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

Wang, Weizhou, E-mail: wzw@lynu.edu.cn, E-mail: ybw@gzu.edu.cn; Zhang, Yu; Sun, Tao

High-level coupled cluster singles, doubles, and perturbative triples [CCSD(T)] computations with up to the aug-cc-pVQZ basis set (1924 basis functions) and various extrapolations toward the complete basis set (CBS) limit are presented for the sandwich, T-shaped, and parallel-displaced benzene⋯naphthalene complex. Using the CCSD(T)/CBS interaction energies as a benchmark, the performance of some newly developed wave function and density functional theory methods has been evaluated. The best performing methods were found to be the dispersion-corrected PBE0 functional (PBE0-D3) and spin-component scaled zeroth-order symmetry-adapted perturbation theory (SCS-SAPT0). The success of SCS-SAPT0 is very encouraging because it provides one method for energy componentmore » analysis of π-stacked complexes with 200 atoms or more. Most newly developed methods do, however, overestimate the interaction energies. The results of energy component analysis show that interaction energies are overestimated mainly due to the overestimation of dispersion energy.« less

Semantic Relevance, Domain Specificity and the Sensory/Functional Theory of Category-Specificity

ERIC Educational Resources Information Center

Sartori, Giuseppe; Gnoato, Francesca; Mariani, Ilenia; Prioni, Sara; Lombardi, Luigi

2007-01-01

According to the sensory/functional theory of semantic memory, Living items rely more on Sensory knowledge than Non-living ones. The sensory/functional explanation of category-specificity assumes that semantic features are organised on the basis of their content. We report here a study on DAT patients with impaired performance on Living items and…

Recursive Techniques for Computing Gluon Scattering in Anti-de-Sitter Space

NASA Astrophysics Data System (ADS)

Shyaka, Claude; Kharel, Savan

2016-03-01

The anti-de Sitter/conformal field theory correspondence is a relationship between two kinds of physical theories. On one side of the duality are special type of quantum (conformal) field theories known as the Yang-Mills theory. These quantum field theories are known to be equivalent to theories of gravity in Anti-de Sitter (AdS) space. The physical observables in the theory are the correlation functions that live in the boundary of AdS space. In general correlation functions are computed using configuration space and the expressions are extremely complicated. Using momentum basis and recursive techniques developed by Raju, we extend tree level correlation functions for four and five-point correlation functions in Yang-Mills theory in Anti-de Sitter space. In addition, we show that for certain external helicity, the correlation functions have simple analytic structure. Finally, we discuss how one can generalize these results to n-point functions. Hendrix college odyssey Grant.

Angle-dependent strong-field molecular ionization rates with tuned range-separated time-dependent density functional theory.

PubMed

Sissay, Adonay; Abanador, Paul; Mauger, François; Gaarde, Mette; Schafer, Kenneth J; Lopata, Kenneth

2016-09-07

Strong-field ionization and the resulting electronic dynamics are important for a range of processes such as high harmonic generation, photodamage, charge resonance enhanced ionization, and ionization-triggered charge migration. Modeling ionization dynamics in molecular systems from first-principles can be challenging due to the large spatial extent of the wavefunction which stresses the accuracy of basis sets, and the intense fields which require non-perturbative time-dependent electronic structure methods. In this paper, we develop a time-dependent density functional theory approach which uses a Gaussian-type orbital (GTO) basis set to capture strong-field ionization rates and dynamics in atoms and small molecules. This involves propagating the electronic density matrix in time with a time-dependent laser potential and a spatial non-Hermitian complex absorbing potential which is projected onto an atom-centered basis set to remove ionized charge from the simulation. For the density functional theory (DFT) functional we use a tuned range-separated functional LC-PBE*, which has the correct asymptotic 1/r form of the potential and a reduced delocalization error compared to traditional DFT functionals. Ionization rates are computed for hydrogen, molecular nitrogen, and iodoacetylene under various field frequencies, intensities, and polarizations (angle-dependent ionization), and the results are shown to quantitatively agree with time-dependent Schrödinger equation and strong-field approximation calculations. This tuned DFT with GTO method opens the door to predictive all-electron time-dependent density functional theory simulations of ionization and ionization-triggered dynamics in molecular systems using tuned range-separated hybrid functionals.

Angle-dependent strong-field molecular ionization rates with tuned range-separated time-dependent density functional theory

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

Sissay, Adonay; Abanador, Paul; Mauger, François

2016-09-07

Strong-field ionization and the resulting electronic dynamics are important for a range of processes such as high harmonic generation, photodamage, charge resonance enhanced ionization, and ionization-triggered charge migration. Modeling ionization dynamics in molecular systems from first-principles can be challenging due to the large spatial extent of the wavefunction which stresses the accuracy of basis sets, and the intense fields which require non-perturbative time-dependent electronic structure methods. In this paper, we develop a time-dependent density functional theory approach which uses a Gaussian-type orbital (GTO) basis set to capture strong-field ionization rates and dynamics in atoms and small molecules. This involves propagatingmore » the electronic density matrix in time with a time-dependent laser potential and a spatial non-Hermitian complex absorbing potential which is projected onto an atom-centered basis set to remove ionized charge from the simulation. For the density functional theory (DFT) functional we use a tuned range-separated functional LC-PBE*, which has the correct asymptotic 1/r form of the potential and a reduced delocalization error compared to traditional DFT functionals. Ionization rates are computed for hydrogen, molecular nitrogen, and iodoacetylene under various field frequencies, intensities, and polarizations (angle-dependent ionization), and the results are shown to quantitatively agree with time-dependent Schrödinger equation and strong-field approximation calculations. This tuned DFT with GTO method opens the door to predictive all-electron time-dependent density functional theory simulations of ionization and ionization-triggered dynamics in molecular systems using tuned range-separated hybrid functionals.« less

Fragment approach to constrained density functional theory calculations using Daubechies wavelets

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

Ratcliff, Laura E.; Genovese, Luigi; Mohr, Stephan

2015-06-21

In a recent paper, we presented a linear scaling Kohn-Sham density functional theory (DFT) code based on Daubechies wavelets, where a minimal set of localized support functions are optimized in situ and therefore adapted to the chemical properties of the molecular system. Thanks to the systematically controllable accuracy of the underlying basis set, this approach is able to provide an optimal contracted basis for a given system: accuracies for ground state energies and atomic forces are of the same quality as an uncontracted, cubic scaling approach. This basis set offers, by construction, a natural subset where the density matrix ofmore » the system can be projected. In this paper, we demonstrate the flexibility of this minimal basis formalism in providing a basis set that can be reused as-is, i.e., without reoptimization, for charge-constrained DFT calculations within a fragment approach. Support functions, represented in the underlying wavelet grid, of the template fragments are roto-translated with high numerical precision to the required positions and used as projectors for the charge weight function. We demonstrate the interest of this approach to express highly precise and efficient calculations for preparing diabatic states and for the computational setup of systems in complex environments.« less

Highly efficient implementation of pseudospectral time-dependent density-functional theory for the calculation of excitation energies of large molecules.

PubMed

Cao, Yixiang; Hughes, Thomas; Giesen, Dave; Halls, Mathew D; Goldberg, Alexander; Vadicherla, Tati Reddy; Sastry, Madhavi; Patel, Bhargav; Sherman, Woody; Weisman, Andrew L; Friesner, Richard A

2016-06-15

We have developed and implemented pseudospectral time-dependent density-functional theory (TDDFT) in the quantum mechanics package Jaguar to calculate restricted singlet and restricted triplet, as well as unrestricted excitation energies with either full linear response (FLR) or the Tamm-Dancoff approximation (TDA) with the pseudospectral length scales, pseudospectral atomic corrections, and pseudospectral multigrid strategy included in the implementations to improve the chemical accuracy and to speed the pseudospectral calculations. The calculations based on pseudospectral time-dependent density-functional theory with full linear response (PS-FLR-TDDFT) and within the Tamm-Dancoff approximation (PS-TDA-TDDFT) for G2 set molecules using B3LYP/6-31G*(*) show mean and maximum absolute deviations of 0.0015 eV and 0.0081 eV, 0.0007 eV and 0.0064 eV, 0.0004 eV and 0.0022 eV for restricted singlet excitation energies, restricted triplet excitation energies, and unrestricted excitation energies, respectively; compared with the results calculated from the conventional spectral method. The application of PS-FLR-TDDFT to OLED molecules and organic dyes, as well as the comparisons for results calculated from PS-FLR-TDDFT and best estimations demonstrate that the accuracy of both PS-FLR-TDDFT and PS-TDA-TDDFT. Calculations for a set of medium-sized molecules, including Cn fullerenes and nanotubes, using the B3LYP functional and 6-31G(**) basis set show PS-TDA-TDDFT provides 19- to 34-fold speedups for Cn fullerenes with 450-1470 basis functions, 11- to 32-fold speedups for nanotubes with 660-3180 basis functions, and 9- to 16-fold speedups for organic molecules with 540-1340 basis functions compared to fully analytic calculations without sacrificing chemical accuracy. The calculations on a set of larger molecules, including the antibiotic drug Ramoplanin, the 46-residue crambin protein, fullerenes up to C540 and nanotubes up to 14×(6,6), using the B3LYP functional and 6-31G(**) basis set with up to 8100 basis functions show that PS-FLR-TDDFT CPU time scales as N(2.05) with the number of basis functions. © 2016 Wiley Periodicals, Inc. © 2016 Wiley Periodicals, Inc.

EMOTIONS AND IMAGES IN LANGUAGE--A LEARNING ANALYSIS OF THEIR ACQUISITION AND FUNCTION.

ERIC Educational Resources Information Center

STAATS, ARTHUR W.

THIS ARTICLE PRESENTED THEORETICAL AND EXPERIMENTAL ANALYSES CONCERNING IMPORTANT ASPECTS OF LANGUAGE. IT WAS SUGGESTED THAT A LEARNING THEORY WHICH INEGRATES INSTRUMENTAL AND CLASSICAL CONDITIONING, CUTTING ACROSS THEORETICAL LINES, COULD SERVE AS THE BASIS FOR A COMPREHENSIVE THEORY OF LANGUAGE ACQUISITION AND FUNCTION. THE PAPER ILLUSTRATED THE…

Full-band quantum simulation of electron devices with the pseudopotential method: Theory, implementation, and applications

NASA Astrophysics Data System (ADS)

Pala, M. G.; Esseni, D.

2018-03-01

This paper presents the theory, implementation, and application of a quantum transport modeling approach based on the nonequilibrium Green's function formalism and a full-band empirical pseudopotential Hamiltonian. We here propose to employ a hybrid real-space/plane-wave basis that results in a significant reduction of the computational complexity compared to a full plane-wave basis. To this purpose, we provide a theoretical formulation in the hybrid basis of the quantum confinement, the self-energies of the leads, and the coupling between the device and the leads. After discussing the theory and the implementation of the new simulation methodology, we report results for complete, self-consistent simulations of different electron devices, including a silicon Esaki diode, a thin-body silicon field effect transistor (FET), and a germanium tunnel FET. The simulated transistors have technologically relevant geometrical features with a semiconductor film thickness of about 4 nm and a channel length ranging from 10 to 17 nm. We believe that the newly proposed formalism may find applications also in transport models based on ab initio Hamiltonians, as those employed in density functional theory methods.

No need for external orthogonality in subsystem density-functional theory.

PubMed

Unsleber, Jan P; Neugebauer, Johannes; Jacob, Christoph R

2016-08-03

Recent reports on the necessity of using externally orthogonal orbitals in subsystem density-functional theory (SDFT) [Annu. Rep. Comput. Chem., 8, 2012, 53; J. Phys. Chem. A, 118, 2014, 9182] are re-investigated. We show that in the basis-set limit, supermolecular Kohn-Sham-DFT (KS-DFT) densities can exactly be represented as a sum of subsystem densities, even if the subsystem orbitals are not externally orthogonal. This is illustrated using both an analytical example and in basis-set free numerical calculations for an atomic test case. We further show that even with finite basis sets, SDFT calculations using accurate reconstructed potentials can closely approach the supermolecular KS-DFT density, and that the deviations between SDFT and KS-DFT decrease as the basis-set limit is approached. Our results demonstrate that formally, there is no need to enforce external orthogonality in SDFT, even though this might be a useful strategy when developing projection-based DFT embedding schemes.

Open-ended recursive calculation of single residues of response functions for perturbation-dependent basis sets.

PubMed

Friese, Daniel H; Ringholm, Magnus; Gao, Bin; Ruud, Kenneth

2015-10-13

We present theory, implementation, and applications of a recursive scheme for the calculation of single residues of response functions that can treat perturbations that affect the basis set. This scheme enables the calculation of nonlinear light absorption properties to arbitrary order for other perturbations than an electric field. We apply this scheme for the first treatment of two-photon circular dichroism (TPCD) using London orbitals at the Hartree-Fock level of theory. In general, TPCD calculations suffer from the problem of origin dependence, which has so far been solved by using the velocity gauge for the electric dipole operator. This work now enables comparison of results from London orbital and velocity gauge based TPCD calculations. We find that the results from the two approaches both exhibit strong basis set dependence but that they are very similar with respect to their basis set convergence.

Scanning tunneling microscopy current from localized basis orbital density functional theory

NASA Astrophysics Data System (ADS)

Gustafsson, Alexander; Paulsson, Magnus

2016-03-01

We present a method capable of calculating elastic scanning tunneling microscopy (STM) currents from localized atomic orbital density functional theory (DFT). To overcome the poor accuracy of the localized orbital description of the wave functions far away from the atoms, we propagate the wave functions, using the total DFT potential. From the propagated wave functions, the Bardeen's perturbative approach provides the tunneling current. To illustrate the method we investigate carbon monoxide adsorbed on a Cu(111) surface and recover the depression/protrusion observed experimentally with normal/CO-functionalized STM tips. The theory furthermore allows us to discuss the significance of s - and p -wave tips.

Projected Hybrid Orbitals: A General QM/MM Method

PubMed Central

2015-01-01

A projected hybrid orbital (PHO) method was described to model the covalent boundary in a hybrid quantum mechanical and molecular mechanical (QM/MM) system. The PHO approach can be used in ab initio wave function theory and in density functional theory with any basis set without introducing system-dependent parameters. In this method, a secondary basis set on the boundary atom is introduced to formulate a set of hybrid atomic orbtials. The primary basis set on the boundary atom used for the QM subsystem is projected onto the secondary basis to yield a representation that provides a good approximation to the electron-withdrawing power of the primary basis set to balance electronic interactions between QM and MM subsystems. The PHO method has been tested on a range of molecules and properties. Comparison with results obtained from QM calculations on the entire system shows that the present PHO method is a robust and balanced QM/MM scheme that preserves the structural and electronic properties of the QM region. PMID:25317748

Density functional theory for molecular and periodic systems using density fitting and continuous fast multipole method: Analytical gradients.

PubMed

Łazarski, Roman; Burow, Asbjörn Manfred; Grajciar, Lukáš; Sierka, Marek

2016-10-30

A full implementation of analytical energy gradients for molecular and periodic systems is reported in the TURBOMOLE program package within the framework of Kohn-Sham density functional theory using Gaussian-type orbitals as basis functions. Its key component is a combination of density fitting (DF) approximation and continuous fast multipole method (CFMM) that allows for an efficient calculation of the Coulomb energy gradient. For exchange-correlation part the hierarchical numerical integration scheme (Burow and Sierka, Journal of Chemical Theory and Computation 2011, 7, 3097) is extended to energy gradients. Computational efficiency and asymptotic O(N) scaling behavior of the implementation is demonstrated for various molecular and periodic model systems, with the largest unit cell of hematite containing 640 atoms and 19,072 basis functions. The overall computational effort of energy gradient is comparable to that of the Kohn-Sham matrix formation. © 2016 Wiley Periodicals, Inc. © 2016 Wiley Periodicals, Inc.

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.

Approaching the basis set limit for DFT calculations using an environment-adapted minimal basis with perturbation theory: Formulation, proof of concept, and a pilot implementation

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

Mao, Yuezhi; Horn, Paul R.; Mardirossian, Narbe

2016-07-28

Recently developed density functionals have good accuracy for both thermochemistry (TC) and non-covalent interactions (NC) if very large atomic orbital basis sets are used. To approach the basis set limit with potentially lower computational cost, a new self-consistent field (SCF) scheme is presented that employs minimal adaptive basis (MAB) functions. The MAB functions are optimized on each atomic site by minimizing a surrogate function. High accuracy is obtained by applying a perturbative correction (PC) to the MAB calculation, similar to dual basis approaches. Compared to exact SCF results, using this MAB-SCF (PC) approach with the same large target basis set producesmore » <0.15 kcal/mol root-mean-square deviations for most of the tested TC datasets, and <0.1 kcal/mol for most of the NC datasets. The performance of density functionals near the basis set limit can be even better reproduced. With further improvement to its implementation, MAB-SCF (PC) is a promising lower-cost substitute for conventional large-basis calculations as a method to approach the basis set limit of modern density functionals.« less

Evaluation of B3LYP, X3LYP, and M06-Class Density Functionals for Predicting the Binding Energies of Neutral, Protonated, and Deprotonated Water Clusters.

PubMed

Bryantsev, Vyacheslav S; Diallo, Mamadou S; van Duin, Adri C T; Goddard, William A

2009-04-14

In this paper we assess the accuracy of the B3LYP, X3LYP, and newly developed M06-L, M06-2X, and M06 functionals to predict the binding energies of neutral and charged water clusters including (H2O)n, n = 2-8, 20), H3O(+)(H2O)n, n = 1-6, and OH(-)(H2O)n, n = 1-6. We also compare the predicted energies of two ion hydration and neutralization reactions on the basis of the calculated binding energies. In all cases, we use as benchmarks calculated binding energies of water clusters extrapolated to the complete basis set limit of the second-order Møller-Plesset perturbation theory with the effects of higher order correlation estimated at the coupled-cluster theory with single, double, and perturbative triple excitations in the aug-cc-pVDZ basis set. We rank the accuracy of the functionals on the basis of the mean unsigned error (MUE) between calculated benchmark and density functional theory energies. The corresponding MUE (kcal/mol) for each functional is listed in parentheses. We find that M06-L (0.73) and M06 (0.84) give the most accurate binding energies using very extended basis sets such as aug-cc-pV5Z. For more affordable basis sets, the best methods for predicting the binding energies of water clusters are M06-L/aug-cc-pVTZ (1.24), B3LYP/6-311++G(2d,2p) (1.29), and M06/aug-cc-PVTZ (1.33). M06-L/aug-cc-pVTZ also gives more accurate energies for the neutralization reactions (1.38), whereas B3LYP/6-311++G(2d,2p) gives more accurate energies for the ion hydration reactions (1.69).

Adaptive local basis set for Kohn–Sham density functional theory in a discontinuous Galerkin framework II: Force, vibration, and molecular dynamics calculations

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

Zhang, Gaigong; Lin, Lin, E-mail: linlin@math.berkeley.edu; Computational Research Division, Lawrence Berkeley National Laboratory, Berkeley, CA 94720

Recently, we have proposed the adaptive local basis set for electronic structure calculations based on Kohn–Sham density functional theory in a pseudopotential framework. The adaptive local basis set is efficient and systematically improvable for total energy calculations. In this paper, we present the calculation of atomic forces, which can be used for a range of applications such as geometry optimization and molecular dynamics simulation. We demonstrate that, under mild assumptions, the computation of atomic forces can scale nearly linearly with the number of atoms in the system using the adaptive local basis set. We quantify the accuracy of the Hellmann–Feynmanmore » forces for a range of physical systems, benchmarked against converged planewave calculations, and find that the adaptive local basis set is efficient for both force and energy calculations, requiring at most a few tens of basis functions per atom to attain accuracies required in practice. Since the adaptive local basis set has implicit dependence on atomic positions, Pulay forces are in general nonzero. However, we find that the Pulay force is numerically small and systematically decreasing with increasing basis completeness, so that the Hellmann–Feynman force is sufficient for basis sizes of a few tens of basis functions per atom. We verify the accuracy of the computed forces in static calculations of quasi-1D and 3D disordered Si systems, vibration calculation of a quasi-1D Si system, and molecular dynamics calculations of H{sub 2} and liquid Al–Si alloy systems, where we show systematic convergence to benchmark planewave results and results from the literature.« less

Adaptive local basis set for Kohn–Sham density functional theory in a discontinuous Galerkin framework II: Force, vibration, and molecular dynamics calculations

DOE PAGES

Zhang, Gaigong; Lin, Lin; Hu, Wei; ...

2017-01-27

Recently, we have proposed the adaptive local basis set for electronic structure calculations based on Kohn–Sham density functional theory in a pseudopotential framework. The adaptive local basis set is efficient and systematically improvable for total energy calculations. In this paper, we present the calculation of atomic forces, which can be used for a range of applications such as geometry optimization and molecular dynamics simulation. We demonstrate that, under mild assumptions, the computation of atomic forces can scale nearly linearly with the number of atoms in the system using the adaptive local basis set. We quantify the accuracy of the Hellmann–Feynmanmore » forces for a range of physical systems, benchmarked against converged planewave calculations, and find that the adaptive local basis set is efficient for both force and energy calculations, requiring at most a few tens of basis functions per atom to attain accuracies required in practice. Sin ce the adaptive local basis set has implicit dependence on atomic positions, Pulay forces are in general nonzero. However, we find that the Pulay force is numerically small and systematically decreasing with increasing basis completeness, so that the Hellmann–Feynman force is sufficient for basis sizes of a few tens of basis functions per atom. We verify the accuracy of the computed forces in static calculations of quasi-1D and 3D disordered Si systems, vibration calculation of a quasi-1D Si system, and molecular dynamics calculations of H 2 and liquid Al–Si alloy systems, where we show systematic convergence to benchmark planewave results and results from the literature.« less

Adaptive local basis set for Kohn–Sham density functional theory in a discontinuous Galerkin framework II: Force, vibration, and molecular dynamics calculations

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

Zhang, Gaigong; Lin, Lin; Hu, Wei

Recently, we have proposed the adaptive local basis set for electronic structure calculations based on Kohn–Sham density functional theory in a pseudopotential framework. The adaptive local basis set is efficient and systematically improvable for total energy calculations. In this paper, we present the calculation of atomic forces, which can be used for a range of applications such as geometry optimization and molecular dynamics simulation. We demonstrate that, under mild assumptions, the computation of atomic forces can scale nearly linearly with the number of atoms in the system using the adaptive local basis set. We quantify the accuracy of the Hellmann–Feynmanmore » forces for a range of physical systems, benchmarked against converged planewave calculations, and find that the adaptive local basis set is efficient for both force and energy calculations, requiring at most a few tens of basis functions per atom to attain accuracies required in practice. Sin ce the adaptive local basis set has implicit dependence on atomic positions, Pulay forces are in general nonzero. However, we find that the Pulay force is numerically small and systematically decreasing with increasing basis completeness, so that the Hellmann–Feynman force is sufficient for basis sizes of a few tens of basis functions per atom. We verify the accuracy of the computed forces in static calculations of quasi-1D and 3D disordered Si systems, vibration calculation of a quasi-1D Si system, and molecular dynamics calculations of H 2 and liquid Al–Si alloy systems, where we show systematic convergence to benchmark planewave results and results from the literature.« less

Adaptive local basis set for Kohn-Sham density functional theory in a discontinuous Galerkin framework II: Force, vibration, and molecular dynamics calculations

NASA Astrophysics Data System (ADS)

Zhang, Gaigong; Lin, Lin; Hu, Wei; Yang, Chao; Pask, John E.

