantum Mechanical (SQM) analysis. Fundamentals were characterised by their total energy distributions. Coordination sensitive modes of 2,2'-bipyridine were determined.

Exotic superconducting states in the extended attractive Hubbard model

NASA Astrophysics Data System (ADS)

Nayak, Swagatam; Kumar, Sanjeev

2018-04-01

We show that the extended attractive Hubbard model on a square lattice allows for a variety of superconducting phases, including exotic mixed-symmetry phases with dx^2-y^2 + i [s + s^*] and dx^2-y^2 + px symmetries, and a novel px + i py state. The calculations are performed within the Hartree-Fock Bardeen-Cooper-Schrieffer framework. The ground states of the mean-field Hamiltonian are obtained via a minimization scheme that relaxes the symmetry constraints on the superconducting solutions, hence allowing for a mixing of s-, p- and d-wave order parameters. The results are obtained within the assumption of uniform-density states. Our results show that extended attractive Hubbard model can serve as an effective model for investigating properties of exotic superconductors.

Probing the 5 f electrons in Am-I by hybrid density functional theory

NASA Astrophysics Data System (ADS)

Atta-Fynn, Raymond; Ray, Asok K.

2009-11-01

The ground states of the actinides and their compounds continue to be matters of considerable controversies. Experimentally, Americium-I (Am-I) is a non-magnetic dhcp metal whereas theoretically an anti-ferromagnetic ground state is predicted. We show that hybrid density functional theory, which admixes a fraction, λ, of exact Hartree-Fock (HF) exchange with approximate DFT exchange, can correctly reproduce the ground state properties of Am. In particular, for λ=0.40, we obtain a non-magnetic ground state with equilibrium atomic volume, bulk modulus, 5 f electron population, and the density of electronic states all in good agreement with experimental data. We argue that the exact HF exchange corrects the overestimation of the approximate DFT exchange interaction.

Theoretical study of the electron affinities of MF6 and MF - 6 (M=Cr, Mo, and W) using a model potential method

NASA Astrophysics Data System (ADS)

Sakai, Yoshiko; Miyoshi, Eisaku

1987-09-01

Electronic structures of MF6, MF-6, and MF2-6 (M=Cr, Mo, and W) were calculated using a model potential method in the Hartree-Fock-Roothaan scheme. Major relativistic effects were taken into account for the calculations on MoFq6 and WFq6 (q=0, -1, and -2). It is shown that the calculated electron affinities (EAs) are extremely high for all the MF6 molecules, and that the CrF-6 and MoF-6 anions also have positive EAs, whereas the WF-6 anion has a slightly negative EA. The behaviors of the EAs are interpreted with reference to the electronic structures of the MFq6 systems.

Variational and robust density fitting of four-center two-electron integrals in local metrics

NASA Astrophysics Data System (ADS)

Reine, Simen; Tellgren, Erik; Krapp, Andreas; Kjærgaard, Thomas; Helgaker, Trygve; Jansik, Branislav; Høst, Stinne; Salek, Paweł

2008-09-01

Density fitting is an important method for speeding up quantum-chemical calculations. Linear-scaling developments in Hartree-Fock and density-functional theories have highlighted the need for linear-scaling density-fitting schemes. In this paper, we present a robust variational density-fitting scheme that allows for solving the fitting equations in local metrics instead of the traditional Coulomb metric, as required for linear scaling. Results of fitting four-center two-electron integrals in the overlap and the attenuated Gaussian damped Coulomb metric are presented, and we conclude that density fitting can be performed in local metrics at little loss of chemical accuracy. We further propose to use this theory in linear-scaling density-fitting developments.

Variational and robust density fitting of four-center two-electron integrals in local metrics.

PubMed

Reine, Simen; Tellgren, Erik; Krapp, Andreas; Kjaergaard, Thomas; Helgaker, Trygve; Jansik, Branislav; Host, Stinne; Salek, Paweł

2008-09-14

Density fitting is an important method for speeding up quantum-chemical calculations. Linear-scaling developments in Hartree-Fock and density-functional theories have highlighted the need for linear-scaling density-fitting schemes. In this paper, we present a robust variational density-fitting scheme that allows for solving the fitting equations in local metrics instead of the traditional Coulomb metric, as required for linear scaling. Results of fitting four-center two-electron integrals in the overlap and the attenuated Gaussian damped Coulomb metric are presented, and we conclude that density fitting can be performed in local metrics at little loss of chemical accuracy. We further propose to use this theory in linear-scaling density-fitting developments.

Calculation of yrast spectra in the doubly even cadmium isotopes

NASA Astrophysics Data System (ADS)

Khosa, S. K.; Mattu, P. K.

1991-02-01

The observed systematics of the low-lying states in 98-110Cd nuclei and the high-spin yrast spectra with Jπmax<=14+ are examined by carrying out Hartree-Fock-Bogoliubov calculations employing a pairing-plus-quadrupole-quadrupole effective interaction operating in a reasonably large valence space outside an inert 80Zr core. Our calculations reveal that the systematics of the low-lying yrast states in 98-110Cd are intricately linked with the deformation producing tendency of the n-p interaction when operating between spin-orbit-partner (SOP) orbits. Our results indicate that such systematics depend crucially on the simultaneous increase of relative occupation probabilities of the (d5/2)-proton and (d3/2)-neutron orbits in the 98-100Cd isotopes.

Neutron Spectroscopic Factors from Transfer Reactions

NASA Astrophysics Data System (ADS)

Lee, Jenny; Tsang, M. B.

2007-05-01

We have extracted the ground state to ground state neutron spectroscopic factors for 80 nuclei ranging in Z from 3 to 24 by analyzing the past measurements of the angular distributions from (d,p) and (p,d) reactions. We demonstrate an approach that provides systematic and consistent values with a minimum of assumptions. A three-body model with global optical potentials and standard geometry of n-potential is applied. For the 60 nuclei where modern shell model calculations are available, such analysis reproduces, to within 20%, the experimental spectroscopic factors for most nuclei. If we constraint the nucleon-target optical potential and the geometries of the bound neutron-wave function with the modern Hartree-Fock calculations, our deduced neutron spectroscopic factors are reduced by 30% on average.

Dirac-Fock-Breit-Gaunt calculations for tungsten hexacarbonyl W(CO)6.

PubMed

Malli, Gulzari L

2016-05-21

The first all-electron fully relativistic Dirac-Fock-Breit-Gaunt (DFBG), Dirac-Fock (DF), and nonrelativistic (NR) Hartree-Fock (HF) calculations are reported for octahedral (Oh) tungsten hexacarbonyl W(CO)6. Our DF and NR HF calculations predict atomization energy of 73.76 and 70.33 eV, respectively. The relativistic contribution of ∼3.4 eV to the atomization energy of W(CO)6 is fairly significant. The DF and NR energy for the reaction W + 6CO → W(CO)6 is calculated as -7.90 and -8.86 eV, respectively. The mean bond energy predicted by our NR and DF calculations is 142.5 kJ/mol and 177.5 kJ/mol, respectively, and our predicted DF mean bond energy is in excellent agreement with the experimental value of 179 kJ/mol quoted in the literature. The relativistic effects contribute ∼35 kJ/mol to the mean bond energy and the calculated BSSE is 1.6 kcal/mol, which indicates that the triple zeta basis set used here is fairly good. The mean bond energy and the atomization energy calculated in our DFBG SCF calculations, which include variationally both the relativistic and magnetic Breit effects, is 157.4 kJ/mol and 68.84 eV, respectively. The magnetic Breit effects lead to a decrease of ∼20 kJ/mol and ∼4.9 eV for the mean bond energy and atomization energy, respectively, for W(CO)6. Our calculated magnetic Breit interaction energy of -9.79 eV for the energy of reaction (ΔE) for W + 6CO → W(CO)6 is lower by ∼1.90 eV as compared to the corresponding DF value (ΔE) and contributes significantly to the ΔE. A detailed discussion is presented of electronic structure, bonding, and molecular energy levels at various levels of theory for W(CO)6.

L i ( i=1,2,3) subshell X-ray production cross-sections and fluorescence yields for Ir, Pt, Pb and Bi

NASA Astrophysics Data System (ADS)

Singh, P.; Sharma, M.; Shahi, J. S.; Mehta, D.; Singh, N.

2003-09-01

The L i ( i=1,2,3) subshell X-ray production (XRP) cross-sections were measured for 77Ir, 78Pt, 82Pb and 83Bi following direct ionization in the L i ( i=1,2,3) subshells by the 59.54 keV γ-rays and the L 3 subshell by the Br/Rb/Sr/Y K X-rays. The photon sources consisting of an 241Am source in (i) the direct excitation mode and (ii) the secondary excitation mode together with the KBr/RbNO 3/SrCO 3 /Y secondary exciter and an Si(Li) detector were used. The L i ( i=1,2,3) subshell fluorescence yields ( ωi) for these elements were deduced using the measured XRP cross-sections and the L i subshell photoionization cross-sections based on the Hartree-Fock-Slater model. The measured ω1 values are found to be higher upto 50% than those based on the relativistic Dirac-Hartree-Slater (RDHS) calculations, while the ω2 and ω3 values exhibit good agreement. The predicted jump in the RDHS based ω1 values from 77Ir to 78Pt due to onset of intense L 1-L 3M 4 CK transition is not observed.

Axially deformed solution of the Skyrme-Hartree-Fock-Bogoliubov equations using the transformed harmonic oscillator basis (II) HFBTHO v2.00d: A new version of the program

NASA Astrophysics Data System (ADS)

Stoitsov, M. V.; Schunck, N.; Kortelainen, M.; Michel, N.; Nam, H.; Olsen, E.; Sarich, J.; Wild, S.