2017-04-01

Recently, we have proposed the adaptive local basis set for electronic structure calculations based on Kohn-Sham density functional theory in a pseudopotential framework. The adaptive local basis set is efficient and systematically improvable for total energy calculations. In this paper, we present the calculation of atomic forces, which can be used for a range of applications such as geometry optimization and molecular dynamics simulation. We demonstrate that, under mild assumptions, the computation of atomic forces can scale nearly linearly with the number of atoms in the system using the adaptive local basis set. We quantify the accuracy of the Hellmann-Feynman forces for a range of physical systems, benchmarked against converged planewave calculations, and find that the adaptive local basis set is efficient for both force and energy calculations, requiring at most a few tens of basis functions per atom to attain accuracies required in practice. Since the adaptive local basis set has implicit dependence on atomic positions, Pulay forces are in general nonzero. However, we find that the Pulay force is numerically small and systematically decreasing with increasing basis completeness, so that the Hellmann-Feynman force is sufficient for basis sizes of a few tens of basis functions per atom. We verify the accuracy of the computed forces in static calculations of quasi-1D and 3D disordered Si systems, vibration calculation of a quasi-1D Si system, and molecular dynamics calculations of H2 and liquid Al-Si alloy systems, where we show systematic convergence to benchmark planewave results and results from the literature.

Complex basis functions for molecular resonances: Methodology and applications

NASA Astrophysics Data System (ADS)

White, Alec; McCurdy, C. William; Head-Gordon, Martin

The computation of positions and widths of metastable electronic states is a challenge for molecular electronic structure theory because, in addition to the difficulty of the many-body problem, such states obey scattering boundary conditions. These resonances cannot be addressed with naïve application of traditional bound state electronic structure theory. Non-Hermitian electronic structure methods employing complex basis functions is one way that we may rigorously treat resonances within the framework of traditional electronic structure theory. In this talk, I will discuss our recent work in this area including the methodological extension from single determinant SCF-based approaches to highly correlated levels of wavefunction-based theory such as equation of motion coupled cluster and many-body perturbation theory. These approaches provide a hierarchy of theoretical methods for the computation of positions and widths of molecular resonances. Within this framework, we may also examine properties of resonances including the dependence of these parameters on molecular geometry. Some applications of these methods to temporary anions and dianions will also be discussed.

Efficient High-Fidelity, Geometrically Exact, Multiphysics Structural Models

DTIC Science & Technology

2011-10-14

fuctionally graded core. International Journal for Numerical Methods in Engineering, 68:940– 966, 2006. 7F. Shang, Z. Wang, and Z. Li. Analysis of...normal deformable plate theory and MLPG method with radial basis fuctions . Composite Structures, 80:539– 552, 2007. 17W. Zhen and W. Chen. A higher-order...functionally graded plates by using higher-order shear and normal deformable plate theory and MLPG method with radial basis fuctions . Composite Structures, 80

Method and basis set dependence of anharmonic ground state nuclear wave functions and zero-point energies: application to SSSH.

PubMed

Kolmann, Stephen J; Jordan, Meredith J T

2010-02-07

One of the largest remaining errors in thermochemical calculations is the determination of the zero-point energy (ZPE). The fully coupled, anharmonic ZPE and ground state nuclear wave function of the SSSH radical are calculated using quantum diffusion Monte Carlo on interpolated potential energy surfaces (PESs) constructed using a variety of method and basis set combinations. The ZPE of SSSH, which is approximately 29 kJ mol(-1) at the CCSD(T)/6-31G* level of theory, has a 4 kJ mol(-1) dependence on the treatment of electron correlation. The anharmonic ZPEs are consistently 0.3 kJ mol(-1) lower in energy than the harmonic ZPEs calculated at the Hartree-Fock and MP2 levels of theory, and 0.7 kJ mol(-1) lower in energy at the CCSD(T)/6-31G* level of theory. Ideally, for sub-kJ mol(-1) thermochemical accuracy, ZPEs should be calculated using correlated methods with as big a basis set as practicable. The ground state nuclear wave function of SSSH also has significant method and basis set dependence. The analysis of the nuclear wave function indicates that SSSH is localized to a single symmetry equivalent global minimum, despite having sufficient ZPE to be delocalized over both minima. As part of this work, modifications to the interpolated PES construction scheme of Collins and co-workers are presented.

Method and basis set dependence of anharmonic ground state nuclear wave functions and zero-point energies: Application to SSSH

NASA Astrophysics Data System (ADS)

Kolmann, Stephen J.; Jordan, Meredith J. T.

2010-02-01

One of the largest remaining errors in thermochemical calculations is the determination of the zero-point energy (ZPE). The fully coupled, anharmonic ZPE and ground state nuclear wave function of the SSSH radical are calculated using quantum diffusion Monte Carlo on interpolated potential energy surfaces (PESs) constructed using a variety of method and basis set combinations. The ZPE of SSSH, which is approximately 29 kJ mol-1 at the CCSD(T)/6-31G∗ level of theory, has a 4 kJ mol-1 dependence on the treatment of electron correlation. The anharmonic ZPEs are consistently 0.3 kJ mol-1 lower in energy than the harmonic ZPEs calculated at the Hartree-Fock and MP2 levels of theory, and 0.7 kJ mol-1 lower in energy at the CCSD(T)/6-31G∗ level of theory. Ideally, for sub-kJ mol-1 thermochemical accuracy, ZPEs should be calculated using correlated methods with as big a basis set as practicable. The ground state nuclear wave function of SSSH also has significant method and basis set dependence. The analysis of the nuclear wave function indicates that SSSH is localized to a single symmetry equivalent global minimum, despite having sufficient ZPE to be delocalized over both minima. As part of this work, modifications to the interpolated PES construction scheme of Collins and co-workers are presented.

Orbital-Dependent Density Functionals for Chemical Catalysis

DTIC Science & Technology

2014-10-17

noncollinear density functional theory to show that the low-spin state of Mn3 in a model of the oxygen -evolving complex of photosystem II avoids...DK, which denotes the cc-pV5Z-DK basis set for 3d metals and hydrogen and the ma-cc- pV5Z-DK basis set for oxygen ) and to nonrelativistic all...cc-pV5Z basis set for oxygen ). As compared to NCBS-DK results, all ECP calculations perform worse than def2-TZVP all-electron relativistic

Quantum Dynamics with Short-Time Trajectories and Minimal Adaptive Basis Sets.

PubMed

Saller, Maximilian A C; Habershon, Scott

2017-07-11

Methods for solving the time-dependent Schrödinger equation via basis set expansion of the wave function can generally be categorized as having either static (time-independent) or dynamic (time-dependent) basis functions. We have recently introduced an alternative simulation approach which represents a middle road between these two extremes, employing dynamic (classical-like) trajectories to create a static basis set of Gaussian wavepackets in regions of phase-space relevant to future propagation of the wave function [J. Chem. Theory Comput., 11, 8 (2015)]. Here, we propose and test a modification of our methodology which aims to reduce the size of basis sets generated in our original scheme. In particular, we employ short-time classical trajectories to continuously generate new basis functions for short-time quantum propagation of the wave function; to avoid the continued growth of the basis set describing the time-dependent wave function, we employ Matching Pursuit to periodically minimize the number of basis functions required to accurately describe the wave function. Overall, this approach generates a basis set which is adapted to evolution of the wave function while also being as small as possible. In applications to challenging benchmark problems, namely a 4-dimensional model of photoexcited pyrazine and three different double-well tunnelling problems, we find that our new scheme enables accurate wave function propagation with basis sets which are around an order-of-magnitude smaller than our original trajectory-guided basis set methodology, highlighting the benefits of adaptive strategies for wave function propagation.

Density functional theory studies of etoricoxib

NASA Astrophysics Data System (ADS)

Sachdeva, Ritika; Kaur, Prabhjot; Singh, V. P.; Saini, G. S. S.

2016-05-01

Etoricoxib is a COX-2 selective inhibitor drug with molecular formula C18H15ClN2O2S. It is primarily used for the treatment of arthritis(rheumatoid, psoriatic, osteoarthritis), ankylosing spondylitis, gout and chronic low back pain. Theoretical studies of the molecule including geometry optimization and vibrational frequency calculations were carried out with the help of density functional theory calculations using 6-311++ g (d, p) basis set and B3LYP functional.

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

Papajak, Ewa; Truhlar, Donald G.

We present sets of convergent, partially augmented basis set levels corresponding to subsets of the augmented “aug-cc-pV(n+d)Z” basis sets of Dunning and co-workers. We show that for many molecular properties a basis set fully augmented with diffuse functions is computationally expensive and almost always unnecessary. On the other hand, unaugmented cc-pV(n+d)Z basis sets are insufficient for many properties that require diffuse functions. Therefore, we propose using intermediate basis sets. We developed an efficient strategy for partial augmentation, and in this article, we test it and validate it. Sequentially deleting diffuse basis functions from the “aug” basis sets yields the “jul”,more » “jun”, “may”, “apr”, etc. basis sets. Tests of these basis sets for Møller-Plesset second-order perturbation theory (MP2) show the advantages of using these partially augmented basis sets and allow us to recommend which basis sets offer the best accuracy for a given number of basis functions for calculations on large systems. Similar truncations in the diffuse space can be performed for the aug-cc-pVxZ, aug-cc-pCVxZ, etc. basis sets.« less

Analysis of STM images with pure and CO-functionalized tips: A first-principles and experimental study

NASA Astrophysics Data System (ADS)

Gustafsson, Alexander; Okabayashi, Norio; Peronio, Angelo; Giessibl, Franz J.; Paulsson, Magnus

2017-08-01

We describe a first-principles method to calculate scanning tunneling microscopy (STM) images, and compare the results to well-characterized experiments combining STM with atomic force microscopy (AFM). The theory is based on density functional theory with a localized basis set, where the wave functions in the vacuum gap are computed by propagating the localized-basis wave functions into the gap using a real-space grid. Constant-height STM images are computed using Bardeen's approximation method, including averaging over the reciprocal space. We consider copper adatoms and single CO molecules adsorbed on Cu(111), scanned with a single-atom copper tip with and without CO functionalization. The calculated images agree with state-of-the-art experiments, where the atomic structure of the tip apex is determined by AFM. The comparison further allows for detailed interpretation of the STM images.

Hamiltonian lattice field theory: Computer calculations using variational methods

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

Zako, Robert L.

1991-12-03

I develop a variational method for systematic numerical computation of physical quantities -- bound state energies and scattering amplitudes -- in quantum field theory. An infinite-volume, continuum theory is approximated by a theory on a finite spatial lattice, which is amenable to numerical computation. I present an algorithm for computing approximate energy eigenvalues and eigenstates in the lattice theory and for bounding the resulting errors. I also show how to select basis states and choose variational parameters in order to minimize errors. The algorithm is based on the Rayleigh-Ritz principle and Kato`s generalizations of Temple`s formula. The algorithm could bemore » adapted to systems such as atoms and molecules. I show how to compute Green`s functions from energy eigenvalues and eigenstates in the lattice theory, and relate these to physical (renormalized) coupling constants, bound state energies and Green`s functions. Thus one can compute approximate physical quantities in a lattice theory that approximates a quantum field theory with specified physical coupling constants. I discuss the errors in both approximations. In principle, the errors can be made arbitrarily small by increasing the size of the lattice, decreasing the lattice spacing and computing sufficiently long. Unfortunately, I do not understand the infinite-volume and continuum limits well enough to quantify errors due to the lattice approximation. Thus the method is currently incomplete. I apply the method to real scalar field theories using a Fock basis of free particle states. All needed quantities can be calculated efficiently with this basis. The generalization to more complicated theories is straightforward. I describe a computer implementation of the method and present numerical results for simple quantum mechanical systems.« less

Cooperative Trust Games

DTIC Science & Technology

2013-01-01

the more widely recognized competitive (non-cooperative) game theory. Cooperative game theory focuses on what groups of self-interested agents can...provides immediate justification for using non-cooperative game theory as the basis for modeling the purely competitive agents. 2.4. Superadditive...the competitive and altruistic contributions of the subset team. Definition: Given a payoff function ( ) in a subset team game , the total marginal

Computational studies of metal-metal and metal-ligand interactions

NASA Technical Reports Server (NTRS)

Barnes, Leslie A.

1992-01-01

The geometric structure of Cr(CO)6 is optimized at the modified coupled-pair functional (MCPF), single and double excitation coupled-cluster (CCSD) and CCSD(T) levels of theory (including a perturbational estimate for connected triple excitations), and the force constants for the totally symmetric representation are determined. The geometry of Cr(CO)5 is partially optimized at the MCPF, CCSD and CCSD(T) levels of theory. Comparison with experimental data shows that the CCSD(T) method gives the best results for the structures and force constants, and that remaining errors are probably due to deficiencies in the one-particle basis sets used for CO. A detailed comparison of the properties of free CO is therefore given, at both the MCPF and CCSD/CCSD(T) levels of treatment, using a variety of basis sets. With very large one-particle basis sets, the SSCD(T) method gives excellent results for the bond distance, dipole moment and harmonic frequency of free CO. The total binding energies of Cr(CO)6 and Cr(CO)5 are also determined at the MCPF, CCSD and CCSD(T) levels of theory. The CCSD(T) method gives a much larger total binding energy than either the MCPF or CCSD methods. An analysis of the basis set superposition error (BSSE) at the MCPF level of treatment points out limitations in the one-particle basis used here and in a previous study. Calculations using larger basis sets reduced the BSSE, but the total binding energy of Cr(CO)6 is still significantly smaller than the experimental value, although the first CO bond dissociation energy of Cr(CO)6 is well described. An investigation of 3s3p correlation reveals only a small effect. The remaining discrepancy between the experimental and theoretical total binding energy of Cr(CO)6 is probably due to limitations in the one-particle basis, rather than limitations in the correlation treatment. In particular an additional d function and an f function on each C and O are needed to obtain quantitative results. This is underscored by the fact that even using a very large primitive se (1042 primitive functions contracted to 300 basis functions), the superposition error for the total binding energy of Cr(CO)6 is 22 kcal/mol at the MCPF level of treatment.

Open-Ended Recursive Approach for the Calculation of Multiphoton Absorption Matrix Elements

PubMed Central

2015-01-01

We present an implementation of single residues for response functions to arbitrary order using a recursive approach. Explicit expressions in terms of density-matrix-based response theory for the single residues of the linear, quadratic, cubic, and quartic response functions are also presented. These residues correspond to one-, two-, three- and four-photon transition matrix elements. The newly developed code is used to calculate the one-, two-, three- and four-photon absorption cross sections of para-nitroaniline and para-nitroaminostilbene, making this the first treatment of four-photon absorption in the framework of response theory. We find that the calculated multiphoton absorption cross sections are not very sensitive to the size of the basis set as long as a reasonably large basis set with diffuse functions is used. The choice of exchange–correlation functional, however, significantly affects the calculated cross sections of both charge-transfer transitions and other transitions, in particular, for the larger para-nitroaminostilbene molecule. We therefore recommend the use of a range-separated exchange–correlation functional in combination with the augmented correlation-consistent double-ζ basis set aug-cc-pVDZ for the calculation of multiphoton absorption properties. PMID:25821415

MONOCULAR DIPLOPIA DUE TO SPHEROCYLINDRICAL REFRACTIVE ERRORS (AN AMERICAN OPHTHALMOLOGICAL SOCIETY THESIS)

PubMed Central

Archer, Steven M.

2007-01-01

Purpose Ordinary spherocylindrical refractive errors have been recognized as a cause of monocular diplopia for over a century, yet explanation of this phenomenon using geometrical optics has remained problematic. This study tests the hypothesis that the diffraction theory treatment of refractive errors will provide a more satisfactory explanation of monocular diplopia. Methods Diffraction theory calculations were carried out for modulation transfer functions, point spread functions, and line spread functions under conditions of defocus, astigmatism, and mixed spherocylindrical refractive errors. Defocused photographs of inked and projected black lines were made to demonstrate the predicted consequences of the theoretical calculations. Results For certain amounts of defocus, line spread functions resulting from spherical defocus are predicted to have a bimodal intensity distribution that could provide the basis for diplopia with line targets. Multimodal intensity distributions are predicted in point spread functions and provide a basis for diplopia or polyopia of point targets under conditions of astigmatism. The predicted doubling effect is evident in defocused photographs of black lines, but the effect is not as robust as the subjective experience of monocular diplopia. Conclusions Monocular diplopia due to ordinary refractive errors can be predicted from diffraction theory. Higher-order aberrations—such as spherical aberration—are not necessary but may, under some circumstances, enhance the features of monocular diplopia. The physical basis for monocular diplopia is relatively subtle, and enhancement by neural processing is probably needed to account for the robustness of the percept. PMID:18427616

Functionalizing Conflict: Jesse Jackson's Rhetorical Strategy at the 1984 Democratic National Convention.

ERIC Educational Resources Information Center

Di Mare, Lesley A.

1987-01-01

Examines Jesse Jackson's rhetorical strategy of functionalizing conflict among divisive Democrats during the 1984 national convention. Applies conflict theory to Jackson's convention address, which serves as the basis for this rhetorical analysis. (JD)

Communication: Extended multi-state complete active space second-order perturbation theory: Energy and nuclear gradients

NASA Astrophysics Data System (ADS)

Shiozaki, Toru; Győrffy, Werner; Celani, Paolo; Werner, Hans-Joachim

2011-08-01

The extended multireference quasi-degenerate perturbation theory, proposed by Granovsky [J. Chem. Phys. 134, 214113 (2011)], is combined with internally contracted multi-state complete active space second-order perturbation theory (XMS-CASPT2). The first-order wavefunction is expanded in terms of the union of internally contracted basis functions generated from all the reference functions, which guarantees invariance of the theory with respect to unitary rotations of the reference functions. The method yields improved potentials in the vicinity of avoided crossings and conical intersections. The theory for computing nuclear energy gradients for MS-CASPT2 and XMS-CASPT2 is also presented and the first implementation of these gradient methods is reported. A number of illustrative applications of the new methods are presented.

Computational models and motor learning paradigms: Could they provide insights for neuroplasticity after stroke? An overview.

PubMed

Kiper, Pawel; Szczudlik, Andrzej; Venneri, Annalena; Stozek, Joanna; Luque-Moreno, Carlos; Opara, Jozef; Baba, Alfonc; Agostini, Michela; Turolla, Andrea

2016-10-15

Computational approaches for modelling the central nervous system (CNS) aim to develop theories on processes occurring in the brain that allow the transformation of all information needed for the execution of motor acts. Computational models have been proposed in several fields, to interpret not only the CNS functioning, but also its efferent behaviour. Computational model theories can provide insights into neuromuscular and brain function allowing us to reach a deeper understanding of neuroplasticity. Neuroplasticity is the process occurring in the CNS that is able to permanently change both structure and function due to interaction with the external environment. To understand such a complex process several paradigms related to motor learning and computational modeling have been put forward. These paradigms have been explained through several internal model concepts, and supported by neurophysiological and neuroimaging studies. Therefore, it has been possible to make theories about the basis of different learning paradigms according to known computational models. Here we review the computational models and motor learning paradigms used to describe the CNS and neuromuscular functions, as well as their role in the recovery process. These theories have the potential to provide a way to rigorously explain all the potential of CNS learning, providing a basis for future clinical studies. Copyright © 2016 Elsevier B.V. All rights reserved.

[The cell theory. Progress in studies on cell-cell communications].

PubMed

Brodskiĭ, V Ia

2009-01-01

Current data confirm the fundamental statement of the cell theory concerning the cell reproduction in a series of generations (omnis cellula e cellula). Cell communities or ensembles integrated by the signaling systems established in prokaryotes and protists and functioning in multicellular organisms including mammals are considered as the structural and functional unit of a multicellular organism. The cell is an elementary unit of life and basis of organism development and functioning. At the same time, the adult organism is not just a totality of cells. Multinucleated cells in some tissues, syncytial structure, and structural-functional units of organs are adaptations for optimal functioning of the multicellular organism and manifestations of cell-cell communications in development and definitive functioning. The cell theory was supplemented and developed by studies on cell-cell communications; however, these studies do not question the main generalizations of the theory.

Meshless Solution of the Problem on the Static Behavior of Thin and Thick Laminated Composite Beams

NASA Astrophysics Data System (ADS)

Xiang, S.; Kang, G. W.

2018-03-01

For the first time, the static behavior of laminated composite beams is analyzed using the meshless collocation method based on a thin-plate-spline radial basis function. In the approximation of a partial differential equation by using a radial basis function, the shape parameter has an important role in ensuring the numerical accuracy. The choice of a shape parameter in the thin plate spline radial basis function is easier than in other radial basis functions. The governing differential equations are derived based on Reddy's third-order shear deformation theory. Numerical results are obtained for symmetric cross-ply laminated composite beams with simple-simple and cantilever boundary conditions under a uniform load. The results found are compared with available published ones and demonstrate the accuracy of the present method.

Ultrasound beam transmission using a discretely orthogonal Gaussian aperture basis

NASA Astrophysics Data System (ADS)

Roberts, R. A.

2018-04-01

Work is reported on development of a computational model for ultrasound beam transmission at an arbitrary geometry transmission interface for generally anisotropic materials. The work addresses problems encountered when the fundamental assumptions of ray theory do not hold, thereby introducing errors into ray-theory-based transmission models. Specifically, problems occur when the asymptotic integral analysis underlying ray theory encounters multiple stationary phase points in close proximity, due to focusing caused by concavity on either the entry surface or a material slowness surface. The approach presented here projects integrands over both the transducer aperture and the entry surface beam footprint onto a Gaussian-derived basis set, thereby distributing the integral over a summation of second-order phase integrals which are amenable to single stationary phase point analysis. Significantly, convergence is assured provided a sufficiently fine distribution of basis functions is used.

Density functional theory calculations of the lowest energy quintet and triplet states of model hemes: role of functional, basis set, and zero-point energy corrections.

PubMed

Khvostichenko, Daria; Choi, Andrew; Boulatov, Roman

2008-04-24

We investigated the effect of several computational variables, including the choice of the basis set, application of symmetry constraints, and zero-point energy (ZPE) corrections, on the structural parameters and predicted ground electronic state of model 5-coordinate hemes (iron(II) porphines axially coordinated by a single imidazole or 2-methylimidazole). We studied the performance of B3LYP and B3PW91 with eight Pople-style basis sets (up to 6-311+G*) and B97-1, OLYP, and TPSS functionals with 6-31G and 6-31G* basis sets. Only hybrid functionals B3LYP, B3PW91, and B97-1 reproduced the quintet ground state of the model hemes. With a given functional, the choice of the basis set caused up to 2.7 kcal/mol variation of the quintet-triplet electronic energy gap (DeltaEel), in several cases, resulting in the inversion of the sign of DeltaEel. Single-point energy calculations with triple-zeta basis sets of the Pople (up to 6-311G++(2d,2p)), Ahlrichs (TZVP and TZVPP), and Dunning (cc-pVTZ) families showed the same trend. The zero-point energy of the quintet state was approximately 1 kcal/mol lower than that of the triplet, and accounting for ZPE corrections was crucial for establishing the ground state if the electronic energy of the triplet state was approximately 1 kcal/mol less than that of the quintet. Within a given model chemistry, effects of symmetry constraints and of a "tense" structure of the iron porphine fragment coordinated to 2-methylimidazole on DeltaEel were limited to 0.3 kcal/mol. For both model hemes the best agreement with crystallographic structural data was achieved with small 6-31G and 6-31G* basis sets. Deviation of the computed frequency of the Fe-Im stretching mode from the experimental value with the basis set decreased in the order: nonaugmented basis sets, basis sets with polarization functions, and basis sets with polarization and diffuse functions. Contraction of Pople-style basis sets (double-zeta or triple-zeta) affected the results insignificantly for iron(II) porphyrin coordinated with imidazole. Poor performance of a "locally dense" basis set with a large number of basis functions on the Fe center was observed in calculation of quintet-triplet gaps. Our results lead to a series of suggestions for density functional theory calculations of quintet-triplet energy gaps in ferrohemes with a single axial imidazole; these suggestions are potentially applicable for other transition-metal complexes.

The application of midbond basis sets in efficient and accurate ab initio calculations on electron-deficient systems

NASA Astrophysics Data System (ADS)

Choi, Chu Hwan

2002-09-01

Ab initio chemistry has shown great promise in reproducing experimental results and in its predictive power. The many complicated computational models and methods seem impenetrable to an inexperienced scientist, and the reliability of the results is not easily interpreted. The application of midbond orbitals is used to determine a general method for use in calculating weak intermolecular interactions, especially those involving electron-deficient systems. Using the criteria of consistency, flexibility, accuracy and efficiency we propose a supermolecular method of calculation using the full counterpoise (CP) method of Boys and Bernardi, coupled with Moller-Plesset (MP) perturbation theory as an efficient electron-correlative method. We also advocate the use of the highly efficient and reliable correlation-consistent polarized valence basis sets of Dunning. To these basis sets, we add a general set of midbond orbitals and demonstrate greatly enhanced efficiency in the calculation. The H2-H2 dimer is taken as a benchmark test case for our method, and details of the computation are elaborated. Our method reproduces with great accuracy the dissociation energies of other previous theoretical studies. The added efficiency of extending the basis sets with conventional means is compared with the performance of our midbond-extended basis sets. The improvement found with midbond functions is notably superior in every case tested. Finally, a novel application of midbond functions to the BH5 complex is presented. The system is an unusual van der Waals complex. The interaction potential curves are presented for several standard basis sets and midbond-enhanced basis sets, as well as for two popular, alternative correlation methods. We report that MP theory appears to be superior to coupled-cluster (CC) in speed, while it is more stable than B3LYP, a widely-used density functional theory (DFT). Application of our general method yields excellent results for the midbond basis sets. Again they prove superior to conventional extended basis sets. Based on these results, we recommend our general approach as a highly efficient, accurate method for calculating weakly interacting systems.

OSA Proceedings of the International Topical Meeting on Photonic Switching, Held in Salt Lake City, Utah on 6 - 8 March, 1992. Volume 8

DTIC Science & Technology

1992-05-22

Frobenius Theory : Why Hilberts Metric ?," Mathematics of Operations Research 7 (1982) pp.198-210. 11. H. S. M. Cnxeter, Regular Complex Poly- topes...can be made to perform logic functions by pre-setting the device to a given state. We can, in theory , achieve arbitrary logical functionality by using...then extrapolating on the basis of this theory , is about 2000 two diffracted spots appear in the focal plane of the channels. output lenslet array

Brain and Cognitive Reserve: Translation via Network Control Theory

PubMed Central

Medaglia, John Dominic; Pasqualetti, Fabio; Hamilton, Roy H.; Thompson-Schill, Sharon L.; Bassett, Danielle S.

2017-01-01

Traditional approaches to understanding the brain’s resilience to neuropathology have identified neurophysiological variables, often described as brain or cognitive “reserve,” associated with better outcomes. However, mechanisms of function and resilience in large-scale brain networks remain poorly understood. Dynamic network theory may provide a basis for substantive advances in understanding functional resilience in the human brain. In this perspective, we describe recent theoretical approaches from network control theory as a framework for investigating network level mechanisms underlying cognitive function and the dynamics of neuroplasticity in the human brain. We describe the theoretical opportunities offered by the application of network control theory at the level of the human connectome to understand cognitive resilience and inform translational intervention. PMID:28104411

Conformational analysis of cellobiose by electronic structure theories

USDA-ARS?s Scientific Manuscript database

Adiabatic phi/psi maps for cellobiose were prepared with B3LYP density functional theory. A mixed basis set was used for minimization, followed with 6-31+G(d) single-point calculations, with and without SMD continuum solvation. Different arrangements of the exocyclic groups (3starting geometries) we...

Electronic Coupling Calculations for Bridge-Mediated Charge Transfer Using Constrained Density Functional Theory (CDFT) and Effective Hamiltonian Approaches at the Density Functional Theory (DFT) and Fragment-Orbital Density Functional Tight Binding (FODFTB) Level

DOE PAGES

Gillet, Natacha; Berstis, Laura; Wu, Xiaojing; ...

2016-09-09

In this paper, four methods to calculate charge transfer integrals in the context of bridge-mediated electron transfer are tested. These methods are based on density functional theory (DFT). We consider two perturbative Green's function effective Hamiltonian methods (first, at the DFT level of theory, using localized molecular orbitals; second, applying a tight-binding DFT approach, using fragment orbitals) and two constrained DFT implementations with either plane-wave or local basis sets. To assess the performance of the methods for through-bond (TB)-dominated or through-space (TS)-dominated transfer, different sets of molecules are considered. For through-bond electron transfer (ET), several molecules that were originally synthesizedmore » by Paddon-Row and co-workers for the deduction of electronic coupling values from photoemission and electron transmission spectroscopies, are analyzed. The tested methodologies prove to be successful in reproducing experimental data, the exponential distance decay constant and the superbridge effects arising from interference among ET pathways. For through-space ET, dedicated p-stacked systems with heterocyclopentadiene molecules were created and analyzed on the basis of electronic coupling dependence on donor-acceptor distance, structure of the bridge, and ET barrier height. The inexpensive fragment-orbital density functional tight binding (FODFTB) method gives similar results to constrained density functional theory (CDFT) and both reproduce the expected exponential decay of the coupling with donor-acceptor distances and the number of bridging units. Finally, these four approaches appear to give reliable results for both TB and TS ET and present a good alternative to expensive ab initio methodologies for large systems involving long-range charge transfers.« less

Electronic Coupling Calculations for Bridge-Mediated Charge Transfer Using Constrained Density Functional Theory (CDFT) and Effective Hamiltonian Approaches at the Density Functional Theory (DFT) and Fragment-Orbital Density Functional Tight Binding (FODFTB) Level

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

Gillet, Natacha; Berstis, Laura; Wu, Xiaojing

In this paper, four methods to calculate charge transfer integrals in the context of bridge-mediated electron transfer are tested. These methods are based on density functional theory (DFT). We consider two perturbative Green's function effective Hamiltonian methods (first, at the DFT level of theory, using localized molecular orbitals; second, applying a tight-binding DFT approach, using fragment orbitals) and two constrained DFT implementations with either plane-wave or local basis sets. To assess the performance of the methods for through-bond (TB)-dominated or through-space (TS)-dominated transfer, different sets of molecules are considered. For through-bond electron transfer (ET), several molecules that were originally synthesizedmore » by Paddon-Row and co-workers for the deduction of electronic coupling values from photoemission and electron transmission spectroscopies, are analyzed. The tested methodologies prove to be successful in reproducing experimental data, the exponential distance decay constant and the superbridge effects arising from interference among ET pathways. For through-space ET, dedicated p-stacked systems with heterocyclopentadiene molecules were created and analyzed on the basis of electronic coupling dependence on donor-acceptor distance, structure of the bridge, and ET barrier height. The inexpensive fragment-orbital density functional tight binding (FODFTB) method gives similar results to constrained density functional theory (CDFT) and both reproduce the expected exponential decay of the coupling with donor-acceptor distances and the number of bridging units. Finally, these four approaches appear to give reliable results for both TB and TS ET and present a good alternative to expensive ab initio methodologies for large systems involving long-range charge transfers.« less

Electronic Coupling Calculations for Bridge-Mediated Charge Transfer Using Constrained Density Functional Theory (CDFT) and Effective Hamiltonian Approaches at the Density Functional Theory (DFT) and Fragment-Orbital Density Functional Tight Binding (FODFTB) Level.

PubMed

Gillet, Natacha; Berstis, Laura; Wu, Xiaojing; Gajdos, Fruzsina; Heck, Alexander; de la Lande, Aurélien; Blumberger, Jochen; Elstner, Marcus

2016-10-11

In this article, four methods to calculate charge transfer integrals in the context of bridge-mediated electron transfer are tested. These methods are based on density functional theory (DFT). We consider two perturbative Green's function effective Hamiltonian methods (first, at the DFT level of theory, using localized molecular orbitals; second, applying a tight-binding DFT approach, using fragment orbitals) and two constrained DFT implementations with either plane-wave or local basis sets. To assess the performance of the methods for through-bond (TB)-dominated or through-space (TS)-dominated transfer, different sets of molecules are considered. For through-bond electron transfer (ET), several molecules that were originally synthesized by Paddon-Row and co-workers for the deduction of electronic coupling values from photoemission and electron transmission spectroscopies, are analyzed. The tested methodologies prove to be successful in reproducing experimental data, the exponential distance decay constant and the superbridge effects arising from interference among ET pathways. For through-space ET, dedicated π-stacked systems with heterocyclopentadiene molecules were created and analyzed on the basis of electronic coupling dependence on donor-acceptor distance, structure of the bridge, and ET barrier height. The inexpensive fragment-orbital density functional tight binding (FODFTB) method gives similar results to constrained density functional theory (CDFT) and both reproduce the expected exponential decay of the coupling with donor-acceptor distances and the number of bridging units. These four approaches appear to give reliable results for both TB and TS ET and present a good alternative to expensive ab initio methodologies for large systems involving long-range charge transfers.

How to compute isomerization energies of organic molecules with quantum chemical methods.

PubMed

Grimme, Stefan; Steinmetz, Marc; Korth, Martin

2007-03-16

The reaction energies for 34 typical organic isomerizations including oxygen and nitrogen heteroatoms are investigated with modern quantum chemical methods that have the perspective of also being applicable to large systems. The experimental reaction enthalpies are corrected for vibrational and thermal effects, and the thus derived "experimental" reaction energies are compared to corresponding theoretical data. A series of standard AO basis sets in combination with second-order perturbation theory (MP2, SCS-MP2), conventional density functionals (e.g., PBE, TPSS, B3-LYP, MPW1K, BMK), and new perturbative functionals (B2-PLYP, mPW2-PLYP) are tested. In three cases, obvious errors of the experimental values could be detected, and accurate coupled-cluster [CCSD(T)] reference values have been used instead. It is found that only triple-zeta quality AO basis sets provide results close enough to the basis set limit and that sets like the popular 6-31G(d) should be avoided in accurate work. Augmentation of small basis sets with diffuse functions has a notable effect in B3-LYP calculations that is attributed to intramolecular basis set superposition error and covers basic deficiencies of the functional. The new methods based on perturbation theory (SCS-MP2, X2-PLYP) are found to be clearly superior to many other approaches; that is, they provide mean absolute deviations of less than 1.2 kcal mol-1 and only a few (<10%) outliers. The best performance in the group of conventional functionals is found for the highly parametrized BMK hybrid meta-GGA. Contrary to accepted opinion, hybrid density functionals offer no real advantage over simple GGAs. For reasonably large AO basis sets, results of poor quality are obtained with the popular B3-LYP functional that cannot be recommended for thermochemical applications in organic chemistry. The results of this study are complementary to often used benchmarks based on atomization energies and should guide chemists in their search for accurate and efficient computational thermochemistry methods.

Useful lower limits to polarization contributions to intermolecular interactions using a minimal basis of localized orthogonal orbitals: theory and analysis of the water dimer.

PubMed

Azar, R Julian; Horn, Paul Richard; Sundstrom, Eric Jon; Head-Gordon, Martin

2013-02-28

The problem of describing the energy-lowering associated with polarization of interacting molecules is considered in the overlapping regime for self-consistent field wavefunctions. The existing approach of solving for absolutely localized molecular orbital (ALMO) coefficients that are block-diagonal in the fragments is shown based on formal grounds and practical calculations to often overestimate the strength of polarization effects. A new approach using a minimal basis of polarized orthogonal local MOs (polMOs) is developed as an alternative. The polMO basis is minimal in the sense that one polarization function is provided for each unpolarized orbital that is occupied; such an approach is exact in second-order perturbation theory. Based on formal grounds and practical calculations, the polMO approach is shown to underestimate the strength of polarization effects. In contrast to the ALMO method, however, the polMO approach yields results that are very stable to improvements in the underlying AO basis expansion. Combining the ALMO and polMO approaches allows an estimate of the range of energy-lowering due to polarization. Extensive numerical calculations on the water dimer using a large range of basis sets with Hartree-Fock theory and a variety of different density functionals illustrate the key considerations. Results are also presented for the polarization-dominated Na(+)CH4 complex. Implications for energy decomposition analysis of intermolecular interactions are discussed.

A new parallel algorithm of MP2 energy calculations.

PubMed

Ishimura, Kazuya; Pulay, Peter; Nagase, Shigeru

2006-03-01

A new parallel algorithm has been developed for second-order Møller-Plesset perturbation theory (MP2) energy calculations. Its main projected applications are for large molecules, for instance, for the calculation of dispersion interaction. Tests on a moderate number of processors (2-16) show that the program has high CPU and parallel efficiency. Timings are presented for two relatively large molecules, taxol (C(47)H(51)NO(14)) and luciferin (C(11)H(8)N(2)O(3)S(2)), the former with the 6-31G* and 6-311G** basis sets (1,032 and 1,484 basis functions, 164 correlated orbitals), and the latter with the aug-cc-pVDZ and aug-cc-pVTZ basis sets (530 and 1,198 basis functions, 46 correlated orbitals). An MP2 energy calculation on C(130)H(10) (1,970 basis functions, 265 correlated orbitals) completed in less than 2 h on 128 processors.

Performance of Frozen Density Embedding for Modeling Hole Transfer Reactions.

PubMed

Ramos, Pablo; Papadakis, Markos; Pavanello, Michele

2015-06-18

We have carried out a thorough benchmark of the frozen density-embedding (FDE) method for calculating hole transfer couplings. We have considered 10 exchange-correlation functionals, 3 nonadditive kinetic energy functionals, and 3 basis sets. Overall, we conclude that with a 7% mean relative unsigned error, the PBE and PW91 functionals coupled with the PW91k nonadditive kinetic energy functional and a TZP basis set constitute the most stable and accurate levels of theory for hole transfer coupling calculations. The FDE-ET method is found to be an excellent tool for computing diabatic couplings for hole transfer reactions.

[The information principle in physiology: an analysis from the position of the general theory of functional systems].

PubMed

Sudakov, K V

1995-01-01

Information principle of the organism functional systems creation is formulated in the article. Transformation of organism biological needs on various levels into dominant motivation, behaviour and processes of basis needs satisfaction without loss in information sense is shown. Information role of emotions is analysed. On the base of experimental data is formulated concept of information environment of organism. Specially analysed the information basis of human psychological activity.

Absolute configuration of (-)-myrtenal by vibrational circular dichroism.

PubMed

Burgueño-Tapia, Eleuterio; Zepeda, L Gerardo; Joseph-Nathan, Pedro

2010-07-01

The VCD spectrum of the monoterpene (-)-myrtenal (1) was compared with theoretical spectra using ab initio density functional theory (DFT) calculations at the B3LYP/6-31G(d,p), B3LYP/6-31G+(d,p), B3LYP/6-311G+(d,p), B3LYP/DGDZVP, and B3PW91/DGTZVP levels of theory. Conformational analysis of 1 indicated that the lowest energy conformer was s-trans-C2-C10, which contributes more than 98.5% to the total conformational population regardless of the employed level of theory. The use of a recently developed confidence level algorithm demonstrated that VCD spectra calculated for the main conformer, using the indicated hybrid functionals and basis set, gave no significant changes, from where it follows that B3LYP/DGDZVP calculations provide a superior balance between computer cost and VCD spectral accuracy. The DGDZVP basis set demanded around a quarter the time than the 6-311G+(d,p) basis set while providing similar results. The spectral comparison also provided evidence that the levorotatory enantiomer of myrtenal has the 1R absolute configuration. 2010 Elsevier Ltd. All rights reserved.

Slater-type geminals in explicitly-correlated perturbation theory: application to n-alkanols and analysis of errors and basis-set requirements.

PubMed

Höfener, Sebastian; Bischoff, Florian A; Glöss, Andreas; Klopper, Wim

2008-06-21

In the recent years, Slater-type geminals (STGs) have been used with great success to expand the first-order wave function in an explicitly-correlated perturbation theory. The present work reports on this theory's implementation in the framework of the Turbomole suite of programs. A formalism is presented for evaluating all of the necessary molecular two-electron integrals by means of the Obara-Saika recurrence relations, which can be applied when the STG is expressed as a linear combination of a small number (n) of Gaussians (STG-nG geminal basis). In the Turbomole implementation of the theory, density fitting is employed and a complementary auxiliary basis set (CABS) is used for the resolution-of-the-identity (RI) approximation of explicitly-correlated theory. By virtue of this RI approximation, the calculation of molecular three- and four-electron integrals is avoided. An approximation is invoked to avoid the two-electron integrals over the commutator between the operators of kinetic energy and the STG. This approximation consists of computing commutators between matrices in place of operators. Integrals over commutators between operators would have occurred if the theory had been formulated and implemented as proposed originally. The new implementation in Turbomole was tested by performing a series of calculations on rotational conformers of the alkanols n-propanol through n-pentanol. Basis-set requirements concerning the orbital basis, the auxiliary basis set for density fitting and the CABS were investigated. Furthermore, various (constrained) optimizations of the amplitudes of the explicitly-correlated double excitations were studied. These amplitudes can be optimized in orbital-variant and orbital-invariant manners, or they can be kept fixed at the values governed by the rational generator approach, that is, by the electron cusp conditions. Electron-correlation effects beyond the level of second-order perturbation theory were accounted for by conventional coupled-cluster calculations with single, double and perturbative triple excitations [CCSD(T)]. The explicitly-correlated perturbation theory results were combined with CCSD(T) results and compared with literature data obtained by basis-set extrapolation.

Benchmarking of density functionals for a soft but accurate prediction and assignment of (1) H and (13)C NMR chemical shifts in organic and biological molecules.

PubMed

Benassi, Enrico

2017-01-15

A number of programs and tools that simulate 1 H and 13 C nuclear magnetic resonance (NMR) chemical shifts using empirical approaches are available. These tools are user-friendly, but they provide a very rough (and sometimes misleading) estimation of the NMR properties, especially for complex systems. Rigorous and reliable ways to predict and interpret NMR properties of simple and complex systems are available in many popular computational program packages. Nevertheless, experimentalists keep relying on these "unreliable" tools in their daily work because, to have a sufficiently high accuracy, these rigorous quantum mechanical methods need high levels of theory. An alternative, efficient, semi-empirical approach has been proposed by Bally, Rablen, Tantillo, and coworkers. This idea consists of creating linear calibrations models, on the basis of the application of different combinations of functionals and basis sets. Following this approach, the predictive capability of a wider range of popular functionals was systematically investigated and tested. The NMR chemical shifts were computed in solvated phase at density functional theory level, using 30 different functionals coupled with three different triple-ζ basis sets. © 2016 Wiley Periodicals, Inc. © 2016 Wiley Periodicals, Inc.

Memory, Critical Theory and the Argument from History.

ERIC Educational Resources Information Center

Cox, J. Robert

1990-01-01

Explores the function of memory in critical theory, particularly in the work of Herbert Marcuse, as the basis for a critical argumentation. Argues that Marcuse's view suggests that argument is a "re-membering" of what had been split asunder--reason, imagination, and the capacity of action. Discusses other implications of Marcuse's…

Correlating Glasser's Choice Theory to the Behavioral Requirements of IDEA 97.

ERIC Educational Resources Information Center

Mishler, James A.; Cherry, Scott

This paper connects the philosophical basis of Glasser's Choice Theory/Reality Therapy to the Functional Assessments of Behavior (FAB) required by the Individuals with Disabilities Education Act (IDEA). The 1997 reauthorization of IDEA states that before a school can place a student with emotional or behavioral difficulties into an alternative…

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

Megala, M.; Rajkumar, Beulah J. M., E-mail: beulah-rajkumar@yahoo.co.in

The electronic and optical transfer properties of Benzene, Benzoic Acid (BA), Nitrobenzene (NB) and Para Nitro Benzoic Acid (PNBA) at ground and first excited state has been investigated by the Density functional theory (DFT)and Time Dependent Density Functional Theory (TDDFT) using SVWN functional/3-21G basis set respectively. Possible intra-molecular charge transfer and n to π* transitions in the ground and the first excitation states have been predicted by the molecular orbitals and the Natural Bond Orbital (NBO) analysis. The simulated absorption spectra have been generated and the result compared with existing experimental results.

Analysis of vibrational, structural, and electronic properties of rivastigmine by density functional theory

NASA Astrophysics Data System (ADS)

Prasad, O.; Sinha, L.; Misra, N.; Narayan, V.; Kumar, N.; Kumar, A.