2013-06-01

We describe the new version 2.00d of the code HFBTHO that solves the nuclear Skyrme-Hartree-Fock (HF) or Skyrme-Hartree-Fock-Bogoliubov (HFB) problem by using the cylindrical transformed deformed harmonic oscillator basis. In the new version, we have implemented the following features: (i) the modified Broyden method for non-linear problems, (ii) optional breaking of reflection symmetry, (iii) calculation of axial multipole moments, (iv) finite temperature formalism for the HFB method, (v) linear constraint method based on the approximation of the Random Phase Approximation (RPA) matrix for multi-constraint calculations, (vi) blocking of quasi-particles in the Equal Filling Approximation (EFA), (vii) framework for generalized energy density with arbitrary density-dependences, and (viii) shared memory parallelism via OpenMP pragmas. Program summaryProgram title: HFBTHO v2.00d Catalog identifier: ADUI_v2_0 Program summary URL:http://cpc.cs.qub.ac.uk/summaries/ADUI_v2_0.html Program obtainable from: CPC Program Library, Queen's University, Belfast, N. Ireland Licensing provisions: GNU General Public License version 3 No. of lines in distributed program, including test data, etc.: 167228 No. of bytes in distributed program, including test data, etc.: 2672156 Distribution format: tar.gz Programming language: FORTRAN-95. Computer: Intel Pentium-III, Intel Xeon, AMD-Athlon, AMD-Opteron, Cray XT5, Cray XE6. Operating system: UNIX, LINUX, WindowsXP. RAM: 200 Mwords Word size: 8 bits Classification: 17.22. Does the new version supercede the previous version?: Yes Catalog identifier of previous version: ADUI_v1_0 Journal reference of previous version: Comput. Phys. Comm. 167 (2005) 43 Nature of problem: The solution of self-consistent mean-field equations for weakly-bound paired nuclei requires a correct description of the asymptotic properties of nuclear quasi-particle wave functions. In the present implementation, this is achieved by using the single-particle wave functions of the transformed harmonic oscillator, which allows for an accurate description of deformation effects and pairing correlations in nuclei arbitrarily close to the particle drip lines. Solution method: The program uses the axial Transformed Harmonic Oscillator (THO) single- particle basis to expand quasi-particle wave functions. It iteratively diagonalizes the Hartree-Fock-Bogoliubov Hamiltonian based on generalized Skyrme-like energy densities and zero-range pairing interactions until a self-consistent solution is found. A previous version of the program was presented in: M.V. Stoitsov, J. Dobaczewski, W. Nazarewicz, P. Ring, Comput. Phys. Commun. 167 (2005) 43-63. Reasons for new version: Version 2.00d of HFBTHO provides a number of new options such as the optional breaking of reflection symmetry, the calculation of axial multipole moments, the finite temperature formalism for the HFB method, optimized multi-constraint calculations, the treatment of odd-even and odd-odd nuclei in the blocking approximation, and the framework for generalized energy density with arbitrary density-dependences. It is also the first version of HFBTHO to contain threading capabilities. Summary of revisions: The modified Broyden method has been implemented, Optional breaking of reflection symmetry has been implemented, The calculation of all axial multipole moments up to λ=8 has been implemented, The finite temperature formalism for the HFB method has been implemented, The linear constraint method based on the approximation of the Random Phase Approximation (RPA) matrix for multi-constraint calculations has been implemented, The blocking of quasi-particles in the Equal Filling Approximation (EFA) has been implemented, The framework for generalized energy density functionals with arbitrary density-dependence has been implemented, Shared memory parallelism via OpenMP pragmas has been implemented. Restrictions: Axial- and time-reversal symmetries are assumed. Unusual features: The user must have access to the LAPACK subroutines DSYEVD, DSYTRF and DSYTRI, and their dependences, which compute eigenvalues and eigenfunctions of real symmetric matrices, the LAPACK subroutines DGETRI and DGETRF, which invert arbitrary real matrices, and the BLAS routines DCOPY, DSCAL, DGEMM and DGEMV for double-precision linear algebra (or provide another set of subroutines that can perform such tasks). The BLAS and LAPACK subroutines can be obtained from the Netlib Repository at the University of Tennessee, Knoxville: http://netlib2.cs.utk.edu/. Running time: Highly variable, as it depends on the nucleus, size of the basis, requested accuracy, requested configuration, compiler and libraries, and hardware architecture. An order of magnitude would be a few seconds for ground-state configurations in small bases N≈8-12, to a few minutes in very deformed configuration of a heavy nucleus with a large basis N>20.

Simultaneous analytical optimization of variational parameters in Gaussian-type functions with full configuration interaction of multicomponent molecular orbital method by elimination of translational and rotational motions: application to isotopomers of the hydrogen molecule.

PubMed

Ishimoto, Takayoshi; Tachikawa, Masanori; Nagashima, Umpei

2008-04-28

We have extended the multicomponent molecular orbital (MCMO) method to the full-configuration interaction (full-CI) fully variational molecular orbital method by elimination of translational and rotational motion components from total Hamiltonian. In the MCMO scheme, the quantum effects of protons and deuterons as well as electrons can be directly taken into account. All variational parameters in the full-CI scheme, i.e., exponents and centers (alpha and R) in the Gaussian-type function (GTF) basis set as well as the CI coefficients, are simultaneously optimized by using their analytical gradients. The total energy of the H(2) molecule calculated using the electronic [6s3p2d1f] and nuclear [1s1p1d1f] GTFs is -1.161 726 hartree, which can be compared to the energy of -1.164 025 hartree reported using a 512 term-explicitly correlated GTF calculation. Although the d- and f-type nuclear GTFs contribute to the improvement of energy convergence, the convergence of electron-nucleus correlation energy is slower than that of electron-electron one. The nuclear wave functions are delocalized due to the electron-nucleus correlation effect compared to the result of Hartree-Fock level of MCMO method. In addition, the average internuclear distances of all diatomic molecules are within 0.001 A of the previously reported experimental results. The dipole moment of the HD molecule estimated by our method is 8.4 x 10(-4) D, which is in excellent agreement with the experimental result of (8-10) x 10(-4) D.

Quantum Monte Carlo calculations of NiO

NASA Astrophysics Data System (ADS)

Maezono, Ryo; Towler, Mike D.; Needs, Richard. J.

2008-03-01

We describe variational and diffusion quantum Monte Carlo (VMC and DMC) calculations [1] of NiO using a 1024-electron simulation cell. We have used a smooth, norm-conserving, Dirac-Fock pseudopotential [2] in our work. Our trial wave functions were of Slater-Jastrow form, containing orbitals generated in Gaussian-basis UHF periodic calculations. Jastrow factor is optimized using variance minimization with optimized cutoff lengths using the same scheme as our previous work. [4] We apply the lattice regulated scheme [5] to evaluate non-local pseudopotentials in DMC and find the scheme improves the smoothness of the energy-volume curve. [1] CASINO ver.2.1 User Manual, University of Cambridge (2007). [2] J.R. Trail et.al., J. Chem. Phys. 122, 014112 (2005). [3] CRYSTAL98 User's Manual, University of Torino (1998). [4] Ryo Maezono et.al., Phys. Rev. Lett., 98, 025701 (2007). [5] Michele Casula, Phys. Rev. B 74, 161102R (2006).

Spiral magnetic order, non-uniform states and electron correlations in the conducting transition metal systems

NASA Astrophysics Data System (ADS)

Igoshev, P. A.; Timirgazin, M. A.; Arzhnikov, A. K.; Antipin, T. V.; Irkhin, V. Yu.

2017-10-01

The ground-state magnetic phase diagram is calculated within the Hubbard and s-d exchange (Kondo) models for square and simple cubic lattices vs. band filling and interaction parameter. The difference of the results owing to the presence of localized moments in the latter model is discussed. We employ a generalized Hartree-Fock approximation (HFA) to treat commensurate ferromagnetic (FM), antiferromagnetic (AFM), and incommensurate (spiral) magnetic phases. The electron correlations are taken into account within the Hubbard model by using the Kotliar-Ruckenstein slave boson approximation (SBA). The main advantage of this approach is a correct qualitative description of the paramagnetic phase: its energy becomes considerably lower as compared with HFA, and the gain in the energy of magnetic phases is substantially reduced.

An Investigation for Ground State Features of Some Structural Fusion Materials

NASA Astrophysics Data System (ADS)

Aytekin, H.; Tel, E.; Baldik, R.; Aydin, A.

2011-02-01

Environmental concerns associated with fossil fuels are creating increased interest in alternative non-fossil energy sources. Nuclear fusion can be one of the most attractive sources of energy from the viewpoint of safety and minimal environmental impact. When considered in all energy systems, the requirements for performance of structural materials in a fusion reactor first wall, blanket or diverter, are arguably more demanding or difficult than for other energy system. The development of fusion materials for the safety of fusion power systems and understanding nuclear properties is important. In this paper, ground state properties for some structural fusion materials as 27Al, 51V, 52Cr, 55Mn, and 56Fe are investigated using Skyrme-Hartree-Fock method. The obtained results have been discussed and compared with the available experimental data.

Modeling Optical Spectra of Large Organic Systems Using Real-Time Propagation of Semiempirical Effective Hamiltonians.

PubMed

Ghosh, Soumen; Andersen, Amity; Gagliardi, Laura; Cramer, Christopher J; Govind, Niranjan

2017-09-12

We present an implementation of a time-dependent semiempirical method (INDO/S) in NWChem using real-time (RT) propagation to address, in principle, the entire spectrum of valence electronic excitations. Adopting this model, we study the UV/vis spectra of medium-sized systems such as P3B2 and f-coronene, and in addition much larger systems such as ubiquitin in the gas phase and the betanin chromophore in the presence of two explicit solvents (water and methanol). RT-INDO/S provides qualitatively and often quantitatively accurate results when compared with RT- TDDFT or experimental spectra. Even though we only consider the INDO/S Hamiltonian in this work, our implementation provides a framework for performing electron dynamics in large systems using semiempirical Hartree-Fock Hamiltonians in general.

Modeling Optical Spectra of Large Organic Systems Using Real-Time Propagation of Semiempirical Effective Hamiltonians

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ghosh, Soumen; Andersen, Amity; Gagliardi, Laura

2017-08-16

We present an implementation of a time-dependent semiempirical method (INDO/S) in NWChem using real-time (RT) propagation to address, in principle, the entire spectrum of valence electronic excitations. Adopting this model, we study the UV-visible spectra of medium-sized systems like P3B2, f-coronene, and in addition much larger systems like ubiquitin in the gas phase and the betanin chromophore in the presence of two explicit solvents (water and methanol). RT-INDO/S provides qualitatively and indeed often quantitatively accurate results when compared with RT- TDDFT or experimental spectra. While demonstrated here for INDO/S in particular, our implementation provides a framework for performing electron dynamicsmore » in large systems using semiempirical Hartree-Fock (HF) Hamiltonians in general.« less

Nuclear Mass Predictions within the Skyrme HFB Theory

NASA Astrophysics Data System (ADS)

Samyn, M.; Goriely, S.; Pearson, J. M.

2005-05-01

To increase the reliability of predictions of highly neutron-rich nuclear masses we systematically analyze the sensitivity of Hartree-Fock-Bogoliubov (HFB) mass formulae to various physical inputs, such as a density dependence of the pairing interaction, a low effective mass, the particle-number projection, the symmetry energy, … We typically use a 10-parameter Skyrme force and a 4-parameter δ-function pairing force. The 14 degrees of freedom are adjusted to the masses of all measured nuclei with N,Z ⩾ 8 given in the 2001 and 2003 Audi et al. compilations. The masses of light and proton-rich nuclei are corrected by a 4-parameter phenomenological Wigner term. With more than ten such parameter sets complete mass tables are constructed, going from one drip line to the other, up to Z = 120.

KIDS Nuclear Energy Density Functional: 1st Application in Nuclei

NASA Astrophysics Data System (ADS)

Gil, Hana; Papakonstantinou, Panagiota; Hyun, Chang Ho; Oh, Yongseok

We apply the KIDS (Korea: IBS-Daegu-Sungkyunkwan) nuclear energy density functional model, which is based on the Fermi momentum expansion, to the study of properties of lj-closed nuclei. The parameters of the model are determined by the nuclear properties at the saturation density and theoretical calculations on pure neutron matter. For applying the model to the study of nuclei, we rely on the Skyrme force model, where the Skyrme force parameters are determined through the KIDS energy density functional. Solving Hartree-Fock equations, we obtain the energies per particle and charge radii of closed magic nuclei, namely, 16O, 28O, 40Ca, 48Ca, 60Ca, 90Zr, 132Sn, and 208Pb. The results are compared with the observed data and further improvement of the model is shortly mentioned.