2010-09-01

The present work deals with the structural, electronic, and vibrational analysis of rivastigmine. Rivastigmine, an antidementia medicament, is credited with significant therapeutic effects on the cognitive, functional, and behavioural problems that are commonly associated with Alzheimer’s dementia. For rivastigmine, a number of minimum energy conformations are possible. The geometry of twelve possible conformers has been analyzed and the most stable conformer was further optimized at a higher basis set. The electronic properties and vibrational frequencies were then calculated using a density functional theory at the B3LYP level with the 6-311+G(d, p) basis set. The different molecular surfaces have also been drawn to understand the activity of the molecule. A narrower frontier orbital energy gap in rivastigmine makes it softer and more reactive than water and dimethylfuran. The calculated value of the dipole moment is 2.58 debye.

Combining Density Functional Theory and Green's Function Theory: Range-Separated, Nonlocal, Dynamic, and Orbital-Dependent Hybrid Functional.

PubMed

Kananenka, Alexei A; Zgid, Dominika

2017-11-14

We present a rigorous framework which combines single-particle Green's function theory with density functional theory based on a separation of electron-electron interactions into short- and long-range components. Short-range contribution to the total energy and exchange-correlation potential is provided by a density functional approximation, while the long-range contribution is calculated using an explicit many-body Green's function method. Such a hybrid results in a nonlocal, dynamic, and orbital-dependent exchange-correlation functional of a single-particle Green's function. In particular, we present a range-separated hybrid functional called srSVWN5-lrGF2 which combines the local-density approximation and the second-order Green's function theory. We illustrate that similarly to density functional approximations, the new functional is weakly basis-set dependent. Furthermore, it offers an improved description of the short-range dynamic correlation. The many-body contribution to the functional mitigates the many-electron self-interaction error present in many density functional approximations and provides a better description of molecular properties. Additionally, we illustrate that the new functional can be used to scale down the self-energy and, therefore, introduce an additional sparsity to the self-energy matrix that in the future can be exploited in calculations for large molecules or periodic systems.

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

Rossi, Tuomas P., E-mail: tuomas.rossi@alumni.aalto.fi; Sakko, Arto; Puska, Martti J.

We present an approach for generating local numerical basis sets of improving accuracy for first-principles nanoplasmonics simulations within time-dependent density functional theory. The method is demonstrated for copper, silver, and gold nanoparticles that are of experimental interest but computationally demanding due to the semi-core d-electrons that affect their plasmonic response. The basis sets are constructed by augmenting numerical atomic orbital basis sets by truncated Gaussian-type orbitals generated by the completeness-optimization scheme, which is applied to the photoabsorption spectra of homoatomic metal atom dimers. We obtain basis sets of improving accuracy up to the complete basis set limit and demonstrate thatmore » the performance of the basis sets transfers to simulations of larger nanoparticles and nanoalloys as well as to calculations with various exchange-correlation functionals. This work promotes the use of the local basis set approach of controllable accuracy in first-principles nanoplasmonics simulations and beyond.« less

Second-order perturbation theory with a density matrix renormalization group self-consistent field reference function: theory and application to the study of chromium dimer.

PubMed

Kurashige, Yuki; Yanai, Takeshi

2011-09-07

We present a second-order perturbation theory based on a density matrix renormalization group self-consistent field (DMRG-SCF) reference function. The method reproduces the solution of the complete active space with second-order perturbation theory (CASPT2) when the DMRG reference function is represented by a sufficiently large number of renormalized many-body basis, thereby being named DMRG-CASPT2 method. The DMRG-SCF is able to describe non-dynamical correlation with large active space that is insurmountable to the conventional CASSCF method, while the second-order perturbation theory provides an efficient description of dynamical correlation effects. The capability of our implementation is demonstrated for an application to the potential energy curve of the chromium dimer, which is one of the most demanding multireference systems that require best electronic structure treatment for non-dynamical and dynamical correlation as well as large basis sets. The DMRG-CASPT2/cc-pwCV5Z calculations were performed with a large (3d double-shell) active space consisting of 28 orbitals. Our approach using large-size DMRG reference addressed the problems of why the dissociation energy is largely overestimated by CASPT2 with the small active space consisting of 12 orbitals (3d4s), and also is oversensitive to the choice of the zeroth-order Hamiltonian. © 2011 American Institute of Physics

The fruits of a functional approach for psychological science.

PubMed

Stewart, Ian

2016-02-01

The current paper introduces relational frame theory (RFT) as a functional contextual approach to complex human behaviour and examines how this theory has contributed to our understanding of several key phenomena in psychological science. I will first briefly outline the philosophical foundation of RFT and then examine its conceptual basis and core concepts. Thereafter, I provide an overview of the empirical findings and applications that RFT has stimulated in a number of key domains such as language development, linguistic generativity, rule-following, analogical reasoning, intelligence, theory of mind, psychopathology and implicit cognition. © 2015 International Union of Psychological Science.

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.

On basis set superposition error corrected stabilization energies for large n-body clusters.

PubMed

Walczak, Katarzyna; Friedrich, Joachim; Dolg, Michael

2011-10-07

In this contribution, we propose an approximate basis set superposition error (BSSE) correction scheme for the site-site function counterpoise and for the Valiron-Mayer function counterpoise correction of second order to account for the basis set superposition error in clusters with a large number of subunits. The accuracy of the proposed scheme has been investigated for a water cluster series at the CCSD(T), CCSD, MP2, and self-consistent field levels of theory using Dunning's correlation consistent basis sets. The BSSE corrected stabilization energies for a series of water clusters are presented. A study regarding the possible savings with respect to computational resources has been carried out as well as a monitoring of the basis set dependence of the approximate BSSE corrections. © 2011 American Institute of Physics

The Integration of the Information and Communication Functions, and the Marketing of the Resulting Products.

ERIC Educational Resources Information Center

Harris, Susan C.

1985-01-01

Discusses the theoretical basis for integration of information functions and communication functions, the relevance of this integration in the scientific information cycle, and its positive effect on commodity research networks. The application of this theory is described using three commodity programs of the Centro Internacional de Agricultura…

Re-evaluating concepts of biological function in clinical medicine: towards a new naturalistic theory of disease.

PubMed

Chin-Yee, Benjamin; Upshur, Ross E G

2017-08-01

Naturalistic theories of disease appeal to concepts of biological function, and use the notion of dysfunction as the basis of their definitions. Debates in the philosophy of biology demonstrate how attributing functions in organisms and establishing the function-dysfunction distinction is by no means straightforward. This problematization of functional ascription has undermined naturalistic theories and led some authors to abandon the concept of dysfunction, favoring instead definitions based in normative criteria or phenomenological approaches. Although this work has enhanced our understanding of disease and illness, we need not necessarily abandon naturalistic concepts of function and dysfunction in the disease debate. This article attempts to move towards a new naturalistic theory of disease that overcomes the limitations of previous definitions and offers advantages in the clinical setting. Our approach involves a re-evaluation of concepts of biological function employed by naturalistic theories. Drawing on recent insights from the philosophy of biology, we develop a contextual and evaluative account of function that is better suited to clinical medicine and remains consistent with contemporary naturalism. We also show how an updated naturalistic view shares important affinities with normativist and phenomenological positions, suggesting a possibility for consilience in the disease debate.

Minimal Cohomological Model of a Scalar Field on a Riemannian Manifold

NASA Astrophysics Data System (ADS)

Arkhipov, V. V.

2018-04-01

Lagrangians of the field-theory model of a scalar field are considered as 4-forms on a Riemannian manifold. The model is constructed on the basis of the Hodge inner product, this latter being an analog of the scalar product of two functions. Including the basis fields in the action of the terms with tetrads makes it possible to reproduce the Klein-Gordon equation and the Maxwell equations, and also the Einstein-Hilbert action. We conjecture that the principle of construction of the Lagrangians as 4-forms can give a criterion restricting possible forms of the field-theory models.

Coupled-cluster, Möller Plesset (MP2), Density Fitted Local MP2, and Density Functional Theory Examination of the Energetic and Structural Features of Hydrophobic Solvation: Water and Pentane

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

Ghadar, Yasaman; Clark, Aurora E.

2012-02-02

The interaction potentials between immiscible polar and non-polar solvents are a major driving force behind the formation of liquid:liquid interfaces. In this work, the interaction energy of water–pentane dimer has been determined using coupled-cluster theory with single double (triple) excitations [CCSD(T)], 2nd order Möller Plesset perturbation theory (MP2), density fitted local MP2 (DF-LMP2), as well as density functional theory using a wide variety of density functionals and several different basis sets. The M05-2X exchange correlation functionals exhibit excellent agreement with CCSD(T) and DF-LMP2 after taking into account basis set superposition error. The gas phase water–pentane interaction energy is found tomore » be quite sensitive to the specific pentane isomer (2,2- dimethylpropane vs. n-pentane) and relative orientation of the monomeric constituents. Subsequent solution phase cluster calculations of 2,2-dimethylpropane and n-pentane solvated by water indicate a positive free energy of solvation that is in good agreement with available experimental data. Structural parameters are quite sensitive to the density functional employed and reflect differences in the two-body interaction energy calculated by each method. In contrast, cluster calculations of pentane solvation of H2O solute are found to be inadequate for describing the organic solvent, likely due to limitations associated with the functionals employed (B3LYP, BHandH, and M05-2X).« less

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.

Ab initio calculation of reaction energies. III. Basis set dependence of relative energies on the FH2 and H2CO potential energy surfaces

NASA Astrophysics Data System (ADS)

Frisch, Michael J.; Binkley, J. Stephen; Schaefer, Henry F., III

1984-08-01

The relative energies of the stationary points on the FH2 and H2CO nuclear potential energy surfaces relevant to the hydrogen atom abstraction, H2 elimination and 1,2-hydrogen shift reactions have been examined using fourth-order Møller-Plesset perturbation theory and a variety of basis sets. The theoretical absolute zero activation energy for the F+H2→FH+H reaction is in better agreement with experiment than previous theoretical studies, and part of the disagreement between earlier theoretical calculations and experiment is found to result from the use of assumed rather than calculated zero-point vibrational energies. The fourth-order reaction energy for the elimination of hydrogen from formaldehyde is within 2 kcal mol-1 of the experimental value using the largest basis set considered. The qualitative features of the H2CO surface are unchanged by expansion of the basis set beyond the polarized triple-zeta level, but diffuse functions and several sets of polarization functions are found to be necessary for quantitative accuracy in predicted reaction and activation energies. Basis sets and levels of perturbation theory which represent good compromises between computational efficiency and accuracy are recommended.

A Simplified Approach to the Basis Functions of Symmetry Operations and Terms of Metal Complexes in an Octahedral Field with d[superscript 1] to d[superscript 9] Configurations

ERIC Educational Resources Information Center

Lee, Liangshiu

2010-01-01

The basis sets for symmetry operations of d[superscript 1] to d[superscript 9] complexes in an octahedral field and the resulting terms are derived for the ground states and spin-allowed excited states. The basis sets are of fundamental importance in group theory. This work addresses such a fundamental issue, and the results are pedagogically…

RG flow from Φ 4 theory to the 2D Ising model

DOE PAGES

Anand, Nikhil; Genest, Vincent X.; Katz, Emanuel; ...

2017-08-16

We study 1+1 dimensional Φ 4 theory using the recently proposed method of conformal truncation. Starting in the UV CFT of free field theory, we construct a complete basis of states with definite conformal Casimir, C. We use these states to express the Hamiltonian of the full interacting theory in lightcone quantization. After truncating to states with C≤C max, we numerically diagonalize the Hamiltonian at strong coupling and study the resulting IR dynamics. We compute non-perturbative spectral densities of several local operators, which are equivalent to real-time, infinite-volume correlation functions. These spectral densities, which include the Zamolodchikov C-function along themore » full RG flow, are calculable at any value of the coupling. Near criticality, our numerical results reproduce correlation functions in the 2D Ising model.« less

Image classification at low light levels

NASA Astrophysics Data System (ADS)

Wernick, Miles N.; Morris, G. Michael

1986-12-01

An imaging photon-counting detector is used to achieve automatic sorting of two image classes. The classification decision is formed on the basis of the cross correlation between a photon-limited input image and a reference function stored in computer memory. Expressions for the statistical parameters of the low-light-level correlation signal are given and are verified experimentally. To obtain a correlation-based system for two-class sorting, it is necessary to construct a reference function that produces useful information for class discrimination. An expression for such a reference function is derived using maximum-likelihood decision theory. Theoretically predicted results are used to compare on the basis of performance the maximum-likelihood reference function with Fukunaga-Koontz basis vectors and average filters. For each method, good class discrimination is found to result in milliseconds from a sparse sampling of the input image.

Adequate representation of charge polarization effects leads to a successful treatment of the CF4 + SiCl4 → CCl4 + SiF4 reaction by density functional theory.

PubMed

Li, Ruifang; Zhao, Yan; Truhlar, Donald G

2011-02-28

Adequate polarization functions reduce the error of density functional theory (DFT) for the heat of reaction for CF(4) + SiCl(4) from ∼9-12 kcal mol(-1) to ∼2-4 kcal mol(-1), and using an improved density functional further reduces it to ∼1 kcal mol(-1). This reaction was previously identified as a stumbling block for DFT, but we show that the problem with the previous calculations was not DFT but rather inadequate basis sets to account for intramolecular charge polarization.

Analytical energy gradients for explicitly correlated wave functions. I. Explicitly correlated second-order Møller-Plesset perturbation theory

NASA Astrophysics Data System (ADS)

Győrffy, Werner; Knizia, Gerald; Werner, Hans-Joachim

2017-12-01

We present the theory and algorithms for computing analytical energy gradients for explicitly correlated second-order Møller-Plesset perturbation theory (MP2-F12). The main difficulty in F12 gradient theory arises from the large number of two-electron integrals for which effective two-body density matrices and integral derivatives need to be calculated. For efficiency, the density fitting approximation is used for evaluating all two-electron integrals and their derivatives. The accuracies of various previously proposed MP2-F12 approximations [3C, 3C(HY1), 3*C(HY1), and 3*A] are demonstrated by computing equilibrium geometries for a set of molecules containing first- and second-row elements, using double-ζ to quintuple-ζ basis sets. Generally, the convergence of the bond lengths and angles with respect to the basis set size is strongly improved by the F12 treatment, and augmented triple-ζ basis sets are sufficient to closely approach the basis set limit. The results obtained with the different approximations differ only very slightly. This paper is the first step towards analytical gradients for coupled-cluster singles and doubles with perturbative treatment of triple excitations, which will be presented in the second part of this series.

Density Functional Theory Study of Cyanoetheneselenol: A Molecule of Astrobiological Interest

NASA Astrophysics Data System (ADS)

Surajbali, P.; Ramanah, D. Kodi; Rhyman, L.; Alswaidan, I. A.; Fun, H.-K.; Somanah, R.; Ramasami, P.

2015-12-01

The interstellar medium has a rich chemistry which involves a wide variety of molecules. Of particular interest are molecules that have a link to prebiotic chemistry which hold the key to understanding of our origins. On the basis of suggestions that selenium may have been involved in the origin and evolution of life, we have studied the selenium analogue of cyanoethenethiol, namely the novel cyanoetheneselenol. Cyanoetheneselenol exhibits conformational and geometrical isomerism. This theoretical work deals with the study of four forms of cyanoetheneselenol in terms of their structural, spectroscopic and thermodynamic parameters. All computations were performed using density functional theory method with the B3LYP functional and the Pople basis set, 6-311 + G(d,p), for all atoms. The relative stability of the four isomers of cyanoetheneselenol was obtained and interpreted. The infrared spectra were generated and assignment of the normal modes of vibration was performed. Probable regions of detection, proposed on the basis of parameters obtained from this study for the four isomers, include comets, the molecular cloud: Sagittarius B2(N), and planetary atmospheres. The molecular and spectroscopic parameters should be useful for future identification of the astrobiological molecule cyanoetheneselenol and the development of the Square Kilometre Array.

Comment on “Rethinking first-principles electron transport theories with projection operators: The problems caused by partitioning the basis set” [J. Chem. Phys. 139, 114104 (2013)

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

Brandbyge, Mads, E-mail: mads.brandbyge@nanotech.dtu.dk

2014-05-07

In a recent paper Reuter and Harrison [J. Chem. Phys. 139, 114104 (2013)] question the widely used mean-field electron transport theories, which employ nonorthogonal localized basis sets. They claim these can violate an “implicit decoupling assumption,” leading to wrong results for the current, different from what would be obtained by using an orthogonal basis, and dividing surfaces defined in real-space. We argue that this assumption is not required to be fulfilled to get exact results. We show how the current/transmission calculated by the standard Greens function method is independent of whether or not the chosen basis set is nonorthogonal, andmore » that the current for a given basis set is consistent with divisions in real space. The ambiguity known from charge population analysis for nonorthogonal bases does not carry over to calculations of charge flux.« less

X-ray absorption in insulators with non-Hermitian real-time time-dependent density functional theory.

PubMed

Fernando, Ranelka G; Balhoff, Mary C; Lopata, Kenneth

2015-02-10

Non-Hermitian real-time time-dependent density functional theory was used to compute the Si L-edge X-ray absorption spectrum of α-quartz using an embedded finite cluster model and atom-centered basis sets. Using tuned range-separated functionals and molecular orbital-based imaginary absorbing potentials, the excited states spanning the pre-edge to ∼20 eV above the ionization edge were obtained in good agreement with experimental data. This approach is generalizable to TDDFT studies of core-level spectroscopy and dynamics in a wide range of materials.

Nekrasov and Argyres-Douglas theories in spherical Hecke algebra representation

NASA Astrophysics Data System (ADS)

Rim, Chaiho; Zhang, Hong

2017-06-01

AGT conjecture connects Nekrasov instanton partition function of 4D quiver gauge theory with 2D Liouville conformal blocks. We re-investigate this connection using the central extension of spherical Hecke algebra in q-coordinate representation, q being the instanton expansion parameter. Based on AFLT basis together with intertwiners we construct gauge conformal state and demonstrate its equivalence to the Liouville conformal state, with careful attention to the proper scaling behavior of the state. Using the colliding limit of regular states, we obtain the formal expression of irregular conformal states corresponding to Argyres-Douglas theory, which involves summation of functions over Young diagrams.

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

Liakh, Dmitry I

While the formalism of multiresolution analysis (MRA), based on wavelets and adaptive integral representations of operators, is actively progressing in electronic structure theory (mostly on the independent-particle level and, recently, second-order perturbation theory), the concepts of multiresolution and adaptivity can also be utilized within the traditional formulation of correlated (many-particle) theory which is based on second quantization and the corresponding (generally nonorthogonal) tensor algebra. In this paper, we present a formalism called scale-adaptive tensor algebra (SATA) which exploits an adaptive representation of tensors of many-body operators via the local adjustment of the basis set quality. Given a series of locallymore » supported fragment bases of a progressively lower quality, we formulate the explicit rules for tensor algebra operations dealing with adaptively resolved tensor operands. The formalism suggested is expected to enhance the applicability and reliability of local correlated many-body methods of electronic structure theory, especially those directly based on atomic orbitals (or any other localized basis functions).« less

Effective empirical corrections for basis set superposition error in the def2-SVPD basis: gCP and DFT-C

NASA Astrophysics Data System (ADS)

Witte, Jonathon; Neaton, Jeffrey B.; Head-Gordon, Martin

2017-06-01

With the aim of mitigating the basis set error in density functional theory (DFT) calculations employing local basis sets, we herein develop two empirical corrections for basis set superposition error (BSSE) in the def2-SVPD basis, a basis which—when stripped of BSSE—is capable of providing near-complete-basis DFT results for non-covalent interactions. Specifically, we adapt the existing pairwise geometrical counterpoise (gCP) approach to the def2-SVPD basis, and we develop a beyond-pairwise approach, DFT-C, which we parameterize across a small set of intermolecular interactions. Both gCP and DFT-C are evaluated against the traditional Boys-Bernardi counterpoise correction across a set of 3402 non-covalent binding energies and isomerization energies. We find that the DFT-C method represents a significant improvement over gCP, particularly for non-covalently-interacting molecular clusters. Moreover, DFT-C is transferable among density functionals and can be combined with existing functionals—such as B97M-V—to recover large-basis results at a fraction of the cost.

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.

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.

Real-Space Density Functional Theory on Graphical Processing Units: Computational Approach and Comparison to Gaussian Basis Set Methods.

PubMed

Andrade, Xavier; Aspuru-Guzik, Alán

2013-10-08

We discuss the application of graphical processing units (GPUs) to accelerate real-space density functional theory (DFT) calculations. To make our implementation efficient, we have developed a scheme to expose the data parallelism available in the DFT approach; this is applied to the different procedures required for a real-space DFT calculation. We present results for current-generation GPUs from AMD and Nvidia, which show that our scheme, implemented in the free code Octopus, can reach a sustained performance of up to 90 GFlops for a single GPU, representing a significant speed-up when compared to the CPU version of the code. Moreover, for some systems, our implementation can outperform a GPU Gaussian basis set code, showing that the real-space approach is a competitive alternative for DFT simulations on GPUs.

The effect of diffuse basis functions on valence bond structural weights

NASA Astrophysics Data System (ADS)

Galbraith, John Morrison; James, Andrew M.; Nemes, Coleen T.

2014-03-01

Structural weights and bond dissociation energies have been determined for H-F, H-X, and F-X molecules (-X = -OH, -NH2, and -CH3) at the valence bond self-consistent field (VBSCF) and breathing orbital valence bond (BOVB) levels of theory with the aug-cc-pVDZ and 6-31++G(d,p) basis sets. At the BOVB level, the aug-cc-pVDZ basis set yields a counterintuitive ordering of ionic structural weights when the initial heavy atom s-type basis functions are included. For H-F, H-OH, and F-X, the ordering follows chemical intuition when these basis functions are not included. These counterintuitive weights are shown to be a result of the diffuse polarisation function on one VB fragment being spatially located, in part, on the other VB fragment. Except in the case of F-CH3, this problem is corrected with the 6-31++G(d,p) basis set. The initial heavy atom s-type functions are shown to make an important contribution to the VB orbitals and bond dissociation energies and, therefore, should not be excluded. It is recommended to not use diffuse basis sets in valence bond calculations unless absolutely necessary. If diffuse basis sets are needed, the 6-31++G(d,p) basis set should be used with caution and the structural weights checked against VBSCF values which have been shown to follow the expected ordering in all cases.

Some considerations about Gaussian basis sets for electric property calculations

NASA Astrophysics Data System (ADS)

Arruda, Priscilla M.; Canal Neto, A.; Jorge, F. E.