Application of the top-on-top model to 135Pr

NASA Astrophysics Data System (ADS)

Sugawara-Tanabe, Kazuko; Tanabe, Kosai

2017-09-01

It is proved that the Holstein-Primakoff (HP) boson expansion method is very effective for a case where both total and single-particle angular momenta have the diagonal representation along the same direction. The algebraic solution is described by two kinds of quantum numbers classifying the rotational band’s characteristic of the particle-rotor model. One is related with the wobbling motion of the rotor, and the other to the precession of the single-particle angular momentum. Employing angular-momentum dependent rigid (rig) moments of inertia (MoI), which simulate Coriolis anti-pairing effect based on the constrained self-consistent Hartree-Fock-Bogoliubov (HFB) equation, we obtain good fitting not only to the energy-level scheme, but also to the electromagnetic transition rates and the mixing ratio for 135Pr.

Time-resolved laser spectroscopy of multiply ionized atoms: natural radiative lifetimes in Ce IV.

PubMed

Zhang, Z G; Svanberg, S; Quinet, P; Palmeri, P; Biémont, E

2001-12-31

Radiative lifetimes have been measured for two excited levels of Ce IV using the time-resolved laser-induced fluorescence technique. Ce3+ ions were produced in a laser-induced plasma. In the measurements, a suitable magnetic field was applied to reduce the recombination between electrons and the ions and thus the background light from the recombination, and special care was exercised to avoid flight-out-of-view effects on the lifetime measurements for the high-velocity ions. The experimental lifetime results, tau = 30(2) ns for the level 49 737 cm(-1) and tau = 30(3) ns for the level 52 226 cm(-1), were compared with relativistic Hartree-Fock calculations (tau = 30.5 and 30.0 ns) indicating a particularly excellent agreement.

Nuclear level densities of 64 , 66 Zn from neutron evaporation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ramirez, A. P. D.; Voinov, A. V.; Grimes, S. M.

Double differential cross sections of neutrons from d+ 63,65Cu reactions have been measured at deuteron energies of 6 and 7.5 MeV. The cross sections measured at backward angles have been compared to theoretical calculations in the framework of the statistical Hauser-Feshbach model. Three different level density models were tested: the Fermi-gas model, the Gilbert-Cameron model, and the microscopic approach through the Hartree-Fock-Bogoliubov method (HFBM). The calculations using the Gilbert-Cameron model are in best agreement with our experimental data. Level densities of the residual nuclei 64Zn and 66Zn have been obtained from statistical neutron evaporation spectra. In conclusion, the angle-integrated crossmore » sections have been analyzed with the exciton model of nuclear reaction.« less

The impact of electron correlations on the energetics and stability of silicon nanoclusters

DOE Office of Scientific and Technical Information (OSTI.GOV)

Matsko, N. L.; Baturin, V. S.; Lepeshkin, S. V.

2016-08-21

The first-principles prediction of stable nanocluster structure is often hampered by the existence of many isomer configurations with energies close to the ground state. This fact attaches additional importance to many-electron effects beyond density functional theory (DFT), because their contributions can change a subtle energy order of competitive structures. To analyze this problem, we consider, as an example, the energetics of silicon nanoclusters passivated by hydrogen Si{sub 10}H{sub 2n} (0 ≤ n ≤ 11), where passivation changes the structure from compact to loosely packed and branched. Our calculations performed with DFT, hybrid functionals, and Hartree-Fock methods, as well as bymore » the GW approximation, confirm a considerable sensitivity of isomer energy ordering to many-electron effects.« less

An investigation of satellites to the resonance lines in some hydrogen-like ions. Ph.D. Thesis - Colo. Univ.

NASA Technical Reports Server (NTRS)

Jalufka, N. W.

1972-01-01

An experimental and theoretical investigation was conducted on the origin of satellite to resonance lines of the hydrogen-like ions of boron, carbon, and nitrogen. A theta pinch was employed with a grazing incidence spectrograph to measure the wavelengths of the satellites. The spectroscopic data also provided an estimate of the satellite/resonance line intensity ratio. Wavelengths of spectral lines due to transition from doubly excited states were calculated by a Hartree-Fock computer program. Wave functions were also calculated and were used to obtain the oscillator strengths of the transitions. Experimental work confirmed that the lines investigated were not satellites but were due to highly ionized argon which was present as an impurity in the filling gas.

Contour-time approach to the Bose-Hubbard model in the strong coupling regime: Studying two-point spatio-temporal correlations at the Hartree-Fock-Bogoliubov level

NASA Astrophysics Data System (ADS)

Fitzpatrick, Matthew R. C.; Kennett, Malcolm P.

2018-05-01

We develop a formalism that allows the study of correlations in space and time in both the superfluid and Mott insulating phases of the Bose-Hubbard Model. Specifically, we obtain a two particle irreducible effective action within the contour-time formalism that allows for both equilibrium and out of equilibrium phenomena. We derive equations of motion for both the superfluid order parameter and two-point correlation functions. To assess the accuracy of this formalism, we study the equilibrium solution of the equations of motion and compare our results to existing strong coupling methods as well as exact methods where possible. We discuss applications of this formalism to out of equilibrium situations.

On the effects of basis set truncation and electron correlation in conformers of 2-hydroxy-acetamide

NASA Astrophysics Data System (ADS)

Szarecka, A.; Day, G.; Grout, P. J.; Wilson, S.

Ab initio quantum chemical calculations have been used to study the differences in energy between two gas phase conformers of the 2-hydroxy-acetamide molecule that possess intramolecular hydrogen bonding. In particular, rotation around the central C-C bond has been considered as a factor determining the structure of the hydrogen bond and stabilization of the conformer. Energy calculations include full geometiy optimization using both the restricted matrix Hartree-Fock model and second-order many-body perturbation theory with a number of commonly used basis sets. The basis sets employed ranged from the minimal STO-3G set to [`]split-valence' sets up to 6-31 G. The effects of polarization functions were also studied. The results display a strong basis set dependence.

Phase Separation of Superconducting Phases in the Penson-Kolb-Hubbard Model

NASA Astrophysics Data System (ADS)

Jerzy Kapcia, Konrad; Czart, Wojciech Robert; Ptok, Andrzej

2016-04-01

In this paper, we determine the phase diagrams (for T = 0 as well as T > 0) of the Penson-Kolb-Hubbard model for two dimensional square lattice within Hartree-Fock mean-field theory focusing on an investigation of superconducting phases and on a possibility of the occurrence of the phase separation. We obtain that the phase separation, which is a state of coexistence of two different superconducting phases (with s- and η-wave symmetries), occurs in definite ranges of the electron concentration. In addition, increasing temperature can change the symmetry of the superconducting order parameter (from η-wave into s-wave). The system considered exhibits also an interesting multicritical behaviour including bicritical points. The relevance of the results to experiments for real materials is also discussed.

Quantal diffusion description of multinucleon transfers in heavy-ion collisions

NASA Astrophysics Data System (ADS)

Ayik, S.; Yilmaz, B.; Yilmaz, O.; Umar, A. S.

2018-05-01

Employing the stochastic mean-field (SMF) approach, we develop a quantal diffusion description of the multi-nucleon transfer in heavy-ion collisions at finite impact parameters. The quantal transport coefficients are determined by the occupied single-particle wave functions of the time-dependent Hartree-Fock equations. As a result, the primary fragment mass and charge distribution functions are determined entirely in terms of the mean-field properties. This powerful description does not involve any adjustable parameter, includes the effects of shell structure, and is consistent with the fluctuation-dissipation theorem of the nonequilibrium statistical mechanics. As a first application of the approach, we analyze the fragment mass distribution in 48Ca+ 238U collisions at the center-of-mass energy Ec.m.=193 MeV and compare the calculations with the experimental data.

Projected quasiparticle theory for molecular electronic structure

NASA Astrophysics Data System (ADS)

Scuseria, Gustavo E.; Jiménez-Hoyos, Carlos A.; Henderson, Thomas M.; Samanta, Kousik; Ellis, Jason K.

2011-09-01

We derive and implement symmetry-projected Hartree-Fock-Bogoliubov (HFB) equations and apply them to the molecular electronic structure problem. All symmetries (particle number, spin, spatial, and complex conjugation) are deliberately broken and restored in a self-consistent variation-after-projection approach. We show that the resulting method yields a comprehensive black-box treatment of static correlations with effective one-electron (mean-field) computational cost. The ensuing wave function is of multireference character and permeates the entire Hilbert space of the problem. The energy expression is different from regular HFB theory but remains a functional of an independent quasiparticle density matrix. All reduced density matrices are expressible as an integration of transition density matrices over a gauge grid. We present several proof-of-principle examples demonstrating the compelling power of projected quasiparticle theory for quantum chemistry.

Calculation of (P,T) -odd electric dipole moments for the diamagnetic atoms X129e , Y171b , H199g , R211n , and R225a

NASA Astrophysics Data System (ADS)

Dzuba, V. A.; Flambaum, V. V.; Porsev, S. G.

2009-09-01

Electric dipole moments of diamagnetic atoms of experimental interest are calculated using the relativistic Hartree-Fock and random-phase approximation methods, the many-body perturbation theory, and the configuration-interaction technique. We consider (P,T) -odd interactions, which give rise to atomic electric dipole moment in the second order of the perturbation theory. These include nuclear Schiff moment, (P,T) -odd electron-nucleon interaction, and electron electric dipole moment. Interpretation of an experimental constraint of a permanent electric dipole moment of H199g [W. C. Griffith, M. D. Swallows, T. H. Loftus, M. V. Romalis, B. R. Heckel, and E. N. Fortson, Phys. Rev. Lett. 102, 101601 (2009)] is discussed.

Nuclear level densities of 64 , 66 Zn from neutron evaporation

DOE PAGES

Ramirez, A. P. D.; Voinov, A. V.; Grimes, S. M.; ...

2013-12-26

Double differential cross sections of neutrons from d+ 63,65Cu reactions have been measured at deuteron energies of 6 and 7.5 MeV. The cross sections measured at backward angles have been compared to theoretical calculations in the framework of the statistical Hauser-Feshbach model. Three different level density models were tested: the Fermi-gas model, the Gilbert-Cameron model, and the microscopic approach through the Hartree-Fock-Bogoliubov method (HFBM). The calculations using the Gilbert-Cameron model are in best agreement with our experimental data. Level densities of the residual nuclei 64Zn and 66Zn have been obtained from statistical neutron evaporation spectra. In conclusion, the angle-integrated crossmore » sections have been analyzed with the exciton model of nuclear reaction.« less

Semi-empirical model for stopping cross sections of p, α and Li ions

NASA Astrophysics Data System (ADS)

Alfaz Uddin, M.; Fazlul Haque, A. K.; Talukder, Tanvir I.; Basak, Arun K.; Saha, Bidhan C.; Malik, Fary B.

2013-10-01

Absolute magnitudes of stopping cross sections (SCS) for H+, He2+ and Li3+ in various stopping media with atomic numbers Z 2 = 2 to 100 are calculated using atomic density functions from Dirac-Hartree-Fock-Slater wave functions in the Lindhard-Schraff theory [J. Lindhard, M. Scharff, Kgl. Danske Videnskab. Selskab. Mat. Fys. Medd. 27, 15 (1953)]. The newly proposed formula, characterizing projectile-specific parameters in the incident energy range considered herein, describes satisfactorily the experimental and SRIM-simulated SCS data from low energies, with projectile velocities nearing v = Z 1 v 0 (with Z 1 as the projectile’s atomic number, v 0 = c / 137, the Bohr velocity and c, the speed of light in vacuum), to high energies up to about 2.5 MeV/u.

Probing neutron-skin thickness with total reaction cross sections

NASA Astrophysics Data System (ADS)

Horiuchi, W.; Suzuki, Y.; Inakura, T.

2014-01-01

We analyze total reaction cross sections, σR, to explore their sensitivity to the neutron-skin thickness of nuclei. We cover 91 nuclei of O, Ne, Mg, Si, S, Ca, and Ni isotopes. The cross sections are calculated in the Glauber theory using the density distributions obtained with the Skyrme-Hartree-Fock method in three-dimensional coordinate space. Defining a reaction radius, aR=√σR/π , to characterize the nuclear size and target (proton or 12C) dependence, we find an empirical formula for expressing aR with the point matter radius and the skin thickness, and assess two practical ways of determining the skin thickness from proton-nucleus σR values measured at different energies or from σR values measured for different targets.

Ab Initio Density Fitting: Accuracy Assessment of Auxiliary Basis Sets from Cholesky Decompositions.

PubMed

Boström, Jonas; Aquilante, Francesco; Pedersen, Thomas Bondo; Lindh, Roland

2009-06-09

The accuracy of auxiliary basis sets derived by Cholesky decompositions of the electron repulsion integrals is assessed in a series of benchmarks on total ground state energies and dipole moments of a large test set of molecules. The test set includes molecules composed of atoms from the first three rows of the periodic table as well as transition metals. The accuracy of the auxiliary basis sets are tested for the 6-31G**, correlation consistent, and atomic natural orbital basis sets at the Hartree-Fock, density functional theory, and second-order Møller-Plesset levels of theory. By decreasing the decomposition threshold, a hierarchy of auxiliary basis sets is obtained with accuracies ranging from that of standard auxiliary basis sets to that of conventional integral treatments.

Theoretical studies of large water clusters: (H2O)28, (H2O)29, (H2O)30, and (H2O)31 hexakaidecahedral structures

NASA Astrophysics Data System (ADS)

Khan, Arshad

1997-04-01

The 28, 29, 30, and 31 mer hexakaidecahedral water clusters were studied by applying the intermediate neglect of differential overlap self-consistent field restricted Hartree-Fock method (INDO SCF RHF) after parametrization for H and O atoms. The most stable 29 and 30 mer clusters have one and two water molecules, respectively within the cavity of the distorted hexakaidecahedral cage with stabilization energy/monomer values of around 10.9 and 11.0 kcal, respectively. The 31 mer cluster with three water molecules within the cavity is less stable than the isomer with two molecules within the cavity and the third one bonded outside of the cage by around 3 kcal/mol.

From the crust to the core of neutron stars on a microscopic basis

NASA Astrophysics Data System (ADS)

Baldo, M.; Burgio, G. F.; Centelles, M.; Sharma, B. K.; Viñas, X.

2014-09-01

Within a microscopic approach the structure of Neutron Stars is usually studied by modelling the homogeneous nuclear matter of the core by a suitable Equation of State, based on a many-body theory, and the crust by a functional based on a more phenomenological approach. We present the first calculation of Neutron Star overall structure by adopting for the core an Equation of State derived from the Brueckner-Hartree-Fock theory and for the crust, including the pasta phase, an Energy Density Functional based on the same Equation of State, and which is able to describe accurately the binding energy of nuclei throughout the mass table. Comparison with other approaches is discussed. The relevance of the crust Equation of State for the Neutron Star radius is particularly emphasised.

Publisher Correction: Imaging the square of the correlated two-electron wave function of a hydrogen molecule.

PubMed

Waitz, M; Bello, R Y; Metz, D; Lower, J; Trinter, F; Schober, C; Keiling, M; Lenz, U; Pitzer, M; Mertens, K; Martins, M; Viefhaus, J; Klumpp, S; Weber, T; Schmidt, L Ph H; Williams, J B; Schöffler, M S; Serov, V V; Kheifets, A S; Argenti, L; Palacios, A; Martín, F; Jahnke, T; Dörner, R

2018-06-05

The original version of this Article contained an error in the fifth sentence of the first paragraph of the 'Application on H 2 ' section of the Results, which incorrectly read 'The role of electron correlation is quite apparent in this presentation: Fig. 1a is empty for the uncorrelated Hartree-Fock wave function, since projection of the latter wave function onto the 2pσ u orbital is exactly zero, while this is not the case for the fully correlated wave function (Fig. 1d); also, Fig. 1b, c for the uncorrelated description are identical, while Fig. 1e, f for the correlated case are significantly different.' The correct version replaces 'Fig. 1e, f' with 'Fig. 2e and f'.

Exact exchange and Wilson-Levy correlation: a pragmatic device for studying complex weakly-bonded systems.

PubMed

Walsh, T R

2005-02-07

The Wilson-Levy (WL) correlation functional is used together with Hartree-Fock (HF) theory to evaluate interaction energies at intermediate separations (i.e. around equilibrium separation) for several weakly-bonded systems. The HF+WL approach reproduces binding trends for all complexes studied: selected rare-gas dimers, isomers of the methane dimer, benzene dimer and naphthalene dimer, and base-pair stacking structures for pyrimidine, cytosine, uracil and guanine dimers. These HF+WL data are contrasted against results obtained from some popular functionals (including B3LYP and PBE), as well as two newly-developed functionals, X3LYP and xPBE. The utility of HF+WL, with reference to exact-exchange (EXX) density-functional theory, is discussed in terms of a suggested EXXWL exchange-correlation functional.

Evaluation of DFT methods for computing the interaction energies of homomolecular and heteromolecular dimers of monosubstituted benzene

NASA Astrophysics Data System (ADS)

Godfrey-Kittle, Andrew; Cafiero, Mauricio

We present density functional theory (DFT) interaction energies for the sandwich and T-shaped conformers of substituted benzene dimers. The DFT functionals studied include TPSS, HCTH407, B3LYP, and X3LYP. We also include Hartree-Fock (HF) and second-order Møller-Plesset perturbation theory calculations (MP2), as well as calculations using a new functional, P3LYP, which includes PBE and HF exchange and LYP correlation. Although DFT methods do not explicitly account for the dispersion interactions important in the benzene-dimer interactions, we find that our new method, P3LYP, as well as HCTH407 and TPSS, match MP2 and CCSD(T) calculations much better than the hybrid methods B3LYP and X3LYP methods do.

An ab-initio study of the relative stability of the ggg and the gtg conformer in hexane

NASA Astrophysics Data System (ADS)

Koglin, Eckhard; Meier, Robert J.

1999-10-01

Earlier ab-initio work suggested, on the basis of MP2 level calculations, that the hexane ggg conformer is more stable than the gtg conformer. Because this is unexpected and if true might have a significant impact on force field parametrisations, we have applied Hartree-Fock and post-HF methods to evaluate the relative stability of these conformers. We find that at levels higher than MP2 the gtg conformer is more stable than the ggg conformer, in agreement with the conventional idea that each additional gauche bond causes a further decrease in stability of the conformer. DFT methods were also applied, but although DFT methods including gradient corrections show correct qualitative behaviour, quantitatively the relative energies are far off compared to the post-HF results.

High quality Gaussian basis sets for fourth-row atoms

NASA Technical Reports Server (NTRS)

Partridge, Harry; Faegri, Knut, Jr.

1992-01-01

Energy optimized Gaussian basis sets of triple-zeta quality for the atoms Rb-Xe have been derived. Two series of basis sets are developed: (24s 16p 10d) and (26s 16p 10d) sets which were expanded to 13d and 19p functions as the 4d and 5p shells become occupied. For the atoms lighter than Cd, the (24s 16p 10d) sets with triple-zeta valence distributions are higher in energy than the corresponding double-zeta distribution. To ensure a triple-zeta distribution and a global energy minimum, the (26s 16p 10d) sets were derived. Total atomic energies from the largest basis sets are between 198 and 284 (mu)E(sub H) above the numerical Hartree-Fock energies.

Explicit polarization (X-Pol) potential using ab initio molecular orbital theory and density functional theory.

PubMed

Song, Lingchun; Han, Jaebeom; Lin, Yen-lin; Xie, Wangshen; Gao, Jiali

2009-10-29

The explicit polarization (X-Pol) method has been examined using ab initio molecular orbital theory and density functional theory. The X-Pol potential was designed to provide a novel theoretical framework for developing next-generation force fields for biomolecular simulations. Importantly, the X-Pol potential is a general method, which can be employed with any level of electronic structure theory. The present study illustrates the implementation of the X-Pol method using ab initio Hartree-Fock theory and hybrid density functional theory. The computational results are illustrated by considering a set of bimolecular complexes of small organic molecules and ions with water. The computed interaction energies and hydrogen bond geometries are in good accord with CCSD(T) calculations and B3LYP/aug-cc-pVDZ optimizations.

Integral processing in beyond-Hartree-Fock calculations

NASA Technical Reports Server (NTRS)

Taylor, P. R.

1986-01-01

The increasing rate at which improvements in processing capacity outstrip improvements in input/output performance of large computers has led to recent attempts to bypass generation of a disk-based integral file. The direct self-consistent field (SCF) method of Almlof and co-workers represents a very successful implementation of this approach. This paper is concerned with the extension of this general approach to configuration interaction (CI) and multiconfiguration-self-consistent field (MCSCF) calculations. After a discussion of the particular types of molecular orbital (MO) integrals for which -- at least for most current generation machines -- disk-based storage seems unavoidable, it is shown how all the necessary integrals can be obtained as matrix elements of Coulomb and exchange operators that can be calculated using a direct approach. Computational implementations of such a scheme are discussed.

Accurate electric multipole moment, static polarizability and hyperpolarizability derivatives for N2

NASA Astrophysics Data System (ADS)

Maroulis, George

2003-02-01

We report accurate values of the electric moments, static polarizabilities, hyperpolarizabilities and their respective derivatives for N2. Our values have been extracted from finite-field Møller-Pleset perturbation theory and coupled cluster calculations performed with carefully designed basis sets. A large [15s12p9d7f] basis set consisting of 290 CGTF is expected to provide reference self-consistent-field values of near-Hartree-Fock quality for all properties. The Hartree-Fock limit for the mean hyperpolarizability is estimated at γ¯=715±4e4a04Eh-3 at the experimental bond length Re=2.074 32a0. Accurate estimates of the electron correlation effects were obtained with a [10s7p6d4f] basis set. Our best values are Θ=-1.1258ea02 for the quadrupole and Φ=-6.75ea04 for the hexadecapole moment, ᾱ=11.7709 and Δα=4.6074e2a02Eh-1 for the mean and the anisotropy of the dipole polarizability, C¯=41.63e2a04Eh-1 for the mean quadrupole polarizability and γ¯=927e4a04Eh-3 for the dipole hyperpolarizability. The latter value is quite close to Shelton's experimental estimate of 917±5e4a04Eh-3 [D. P. Shelton, Phys. Rev. A 42, 2578 (1990)]. The R dependence of all properties has been calculated with a [7s5p4d2f] basis set. At the CCSD(T) level of theory the dipole polarizability varies around Re as ᾱ(R)/e2a02Eh-1=11.8483+6.1758(R-Re)+0.9191(R-Re)2-0.8212(R-Re)3-0.0006(R-Re)4, Δα(R)/e2a02Eh-1=4.6032+7.0301(R-Re)+1.9340(R-Re)2-0.5708(R-Re)3+0.1949(R-Re)4. For the Cartesian components and the mean of γαβγδ, (dγzzzz/dR)e=1398, (dγxxxx/dR)e=867, (dγxxzz/dR)e=317, and (dγ¯/dR)e=994e4a03Eh-3. For the quadrupole polarizability Cαβ,γδ, we report (dCzz,zz/dR)e=19.20, (dCxz,xz/dR)e=16.55, (dCxx,xx/dR)e=10.20, and (dC¯/dR)e=23.31e2a03Eh-1. At the MP2 level of theory the components of the dipole-octopole polarizability (Eα,βγδ) and the mean dipole-dipole-octopole hyperpolarizability B¯ we have obtained (dEz,zzz/dR)e=36.71, (dEx,xxx/dR)e=-12.94e2a03Eh-1, and (dB¯/dR)e=-108e3a03Eh-2. In comparison with some other 14-electron systems, N2 appears to be less (hyper)polarizable than most, as near the Hartree-Fock limit we observe ᾱ(N2)<ᾱ(CO)<ᾱ(HCN)<ᾱ(BF)<ᾱ(HCCH) and γ¯(N2)<γ¯(CO)<γ¯(HCN)<γ¯(HCCH)<γ¯(BF).