Recently, segmented contracted basis sets of double, triple, and quadruple zeta valence quality plus polarization functions (XZP, X = D, T, and Q, respectively) for the atoms from H to Ar were reported. In this work, with the objective of having a better description of polarizabilities, the QZP set was augmented with diffuse (s and p symmetries) and polarization (p, d, f, and g symmetries) functions that were chosen to maximize the mean dipole polarizability at the UHF and UMP2 levels, respectively. At the HF and B3LYP levels of theory, electric dipole moment and static polarizability for a sample of molecules were evaluated. Comparison with experimental data and results obtained with a similar size basis set, whose diffuse functions were optimized for the ground state energy of the anion, was done.

Rhetorical Interpretation of Abstracts in Sci-Tech Theses Based on Burke's Identification Theory

ERIC Educational Resources Information Center

Zhong, Jihong

2017-01-01

Abstract of a thesis is the brief and accurate representation of the thesis, with the important function of persuading readers to read on the thesis. So how the writer constructs the abstract and wins readers' recognition is our main focus. On the basis of Burke's Identification Theory, this paper analyzed 10 abstracts from "Nature" from…

Communication: Density functional theory embedding with the orthogonality constrained basis set expansion procedure

NASA Astrophysics Data System (ADS)

Culpitt, Tanner; Brorsen, Kurt R.; Hammes-Schiffer, Sharon

2017-06-01

Density functional theory (DFT) embedding approaches have generated considerable interest in the field of computational chemistry because they enable calculations on larger systems by treating subsystems at different levels of theory. To circumvent the calculation of the non-additive kinetic potential, various projector methods have been developed to ensure the orthogonality of molecular orbitals between subsystems. Herein the orthogonality constrained basis set expansion (OCBSE) procedure is implemented to enforce this subsystem orbital orthogonality without requiring a level shifting parameter. This scheme is a simple alternative to existing parameter-free projector-based schemes, such as the Huzinaga equation. The main advantage of the OCBSE procedure is that excellent convergence behavior is attained for DFT-in-DFT embedding without freezing any of the subsystem densities. For the three chemical systems studied, the level of accuracy is comparable to or higher than that obtained with the Huzinaga scheme with frozen subsystem densities. Allowing both the high-level and low-level DFT densities to respond to each other during DFT-in-DFT embedding calculations provides more flexibility and renders this approach more generally applicable to chemical systems. It could also be useful for future extensions to embedding approaches combining wavefunction theories and DFT.

Density functional theory study of the interaction of vinyl radical, ethyne, and ethene with benzene, aimed to define an affordable computational level to investigate stability trends in large van der Waals complexes

NASA Astrophysics Data System (ADS)

Maranzana, Andrea; Giordana, Anna; Indarto, Antonius; Tonachini, Glauco; Barone, Vincenzo; Causà, Mauro; Pavone, Michele

2013-12-01

Our purpose is to identify a computational level sufficiently dependable and affordable to assess trends in the interaction of a variety of radical or closed shell unsaturated hydro-carbons A adsorbed on soot platelet models B. These systems, of environmental interest, would unavoidably have rather large sizes, thus prompting to explore in this paper the performances of relatively low-level computational methods and compare them with higher-level reference results. To this end, the interaction of three complexes between non-polar species, vinyl radical, ethyne, or ethene (A) with benzene (B) is studied, since these species, involved themselves in growth processes of polycyclic aromatic hydrocarbons (PAHs) and soot particles, are small enough to allow high-level reference calculations of the interaction energy ΔEAB. Counterpoise-corrected interaction energies ΔEAB are used at all stages. (1) Density Functional Theory (DFT) unconstrained optimizations of the A-B complexes are carried out, using the B3LYP-D, ωB97X-D, and M06-2X functionals, with six basis sets: 6-31G(d), 6-311 (2d,p), and 6-311++G(3df,3pd); aug-cc-pVDZ and aug-cc-pVTZ; N07T. (2) Then, unconstrained optimizations by Møller-Plesset second order Perturbation Theory (MP2), with each basis set, allow subsequent single point Coupled Cluster Singles Doubles and perturbative estimate of the Triples energy computations with the same basis sets [CCSD(T)//MP2]. (3) Based on an additivity assumption of (i) the estimated MP2 energy at the complete basis set limit [EMP2/CBS] and (ii) the higher-order correlation energy effects in passing from MP2 to CCSD(T) at the aug-cc-pVTZ basis set, ΔECC-MP, a CCSD(T)/CBS estimate is obtained and taken as a computational energy reference. At DFT, variations in ΔEAB with basis set are not large for the title molecules, and the three functionals perform rather satisfactorily even with rather small basis sets [6-31G(d) and N07T], exhibiting deviation from the computational reference of less than 1 kcal mol-1. The zero-point vibrational energy corrected estimates Δ(EAB+ZPE), obtained with the three functionals and the 6-31G(d) and N07T basis sets, are compared with experimental D0 measures, when available. In particular, this comparison is finally extended to the naphthalene and coronene dimers and to three π-π associations of different PAHs (R, made by 10, 16, or 24 C atoms) and P (80 C atoms).

Density functional theory study of the interaction of vinyl radical, ethyne, and ethene with benzene, aimed to define an affordable computational level to investigate stability trends in large van der Waals complexes.

PubMed

Maranzana, Andrea; Giordana, Anna; Indarto, Antonius; Tonachini, Glauco; Barone, Vincenzo; Causà, Mauro; Pavone, Michele

2013-12-28

Our purpose is to identify a computational level sufficiently dependable and affordable to assess trends in the interaction of a variety of radical or closed shell unsaturated hydro-carbons A adsorbed on soot platelet models B. These systems, of environmental interest, would unavoidably have rather large sizes, thus prompting to explore in this paper the performances of relatively low-level computational methods and compare them with higher-level reference results. To this end, the interaction of three complexes between non-polar species, vinyl radical, ethyne, or ethene (A) with benzene (B) is studied, since these species, involved themselves in growth processes of polycyclic aromatic hydrocarbons (PAHs) and soot particles, are small enough to allow high-level reference calculations of the interaction energy ΔEAB. Counterpoise-corrected interaction energies ΔEAB are used at all stages. (1) Density Functional Theory (DFT) unconstrained optimizations of the A-B complexes are carried out, using the B3LYP-D, ωB97X-D, and M06-2X functionals, with six basis sets: 6-31G(d), 6-311 (2d,p), and 6-311++G(3df,3pd); aug-cc-pVDZ and aug-cc-pVTZ; N07T. (2) Then, unconstrained optimizations by Møller-Plesset second order Perturbation Theory (MP2), with each basis set, allow subsequent single point Coupled Cluster Singles Doubles and perturbative estimate of the Triples energy computations with the same basis sets [CCSD(T)//MP2]. (3) Based on an additivity assumption of (i) the estimated MP2 energy at the complete basis set limit [EMP2/CBS] and (ii) the higher-order correlation energy effects in passing from MP2 to CCSD(T) at the aug-cc-pVTZ basis set, ΔECC-MP, a CCSD(T)/CBS estimate is obtained and taken as a computational energy reference. At DFT, variations in ΔEAB with basis set are not large for the title molecules, and the three functionals perform rather satisfactorily even with rather small basis sets [6-31G(d) and N07T], exhibiting deviation from the computational reference of less than 1 kcal mol(-1). The zero-point vibrational energy corrected estimates Δ(EAB+ZPE), obtained with the three functionals and the 6-31G(d) and N07T basis sets, are compared with experimental D0 measures, when available. In particular, this comparison is finally extended to the naphthalene and coronene dimers and to three π-π associations of different PAHs (R, made by 10, 16, or 24 C atoms) and P (80 C atoms).

Carbon-Hydrogen Bond Activation in Hydridotris(pyrazolyl)borate Platinum(IV) Complexes:  Comparison of Density Functionals, Basis Sets, and Bonding Patterns.

PubMed

Vastine, Benjamin Alan; Webster, Charles Edwin; Hall, Michael B

2007-11-01

The reaction mechanism for the cycle beginning with the reductive elimination (RE) of methane from κ(3)-TpPt(IV)(CH3)2H (1) (Tp = hydridotris(pyrazolyl)borate) and subsequent oxidative addition (OA) of benzene to form finally κ(3)-TpPt(IV)(Ph)2H (19) was investigated by density functional theory (DFT). Two mechanistic steps are of particular interest, namely the barrier to C-H coupling (barrier 1 - Ba1) and the barrier to methane release (barrier 2 - Ba2). For 31 density functionals, the calculated values for Ba1 and Ba2 were benchmarked against the experimentally reported values of 26 (Ba1) and 35 (Ba2) kcal·mol(-1), respectively. Specifically, the values for Ba1 and Ba2, calculated at the B3LYP/double-ζ plus polarization level of theory, are 24.6 and 34.3 kcal·mol(-1), respectively. Overall, the best performing functional was BPW91 where the mae associated with the calculated values of the two barriers is 0.68 kcal·mol(-1). The calculated B3LYP values of Ba1 ranged between 20 and 26 kcal·mol(-1) for 12 effective core potential basis sets for platinum and 29 all-electron basis sets for the first row elements. Polarization functions for the first row elements were important for accurate values, but the addition of diffuse functions to non-hydrogen (+) and hydrogen atoms (++) had little effect on the calculated values. Basis set saturation was achieved with APNO basis sets utilized for first-row atoms. Bader's "Atoms in Molecules" was used to analyze the electron density of several complexes, and the electron density at the Pt-Nax bond critical point (trans to the active site for C-H coupling) varied over a wider range than any of the other Pt-N bonds.

Renormalization in Large Momentum Effective Theory of Parton Physics.

PubMed

Ji, Xiangdong; Zhang, Jian-Hui; Zhao, Yong

2018-03-16

In the large-momentum effective field theory approach to parton physics, the matrix elements of nonlocal operators of quark and gluon fields, linked by straight Wilson lines in a spatial direction, are calculated in lattice quantum chromodynamics as a function of hadron momentum. Using the heavy-quark effective theory formalism, we show a multiplicative renormalization of these operators at all orders in perturbation theory, both in dimensional and lattice regularizations. The result provides a theoretical basis for extracting parton properties through properly renormalized observables in Monte Carlo simulations.

DFT benchmark study for the oxidative addition of CH 4 to Pd. Performance of various density functionals

NASA Astrophysics Data System (ADS)

de Jong, G. Theodoor; Geerke, Daan P.; Diefenbach, Axel; Matthias Bickelhaupt, F.

2005-06-01

We have evaluated the performance of 24 popular density functionals for describing the potential energy surface (PES) of the archetypal oxidative addition reaction of the methane C-H bond to the palladium atom by comparing the results with our recent ab initio [CCSD(T)] benchmark study of this reaction. The density functionals examined cover the local density approximation (LDA), the generalized gradient approximation (GGA), meta-GGAs as well as hybrid density functional theory. Relativistic effects are accounted for through the zeroth-order regular approximation (ZORA). The basis-set dependence of the density-functional-theory (DFT) results is assessed for the Becke-Lee-Yang-Parr (BLYP) functional using a hierarchical series of Slater-type orbital (STO) basis sets ranging from unpolarized double-ζ (DZ) to quadruply polarized quadruple-ζ quality (QZ4P). Stationary points on the reaction surface have been optimized using various GGA functionals, all of which yield geometries that differ only marginally. Counterpoise-corrected relative energies of stationary points are converged to within a few tenths of a kcal/mol if one uses the doubly polarized triple-ζ (TZ2P) basis set and the basis-set superposition error (BSSE) drops to 0.0 kcal/mol for our largest basis set (QZ4P). Best overall agreement with the ab initio benchmark PES is achieved by functionals of the GGA, meta-GGA, and hybrid-DFT type, with mean absolute errors of 1.3-1.4 kcal/mol and errors in activation energies ranging from +0.8 to -1.4 kcal/mol. Interestingly, the well-known BLYP functional compares very reasonably with an only slightly larger mean absolute error of 2.5 kcal/mol and an underestimation by -1.9 kcal/mol of the overall barrier (i.e., the difference in energy between the TS and the separate reactants). For comparison, with B3LYP we arrive at a mean absolute error of 3.8 kcal/mol and an overestimation of the overall barrier by 4.5 kcal/mol.

Relativistic hydrodynamics from quantum field theory on the basis of the generalized Gibbs ensemble method

NASA Astrophysics Data System (ADS)

Hayata, Tomoya; Hidaka, Yoshimasa; Noumi, Toshifumi; Hongo, Masaru

2015-09-01

We derive relativistic hydrodynamics from quantum field theories by assuming that the density operator is given by a local Gibbs distribution at initial time. We decompose the energy-momentum tensor and particle current into nondissipative and dissipative parts, and analyze their time evolution in detail. Performing the path-integral formulation of the local Gibbs distribution, we microscopically derive the generating functional for the nondissipative hydrodynamics. We also construct a basis to study dissipative corrections. In particular, we derive the first-order dissipative hydrodynamic equations without a choice of frame such as the Landau-Lifshitz or Eckart frame.

The theory of constructed emotion: an active inference account of interoception and categorization

PubMed Central

2017-01-01

Abstract The science of emotion has been using folk psychology categories derived from philosophy to search for the brain basis of emotion. The last two decades of neuroscience research have brought us to the brink of a paradigm shift in understanding the workings of the brain, however, setting the stage to revolutionize our understanding of what emotions are and how they work. In this article, we begin with the structure and function of the brain, and from there deduce what the biological basis of emotions might be. The answer is a brain-based, computational account called the theory of constructed emotion. PMID:27798257

51V solid-state NMR and density functional theory studies of vanadium environments in V(V)O2 dipicolinic acid complexes

NASA Astrophysics Data System (ADS)

Bolte, Stephanie E.; Ooms, Kristopher J.; Polenova, Tatyana; Baruah, Bharat; Crans, Debbie C.; Smee, Jason J.

2008-02-01

V51 solid-state NMR and density functional theory (DFT) investigations are reported for a series of pentacoordinate dioxovanadium(V)-dipicolinate [V(V )O2-dipicolinate] and heptacoordinate aquahydroxylamidooxovanadium(V)-dipicolinate [V(V)O-dipicolinate] complexes. These compounds are of interest because of their potency as phosphatase inhibitors as well as their insulin enhancing properties and potential for the treatment of diabetes. Experimental solid-state NMR results show that the electric field gradient tensors in the V(V )O2-dipicolinate derivatives are affected significantly by substitution on the dipicolinate ring and range from 5.8to8.3MHz. The chemical shift anisotropies show less dramatic variations with respect to the ligand changes and range between -550 and -600ppm. To gain insights on the origins of the NMR parameters, DFT calculations were conducted for an extensive series of the V(V )O2- and V(V)O-dipicolinate complexes. To assess the level of theory required for the accurate calculation of the V51 NMR parameters, different functionals, basis sets, and structural models were explored in the DFT study. It is shown that the original x-ray crystallographic geometries, including all counterions and solvation water molecules within 5Å of the vanadium, lead to the most accurate results. The choice of the functional and the basis set at a high level of theory has a relatively minor impact on the outcome of the chemical shift anisotropy calculations; however, the use of large basis sets is necessary for accurate calculations of the quadrupole coupling constants for several compounds of the V(V )O2 series. These studies demonstrate that even though the vanadium compounds under investigations exhibit distorted trigonal bipyramidal coordination geometry, they have a "perfect" trigonal bipyramidal electronic environment. This observation could potentially explain why vanadate and vanadium(V) adducts are often recognized as potent transition state analogs.

A bio-physical basis of mathematics in synaptic function of the nervous system: a theory.

PubMed

Dempsher, J

1980-01-01

The purpose of this paper is to present a bio-physical basis of mathematics. The essence of the theory is that function in the nervous system is mathematical. The mathematics arises as a result of the interaction of energy (a wave with a precise curvature in space and time) and matter (a molecular or ionic structure with a precise form in space and time). In this interaction, both energy and matter play an active role. That is, the interaction results in a change in form of both energy and matter. There are at least six mathematical operations in a simple synaptic region. It is believed the form of both energy and matter are specific, and their interaction is specific, that is, function in most of the 'mind' and placed where it belongs - in nature and the synaptic regions of the nervous system; it results in both places from a precise interaction between energy (in a precise form) and matter ( in a precise structure).

Multiconfiguration Pair-Density Functional Theory Spectral Calculations Are Stable to Adding Diffuse Basis Functions.

PubMed

Hoyer, Chad E; Gagliardi, Laura; Truhlar, Donald G

2015-11-05

Time-dependent Kohn-Sham density functional theory (TD-KS-DFT) is useful for calculating electronic excitation spectra of large systems, but the low-energy spectra are often complicated by artificially lowered higher-energy states. This affects even the lowest energy excited states. Here, by calculating the lowest energy spin-conserving excited state for atoms from H to K and for formaldehyde, we show that this problem does not occur in multiconfiguration pair-density functional theory (MC-PDFT). We use the tPBE on-top density functional, which is a translation of the PBE exchange-correlation functional. We compare to a robust multireference method, namely, complete active space second-order perturbation theory (CASPT2), and to TD-KS-DFT with two popular exchange-correlation functionals, PBE and PBE0. We find for atoms that the mean unsigned error (MUE) of MC-PDFT with the tPBE functional improves from 0.42 to 0.40 eV with a double set of diffuse functions, whereas the MUEs for PBE and PBE0 drastically increase from 0.74 to 2.49 eV and from 0.45 to 1.47 eV, respectively.

Affordable and accurate large-scale hybrid-functional calculations on GPU-accelerated supercomputers

NASA Astrophysics Data System (ADS)

Ratcliff, Laura E.; Degomme, A.; Flores-Livas, José A.; Goedecker, Stefan; Genovese, Luigi

2018-03-01

Performing high accuracy hybrid functional calculations for condensed matter systems containing a large number of atoms is at present computationally very demanding or even out of reach if high quality basis sets are used. We present a highly optimized multiple graphics processing unit implementation of the exact exchange operator which allows one to perform fast hybrid functional density-functional theory (DFT) calculations with systematic basis sets without additional approximations for up to a thousand atoms. With this method hybrid DFT calculations of high quality become accessible on state-of-the-art supercomputers within a time-to-solution that is of the same order of magnitude as traditional semilocal-GGA functionals. The method is implemented in a portable open-source library.

The harmonic frequencies of benzene

NASA Astrophysics Data System (ADS)

Handy, Nicholas C.; Maslen, Paul E.; Amos, Roger D.; Andrews, Jamie S.; Murray, Christopher W.; Laming, Gregory J.

1992-09-01

We report calculations for the harmonic frequencies of C 6H 6 and C 6D 6. Our most sophisticated quantum chemistry values are obtained with the MP2 method and a TZ2P+f basis set (288 basis functions), which are the largest such calculations reported on benzene to date. Using the SCF density, we also calculate the frequencies using the exchange and correlation expressions of density functional theory. We compare our calculated harmonic frequencies with those deduced from experiment by Goodman, Ozkabak and Thakur. The density functional frequencies appear to be more reliable predictions than the MP2 frequencies and they are obtained at significantly less cost.

Neural-like computing with populations of superparamagnetic basis functions.

PubMed

Mizrahi, Alice; Hirtzlin, Tifenn; Fukushima, Akio; Kubota, Hitoshi; Yuasa, Shinji; Grollier, Julie; Querlioz, Damien

2018-04-18

In neuroscience, population coding theory demonstrates that neural assemblies can achieve fault-tolerant information processing. Mapped to nanoelectronics, this strategy could allow for reliable computing with scaled-down, noisy, imperfect devices. Doing so requires that the population components form a set of basis functions in terms of their response functions to inputs, offering a physical substrate for computing. Such a population can be implemented with CMOS technology, but the corresponding circuits have high area or energy requirements. Here, we show that nanoscale magnetic tunnel junctions can instead be assembled to meet these requirements. We demonstrate experimentally that a population of nine junctions can implement a basis set of functions, providing the data to achieve, for example, the generation of cursive letters. We design hybrid magnetic-CMOS systems based on interlinked populations of junctions and show that they can learn to realize non-linear variability-resilient transformations with a low imprint area and low power.

Time-Dependent Density Functional Theory Analysis of Triphenylamine-Functionalized Graphene Doped with Transition Metals for Photocatalytic Hydrogen Production.

PubMed

Mota, Elder A V; Neto, Abel F G; Marques, Francisco C; Mota, Gunar V S; Martins, Marcelo G; Costa, Fabio L P; Borges, Rosivaldo S; Neto, Antonio M J C

2018-07-01

The electronic structures and optical properties of triphenylamine-functionalized graphene (G-TPA) doped with transition metals, using water as a solvent, were theoretically investigated to verify the efficiency of photocatalytic hydrogen production with the use of transition metals. This study was performed by Density Functional Theory and Time-dependent Density Functional Theory through Gaussian 09W software, adopting the B3LYP functional for all structures. The 6-31g(d) basis set was used for H, C and N atoms, and the LANL2DZ basis set for transition metals using the Effective Core Potentials method. Two approaches were adopted: (1) using single metallic dopants (Ni, Pd, Fe, Os and Pt) and (2) using combinations of Ni with the other dopants (NiPd, NiPt, NiFe and NiOs). The DOS spectra reveal an increase of accessible states in the valence shell, in addition to a gap decrease for all dopants. This doping also increases the absorption in the visible region of solar radiation where sunlight is most intense (400 nm to 700 nm), with additional absorption peaks. The results lead us to propose the G-TPA structures doped with Ni, Pd, Pt, NiPt or NiPd to be novel catalysts for the conversion of solar energy for photocatalytic hydrogen production, since they improve the absorption of solar energy in the range of interest for solar radiation; and act as reaction centers, reducing the required overpotential for hydrogen production from water.

Accurate donor electron wave functions from a multivalley effective mass theory.

NASA Astrophysics Data System (ADS)

Pendo, Luke; Hu, Xuedong

Multivalley effective mass (MEM) theories combine physical intuition with a marginal need for computational resources, but they tend to be insensitive to variations in the wavefunction. However, recent papers suggest full Bloch functions and suitable central cell donor potential corrections are essential to replicating qualitative and quantitative features of the wavefunction. In this talk, we consider a variational MEM method that can accurately predict both spectrum and wavefunction of isolated phosphorus donors. As per Gamble et. al, we employ a truncated series representation of the Bloch function with a tetrahedrally symmetric central cell correction. We use a dynamic dielectric constant, a feature commonly seen in tight-binding methods. Uniquely, we use a freely extensible basis of either all Slater- or all Gaussian-type functions. With a large basis able to capture the influence of higher energy eigenstates, this method is well positioned to consider the influence of external perturbations, such as electric field or applied strain, on the charge density. This work is supported by the US Army Research Office (W911NF1210609).

High-order nonlinear susceptibilities of He

NASA Astrophysics Data System (ADS)

Liu, W.-C.; Clark, Charles W.