Self-consistent RPA calculations with Skyrme-type interactions: The skyrme_rpa program

NASA Astrophysics Data System (ADS)

Colò, Gianluca; Cao, Ligang; Van Giai, Nguyen; Capelli, Luigi

2013-01-01

Random Phase Approximation (RPA) calculations are nowadays an indispensable tool in nuclear physics studies. We present here a complete version implemented with Skyrme-type interactions, with the spherical symmetry assumption, that can be used in cases where the effects of pairing correlations and of deformation can be ignored. The full self-consistency between the Hartree-Fock mean field and the RPA excitations is enforced, and it is numerically controlled by comparison with energy-weighted sum rules. The main limitations are that charge-exchange excitations and transitions involving spin operators are not included in this version. Program summaryProgram title: skyrme_rpa (v 1.00) Catalogue identifier: AENF_v1_0 Program summary URL: http://cpc.cs.qub.ac.uk/summaries/AENF_v1_0.html Program obtainable from: CPC Program Library, Queen's University, Belfast, N. Ireland Licensing provisions: Standard CPC licence, http://cpc.cs.qub.ac.uk/licence/licence.html No. of lines in distributed program, including test data, etc.: 5531 No. of bytes in distributed program, including test data, etc.: 39435 Distribution format: tar.gz Programming language: FORTRAN-90/95; easily downgradable to FORTRAN-77. Computer: PC with Intel Celeron, Intel Pentium, AMD Athlon and Intel Core Duo processors. Operating system: Linux, Windows. RAM: From 4 MBytes to 150 MBytes, depending on the size of the nucleus and of the model space for RPA. Word size: The code is written with a prevalent use of double precision or REAL(8) variables; this assures 15 significant digits. Classification: 17.24. Nature of problem: Systematic observations of excitation properties in finite nuclear systems can lead to improved knowledge of the nuclear matter equation of state as well as a better understanding of the effective interaction in the medium. This is the case of the nuclear giant resonances and low-lying collective excitations, which can be described as small amplitude collective motions in the framework of the Random Phase Approximation (RPA). This work provides a tool where one starts from an assumed form of nuclear effective interaction (the Skyrme forces) and builds the self-consistent Hartree-Fock mean field of a given nucleus, and then the RPA multipole excitations of that nucleus. Solution method: The Hartree-Fock (HF) equations are solved in a radial mesh, using a Numerov algorithm. The solutions are iterated until self-consistency is achieved (in practice, when the energy eigenvalues are stable within a desired accuracy). In the obtained mean field, unoccupied states necessary for the RPA calculations are found. For all single-particle states, box boundary conditions are assumed. To solve the RPA problem for a given value of total angular momentum and parity Jπ a coupled basis is constructed and the RPA matrix is diagonalized (protons and neutrons are treated explicitly, and no approximation related to the use of isospin formalism is introduced). The transition amplitudes and transition strengths associated to given external operators are calculated. The HF densities and RPA transition densities are also evaluated. Restrictions: The main restrictions are related to the assumed spherical symmetry and absence of pairing correlations. Running time: The typical running time depends strongly on the nucleus, on the multipolarity, on the choice of the model space and of course on the computer. It can vary from a few minutes to several hours.

Assessing the performance of dispersionless and dispersion-accounting methods: helium interaction with cluster models of the TiO2(110) surface.

PubMed

de Lara-Castells, María Pilar; Stoll, Hermann; Mitrushchenkov, Alexander O

2014-08-21

As a prototypical dispersion-dominated physisorption problem, we analyze here the performance of dispersionless and dispersion-accounting methodologies on the helium interaction with cluster models of the TiO2(110) surface. A special focus has been given to the dispersionless density functional dlDF and the dlDF+Das construction for the total interaction energy (K. Pernal, R. Podeswa, K. Patkowski, and K. Szalewicz, Phys. Rev. Lett. 2009, 109, 263201), where Das is an effective interatomic pairwise functional form for the dispersion. Likewise, the performance of symmetry-adapted perturbation theory (SAPT) method is evaluated, where the interacting monomers are described by density functional theory (DFT) with the dlDF, PBE, and PBE0 functionals. Our benchmarks include CCSD(T)-F12b calculations and comparative analysis on the nuclear bound states supported by the He-cluster potentials. Moreover, intra- and intermonomer correlation contributions to the physisorption interaction are analyzed through the method of increments (H. Stoll, J. Chem. Phys. 1992, 97, 8449) at the CCSD(T) level of theory. This method is further applied in conjunction with a partitioning of the Hartree-Fock interaction energy to estimate individual interaction energy components, comparing them with those obtained using the different SAPT(DFT) approaches. The cluster size evolution of dispersionless and dispersion-accounting energy components is then discussed, revealing the reduced role of the dispersionless interaction and intramonomer correlation when the extended nature of the surface is better accounted for. On the contrary, both post-Hartree-Fock and SAPT(DFT) results clearly demonstrate the high-transferability character of the effective pairwise dispersion interaction whatever the cluster model is. Our contribution also illustrates how the method of increments can be used as a valuable tool not only to achieve the accuracy of CCSD(T) calculations using large cluster models but also to evaluate the performance of SAPT(DFT) methods for the physically well-defined contributions to the total interaction energy. Overall, our work indicates the excellent performance of a dlDF+Das approach in which the parameters are optimized using the smallest cluster model of the target surface to treat van der Waals adsorbate-surface interactions.

Dependence of Excited State Potential Energy Surfaces on the Spatial Overlap of the Kohn-Sham Orbitals and the Amount of Nonlocal Hartree-Fock Exchange in Time-Dependent Density Functional Theory.

PubMed

Plötner, Jürgen; Tozer, David J; Dreuw, Andreas

2010-08-10

Time-dependent density functional theory (TDDFT) with standard GGA or hybrid exchange-correlation functionals is not capable of describing the potential energy surface of the S1 state of Pigment Yellow 101 correctly; an additional local minimum is observed at a twisted geometry with substantial charge transfer (CT) character. To investigate the influence of nonlocal exact orbital (Hartree-Fock) exchange on the shape of the potential energy surface of the S1 state in detail, it has been computed along the twisting coordinate employing the standard BP86, B3LYP, and BHLYP xc-functionals as well as the long-range separated (LRS) exchange-correlation (xc)-functionals LC-BOP, ωB97X, ωPBE, and CAM-B3LYP and compared to RI-CC2 benchmark results. Additionally, a recently suggested Λ-parameter has been employed that measures the amount of CT in an excited state by calculating the spatial overlap of the occupied and virtual molecular orbitals involved in the transition. Here, the error in the calculated S1 potential energy curves at BP86, B3LYP, and BHLYP can be clearly related to the Λ-parameter, i.e., to the extent of charge transfer. Additionally, it is demonstrated that the CT problem is largely alleviated when the BHLYP xc-functional is employed, although it still exhibits a weak tendency to underestimate the energy of CT states. The situation improves drastically when LRS-functionals are employed within TDDFT excited state calculations. All tested LRS-functionals give qualitatively the correct potential energy curves of the energetically lowest excited states of P. Y. 101 along the twisting coordinate. While LC-BOP and ωB97X overcorrect the CT problem and now tend to give too large excitation energies compared to other non-CT states, ωPBE and CAM-B3LYP are in excellent agreement with the RI-CC2 results, with respect to both the correct shape of the potential energy curve as well as the absolute values of the calculated excitation energies.

Relativistic calculation of nuclear magnetic shielding using normalized elimination of the small component

NASA Astrophysics Data System (ADS)

Kudo, K.; Maeda, H.; Kawakubo, T.; Ootani, Y.; Funaki, M.; Fukui, H.

2006-06-01

The normalized elimination of the small component (NESC) theory, recently proposed by Filatov and Cremer [J. Chem. Phys. 122, 064104 (2005)], is extended to include magnetic interactions and applied to the calculation of the nuclear magnetic shielding in HX (X =F,Cl,Br,I) systems. The NESC calculations are performed at the levels of the zeroth-order regular approximation (ZORA) and the second-order regular approximation (SORA). The calculations show that the NESC-ZORA results are very close to the NESC-SORA results, except for the shielding of the I nucleus. Both the NESC-ZORA and NESC-SORA calculations yield very similar results to the previously reported values obtained using the relativistic infinite-order two-component coupled Hartree-Fock method. The difference between NESC-ZORA and NESC-SORA results is significant for the shieldings of iodine.

Spectral properties from Matsubara Green's function approach: Application to molecules

NASA Astrophysics Data System (ADS)

Schüler, M.; Pavlyukh, Y.

2018-03-01

We present results for many-body perturbation theory for the one-body Green's function at finite temperatures using the Matsubara formalism. Our method relies on the accurate representation of the single-particle states in standard Gaussian basis sets, allowing to efficiently compute, among other observables, quasiparticle energies and Dyson orbitals of atoms and molecules. In particular, we challenge the second-order treatment of the Coulomb interaction by benchmarking its accuracy for a well-established test set of small molecules, which includes also systems where the usual Hartree-Fock treatment encounters difficulties. We discuss different schemes how to extract quasiparticle properties and assess their range of applicability. With an accurate solution and compact representation, our method is an ideal starting point to study electron dynamics in time-resolved experiments by the propagation of the Kadanoff-Baym equations.

Comparative study of the requantization of the time-dependent mean field for the dynamics of nuclear pairing

NASA Astrophysics Data System (ADS)

Ni, Fang; Nakatsukasa, Takashi

2018-04-01

To describe quantal collective phenomena, it is useful to requantize the time-dependent mean-field dynamics. We study the time-dependent Hartree-Fock-Bogoliubov (TDHFB) theory for the two-level pairing Hamiltonian, and compare results of different quantization methods. The one constructing microscopic wave functions, using the TDHFB trajectories fulfilling the Einstein-Brillouin-Keller quantization condition, turns out to be the most accurate. The method is based on the stationary-phase approximation to the path integral. We also examine the performance of the collective model which assumes that the pairing gap parameter is the collective coordinate. The applicability of the collective model is limited for the nuclear pairing with a small number of single-particle levels, because the pairing gap parameter represents only a half of the pairing collective space.

Nuclear Mass Predictions within the Skyrme HFB Theory

DOE Office of Scientific and Technical Information (OSTI.GOV)

Samyn, M.; Goriely, S.; Pearson, J.M.

To increase the reliability of predictions of highly neutron-rich nuclear masses we systematically analyze the sensitivity of Hartree-Fock-Bogoliubov (HFB) mass formulae to various physical inputs, such as a density dependence of the pairing interaction, a low effective mass, the particle-number projection, the symmetry energy, ... We typically use a 10-parameter Skyrme force and a 4-parameter {delta}-function pairing force. The 14 degrees of freedom are adjusted to the masses of all measured nuclei with N,Z {>=} 8 given in the 2001 and 2003 Audi et al. compilations. The masses of light and proton-rich nuclei are corrected by a 4-parameter phenomenological Wignermore » term. With more than ten such parameter sets complete mass tables are constructed, going from one drip line to the other, up to Z = 120.« less

Spectroscopic investigation of some building blocks of organic conductors: A comparative study

NASA Astrophysics Data System (ADS)

Mukherjee, V.; Yadav, T.

2017-04-01

Theoretical molecular structures and IR and Raman spectra of di and tetra methyl substituted tetrathiafulvalene and tetraselenafulvalene molecules have been studied. These molecules belong to the organic conductor family and are immensely used as building blocks of several organic conducting devices. The Hartree-Fock and density functional theory with exchange functional B3LYP have been employed for computational purpose. We have also performed normal coordinate analysis to scale the theoretical frequencies and to calculate potential energy distributions for the conspicuous assignments. The exciting frequency and temperature dependent Raman spectra have also presented. Optimization results reveal that the sulphur derivatives possess boat shape while selenium derivatives possess planner structures. Natural bond orbitals analysis has also been performed to study second order interaction between donors and acceptors and to compute molecular orbital occupancy and energy.

Strong electronic interaction and multiple quantum Hall ferromagnetic phases in trilayer graphene

NASA Astrophysics Data System (ADS)

Datta, Biswajit; Dey, Santanu; Samanta, Abhisek; Agarwal, Hitesh; Borah, Abhinandan; Watanabe, Kenji; Taniguchi, Takashi; Sensarma, Rajdeep; Deshmukh, Mandar M.

2017-02-01

Quantum Hall effect provides a simple way to study the competition between single particle physics and electronic interaction. However, electronic interaction becomes important only in very clean graphene samples and so far the trilayer graphene experiments are understood within non-interacting electron picture. Here, we report evidence of strong electronic interactions and quantum Hall ferromagnetism seen in Bernal-stacked trilayer graphene. Due to high mobility ~500,000 cm2 V-1 s-1 in our device compared to previous studies, we find all symmetry broken states and that Landau-level gaps are enhanced by interactions; an aspect explained by our self-consistent Hartree-Fock calculations. Moreover, we observe hysteresis as a function of filling factor and spikes in the longitudinal resistance which, together, signal the formation of quantum Hall ferromagnetic states at low magnetic field.

Nature of magnetization and lateral spin-orbit interaction in gated semiconductor nanowires.

PubMed

Karlsson, H; Yakimenko, I I; Berggren, K-F

2018-05-31

Semiconductor nanowires are interesting candidates for realization of spintronics devices. In this paper we study electronic states and effects of lateral spin-orbit coupling (LSOC) in a one-dimensional asymmetrically biased nanowire using the Hartree-Fock method with Dirac interaction. We have shown that spin polarization can be triggered by LSOC at finite source-drain bias,as a result of numerical noise representing a random magnetic field due to wiring or a random background magnetic field by Earth magnetic field, for instance. The electrons spontaneously arrange into spin rows in the wire due to electron interactions leading to a finite spin polarization. The direction of polarization is, however, random at zero source-drain bias. We have found that LSOC has an effect on orientation of spin rows only in the case when source-drain bias is applied.

Entanglement and magnetism in high-spin graphene nanodisks

NASA Astrophysics Data System (ADS)

Hagymási, I.; Legeza, Ö.

2018-01-01

We investigate the ground-state properties of triangular graphene nanoflakes with zigzag edge configurations. The description of zero-dimensional nanostructures requires accurate many-body techniques since the widely used density-functional theory with local density approximation or Hartree-Fock methods cannot handle the strong quantum fluctuations. Applying the unbiased density-matrix renormalization group algorithm we calculate the magnetization and entanglement patterns with high accuracy for different interaction strengths and compare them to the mean-field results. With the help of quantum information analysis and subsystem density matrices we reveal that the edges are strongly entangled with each other. We also address the effect of electron and hole doping and demonstrate that the magnetic properties of triangular nanoflakes can be controlled by an electric field, which reveals features of flat-band ferromagnetism. This may open up new avenues in graphene based spintronics.

Zeroth order regular approximation approach to electric dipole moment interactions of the electron.

PubMed

Gaul, Konstantin; Berger, Robert

2017-07-07

A quasi-relativistic two-component approach for an efficient calculation of P,T-odd interactions caused by a permanent electric dipole moment of the electron (eEDM) is presented. The approach uses a (two-component) complex generalized Hartree-Fock and a complex generalized Kohn-Sham scheme within the zeroth order regular approximation. In applications to select heavy-elemental polar diatomic molecular radicals, which are promising candidates for an eEDM experiment, the method is compared to relativistic four-component electron-correlation calculations and confirms values for the effective electric field acting on the unpaired electron for RaF, BaF, YbF, and HgF. The calculations show that purely relativistic effects, involving only the lower component of the Dirac bi-spinor, are well described by treating only the upper component explicitly.

Zeroth order regular approximation approach to electric dipole moment interactions of the electron

NASA Astrophysics Data System (ADS)

Gaul, Konstantin; Berger, Robert

2017-07-01

A quasi-relativistic two-component approach for an efficient calculation of P ,T -odd interactions caused by a permanent electric dipole moment of the electron (eEDM) is presented. The approach uses a (two-component) complex generalized Hartree-Fock and a complex generalized Kohn-Sham scheme within the zeroth order regular approximation. In applications to select heavy-elemental polar diatomic molecular radicals, which are promising candidates for an eEDM experiment, the method is compared to relativistic four-component electron-correlation calculations and confirms values for the effective electric field acting on the unpaired electron for RaF, BaF, YbF, and HgF. The calculations show that purely relativistic effects, involving only the lower component of the Dirac bi-spinor, are well described by treating only the upper component explicitly.

Accurate study on the properties of spectral lines for Br-like W39+

NASA Astrophysics Data System (ADS)

Guo, X. L.; Li, M. C.; Si, R.; He, X. D.; Wang, K.; Dai, Z. T.; Liu, Y. M.; Zhang, H. J.; Chen, C. Y.

2018-01-01

As a primary candidate in tokamak plasmas, the spectroscopic parameters of tungsten ions have been studied extensively over the past decade. In this paper, we perform calculations of excitation energies, lifetimes, wavelengths and transition rates for all levels of the 4{s}24{p}5, 4{s}24{p}44d, and 4s4{p}6 configurations of {{{W}}}39+ by using the multiconfiguration Dirac-Hartree-Fock (MCDHF) method, and also the relativistic many-body perturbation theory (RMBPT) method. Detailed convergence studies on excitation energy from electron-correlation effects and relativistic effects are presented. It is necessary to include the core-valence correlation from deep lying subshells, e.g. 3d and 3p, to produce reliable atomic parameters. Results are compared with available theoretical and experimental work, and the accuracy of the results is confirmed.

Dynamical photoionization observables of the CS molecule: The role of electron correlation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ponzi, Aurora; Coriani, Sonia; Decleva, Piero

2014-05-28

Highly correlated calculations are performed on the primary ionic states and the prominent satellite present in the outer valence photoelectron spectrum of carbon monosulfide (CS). Dyson orbitals are coupled to accurate one particle continuum orbitals to provide a correlated description of energy dependent cross sections, asymmetry parameters, branching ratios, and molecular frame photoelectron angular distributions. The comparison with results obtained at the Hartree-Fock and Density Functional Theory level shows the strong sensitivity of these observables to details of the correlation in the bound states. The behaviour of the well characterized satellite state is analyzed in detail, and shows differences frommore » the relevant primary states, revealing the limitations of a simple intensity borrowing mechanism. The results resolve the intensity disagreement with experiment obtained at the level of the sudden approximation.« less

Solvent effects on the vibronic one-photon absorption profiles of dioxaborine heterocycles

NASA Astrophysics Data System (ADS)

Wang, Yan-Hua; Halik, Marcus; Wang, Chuan-Kui; Marder, Seth R.; Luo, Yi

2005-11-01

The vibronic profiles of one-photon absorption spectra of dioxaborine heterocycles in gas phase and solution have been calculated at the Hartree-Fock and density-functional-theory levels. The polarizable continuum model has been applied to simulate the solvent effect, while the linear coupling model is used to compute the Franck-Condon and Herzberg-Teller contributions. It is found that a good agreement between theory and experiment can be achieved when the solvent effect and electron correlation are taken into account simultaneously. For the first excited charge-transfer state, the maximum of its Herzberg-Teller profile is blueshifted from that of the Franck-Condon profile. The shifted energy is found to be around 0.2eV, which agrees well with the measured energy difference between two- and one-photon absorptions of the first excited state.

Benchmarking Hydrogen and Carbon NMR Chemical Shifts at HF, DFT, and MP2 Levels.

PubMed

Flaig, Denis; Maurer, Marina; Hanni, Matti; Braunger, Katharina; Kick, Leonhard; Thubauville, Matthias; Ochsenfeld, Christian

2014-02-11

An extensive study of error distributions for calculating hydrogen and carbon NMR chemical shifts at Hartree-Fock (HF), density functional theory (DFT), and Møller-Plesset second-order perturbation theory (MP2) levels is presented. Our investigation employs accurate CCSD(T)/cc-pVQZ calculations for providing reference data for 48 hydrogen and 40 carbon nuclei within an extended set of chemical compounds covering a broad range of the NMR scale with high relevance to chemical applications, especially in organic chemistry. Besides the approximations of HF, a variety of DFT functionals, and conventional MP2, we also present results with respect to a spin component-scaled MP2 (GIAO-SCS-MP2) approach. For each method, the accuracy is analyzed in detail for various basis sets, allowing identification of efficient combinations of method and basis set approximations.

Insights into the Hydrogen-Atom Transfer of the Blue Aroxyl.

PubMed

Bächle, Josua; Marković, Marijana; Kelterer, Anne-Marie; Grampp, Günter

2017-10-19

An experimental and theoretical study on hydrogen-atom transfer dynamics in the hydrogen-bonded substituted phenol/phenoxyl complex of the blue aroxyl (2,4,6-tri-tert-butylphenoxyl) is presented. The experimental exchange dynamics is determined in different organic solvents from the temperature-dependent alternating line-width effect in the continuous-wave ESR spectrum. From bent Arrhenius plots, effective tunnelling contributions with parallel heavy-atom motion are concluded. To clarify the transfer mechanism, reaction paths for different conformers of the substituted phenol/phenoxyl complex are modelled theoretically. Various DFT and post-Hartree-Fock methods including multireference methods are applied. From the comparison of experimental and theoretical data it is concluded that the system favours concerted hydrogen-atom transfer along a parabolic reaction path caused by heavy-atom motion. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Energy levels and radiative rates for transitions in Cr-like Co IV and Ni V

NASA Astrophysics Data System (ADS)

Aggarwal, K. M.; Bogdanovich, P.; Karpuškienė, R.; Keenan, F. P.; Kisielius, R.; Stancalie, V.