1996-05-01

High-order nonlinear optical response of noble gases to intense laser radiation is of considerable experimental interest, but is difficult to measure or calculate accurately. We have begun a set of calculations of frequency-dependent nonlinear susceptibilities of He 1s^2, within the framework of Rayleigh-Schrödinger perturbation theory at lowest applicable order, with the goal of providing critically evaluated atomic data for modelling high harmonic generation processes. The atomic Hamiltonian is decomposed in term of Hylleraas coordinates and spherical harmonics using the formalism of Pont and Shakeshaft (M. Pont and R. Shakeshaft, Phy. Rev. A 51), 257 (1995), and the hierarchy of inhomogeneous equations of perturbation theory is solved iteratively. A combination of Hylleraas and Frankowski basis functions is used(J. D. Baker, Master thesis, U. Delaware (1988); J. D. Baker, R. N. Hill, and J. D. Morgan, AIP Conference Proceedings 189) 123(1989); the compact Hylleraas basis provides a highly accurate representation of the ground state wavefunction, whereas the diffuse Frankowski basis functions efficiently reproduce the correct asymptotic structure of the perturbed orbitals.

Analytic model of a multi-electron atom

NASA Astrophysics Data System (ADS)

Skoromnik, O. D.; Feranchuk, I. D.; Leonau, A. U.; Keitel, C. H.

2017-12-01

A fully analytical approximation for the observable characteristics of many-electron atoms is developed via a complete and orthonormal hydrogen-like basis with a single-effective charge parameter for all electrons of a given atom. The basis completeness allows us to employ the secondary-quantized representation for the construction of regular perturbation theory, which includes in a natural way correlation effects, converges fast and enables an effective calculation of the subsequent corrections. The hydrogen-like basis set provides a possibility to perform all summations over intermediate states in closed form, including both the discrete and continuous spectra. This is achieved with the help of the decomposition of the multi-particle Green function in a convolution of single-electronic Coulomb Green functions. We demonstrate that our fully analytical zeroth-order approximation describes the whole spectrum of the system, provides accuracy, which is independent of the number of electrons and is important for applications where the Thomas-Fermi model is still utilized. In addition already in second-order perturbation theory our results become comparable with those via a multi-configuration Hartree-Fock approach.

Sensitivity of the Properties of Ruthenium “Blue Dimer” to Method, Basis Set, and Continuum Model

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

Ozkanlar, Abdullah; Clark, Aurora E.

2012-05-23

The ruthenium “blue dimer” [(bpy)2RuIIIOH2]2O4+ is best known as the first well-defined molecular catalyst for water oxidation. It has been subject to numerous computational studies primarily employing density functional theory. However, those studies have been limited in the functionals, basis sets, and continuum models employed. The controversy in the calculated electronic structure and the reaction energetics of this catalyst highlights the necessity of benchmark calculations that explore the role of density functionals, basis sets, and continuum models upon the essential features of blue-dimer reactivity. In this paper, we report Kohn-Sham complete basis set (KS-CBS) limit extrapolations of the electronic structuremore » of “blue dimer” using GGA (BPW91 and BP86), hybrid-GGA (B3LYP), and meta-GGA (M06-L) density functionals. The dependence of solvation free energy corrections on the different cavity types (UFF, UA0, UAHF, UAKS, Bondi, and Pauling) within polarizable and conductor-like polarizable continuum model has also been investigated. The most common basis sets of double-zeta quality are shown to yield results close to the KS-CBS limit; however, large variations are observed in the reaction energetics as a function of density functional and continuum cavity model employed.« less

Noncovalent Interactions of DNA Bases with Naphthalene and Graphene.

PubMed

Cho, Yeonchoo; Min, Seung Kyu; Yun, Jeonghun; Kim, Woo Youn; Tkatchenko, Alexandre; Kim, Kwang S

2013-04-09

The complexes of a DNA base bound to graphitic systems are studied. Considering naphthalene as the simplest graphitic system, DNA base-naphthalene complexes are scrutinized at high levels of ab initio theory including coupled cluster theory with singles, doubles, and perturbative triples excitations [CCSD(T)] at the complete basis set (CBS) limit. The stacked configurations are the most stable, where the CCSD(T)/CBS binding energies of guanine, adenine, thymine, and cytosine are 9.31, 8.48, 8.53, 7.30 kcal/mol, respectively. The energy components are investigated using symmetry-adapted perturbation theory based on density functional theory including the dispersion energy. We compared the CCSD(T)/CBS results with several density functional methods applicable to periodic systems. Considering accuracy and availability, the optB86b nonlocal functional and the Tkatchenko-Scheffler functional are used to study the binding energies of nucleobases on graphene. The predicted values are 18-24 kcal/mol, though many-body effects on screening and energy need to be further considered.

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

Anand, Nikhil; Genest, Vincent X.; Katz, Emanuel

We study 1+1 dimensional Φ 4 theory using the recently proposed method of conformal truncation. Starting in the UV CFT of free field theory, we construct a complete basis of states with definite conformal Casimir, C. We use these states to express the Hamiltonian of the full interacting theory in lightcone quantization. After truncating to states with C≤C max, we numerically diagonalize the Hamiltonian at strong coupling and study the resulting IR dynamics. We compute non-perturbative spectral densities of several local operators, which are equivalent to real-time, infinite-volume correlation functions. These spectral densities, which include the Zamolodchikov C-function along themore » full RG flow, are calculable at any value of the coupling. Near criticality, our numerical results reproduce correlation functions in the 2D Ising model.« less

Prospect theory does not describe the feedback-related negativity value function.

PubMed

Sambrook, Thomas D; Roser, Matthew; Goslin, Jeremy

2012-12-01

Humans handle uncertainty poorly. Prospect theory accounts for this with a value function in which possible losses are overweighted compared to possible gains, and the marginal utility of rewards decreases with size. fMRI studies have explored the neural basis of this value function. A separate body of research claims that prediction errors are calculated by midbrain dopamine neurons. We investigated whether the prospect theoretic effects shown in behavioral and fMRI studies were present in midbrain prediction error coding by using the feedback-related negativity, an ERP component believed to reflect midbrain prediction errors. Participants' stated satisfaction with outcomes followed prospect theory but their feedback-related negativity did not, instead showing no effect of marginal utility and greater sensitivity to potential gains than losses. Copyright © 2012 Society for Psychophysiological Research.

A theoretical study of the reaction of Ti+ with ethane

NASA Astrophysics Data System (ADS)

Moc, Jerzy; Fedorov, Dmitri G.; Gordon, Mark S.

2000-06-01

The doublet and quartet potential energy surfaces for the Ti++C2H6→TiC2H4++H2 and Ti++C2H6→TiCH2++CH4 reactions are studied using density functional theory (DFT) with the B3LYP functional and ab initio coupled cluster CCSD(T) methods with high quality basis sets. Structures have been optimized at the DFT level and the minima connected to each transition state (TS) by following the intrinsic reaction coordinate (IRC). Relative energies are calculated both at the DFT and coupled-cluster levels of theory. The relevant parts of the potential energy surface, especially key transition states, are also studied using multireference wave functions with the final energetics obtained with multireference second-order perturbation theory.

Application of ab initio many-body perturbation theory with Gaussian basis sets to the singlet and triplet excitations of organic molecules

NASA Astrophysics Data System (ADS)

Hamed, Samia; Rangel, Tonatiuh; Bruneval, Fabien; Neaton, Jeffrey B.

Quantitative understanding of charged and neutral excitations of organic molecules is critical in diverse areas of study that include astrophysics and the development of energy technologies that are clean and efficient. The recent use of local basis sets with ab initio many-body perturbation theory in the GW approximation and the Bethe-Saltpeter equation approach (BSE), methods traditionally applied to periodic condensed phases with a plane-wave basis, has opened the door to detailed study of such excitations for molecules, as well as accurate numerical benchmarks. Here, through a series of systematic benchmarks with a Gaussian basis, we report on the extent to which the predictive power and utility of this approach depend critically on interdependent underlying approximations and choices for molecules, including the mean-field starting point (eg optimally-tuned range separated hybrids, pure DFT functionals, and untuned hybrids), the GW scheme, and the Tamm Dancoff approximation. We demonstrate the effects of these choices in the context of Thiels' set while drawing analogies to linear-response time-dependent DFT and making comparisons to best theoretical estimates from higher-order wavefunction-based theories.

Electronic coupling matrix elements from charge constrained density functional theory calculations using a plane wave basis set

NASA Astrophysics Data System (ADS)

Oberhofer, Harald; Blumberger, Jochen

2010-12-01

We present a plane wave basis set implementation for the calculation of electronic coupling matrix elements of electron transfer reactions within the framework of constrained density functional theory (CDFT). Following the work of Wu and Van Voorhis [J. Chem. Phys. 125, 164105 (2006)], the diabatic wavefunctions are approximated by the Kohn-Sham determinants obtained from CDFT calculations, and the coupling matrix element calculated by an efficient integration scheme. Our results for intermolecular electron transfer in small systems agree very well with high-level ab initio calculations based on generalized Mulliken-Hush theory, and with previous local basis set CDFT calculations. The effect of thermal fluctuations on the coupling matrix element is demonstrated for intramolecular electron transfer in the tetrathiafulvalene-diquinone (Q-TTF-Q-) anion. Sampling the electronic coupling along density functional based molecular dynamics trajectories, we find that thermal fluctuations, in particular the slow bending motion of the molecule, can lead to changes in the instantaneous electron transfer rate by more than an order of magnitude. The thermal average, ( {< {| {H_ab } |^2 } > } )^{1/2} = 6.7 {mH}, is significantly higher than the value obtained for the minimum energy structure, | {H_ab } | = 3.8 {mH}. While CDFT in combination with generalized gradient approximation (GGA) functionals describes the intermolecular electron transfer in the studied systems well, exact exchange is required for Q-TTF-Q- in order to obtain coupling matrix elements in agreement with experiment (3.9 mH). The implementation presented opens up the possibility to compute electronic coupling matrix elements for extended systems where donor, acceptor, and the environment are treated at the quantum mechanical (QM) level.

Lattice dynamics calculations based on density-functional perturbation theory in real space

NASA Astrophysics Data System (ADS)

Shang, Honghui; Carbogno, Christian; Rinke, Patrick; Scheffler, Matthias

2017-06-01

A real-space formalism for density-functional perturbation theory (DFPT) is derived and applied for the computation of harmonic vibrational properties in molecules and solids. The practical implementation using numeric atom-centered orbitals as basis functions is demonstrated exemplarily for the all-electron Fritz Haber Institute ab initio molecular simulations (FHI-aims) package. The convergence of the calculations with respect to numerical parameters is carefully investigated and a systematic comparison with finite-difference approaches is performed both for finite (molecules) and extended (periodic) systems. Finally, the scaling tests and scalability tests on massively parallel computer systems demonstrate the computational efficiency.

Second order Møller-Plesset and coupled cluster singles and doubles methods with complex basis functions for resonances in electron-molecule scattering

DOE PAGES

White, Alec F.; Epifanovsky, Evgeny; McCurdy, C. William; ...

2017-06-21

The method of complex basis functions is applied to molecular resonances at correlated levels of theory. Møller-Plesset perturbation theory at second order and equation-of-motion electron attachment coupled-cluster singles and doubles (EOM-EA-CCSD) methods based on a non-Hermitian self-consistent-field reference are used to compute accurate Siegert energies for shape resonances in small molecules including N 2 - , CO - , CO 2 - , and CH 2 O - . Analytic continuation of complex θ-trajectories is used to compute Siegert energies, and the θ-trajectories of energy differences are found to yield more consistent results than those of total energies.more » Furthermore, the ability of such methods to accurately compute complex potential energy surfaces is investigated, and the possibility of using EOM-EA-CCSD for Feshbach resonances is explored in the context of e-helium scattering.« less

Second order Møller-Plesset and coupled cluster singles and doubles methods with complex basis functions for resonances in electron-molecule scattering

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

White, Alec F.; Epifanovsky, Evgeny; McCurdy, C. William

The method of complex basis functions is applied to molecular resonances at correlated levels of theory. Møller-Plesset perturbation theory at second order and equation-of-motion electron attachment coupled-cluster singles and doubles (EOM-EA-CCSD) methods based on a non-Hermitian self-consistent-field reference are used to compute accurate Siegert energies for shape resonances in small molecules including N 2 - , CO - , CO 2 - , and CH 2 O - . Analytic continuation of complex θ-trajectories is used to compute Siegert energies, and the θ-trajectories of energy differences are found to yield more consistent results than those of total energies.more » Furthermore, the ability of such methods to accurately compute complex potential energy surfaces is investigated, and the possibility of using EOM-EA-CCSD for Feshbach resonances is explored in the context of e-helium scattering.« less

Efficient evaluation of Coulomb integrals in a mixed Gaussian and plane-wave basis using the density fitting and Cholesky decomposition.

PubMed

Čársky, Petr; Čurík, Roman; Varga, Štefan

2012-03-21

The objective of this paper is to show that the density fitting (resolution of the identity approximation) can also be applied to Coulomb integrals of the type (k(1)(1)k(2)(1)|g(1)(2)g(2)(2)), where k and g symbols refer to plane-wave functions and gaussians, respectively. We have shown how to achieve the accuracy of these integrals that is needed in wave-function MO and density functional theory-type calculations using mixed Gaussian and plane-wave basis sets. The crucial issues for achieving such a high accuracy are application of constraints for conservation of the number electrons and components of the dipole moment, optimization of the auxiliary basis set, and elimination of round-off errors in the matrix inversion. © 2012 American Institute of Physics

Magnetic exchange couplings from noncollinear perturbation theory: dinuclear CuII complexes.

PubMed

Phillips, Jordan J; Peralta, Juan E

2014-08-07

To benchmark the performance of a new method based on noncollinear coupled-perturbed density functional theory [J. Chem. Phys. 138, 174115 (2013)], we calculate the magnetic exchange couplings in a series of triply bridged ferromagnetic dinuclear Cu(II) complexes that have been recently synthesized [Phys. Chem. Chem. Phys. 15, 1966 (2013)]. We find that for any basis-set the couplings from our noncollinear coupled-perturbed methodology are practically identical to those of spin-projected energy-differences when a hybrid density functional approximation is employed. This demonstrates that our methodology properly recovers a Heisenberg description for these systems, and is robust in its predictive power of magnetic couplings. Furthermore, this indicates that the failure of density functional theory to capture the subtle variation of the exchange couplings in these complexes is not simply an artifact of broken-symmetry methods, but rather a fundamental weakness of current approximate density functionals for the description of magnetic couplings.

Structure and energetics of Cr(CO)6 and Cr(CO)5

NASA Technical Reports Server (NTRS)

Barnes, Leslie A.; Liu, Bowen; Lindh, Roland

1993-01-01

The geometric structures and energetics of Cr(CO)6 and Cr(CO)5 are determined at the modified coupled-pair functional, single and double excitation coupled-cluster (CCSD), and CCSD(T) levels of theory. For Cr(CO)6, the structure and force constants for the totally symmetric representation are in good agreement with experimental data once basis set constants are taken into account. In the largest basis set at the CCSD(T) level of theory, the total binding energy of CR(CO)6 is estimated at around 140 kcal/mol, or about 86 percent of the experimental value. In contrast, the first bond energy of Cr(CO)6 is very well described at the CCSD(T) level of theory, with the best estimated value of 38 kcal/mol being within the experimental uncertainty.

Excited State Charge Transfer reaction with dual emission from 5-(4-dimethylamino-phenyl)-penta-2,4-dienenitrile: Spectral measurement and theoretical density functional theory calculation

NASA Astrophysics Data System (ADS)

Jana, Sankar; Dalapati, Sasanka; Ghosh, Shalini; Kar, Samiran; Guchhait, Nikhil

2011-07-01

The excited state intramolecular charge transfer process in donor-chromophore-acceptor system 5-(4-dimethylamino-phenyl)-penta-2,4-dienenitrile (DMAPPDN) has been investigated by steady state absorption and emission spectroscopy in combination with Density Functional Theory (DFT) calculations. This flexible donor acceptor molecule DMAPPDN shows dual fluorescence corresponding to emission from locally excited and charge transfer state in polar solvent. Large solvatochromic emission shift, effect of variation of pH and HOMO-LUMO molecular orbital pictures support excited state intramolecular charge transfer process. The experimental findings have been correlated with the calculated structure and potential energy surfaces based on the Twisted Intramolecular Charge Transfer (TICT) model obtained at DFT level using B3LYP functional and 6-31+G( d, p) basis set. The theoretical potential energy surfaces for the excited states have been generated in vacuo and acetonitrile solvent using Time Dependent Density Functional Theory (TDDFT) and Time Dependent Density Functional Theory Polarized Continuum Model (TDDFT-PCM) method, respectively. All the theoretical results show well agreement with the experimental observations.

Efficient algorithm for multiconfiguration pair-density functional theory with application to the heterolytic dissociation energy of ferrocene

NASA Astrophysics Data System (ADS)

Sand, Andrew M.; Truhlar, Donald G.; Gagliardi, Laura

2017-01-01

The recently developed multiconfiguration pair-density functional theory (MC-PDFT) combines multiconfiguration wave function theory with a density functional that depends on the on-top pair density of an electronic system. In an MC-PDFT calculation, there are two steps: a conventional multiconfiguration self-consistent-field (MCSCF) calculation and a post-MCSCF evaluation of the energy with an on-top density functional. In this work, we present the details of the MC-PDFT algorithm that avoids steeply scaling steps that are present in other post-self-consistent-field multireference calculations of dynamic correlation energy. We demonstrate the favorable scaling by considering systems of H2 molecules with active spaces of several different sizes. We then apply the MC-PDFT method to calculate the heterolytic dissociation enthalpy of ferrocene. We find that MC-PDFT yields results that are at least as accurate as complete active space second-order perturbation theory and are more stable with respect to basis set, but at a fraction of the cost in both time and memory.

Efficient algorithm for multiconfiguration pair-density functional theory with application to the heterolytic dissociation energy of ferrocene.

PubMed

Sand, Andrew M; Truhlar, Donald G; Gagliardi, Laura

2017-01-21

The recently developed multiconfiguration pair-density functional theory (MC-PDFT) combines multiconfiguration wave function theory with a density functional that depends on the on-top pair density of an electronic system. In an MC-PDFT calculation, there are two steps: a conventional multiconfiguration self-consistent-field (MCSCF) calculation and a post-MCSCF evaluation of the energy with an on-top density functional. In this work, we present the details of the MC-PDFT algorithm that avoids steeply scaling steps that are present in other post-self-consistent-field multireference calculations of dynamic correlation energy. We demonstrate the favorable scaling by considering systems of H 2 molecules with active spaces of several different sizes. We then apply the MC-PDFT method to calculate the heterolytic dissociation enthalpy of ferrocene. We find that MC-PDFT yields results that are at least as accurate as complete active space second-order perturbation theory and are more stable with respect to basis set, but at a fraction of the cost in both time and memory.

Resolution-of-identity stochastic time-dependent configuration interaction for dissipative electron dynamics in strong fields.

PubMed

Klinkusch, Stefan; Tremblay, Jean Christophe

2016-05-14

In this contribution, we introduce a method for simulating dissipative, ultrafast many-electron dynamics in intense laser fields. The method is based on the norm-conserving stochastic unraveling of the dissipative Liouville-von Neumann equation in its Lindblad form. The N-electron wave functions sampling the density matrix are represented in the basis of singly excited configuration state functions. The interaction with an external laser field is treated variationally and the response of the electronic density is included to all orders in this basis. The coupling to an external environment is included via relaxation operators inducing transition between the configuration state functions. Single electron ionization is represented by irreversible transition operators from the ionizing states to an auxiliary continuum state. The method finds its efficiency in the representation of the operators in the interaction picture, where the resolution-of-identity is used to reduce the size of the Hamiltonian eigenstate basis. The zeroth-order eigenstates can be obtained either at the configuration interaction singles level or from a time-dependent density functional theory reference calculation. The latter offers an alternative to explicitly time-dependent density functional theory which has the advantage of remaining strictly valid for strong field excitations while improving the description of the correlation as compared to configuration interaction singles. The method is tested on a well-characterized toy system, the excitation of the low-lying charge transfer state in LiCN.

Resolution-of-identity stochastic time-dependent configuration interaction for dissipative electron dynamics in strong fields

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

Klinkusch, Stefan; Tremblay, Jean Christophe

In this contribution, we introduce a method for simulating dissipative, ultrafast many-electron dynamics in intense laser fields. The method is based on the norm-conserving stochastic unraveling of the dissipative Liouville-von Neumann equation in its Lindblad form. The N-electron wave functions sampling the density matrix are represented in the basis of singly excited configuration state functions. The interaction with an external laser field is treated variationally and the response of the electronic density is included to all orders in this basis. The coupling to an external environment is included via relaxation operators inducing transition between the configuration state functions. Single electronmore » ionization is represented by irreversible transition operators from the ionizing states to an auxiliary continuum state. The method finds its efficiency in the representation of the operators in the interaction picture, where the resolution-of-identity is used to reduce the size of the Hamiltonian eigenstate basis. The zeroth-order eigenstates can be obtained either at the configuration interaction singles level or from a time-dependent density functional theory reference calculation. The latter offers an alternative to explicitly time-dependent density functional theory which has the advantage of remaining strictly valid for strong field excitations while improving the description of the correlation as compared to configuration interaction singles. The method is tested on a well-characterized toy system, the excitation of the low-lying charge transfer state in LiCN.« less

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

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

Choi, Sunghwan; Hong, Kwangwoo; Kim, Jaewook

2015-03-07

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

Edge reconstruction in armchair phosphorene nanoribbons revealed by discontinuous Galerkin density functional theory.

PubMed

Hu, Wei; Lin, Lin; Yang, Chao

2015-12-21

With the help of our recently developed massively parallel DGDFT (Discontinuous Galerkin Density Functional Theory) methodology, we perform large-scale Kohn-Sham density functional theory calculations on phosphorene nanoribbons with armchair edges (ACPNRs) containing a few thousands to ten thousand atoms. The use of DGDFT allows us to systematically achieve a conventional plane wave basis set type of accuracy, but with a much smaller number (about 15) of adaptive local basis (ALB) functions per atom for this system. The relatively small number of degrees of freedom required to represent the Kohn-Sham Hamiltonian, together with the use of the pole expansion the selected inversion (PEXSI) technique that circumvents the need to diagonalize the Hamiltonian, results in a highly efficient and scalable computational scheme for analyzing the electronic structures of ACPNRs as well as their dynamics. The total wall clock time for calculating the electronic structures of large-scale ACPNRs containing 1080-10,800 atoms is only 10-25 s per self-consistent field (SCF) iteration, with accuracy fully comparable to that obtained from conventional planewave DFT calculations. For the ACPNR system, we observe that the DGDFT methodology can scale to 5000-50,000 processors. We use DGDFT based ab initio molecular dynamics (AIMD) calculations to study the thermodynamic stability of ACPNRs. Our calculations reveal that a 2 × 1 edge reconstruction appears in ACPNRs at room temperature.