2016-01-01

We report calculations of energy levels and radiative rates (A-values) for transitions in Cr-like Co IV and Ni V. The quasi-relativistic Hartree-Fock (QRHF) code is adopted for calculating the data although GRASP (general-purpose relativistic atomic structure package) and flexible atomic code (FAC) have also been employed for comparison purposes. No radiative rates are available in the literature to compare with our results, but our calculated energies are in close agreement with those compiled by NIST for a majority of the levels. However, there are discrepancies for a few levels of up to 3%. The A-values are listed for all significantly contributing E1, E2 and M1 transitions, and the corresponding lifetimes reported, although unfortunately no previous theoretical or experimental results exist to compare with our data.

Predictive data-based exposition of 5s5p{sup 1,3}P{sub 1} lifetimes in the Cd isoelectronic sequence

DOE Office of Scientific and Technical Information (OSTI.GOV)

Curtis, L. J.; Matulioniene, R.; Ellis, D. G.

2000-11-01

Experimental and theoretical values for the lifetimes of the 5s5p{sup 1}P{sub 1} and {sup 3}P{sub 1} levels in the Cd isoelectronic sequence are examined in the context of a data-based isoelectronic systematization. Lifetime and energy-level data are combined to account for the effects of intermediate coupling, thereby reducing the data to a regular and slowly varying parametric mapping. This empirically characterizes small contributions due to spin-other-orbit interaction, spin dependences of the radial wave functions, and configuration interaction, and yields accurate interpolative and extrapolative predictions. Multiconfiguration Dirac-Hartree-Fock calculations are used to verify the regularity of these trends, and to examine themore » extent to which they can be extrapolated to high nuclear charge.« less

Photon scattering cross sections of H2 and He measured with synchrotron radiation

NASA Technical Reports Server (NTRS)

Ice, G. E.

1977-01-01

Total (elastic + inelastic) differential photon scattering cross sections have been measured for H2 gas and He, using an X-ray beam. Absolute measured cross sections agree with theory within the probable errors. Relative cross sections (normalized to theory at large S) agree to better than one percent with theoretical values calculated from wave functions that include the effect of electron-electron Coulomb correlation, but the data deviate significantly from theoretical independent-particle (e.g., Hartree-Fock) results. The ratios of measured absolute He cross sections to those of H2, at any given S, also agree to better than one percent with theoretical He-to-H2 cross-section ratios computed from correlated wave functions. It appears that photon scattering constitutes a very promising tool for probing electron correlation in light atoms and molecules.

Potential energy curves of the Na2+ molecular ion from all-electron ab initio relativistic calculations

NASA Astrophysics Data System (ADS)

Bewicz, Anna; Musiał, Monika; Kucharski, Stanisław A.

2017-11-01

The equation-of-motion coupled-cluster method for electron affinity calculations has been used to study potential energy curves (PECs) for the Na+2 molecular ion. Although the studied molecule represents the open shell system the applied approach employs the closed shell Na+ 22 ion as the reference. In addition the Na+ 22 system dissociates into the closed shell fragments; hence, the restricted Hartree-Fock scheme can be used within the whole range of interatomic distances, from 2 to 45 Å. We used large basis set engaging 268 basis functions with all 21 electrons correlated. The relativistic effects are included via second-order Douglas-Kroll method. The computed PECs, spectroscopic molecular constants and vibrational energy levels agree well with experimental values if the latter are available or with other theoretical data.

Excitonic condensation with different pairing symmetries in double quantum wells

NASA Astrophysics Data System (ADS)

Jamell, Christopher

2009-03-01

Double quantum wells with one containing electrons and the other containing holes as carriers are a promising candidate for condensation of dipolar excitons with lifetime much larger than lifetime of excitons in bulk semiconductors. When the inter-well distance is comparable to the interparticle distance within a single well, d <=rsaB, inter-well coherence is expected to lead to an excitonic condensation. We explore the ground state of a balanced system as a function of inter-well distance d and the carrier density n2D. We present Hartree-Fock mean-field results for the quasiparticle and order parameter dispersion with different pairing symmetries. We obtain the quasiparticle density of states in each case. These results lay the ground work for mean-field study of excitonic condensate states with spontaneously broken translational symmetry.

Molecular structure of the lithium enolate of acetaldehyde

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lynch, T.J.; Newcomb, M.; Bergbreiter, D.E.

1980-11-21

Calculations of the structures of isomers of the lithium enolate of acetaldehyde done at the restricted Hartree-Fock level with the HONDO program on the CDC 7600 are reported. Using the standard 4-31 G basis set, these calculations produce excessively large bond angles, and this favors the most open of the three isomeric structures. Including the polarization functions on the carbons and oxygen and using the recent Dunning and Hayes (3s2p/2s) contraction indicates that the chirol enolates are the lowest energy structure. However, the differences of the various enolate structures are small and could be modified by solvent effects. These resultsmore » are proported to suggest that the enolates containing internal ligands may be prepared such that a new chirol center would exist by virtue of the counterion position. (BLM)« less

Hybridization wave as the cause of the metal-insulator transition in rare earth nickelates

NASA Astrophysics Data System (ADS)

Park, Hyowon; Marianetti, Chris A.; Millis, Andrew J.

2012-02-01

The metal-insulator transition driven by varying rare earth (Re) ion in ReNiO3 has been a longstanding challenge to materials theory. Experimental evidence suggesting charge order is seemingly incompatible with the strong Mott-Hubbard correlations characteristic of transition metals. We present density functional, Hartree-Fock and Dynamical Mean field calculations showing that the origin of the insulating phase is a hybridization wave, in which a two sublattice ordering of the oxygen breathing mode produces two Ni sites with almost identical Ni d-charge densities but very different magnetic moments and other properties. The high temperature crystal structure associated with smaller Re ions such as Lu is shown to be more susceptible to the distortion than the high temperature structure associated with larger Re ions such as La.

Impact of Many-Body Effects on Landau Levels in Graphene

NASA Astrophysics Data System (ADS)

Sonntag, J.; Reichardt, S.; Wirtz, L.; Beschoten, B.; Katsnelson, M. I.; Libisch, F.; Stampfer, C.

2018-05-01

We present magneto-Raman spectroscopy measurements on suspended graphene to investigate the charge carrier density-dependent electron-electron interaction in the presence of Landau levels. Utilizing gate-tunable magnetophonon resonances, we extract the charge carrier density dependence of the Landau level transition energies and the associated effective Fermi velocity vF. In contrast to the logarithmic divergence of vF at zero magnetic field, we find a piecewise linear scaling of vF as a function of the charge carrier density, due to a magnetic-field-induced suppression of the long-range Coulomb interaction. We quantitatively confirm our experimental findings by performing tight-binding calculations on the level of the Hartree-Fock approximation, which also allow us to estimate an excitonic binding energy of ≈6 meV contained in the experimentally extracted Landau level transitions energies.

Lifetimes and oscillator strengths for the 5s5p6s, 5s5p5d and 5p3 levels in single-ionized tin

NASA Astrophysics Data System (ADS)

Colón, C.; Alonso-Medina, A.

2004-08-01

Radiative oscillator strengths for 103 lines arising from 5s5p6s, 5s5p5d and 5p3 configurations of Sn II and lifetimes corresponding to several levels of these configurations have been calculated. These values were obtained in intermediate coupling (IC) and using ab initio relativistic Hartree-Fock (HFR) calculations. We use the standard method of least square fitting of experimental energy levels for the IC calculations by means of computer codes from Cowan. Tables 1 and 2 are only available in electronic form at the CDS via anonymous ftp to cdsarc.u-strasbg.fr (130.79.128.5) or via http://cdsweb.u-strasbg.fr/cgi-bin/qcat?J/A+A/422/1109

Probing Neutron-Skin Thickness of Unstable Nuclei with Total Reaction Cross Sections

NASA Astrophysics Data System (ADS)

Horiuchi, Wataru; Suzuki, Yasuyuki; Inakura, Tsunenori

We present our recent analysis of the total reaction cross sections, σR, of unstable nuclei and discuss their sensitivity to the neutron-skin thickness. The σR is calculated with the Glauber model using projectile densities obtained with the Skyrme-Hartree-Fock method on the three-dimensional coordinate space. We cover 91 nuclei of O, Ne, Mg, Si, S, Ca, and Ni isotopes. Defining a reaction radius, aR = √{σ R/π } , to characterize the nuclear size and target (proton or 12C) dependence, we see the 12C target probes the matter radius while the proton target is sensitive to the skin-thickness. We find an empirical formula for expressing aR with the point matter radius and the skin thickness, which can be used to determine the skin thickness.

Structural and spectroscopic investigation of the N-methylformamide-water (NMF···3H2O) complex

NASA Astrophysics Data System (ADS)

Hammami, F.; Ghalla, H.; Chebaane, A.; Nasr, S.

2015-01-01

In this work, theoretical studies on the structure, molecular properties, hydrogen bonding, and vibrational spectra of the N-methylformamide-water (NMF...3H2O) complex will be presented. The molecular geometry was optimised by using Hartree-Fock (HF), second Møller-Plesset (MP2), and density functional theory methods with different basis sets. The harmonic vibrational frequencies are computed by using the B3LYP method with 6-311++G(d,p) as a basis set and then scaled with a suitable scale factor to yield good coherence with the observed values. The temperature dependence of various thermodynamic functions (heat capacity, entropy, and enthalpy changes) was also studied. A detailed analysis of the nature of the hydrogen bonding, using natural bond orbital (NBO) and topological atoms in molecules theory, has been reported.

Imaging of the outer valence orbitals of CO by electron momentum spectroscopy — Comparison with high level MRSD-CI and DFT calculations

NASA Astrophysics Data System (ADS)

Fan, X. W.; Chen, X. J.; Zhou, S. J.; Zheng, Y.; Brion, C. E.; Frey, R.; Davidson, E. R.

1997-09-01

A newly constructed energy dispersive multichannel electron momentum spectrometer has been used to image the electron density of the outer valence orbitals of CO with high precision. Binding energy spectra are obtained at a coincidence energy resolution of 1.2 eV fwhm. The measured electron density profiles in momentum space for the outer valence orbitals of CO are compared with cross sections calculated using SCF wavefunctions with basis sets of varying complexity up to near-Hartree-Fock limit in quality. The effects of correlation and electronic relaxation on the calculated momentum profiles are investigated using large MRSD-CI calculations of the full ion-neutral overlap distributions, as well as large basis set DFT calculations with local and non-local (gradient corrected) functionals.

Ab initio quantum chemical calculation of electron transfer matrix elements for large molecules

NASA Astrophysics Data System (ADS)

Zhang, Linda Yu; Friesner, Richard A.; Murphy, Robert B.

1997-07-01

Using a diabatic state formalism and pseudospectral numerical methods, we have developed an efficient ab initio quantum chemical approach to the calculation of electron transfer matrix elements for large molecules. The theory is developed at the Hartree-Fock level and validated by comparison with results in the literature for small systems. As an example of the power of the method, we calculate the electronic coupling between two bacteriochlorophyll molecules in various intermolecular geometries. Only a single self-consistent field (SCF) calculation on each of the monomers is needed to generate coupling matrix elements for all of the molecular pairs. The largest calculations performed, utilizing 1778 basis functions, required ˜14 h on an IBM 390 workstation. This is considerably less cpu time than would be necessitated with a supermolecule adiabatic state calculation and a conventional electronic structure code.

Electronic structure of free and doped actinides: N and Z dependences of energy levels and electronic structure parameters

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kulagin, N.