First-principles investigation on Rydberg and resonance excitations: A case study of the firefly luciferin anion

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

Noguchi, Yoshifumi, E-mail: y.noguchi@issp.u-tokyo.ac.jp; Hiyama, Miyabi; Akiyama, Hidefumi

2014-07-28

The optical properties of an isolated firefly luciferin anion are investigated by using first-principles calculations, employing the many-body perturbation theory to take into account the excitonic effect. The calculated photoabsorption spectra are compared with the results obtained using the time-dependent density functional theory (TDDFT) employing the localized atomic orbital (AO) basis sets and a recent experiment in vacuum. The present method well reproduces the line shape at the photon energy corresponding to the Rydberg and resonance excitations but overestimates the peak positions by about 0.5 eV. However, the TDDFT-calculated positions of some peaks are closer to those of the experiment.more » We also investigate the basis set dependency in describing the free electron states above vacuum level and the excitons involving the transitions to the free electron states and conclude that AO-only basis sets are inaccurate for free electron states and the use of a plane wave basis set is required.« less

Materials Data on BaSi3SnO9 (SG:188) by Materials Project

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

Kristin Persson

2014-11-02

Computed materials data using density functional theory calculations. These calculations determine the electronic structure of bulk materials by solving approximations to the Schrodinger equation. For more information, see https://materialsproject.org/docs/calculations

Materials Data on BaSi4O9 (SG:188) by Materials Project

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

Kristin Persson

2014-07-09

Computed materials data using density functional theory calculations. These calculations determine the electronic structure of bulk materials by solving approximations to the Schrodinger equation. For more information, see https://materialsproject.org/docs/calculations

Shannon: Theory and cryptography

NASA Astrophysics Data System (ADS)

Roefs, H. F. A.

1982-11-01

The ideas of Shannon as a theoretical basis for cryptography are discussed. The notion of mutual information is introduced to provide a deeper understanding of the functioning of cryptographic systems. Shannon's absolute secure cryptosystem and his notion of unicity distance are explained.

[Identification of ecological corridors and its importance by integrating circuit theory].

PubMed

Song, Li Li; Qin, Ming Zhou

2016-10-01

Landscape connectivity is considered as an extraordinarily important factor affecting various ecological processes. The least cost path (LCP) on the basis of minimum cumulative resis-tance model (MCRM) may provide a more efficient approach to identify functional connectivity in heterogeneous landscapes, and is already adopted by the research of landscape functional connecti-vity assessment and ecological corridor simulation. Connectivity model on circuit theory (CMCT) replaced the edges in the graph theory with resistors, cost distance with resistance distance to measure the functional connectivity in heterogeneous landscapes. By means of Linkage Mapper tool and Circuitscape software, the simulated landscape generated from SIMMAP 2.0 software was viewed as the study object in this article, aimed at exploring how to integrate MCRM with CMCT to identify ecological corridors and relative importance of landscape factors. The results showed that two models had their individual advantages and mutual complement. MCRM could effectively identify least cost corridors among habitats. CMCT could effectively identify important landscape factor and pinch point, which had important influence on landscape connectivity. We also found that the position of pinch point was not affected by corridor width, which had obvious advantage in the research of identifying the importance of corridors. The integrated method could provide certain scientific basis for regional ecological protection planning and ecological corridor design.

Approach to the origin of turbulence on the basis of two-point kinetic theory

NASA Technical Reports Server (NTRS)

Tsuge, S.

1974-01-01

Equations for the fluctuation correlation in an incompressible shear flow are derived on the basis of kinetic theory, utilizing the two-point distribution function which obeys the BBGKY hierarchy equation truncated with the hypothesis of 'ternary' molecular chaos. The step from the molecular to the hydrodynamic description is accomplished by a moment expansion which is a two-point version of the thirteen-moment method, and which leads to a series of correlation equations, viz., the two-point counterparts of the continuity equation, the Navier-Stokes equation, etc. For almost parallel shearing flows the two-point equation is separable and reduces to two Orr-Sommerfeld equations with different physical implications.

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

McKemmish, Laura K., E-mail: laura.mckemmish@gmail.com; Research School of Chemistry, Australian National University, Canberra

Algorithms for the efficient calculation of two-electron integrals in the newly developed mixed ramp-Gaussian basis sets are presented, alongside a Fortran90 implementation of these algorithms, RAMPITUP. These new basis sets have significant potential to (1) give some speed-up (estimated at up to 20% for large molecules in fully optimised code) to general-purpose Hartree-Fock (HF) and density functional theory quantum chemistry calculations, replacing all-Gaussian basis sets, and (2) give very large speed-ups for calculations of core-dependent properties, such as electron density at the nucleus, NMR parameters, relativistic corrections, and total energies, replacing the current use of Slater basis functions or verymore » large specialised all-Gaussian basis sets for these purposes. This initial implementation already demonstrates roughly 10% speed-ups in HF/R-31G calculations compared to HF/6-31G calculations for large linear molecules, demonstrating the promise of this methodology, particularly for the second application. As well as the reduction in the total primitive number in R-31G compared to 6-31G, this timing advantage can be attributed to the significant reduction in the number of mathematically complex intermediate integrals after modelling each ramp-Gaussian basis-function-pair as a sum of ramps on a single atomic centre.« less

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

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.

Evaluation of the mathematical and economic basis for conversion processes in the LEAP energy-economy model

NASA Astrophysics Data System (ADS)

Oblow, E. M.

1982-10-01

An evaluation was made of the mathematical and economic basis for conversion processes in the Long-term Energy Analysis Program (LEAP) energy economy model. Conversion processes are the main modeling subunit in LEAP used to represent energy conversion industries and are supposedly based on the classical economic theory of the firm. Questions about uniqueness and existence of LEAP solutions and their relation to classical equilibrium economic theory prompted the study. An analysis of classical theory and LEAP model equations was made to determine their exact relationship. The conclusions drawn from this analysis were that LEAP theory is not consistent with the classical theory of the firm. Specifically, the capacity factor formalism used by LEAP does not support a classical interpretation in terms of a technological production function for energy conversion processes. The economic implications of this inconsistency are suboptimal process operation and short term negative profits in years where plant operation should be terminated. A new capacity factor formalism, which retains the behavioral features of the original model, is proposed to resolve these discrepancies.

Theoretical calculations of Electron Paramagnetic Resonance parameters of liquid phase Orotic acid radical

NASA Astrophysics Data System (ADS)

Sarikaya, Ebru Karakaş; Dereli, Ömer

2017-02-01

To obtain liquid phase molecular structure, conformational analysis of Orotic acid was performed and six conformers were determined. For these conformations, eight possible radicals were modelled by using Density Functional Theory computations with respect to molecular structure. Electron Paramagnetic Resonance parameters of these model radicals were calculated and then they were compared with the experimental ones. Geometry optimizations of the molecule and modeled radicals were performed using Becke's three-parameter hybrid-exchange functional combined with the Lee-Yang-Parr correlation functional of Density Functional Theory and 6-311++G(d,p) basis sets in p-dioxane solution. Because Orotic acid can be mutagenic in mammalian somatic cells and it is also mutagenic for bacteria and yeast, it has been studied.

Time-dependent density functional theory description of total photoabsorption cross sections

NASA Astrophysics Data System (ADS)

Tenorio, Bruno Nunes Cabral; Nascimento, Marco Antonio Chaer; Rocha, Alexandre Braga

2018-02-01

The time-dependent version of the density functional theory (TDDFT) has been used to calculate the total photoabsorption cross section of a number of molecules, namely, benzene, pyridine, furan, pyrrole, thiophene, phenol, naphthalene, and anthracene. The discrete electronic pseudo-spectra, obtained in a L2 basis set calculation were used in an analytic continuation procedure to obtain the photoabsorption cross sections. The ammonia molecule was chosen as a model system to compare the results obtained with TDDFT to those obtained with the linear response coupled cluster approach in order to make a link with our previous work and establish benchmarks.

Light-propagation management in coupled waveguide arrays: Quantitative experimental and theoretical assessment from band structures to functional patterns

NASA Astrophysics Data System (ADS)

Moison, Jean-Marie; Belabas, Nadia; Levenson, Juan Ariel; Minot, Christophe

2012-09-01

We assess the band structure of arrays of coupled optical waveguides both by ab initio calculations and by experiments, with an excellent quantitative agreement without any adjustable physical parameter. The band structures we obtain can deviate strongly from the expectations of the standard coupled mode theory approximation, but we describe them efficiently by a few parameters within an extended coupled mode theory. We also demonstrate that this description is in turn a firm and simple basis for accurate beam management in functional patterns of coupled waveguides, in full accordance with their design.

Differentiability of energy functionals in spin-density-functional theory

NASA Astrophysics Data System (ADS)

Gál, Tamás

2007-06-01

Recently, nonuniqueness of external electrostatic and magnetic fields yielding a given many-electron ground state has been pointed out [K. Capelle and G. Vignale, Phys. Rev. Lett. 86, 5546 (2001); H. Eschrig and W. E. Pickett, Solid State Commun. 118, 123 (2001)], implying the nondifferentiability of the ground-state energy functional of spin-density-functional theory (SDFT), on the basis of which the applicability of widely used DFT methods in SDFT has been put into question and the need for a critical reexamination of those applications has been concluded. Here it is shown, for collinear magnetic fields, that the nonuniqueness of the external potentials in SDFT does not imply the nonexistence of number-conserving functional derivatives as well, with the use of which therefore problems arising from the nondifferentiability are avoided.

Game theory and neural basis of social decision making

PubMed Central

Lee, Daeyeol

2008-01-01

Decision making in a social group displays two unique features. First, humans and other animals routinely alter their behaviors in response to changes in their physical and social environment. As a result, the outcomes of decisions that depend on the behaviors of multiple decision makers are difficult to predict, and this requires highly adaptive decision-making strategies. Second, decision makers may have other-regarding preferences and therefore choose their actions to improve or reduce the well-beings of others. Recently, many neurobiological studies have exploited game theory to probe the neural basis of decision making, and found that these unique features of social decision making might be reflected in the functions of brain areas involved in reward evaluation and reinforcement learning. Molecular genetic studies have also begun to identify genetic mechanisms for personal traits related to reinforcement learning and complex social decision making, further illuminating the biological basis of social behavior. PMID:18368047

Plato: A localised orbital based density functional theory code

NASA Astrophysics Data System (ADS)

Kenny, S. D.; Horsfield, A. P.

2009-12-01

The Plato package allows both orthogonal and non-orthogonal tight-binding as well as density functional theory (DFT) calculations to be performed within a single framework. The package also provides extensive tools for analysing the results of simulations as well as a number of tools for creating input files. The code is based upon the ideas first discussed in Sankey and Niklewski (1989) [1] with extensions to allow high-quality DFT calculations to be performed. DFT calculations can utilise either the local density approximation or the generalised gradient approximation. Basis sets from minimal basis through to ones containing multiple radial functions per angular momenta and polarisation functions can be used. Illustrations of how the package has been employed are given along with instructions for its utilisation. Program summaryProgram title: Plato Catalogue identifier: AEFC_v1_0 Program summary URL:http://cpc.cs.qub.ac.uk/summaries/AEFC_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.: 219 974 No. of bytes in distributed program, including test data, etc.: 1 821 493 Distribution format: tar.gz Programming language: C/MPI and PERL Computer: Apple Macintosh, PC, Unix machines Operating system: Unix, Linux and Mac OS X Has the code been vectorised or parallelised?: Yes, up to 256 processors tested RAM: Up to 2 Gbytes per processor Classification: 7.3 External routines: LAPACK, BLAS and optionally ScaLAPACK, BLACS, PBLAS, FFTW Nature of problem: Density functional theory study of electronic structure and total energies of molecules, crystals and surfaces. Solution method: Localised orbital based density functional theory. Restrictions: Tight-binding and density functional theory only, no exact exchange. Unusual features: Both atom centred and uniform meshes available. Can deal with arbitrary angular momenta for orbitals, whilst still retaining Slater-Koster tables for accuracy. Running time: Test cases will run in a few minutes, large calculations may run for several days.

Simplified DFT methods for consistent structures and energies of large systems

NASA Astrophysics Data System (ADS)

Caldeweyher, Eike; Gerit Brandenburg, Jan

2018-05-01

Kohn–Sham density functional theory (DFT) is routinely used for the fast electronic structure computation of large systems and will most likely continue to be the method of choice for the generation of reliable geometries in the foreseeable future. Here, we present a hierarchy of simplified DFT methods designed for consistent structures and non-covalent interactions of large systems with particular focus on molecular crystals. The covered methods are a minimal basis set Hartree–Fock (HF-3c), a small basis set screened exchange hybrid functional (HSE-3c), and a generalized gradient approximated functional evaluated in a medium-sized basis set (B97-3c), all augmented with semi-classical correction potentials. We give an overview on the methods design, a comprehensive evaluation on established benchmark sets for geometries and lattice energies of molecular crystals, and highlight some realistic applications on large organic crystals with several hundreds of atoms in the primitive unit cell.

SO(N) restricted Schur polynomials

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

Kemp, Garreth, E-mail: garreth.kemp@students.wits.ac.za

2015-02-15

We focus on the 1/4-BPS sector of free super Yang-Mills theory with an SO(N) gauge group. This theory has an AdS/CFT (an equivalence between a conformal field theory in d-1 dimensions and type II string theory defined on an AdS space in d-dimensions) dual in the form of type IIB string theory with AdS{sub 5}×RP{sup 5} geometry. With the aim of studying excited giant graviton dynamics, we construct an orthogonal basis for this sector of the gauge theory in this work. First, we demonstrate that the counting of states, as given by the partition function, and the counting of restrictedmore » Schur polynomials match by restricting to a particular class of Young diagram labels. We then give an explicit construction of these gauge invariant operators and evaluate their two-point function exactly. This paves the way to studying the spectral problem of these operators and their D-brane duals.« less

First-Principles Momentum-Dependent Local Ansatz Wavefunction and Momentum Distribution Function Bands of Iron

NASA Astrophysics Data System (ADS)

Kakehashi, Yoshiro; Chandra, Sumal

2016-04-01

We have developed a first-principles local ansatz wavefunction approach with momentum-dependent variational parameters on the basis of the tight-binding LDA+U Hamiltonian. The theory goes beyond the first-principles Gutzwiller approach and quantitatively describes correlated electron systems. Using the theory, we find that the momentum distribution function (MDF) bands of paramagnetic bcc Fe along high-symmetry lines show a large deviation from the Fermi-Dirac function for the d electrons with eg symmetry and yield the momentum-dependent mass enhancement factors. The calculated average mass enhancement m*/m = 1.65 is consistent with low-temperature specific heat data as well as recent angle-resolved photoemission spectroscopy (ARPES) data.

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).

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.

Operator bases, S-matrices, and their partition functions

NASA Astrophysics Data System (ADS)

Henning, Brian; Lu, Xiaochuan; Melia, Tom; Murayama, Hitoshi

2017-10-01

Relativistic quantum systems that admit scattering experiments are quantitatively described by effective field theories, where S-matrix kinematics and symmetry considerations are encoded in the operator spectrum of the EFT. In this paper we use the S-matrix to derive the structure of the EFT operator basis, providing complementary descriptions in (i) position space utilizing the conformal algebra and cohomology and (ii) momentum space via an algebraic formulation in terms of a ring of momenta with kinematics implemented as an ideal. These frameworks systematically handle redundancies associated with equations of motion (on-shell) and integration by parts (momentum conservation). We introduce a partition function, termed the Hilbert series, to enumerate the operator basis — correspondingly, the S-matrix — and derive a matrix integral expression to compute the Hilbert series. The expression is general, easily applied in any spacetime dimension, with arbitrary field content and (linearly realized) symmetries. In addition to counting, we discuss construction of the basis. Simple algorithms follow from the algebraic formulation in momentum space. We explicitly compute the basis for operators involving up to n = 5 scalar fields. This construction universally applies to fields with spin, since the operator basis for scalars encodes the momentum dependence of n-point amplitudes. We discuss in detail the operator basis for non-linearly realized symmetries. In the presence of massless particles, there is freedom to impose additional structure on the S- matrix in the form of soft limits. The most na¨ıve implementation for massless scalars leads to the operator basis for pions, which we confirm using the standard CCWZ formulation for non-linear realizations. Although primarily discussed in the language of EFT, some of our results — conceptual and quantitative — may be of broader use in studying conformal field theories as well as the AdS/CFT correspondence.

Inner Space Perturbation Theory in Matrix Product States: Replacing Expensive Iterative Diagonalization.

PubMed

Ren, Jiajun; Yi, Yuanping; Shuai, Zhigang

2016-10-11

We propose an inner space perturbation theory (isPT) to replace the expensive iterative diagonalization in the standard density matrix renormalization group theory (DMRG). The retained reduced density matrix eigenstates are partitioned into the active and secondary space. The first-order wave function and the second- and third-order energies are easily computed by using one step Davidson iteration. Our formulation has several advantages including (i) keeping a balance between the efficiency and accuracy, (ii) capturing more entanglement with the same amount of computational time, (iii) recovery of the standard DMRG when all the basis states belong to the active space. Numerical examples for the polyacenes and periacene show that the efficiency gain is considerable and the accuracy loss due to the perturbation treatment is very small, when half of the total basis states belong to the active space. Moreover, the perturbation calculations converge in all our numerical examples.

Potential Energy Surface of the Chromium Dimer Re-re-revisited with Multiconfigurational Perturbation Theory.

PubMed

Vancoillie, Steven; Malmqvist, Per Åke; Veryazov, Valera

2016-04-12

The chromium dimer has long been a benchmark molecule to evaluate the performance of different computational methods ranging from density functional theory to wave function methods. Among the latter, multiconfigurational perturbation theory was shown to be able to reproduce the potential energy surface of the chromium dimer accurately. However, for modest active space sizes, it was later shown that different definitions of the zeroth-order Hamiltonian have a large impact on the results. In this work, we revisit the system for the third time with multiconfigurational perturbation theory, now in order to increase the active space of the reference wave function. This reduces the impact of the choice of zeroth-order Hamiltonian and improves the shape of the potential energy surface significantly. We conclude by comparing our results of the dissocation energy and vibrational spectrum to those obtained from several highly accurate multiconfigurational methods and experiment. For a meaningful comparison, we used the extrapolation to the complete basis set for all methods involved.

A New Energy Ordering and the Dipole Moment of Gas Phase Glycine via Plane-Wave Density Functional Theory Calculations

NASA Astrophysics Data System (ADS)

Min, Byeong June

2018-03-01

The abundance of glycine (Gly), the simplest amino acid, in meteorites leads us to the next question about its extraterrestrial origin. However, astronomers have not yet found glycine signature in interstellar medium. Laboratory microwave spectroscopy experiments report the most stable Gly conformer has a dipole moment of 4.5 - 5.45 Debye. Theoretical calculations, so far performed only with Gaussian basis functions, has predicted a dipole moment of about 1 Debye. This discrepancy has baffled astronomers. We study the energetics of glycine and its isomers and conformers via plane-wave density functional theory calculations. The geometric structures of the isomers and their conformers are identified, along with their relative stability and their dipole moment. In the case of glycine, we obtain the most stable conformer with a dipole moment of 5.76 Debye, close to the microwave spectroscopy experiments. If the plane wave energy cutoff is reduced to a lower value ( 400 eV) on purpose, the energy ordering reverses to the case with Gaussian basis calculations.

Neuropsychological implications of selective attentional functioning in psychopathic offenders.

PubMed

Mayer, Andrew R; Kosson, David S; Bedrick, Edward J

2006-09-01

Several core characteristics of the psychopathic personality disorder (i.e., impulsivity, failure to attend to interpersonal cues) suggest that psychopaths suffer from disordered attention. However, there is mixed evidence from the cognitive literature as to whether they exhibit superior or deficient selective attention, which has led to the formation of several distinct theories of attentional functioning in psychopathy. The present experiment investigated participants' abilities to purposely allocate attentional resources on the basis of auditory or visual linguistic information and directly tested both theories of deficient or superior selective attention in psychopathy. Specifically, 91 male inmates at a county jail were presented with either auditory or visual linguistic cues (with and without distractors) that correctly indicated the position of an upcoming visual target in 75% of the trials. The results indicated that psychopaths did not exhibit evidence of superior selective attention in any of the conditions but were generally less efficient in shifting attention on the basis of linguistic cues, especially in regard to auditory information. Implications for understanding psychopaths' cognitive functioning and possible neuropsychological deficits are addressed. ((c) 2006 APA, all rights reserved).

Push it to the limit: Characterizing the convergence of common sequences of basis sets for intermolecular interactions as described by density functional theory

NASA Astrophysics Data System (ADS)

Witte, Jonathon; Neaton, Jeffrey B.; Head-Gordon, Martin

2016-05-01

With the aim of systematically characterizing the convergence of common families of basis sets such that general recommendations for basis sets can be made, we have tested a wide variety of basis sets against complete-basis binding energies across the S22 set of intermolecular interactions—noncovalent interactions of small and medium-sized molecules consisting of first- and second-row atoms—with three distinct density functional approximations: SPW92, a form of local-density approximation; B3LYP, a global hybrid generalized gradient approximation; and B97M-V, a meta-generalized gradient approximation with nonlocal correlation. We have found that it is remarkably difficult to reach the basis set limit; for the methods and systems examined, the most complete basis is Jensen's pc-4. The Dunning correlation-consistent sequence of basis sets converges slowly relative to the Jensen sequence. The Karlsruhe basis sets are quite cost effective, particularly when a correction for basis set superposition error is applied: counterpoise-corrected def2-SVPD binding energies are better than corresponding energies computed in comparably sized Dunning and Jensen bases, and on par with uncorrected results in basis sets 3-4 times larger. These trends are exhibited regardless of the level of density functional approximation employed. A sense of the magnitude of the intrinsic incompleteness error of each basis set not only provides a foundation for guiding basis set choice in future studies but also facilitates quantitative comparison of existing studies on similar types of systems.

Angular coherence in ultrasound imaging: Theory and applications

PubMed Central

Li, You Leo; Dahl, Jeremy J.

2017-01-01

The popularity of plane-wave transmits at multiple transmit angles for synthetic transmit aperture (or coherent compounding) has spawned a number of adaptations and new developments of ultrasonic imaging. However, the coherence properties of backscattered signals with plane-wave transmits at different angles are unknown and may impact a subset of these techniques. To provide a framework for the analysis of the coherence properties of such signals, this article introduces the angular coherence theory in medical ultrasound imaging. The theory indicates that the correlation function of such signals forms a Fourier transform pair with autocorrelation function of the receive aperture function. This conclusion can be considered as an extended form of the van Cittert Zernike theorem. The theory is validated with simulation and experimental results obtained on speckle targets. On the basis of the angular coherence of the backscattered wave, a new short-lag angular coherence beamformer is proposed and compared with an existing spatial-coherence-based beamformer. An application of the theory in phase shift estimation and speed of sound estimation is also presented. PMID:28372139

Neural network approach to quantum-chemistry data: accurate prediction of density functional theory energies.