2005-02-15

Theoretical study of electronic structure of antinide ions and its dependence on N and Z are presented in this paper. The main 5f{sup N} and excited 5f{sup N}n'l'{sup N'} configurations of actinides have been studied using Hartree-Fock-Pauli approximation. Results of calculations of radial integrals and the energy of X-ray lines for all 5f ions with electronic state AC{sup +1}-AC{sup +4} show approximate dependence on N and Z. A square of N and cubic of Z are ewalized for the primary electronic parameters of the actinides. Theoretical values of radial integrals for free actinides and for ions in a cluster AC{supmore » +n}:[L]{sub k} are compared, too.« less

Density functional study of molecular interactions in secondary structures of proteins.

PubMed

Takano, Yu; Kusaka, Ayumi; Nakamura, Haruki

2016-01-01

Proteins play diverse and vital roles in biology, which are dominated by their three-dimensional structures. The three-dimensional structure of a protein determines its functions and chemical properties. Protein secondary structures, including α-helices and β-sheets, are key components of the protein architecture. Molecular interactions, in particular hydrogen bonds, play significant roles in the formation of protein secondary structures. Precise and quantitative estimations of these interactions are required to understand the principles underlying the formation of three-dimensional protein structures. In the present study, we have investigated the molecular interactions in α-helices and β-sheets, using ab initio wave function-based methods, the Hartree-Fock method (HF) and the second-order Møller-Plesset perturbation theory (MP2), density functional theory, and molecular mechanics. The characteristic interactions essential for forming the secondary structures are discussed quantitatively.

Two-component hybrid time-dependent density functional theory within the Tamm-Dancoff approximation.

PubMed

Kühn, Michael; Weigend, Florian

2015-01-21

We report the implementation of a two-component variant of time-dependent density functional theory (TDDFT) for hybrid functionals that accounts for spin-orbit effects within the Tamm-Dancoff approximation (TDA) for closed-shell systems. The influence of the admixture of Hartree-Fock exchange on excitation energies is investigated for several atoms and diatomic molecules by comparison to numbers for pure density functionals obtained previously [M. Kühn and F. Weigend, J. Chem. Theory Comput. 9, 5341 (2013)]. It is further related to changes upon switching to the local density approximation or using the full TDDFT formalism instead of TDA. Efficiency is demonstrated for a comparably large system, Ir(ppy)3 (61 atoms, 1501 basis functions, lowest 10 excited states), which is a prototype molecule for organic light-emitting diodes, due to its "spin-forbidden" triplet-singlet transition.

Effects of relativity for atomization and isomerization energies of seaborgium carbonyl SgCO and seaborgium isocarbonyl SgOC: Relativity predicts SgOC to be more stable than SgCO

DOE PAGES

Malli, Gulzari L.

2015-12-31

Our ab initio all-electron fully relativistic Dirac-Fock (DF) and nonrelativistic Hartree-Fock (NR) calculations for seaborgium isocarbonyl SgOC predict atomization energy (AE) of 13.04 and 11.05 eV, respectively. However, the corresponding DF and NR atomization energies for the seaborgium carbonyl SgCO are predicted as 12.75 and 12.45 eV, respectively. This is the first such result in Chemistry where an isocarbonyl (and especially for a system of superheavy element Sg) is predicted to be more stable at the DF level of theory than the corresponding carbonyl. The predicted energy for the formation of the carbonyl SgCO at the relativistic DF and NRmore » levels of theory is -54.90 and -50.95 kJ /mol, whereas the corresponding energy of formation of the isocarbonyl SgOC is -64.44 and -18.64 kJ/mol, respectively. Ours are the first results of relativistic effects for isomerization and atomization energies of the superheavy seaborgium isocarbonyl SgOC and its isomer SgCO. Lastly, the formation of isocarbonyl SgOC, should be favored over the carbonyl isomer SgCO in the first step of the reaction Sg+CO →SgOC.« less

Vibrational assignment of aluminum(III) Tris-acetylacetone

NASA Astrophysics Data System (ADS)

Tayyari, Sayyed Faramarz; Raissi, Haydar; Ahmadabadi, Zahra

2002-10-01

The geometry, frequency and intensity of the vibrational bands of aluminum(III) Tris-acetylacetone Al(AA) 3 and its 1, 3, 5- 13C derivative were obtained by the Hartree-Fock (HF) and Density Functional Theory (DFT) with the B3LYP, B1LYP, and G96LYP functionals and using the 6-31G* basis set. The calculated frequencies are compared with the solid IR and Raman spectra. All of the measured IR and Raman bands were interpreted in terms of the calculated vibrational modes. Most computed bands are predicted to be at higher wavenumbers than the experimental bands. The calculated bond lengths and bond angles are in good agreement with the experimental results. Analysis of the vibrational spectra indicates a strong coupling between the chelated ring modes. Four bands in the 500-390 cm -1 frequency range are assigned to the vibrations of metalligand bonds.

Many-body Effects in a Laterally Inhomogeneous Semiconductor Quantum Well

NASA Technical Reports Server (NTRS)

Ning, Cun-Zheng; Li, Jian-Zhong; Biegel, Bryan A. (Technical Monitor)

2002-01-01

Many body effects on conduction and diffusion of electrons and holes in a semiconductor quantum well are studied using a microscopic theory. The roles played by the screened Hartree-Fock (SHE) terms and the scattering terms are examined. It is found that the electron and hole conductivities depend only on the scattering terms, while the two-component electron-hole diffusion coefficients depend on both the SHE part and the scattering part. We show that, in the limit of the ambipolax diffusion approximation, however, the diffusion coefficients for carrier density and temperature are independent of electron-hole scattering. In particular, we found that the SHE terms lead to a reduction of density-diffusion coefficients and an increase in temperature-diffusion coefficients. Such a reduction or increase is explained in terms of a density-and temperature dependent energy landscape created by the bandgap renormalization.

The polarizability of diatomic helium. Ph.D. Thesis

NASA Technical Reports Server (NTRS)

Fortune, P. J.

1974-01-01

The calculation of the electric dipole polarizability tensor of the He 2 dimer is described, and the results are used in the computation of several dielectric and optical properties of helium gas, at both high (322 K) and low (4 K) temperatures. The properties considered are the second dielectric virial coefficient, the second Kerr virial coefficient, and the depolarization ratio of the integrated intensities for the Raman scattering experiments. The thesis consists of five parts: the polarizability and various properties are defined; the calculation of the polarizability in the long-range region in terms of a quantum mechanical multipole expansion is described; the calculation of the He2 polarizability in the overlap region via coupled Hartree-Fock perturbation theory is described; the calculation of the quantum pair distribution function for both the He-3 and He-4 isotopes at 4 K is discussed; and the calculated values of the properties of helium gas are given.

Quantum cluster theory for the polarizable continuum model. I. The CCSD level with analytical first and second derivatives.

PubMed

Cammi, R

2009-10-28

We present a general formulation of the coupled-cluster (CC) theory for a molecular solute described within the framework of the polarizable continuum model (PCM). The PCM-CC theory is derived in its complete form, called PTDE scheme, in which the correlated electronic density is used to have a self-consistent reaction field, and in an approximate form, called PTE scheme, in which the PCM-CC equations are solved assuming the fixed Hartree-Fock solvent reaction field. Explicit forms for the PCM-CC-PTDE equations are derived at the single and double (CCSD) excitation level of the cluster operator. At the same level, explicit equations for the analytical first derivatives of the PCM basic energy functional are presented, and analytical second derivatives are also discussed. The corresponding PCM-CCSD-PTE equations are given as a special case of the full theory.

Extended calculations of energies, transition rates, and lifetimes for F-like Kr XXVIII

NASA Astrophysics Data System (ADS)

Zhang, C. Y.; Si, R.; Yao, K.; Gu, M. F.; Wang, K.; Chen, C. Y.

2018-02-01

The excitation energies, lifetimes, wavelengths and E1, E2, M1 and M2 transition rates for the lowest 389 levels of the 2l7, 2l63l‧, 2l64l‧, and 2l65l‧ configurations from second-order many-body perturbation theory (MBPT) calculations, and the results for the lowest 200 states of the 2l7, 2l63l‧, and 2l64l‧ configurations from multi-configuration Dirac-Hartree-Fock (MCDHF) calculations in F-like Kr XXVIII are presented in this work. The relative differences between our two sets of level energies are mostly within 0.005% for the lowest 200 levels. Comparisons are made with experimental and other available theoretical results to assess the reliability and accuracy of the present calculations. We believe them to be the most complete and accurate results for Kr XXVIII at present.

Is the Pauli exclusion principle the origin of electron localisation?

NASA Astrophysics Data System (ADS)

Rincón, Luis; Torres, F. Javier; Almeida, Rafael

2018-03-01

In this work, we inquire into the origins of the electron localisation as obtained from the information content of the same-spin pair density, γσ, σ(r2∣r1). To this end, we consider systems of non-interacting and interacting identical Fermions contained in two simple 1D potential models: (1) an infinite potential well and (2) the Kronig-Penney periodic potential. The interparticle interaction is considered through the Hartree-Fock approximation as well as the configuration interaction expansion. Morover, the electron localisation is described through the Kullback-Leibler divergence between γσ, σ(r2∣r1) and its associated marginal probability. The results show that, as long as the adopted method properly includes the Pauli principle, the electronic localisation depends only modestly on the interparticle interaction. In view of the latter, one may conclude that the Pauli principle is the main responsible for the electron localisation.

Communication: Biological applications of coupled-cluster frozen-density embedding

NASA Astrophysics Data System (ADS)

Heuser, Johannes; Höfener, Sebastian

2018-04-01

We report the implementation of the Laplace-transform scaled opposite-spin (LT-SOS) resolution-of-the-identity second-order approximate coupled-cluster singles and doubles (RICC2) combined with frozen-density embedding for excitation energies and molecular properties. In the present work, we furthermore employ the Hartree-Fock density for the interaction energy leading to a simplified Lagrangian which is linear in the Lagrangian multipliers. This approximation has the key advantage of a decoupling of the coupled-cluster amplitude and multipliers, leading also to a significant reduction in computation time. Using the new simplified Lagrangian in combination with efficient wavefunction models such as RICC2 or LT-SOS-RICC2 and density-functional theory (DFT) for the environment molecules (CC2-in-DFT) enables the efficient study of biological applications such as the rhodopsin and visual cone pigments using ab initio methods as routine applications.

Beyond the random-phase approximation for the electron correlation energy: the importance of single excitations.

PubMed

Ren, Xinguo; Tkatchenko, Alexandre; Rinke, Patrick; Scheffler, Matthias

2011-04-15

The random-phase approximation (RPA) for the electron correlation energy, combined with the exact-exchange (EX) energy, represents the state-of-the-art exchange-correlation functional within density-functional theory. However, the standard RPA practice--evaluating both the EX and the RPA correlation energies using Kohn-Sham (KS) orbitals from local or semilocal exchange-correlation functionals--leads to a systematic underbinding of molecules and solids. Here we demonstrate that this behavior can be corrected by adding a "single excitation" contribution, so far not included in the standard RPA scheme. A similar improvement can also be achieved by replacing the non-self-consistent EX total energy by the corresponding self-consistent Hartree-Fock total energy, while retaining the RPA correlation energy evaluated using KS orbitals. Both schemes achieve chemical accuracy for a standard benchmark set of noncovalent intermolecular interactions.