PubMed

Balabin, Roman M; Lomakina, Ekaterina I

2009-08-21

Artificial neural network (ANN) approach has been applied to estimate the density functional theory (DFT) energy with large basis set using lower-level energy values and molecular descriptors. A total of 208 different molecules were used for the ANN training, cross validation, and testing by applying BLYP, B3LYP, and BMK density functionals. Hartree-Fock results were reported for comparison. Furthermore, constitutional molecular descriptor (CD) and quantum-chemical molecular descriptor (QD) were used for building the calibration model. The neural network structure optimization, leading to four to five hidden neurons, was also carried out. The usage of several low-level energy values was found to greatly reduce the prediction error. An expected error, mean absolute deviation, for ANN approximation to DFT energies was 0.6+/-0.2 kcal mol(-1). In addition, the comparison of the different density functionals with the basis sets and the comparison of multiple linear regression results were also provided. The CDs were found to overcome limitation of the QD. Furthermore, the effective ANN model for DFT/6-311G(3df,3pd) and DFT/6-311G(2df,2pd) energy estimation was developed, and the benchmark results were provided.

Reduction of parameters in Finite Unified Theories and the MSSM

NASA Astrophysics Data System (ADS)

Heinemeyer, Sven; Mondragón, Myriam; Tracas, Nicholas; Zoupanos, George

2018-02-01

The method of reduction of couplings developed by W. Zimmermann, combined with supersymmetry, can lead to realistic quantum field theories, where the gauge and Yukawa sectors are related. It is the basis to find all-loop Finite Unified Theories, where the β-function vanishes to all-loops in perturbation theory. It can also be applied to the Minimal Supersymmetric Standard Model, leading to a drastic reduction in the number of parameters. Both Finite Unified Theories and the reduced MSSM lead to successful predictions for the masses of the third generation of quarks and the Higgs boson, and also predict a heavy supersymmetric spectrum, consistent with the non-observation of supersymmetry so far.

An ab initio benchmark study of the H + CO --> HCO reaction

NASA Technical Reports Server (NTRS)

Woon, D. E.

1996-01-01

The H + CO --> HCO reaction has been characterized with correlation consistent basis sets at five levels of theory in order to benchmark the sensitivities of the barrier height and reaction ergicity to the one-electron and n-electron expansions of the electronic wave function. Single and multireference methods are compared and contrasted. The coupled cluster method RCCSD(T) was found to be in very good agreement with Davidson-corrected internally-contracted multireference configuration interaction (MRCI+Q). Second-order Moller-Plesset perturbation theory (MP2) was also employed. The estimated complete basis set (CBS) limits for the barrier height (in kcal/mol) for the five methods, including harmonic zero-point energy corrections, are MP2, 4.66; RCCSD, 4.78; RCCSD(T), 4.15; MRCI, 5.10; and MRCI+Q, 4.07. Similarly, the estimated CBS limits for the ergicity of the reaction are: MP2, -17.99; RCCSD, -13.34; RCCSD(T), -13.79; MRCI, -11.46; and MRCI+Q, -13.70. Additional basis set explorations for the RCCSD(T) method demonstrate that aug-cc-pVTZ sets, even with some functions removed, are sufficient to reproduce the CBS limits to within 0.1-0.3 kcal/mol.

Kohn-Sham potentials from electron densities using a matrix representation within finite atomic orbital basis sets

NASA Astrophysics Data System (ADS)

Zhang, Xing; Carter, Emily A.

2018-01-01

We revisit the static response function-based Kohn-Sham (KS) inversion procedure for determining the KS effective potential that corresponds to a given target electron density within finite atomic orbital basis sets. Instead of expanding the potential in an auxiliary basis set, we directly update the potential in its matrix representation. Through numerical examples, we show that the reconstructed density rapidly converges to the target density. Preliminary results are presented to illustrate the possibility of obtaining a local potential in real space from the optimized potential in its matrix representation. We have further applied this matrix-based KS inversion approach to density functional embedding theory. A proof-of-concept study of a solvated proton transfer reaction demonstrates the method's promise.

Green's function multiple-scattering theory with a truncated basis set: An augmented-KKR formalism

NASA Astrophysics Data System (ADS)

Alam, Aftab; Khan, Suffian N.; Smirnov, A. V.; Nicholson, D. M.; Johnson, Duane D.

2014-11-01

The Korringa-Kohn-Rostoker (KKR) Green's function, multiple-scattering theory is an efficient site-centered, electronic-structure technique for addressing an assembly of N scatterers. Wave functions are expanded in a spherical-wave basis on each scattering center and indexed up to a maximum orbital and azimuthal number Lmax=(l,mmax), while scattering matrices, which determine spectral properties, are truncated at Lt r=(l,mt r) where phase shifts δl >ltr are negligible. Historically, Lmax is set equal to Lt r, which is correct for large enough Lmax but not computationally expedient; a better procedure retains higher-order (free-electron and single-site) contributions for Lmax>Lt r with δl >ltr set to zero [X.-G. Zhang and W. H. Butler, Phys. Rev. B 46, 7433 (1992), 10.1103/PhysRevB.46.7433]. We present a numerically efficient and accurate augmented-KKR Green's function formalism that solves the KKR equations by exact matrix inversion [R3 process with rank N (ltr+1 ) 2 ] and includes higher-L contributions via linear algebra [R2 process with rank N (lmax+1) 2 ]. The augmented-KKR approach yields properly normalized wave functions, numerically cheaper basis-set convergence, and a total charge density and electron count that agrees with Lloyd's formula. We apply our formalism to fcc Cu, bcc Fe, and L 1 0 CoPt and present the numerical results for accuracy and for the convergence of the total energies, Fermi energies, and magnetic moments versus Lmax for a given Lt r.

Green's function multiple-scattering theory with a truncated basis set: An augmented-KKR formalism

DOE PAGES

Alam, Aftab; Khan, Suffian N.; Smirnov, A. V.; ...

2014-11-04

Korringa-Kohn-Rostoker (KKR) Green's function, multiple-scattering theory is an ecient sitecentered, electronic-structure technique for addressing an assembly of N scatterers. Wave-functions are expanded in a spherical-wave basis on each scattering center and indexed up to a maximum orbital and azimuthal number L max = (l,m) max, while scattering matrices, which determine spectral properties, are truncated at L tr = (l,m) tr where phase shifts δl>l tr are negligible. Historically, L max is set equal to L tr, which is correct for large enough L max but not computationally expedient; a better procedure retains higher-order (free-electron and single-site) contributions for L maxmore » > L tr with δl>l tr set to zero [Zhang and Butler, Phys. Rev. B 46, 7433]. We present a numerically ecient and accurate augmented-KKR Green's function formalism that solves the KKR equations by exact matrix inversion [R 3 process with rank N(l tr + 1) 2] and includes higher-L contributions via linear algebra [R 2 process with rank N(l max +1) 2]. Augmented-KKR approach yields properly normalized wave-functions, numerically cheaper basis-set convergence, and a total charge density and electron count that agrees with Lloyd's formula. We apply our formalism to fcc Cu, bcc Fe and L1 0 CoPt, and present the numerical results for accuracy and for the convergence of the total energies, Fermi energies, and magnetic moments versus L max for a given L tr.« less

Crystal growth, spectroscopic, DFT computational and third harmonic generation studies of nicotinic acid

NASA Astrophysics Data System (ADS)

Thaya Kumari, C. Rathika; Nageshwari, M.; Raman, R. Ganapathi; Caroline, M. Lydia

2018-07-01

An organic centrosymmetric nicotinic acid (NA) single crystal has been grown employing slow evaporation method in water. NA crystallizes in monoclinic system with centric space group P21/C. The experimental and theoretical investigation includes vibrational spectra based on Hartree - Fock (HF) and density functional theory (DFT) has been applied using different function at B3LYP level of theory using 6-311G++(d,p) basis set. The optical transparency of the title molecule was examined by TD- DFT analysis and for comparison basis experimental UV-Vis spectrum was recorded. The interaction of charge within the molecule was analyzed and the HOMO - LUMO energy gap was evaluated. The value of dipole moment, Mulliken charge and molecular electrostatic potential were estimated at the same level of theory. Also the first order hyper polarizability for NA was calculated. The dielectric behavior of the grown crystal was determined for few selected temperatures. The third order nonlinear response of NA has been examined using Z-scan technique and nonlinear susceptibility (χ3), nonlinear refraction (n2) and nonlinear absorption coefficient (β) has been calculated. The current results clearly indicate that the title compound is an excellent applicant in the domain of opto - electronic applications.

Solving the Schrödinger equation of molecules by relaxing the antisymmetry rule: Inter-exchange theory.

PubMed

Nakatsuji, Hiroshi; Nakashima, Hiroyuki

2015-05-21

The Schrödinger equation (SE) and the antisymmetry principle constitute the governing principle of chemistry. A general method of solving the SE was presented before as the free complement (FC) theory, which gave highly accurate solutions for small atoms and molecules. We assume here to use the FC theory starting from the local valence bond wave function. When this theory is applied to larger molecules, antisymmetrizations of electronic wave functions become time-consuming and therefore, an additional breakthrough is necessary concerning the antisymmetry principle. Usually, in molecular calculations, we first construct the wave function to satisfy the antisymmetry rule, "electronic wave functions must be prescribed to be antisymmetric for all exchanges of electrons, otherwise bosonic interference may disturb the basis of the science." Starting from determinantal wave functions is typical. Here, we give an antisymmetrization theory, called inter-exchange (iExg) theory, by dividing molecular antisymmetrizations to those within atoms and between atoms. For the electrons belonging to distant atoms in a molecule, only partial antisymmetrizations or even no antisymmetrizations are necessary, depending on the distance between the atoms. So, the above antisymmetry rule is not necessarily followed strictly to get the results of a desired accuracy. For this and other reasons, the necessary parts of the antisymmetrization operations become very small as molecules become larger, leading finally to the operation counts of lower orders of N, the number of electrons. This theory creates a natural antisymmetrization method that is useful for large molecules.

Embedded-cluster calculations in a numeric atomic orbital density-functional theory framework.

PubMed

Berger, Daniel; Logsdail, Andrew J; Oberhofer, Harald; Farrow, Matthew R; Catlow, C Richard A; Sherwood, Paul; Sokol, Alexey A; Blum, Volker; Reuter, Karsten

2014-07-14

We integrate the all-electron electronic structure code FHI-aims into the general ChemShell package for solid-state embedding quantum and molecular mechanical (QM/MM) calculations. A major undertaking in this integration is the implementation of pseudopotential functionality into FHI-aims to describe cations at the QM/MM boundary through effective core potentials and therewith prevent spurious overpolarization of the electronic density. Based on numeric atomic orbital basis sets, FHI-aims offers particularly efficient access to exact exchange and second order perturbation theory, rendering the established QM/MM setup an ideal tool for hybrid and double-hybrid level density functional theory calculations of solid systems. We illustrate this capability by calculating the reduction potential of Fe in the Fe-substituted ZSM-5 zeolitic framework and the reaction energy profile for (photo-)catalytic water oxidation at TiO2(110).

Embedded-cluster calculations in a numeric atomic orbital density-functional theory framework

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

Berger, Daniel, E-mail: daniel.berger@ch.tum.de; Oberhofer, Harald; Reuter, Karsten

2014-07-14

We integrate the all-electron electronic structure code FHI-aims into the general ChemShell package for solid-state embedding quantum and molecular mechanical (QM/MM) calculations. A major undertaking in this integration is the implementation of pseudopotential functionality into FHI-aims to describe cations at the QM/MM boundary through effective core potentials and therewith prevent spurious overpolarization of the electronic density. Based on numeric atomic orbital basis sets, FHI-aims offers particularly efficient access to exact exchange and second order perturbation theory, rendering the established QM/MM setup an ideal tool for hybrid and double-hybrid level density functional theory calculations of solid systems. We illustrate this capabilitymore » by calculating the reduction potential of Fe in the Fe-substituted ZSM-5 zeolitic framework and the reaction energy profile for (photo-)catalytic water oxidation at TiO{sub 2}(110)« less

Orthogonal bases of invariants in tensor models

NASA Astrophysics Data System (ADS)

Diaz, Pablo; Rey, Soo-Jong

2018-02-01

Representation theory provides an efficient framework to count and classify invariants in tensor models of (gauge) symmetry G d = U( N 1) ⊗ · · · ⊗ U( N d ) . We show that there are two natural ways of counting invariants, one for arbitrary G d and another valid for large rank of G d . We construct basis of invariant operators based on the counting, and compute correlators of their elements. The basis associated with finite rank of G d diagonalizes two-point function. It is analogous to the restricted Schur basis used in matrix models. We comment on future directions for investigation.

Ab initio molecular simulations with numeric atom-centered orbitals

NASA Astrophysics Data System (ADS)

Blum, Volker; Gehrke, Ralf; Hanke, Felix; Havu, Paula; Havu, Ville; Ren, Xinguo; Reuter, Karsten; Scheffler, Matthias

2009-11-01

We describe a complete set of algorithms for ab initio molecular simulations based on numerically tabulated atom-centered orbitals (NAOs) to capture a wide range of molecular and materials properties from quantum-mechanical first principles. The full algorithmic framework described here is embodied in the Fritz Haber Institute "ab initio molecular simulations" (FHI-aims) computer program package. Its comprehensive description should be relevant to any other first-principles implementation based on NAOs. The focus here is on density-functional theory (DFT) in the local and semilocal (generalized gradient) approximations, but an extension to hybrid functionals, Hartree-Fock theory, and MP2/GW electron self-energies for total energies and excited states is possible within the same underlying algorithms. An all-electron/full-potential treatment that is both computationally efficient and accurate is achieved for periodic and cluster geometries on equal footing, including relaxation and ab initio molecular dynamics. We demonstrate the construction of transferable, hierarchical basis sets, allowing the calculation to range from qualitative tight-binding like accuracy to meV-level total energy convergence with the basis set. Since all basis functions are strictly localized, the otherwise computationally dominant grid-based operations scale as O(N) with system size N. Together with a scalar-relativistic treatment, the basis sets provide access to all elements from light to heavy. Both low-communication parallelization of all real-space grid based algorithms and a ScaLapack-based, customized handling of the linear algebra for all matrix operations are possible, guaranteeing efficient scaling (CPU time and memory) up to massively parallel computer systems with thousands of CPUs.

Block-localized wavefunction (BLW) method at the density functional theory (DFT) level.

PubMed

Mo, Yirong; Song, Lingchun; Lin, Yuchun

2007-08-30

The block-localized wavefunction (BLW) approach is an ab initio valence bond (VB) method incorporating the efficiency of molecular orbital (MO) theory. It can generate the wavefunction for a resonance structure or diabatic state self-consistently by partitioning the overall electrons and primitive orbitals into several subgroups and expanding each block-localized molecular orbital in only one subspace. Although block-localized molecular orbitals in the same subspace are constrained to be orthogonal (a feature of MO theory), orbitals between different subspaces are generally nonorthogonal (a feature of VB theory). The BLW method is particularly useful in the quantification of the electron delocalization (resonance) effect within a molecule and the charge-transfer effect between molecules. In this paper, we extend the BLW method to the density functional theory (DFT) level and implement the BLW-DFT method to the quantum mechanical software GAMESS. Test applications to the pi conjugation in the planar allyl radical and ions with the basis sets of 6-31G(d), 6-31+G(d), 6-311+G(d,p), and cc-pVTZ show that the basis set dependency is insignificant. In addition, the BLW-DFT method can also be used to elucidate the nature of intermolecular interactions. Examples of pi-cation interactions and solute-solvent interactions will be presented and discussed. By expressing each diabatic state with one BLW, the BLW method can be further used to study chemical reactions and electron-transfer processes whose potential energy surfaces are typically described by two or more diabatic states.

Accurate energetics of small molecules containing third-row atoms Ga-Kr: A comparison of advanced ab initio and density functional theory

NASA Astrophysics Data System (ADS)

Yockel, Scott; Mintz, Benjamin; Wilson, Angela K.

2004-07-01

Advanced ab initio [coupled cluster theory through quasiperturbative triple excitations (CCSD(T))] and density functional (B3LYP) computational chemistry approaches were used in combination with the standard and augmented correlation consistent polarized valence basis sets [cc-pVnZ and aug-cc-pVnZ, where n=D(2), T(3), Q(4), and 5] to investigate the energetic and structural properties of small molecules containing third-row (Ga-Kr) atoms. These molecules were taken from the Gaussian-2 (G2) extended test set for third-row atoms. Several different schemes were used to extrapolate the calculated energies to the complete basis set (CBS) limit for CCSD(T) and the Kohn-Sham (KS) limit for B3LYP. Zero point energy and spin orbital corrections were included in the results. Overall, CCSD(T) atomization energies, ionization energies, proton affinities, and electron affinities are in good agreement with experiment, within 1.1 kcal/mol when the CBS limit has been determined using a series of two basis sets of at least triple zeta quality. For B3LYP, the overall mean absolute deviation from experiment for the three properties and the series of molecules is more significant at the KS limit, within 2.3 and 2.6 kcal/mol for the cc-pVnZ and aug-cc-pVnZ basis set series, respectively.

Approaching the theoretical limit in periodic local MP2 calculations with atomic-orbital basis sets: the case of LiH.

PubMed

Usvyat, Denis; Civalleri, Bartolomeo; Maschio, Lorenzo; Dovesi, Roberto; Pisani, Cesare; Schütz, Martin

2011-06-07

The atomic orbital basis set limit is approached in periodic correlated calculations for solid LiH. The valence correlation energy is evaluated at the level of the local periodic second order Møller-Plesset perturbation theory (MP2), using basis sets of progressively increasing size, and also employing "bond"-centered basis functions in addition to the standard atom-centered ones. Extended basis sets, which contain linear dependencies, are processed only at the MP2 stage via a dual basis set scheme. The local approximation (domain) error has been consistently eliminated by expanding the orbital excitation domains. As a final result, it is demonstrated that the complete basis set limit can be reached for both HF and local MP2 periodic calculations, and a general scheme is outlined for the definition of high-quality atomic-orbital basis sets for solids. © 2011 American Institute of Physics

The Interpolation Theory of Radial Basis Functions

NASA Astrophysics Data System (ADS)

Baxter, Brad

2010-06-01

In this dissertation, it is first shown that, when the radial basis function is a p-norm and 1 < p < 2, interpolation is always possible when the points are all different and there are at least two of them. We then show that interpolation is not always possible when p > 2. Specifically, for every p > 2, we construct a set of different points in some Rd for which the interpolation matrix is singular. The greater part of this work investigates the sensitivity of radial basis function interpolants to changes in the function values at the interpolation points. Our early results show that it is possible to recast the work of Ball, Narcowich and Ward in the language of distributional Fourier transforms in an elegant way. We then use this language to study the interpolation matrices generated by subsets of regular grids. In particular, we are able to extend the classical theory of Toeplitz operators to calculate sharp bounds on the spectra of such matrices. Applying our understanding of these spectra, we construct preconditioners for the conjugate gradient solution of the interpolation equations. Our main result is that the number of steps required to achieve solution of the linear system to within a required tolerance can be independent of the number of interpolation points. The Toeplitz structure allows us to use fast Fourier transform techniques, which imp lies that the total number of operations is a multiple of n log n, where n is the number of interpolation points. Finally, we use some of our methods to study the behaviour of the multiquadric when its shape parameter increases to infinity. We find a surprising link with the sinus cardinalis or sinc function of Whittaker. Consequently, it can be highly useful to use a large shape parameter when approximating band-limited functions.

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.

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

Ren, X. G.; Ning, C. G.; Zhang, S. F.

The measurements of electron density distributions and binding-energy spectrum of the complete valence shell of cyclopentene (C{sub 5}H{sub 8}) using a binary (e,2e) electron momentum spectrometer are reported. The experimental momentum profiles of the valence orbitals are compared with the theoretical distributions calculated using Hartree-Fock and density-functional-theory (DFT) methods with various basis sets. The agreement between theory and experiment for the shape and intensity of the orbital electron momentum distributions is generally good. The DFT calculations employing B3LYP hybrid functional with a saturated and diffuse AUG-CC-PVTZ basis set provide the better descriptions of the experimental data. Some ''turn up'' effectsmore » in the low momentum region of the measured (e,2e) cross section compared with the calculations of 3a{sup ''}, 2a{sup ''}, and 3a{sup '} orbitals could be mainly attributed to distorted-wave effects. The pole strengths of the main ionization peaks from the orbitals in the inner valence are estimated.« less

An experimental and theoretical study of molecular structure and vibrational spectra of 2-methylphenyl boronic acid by density functional theory calculations

NASA Astrophysics Data System (ADS)

Hiremath, Sudhir M.; Hiremath, C. S.; Khemalapure, S. S.; Patil, N. R.

2018-05-01

This paper reports the experimental and theoretical study on the structure and vibrations of 2-Methylphenyl boronic acid (2MPBA). The different spectroscopic techniques such as FT-IR (4000-400 cm-1) and FT-Raman (4000-50 cm-1) of the title molecule in the solid phase were recorded. The geometry of the molecule was fully optimized using density functional theory (DFT) (B3LYP) with 6-311++G(d, p) basis set calculations. The vibrational wavenumbers were also corrected with scale factor to take better results for the calculated data. Vibrational spectra were calculated and fundamental vibrations were assigned on the basis of the potential energy distribution (PED) of the vibrational modes obtained from VEDA 4 program. The calculated wavenumbers showed the best agreement with the experimental results. Whereas, it is observed that, the theoretical frequencies are more than the experimental one for O-H stretching vibration modes of the title molecule.

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

Trevisanutto, Paolo E.; Vignale, Giovanni, E-mail: vignaleg@missouri.edu

Ab initio electronic structure calculations of two-dimensional layered structures are typically performed using codes that were developed for three-dimensional structures, which are periodic in all three directions. The introduction of a periodicity in the third direction (perpendicular to the layer) is completely artificial and may lead in some cases to spurious results and to difficulties in treating the action of external fields. In this paper we develop a new approach, which is “native” to quasi-2D materials, making use of basis function that are periodic in the plane, but atomic-like in the perpendicular direction. We show how some of the basicmore » tools of ab initio electronic structure theory — density functional theory, GW approximation and Bethe-Salpeter equation — are implemented in the new basis. We argue that the new approach will be preferable to the conventional one in treating the peculiarities of layered materials, including the long range of the unscreened Coulomb interaction in insulators, and the effects of strain, corrugations, and external fields.« less

Mechanism insight into the cyanide-catalyzed benzoin condensation: a density functional theory study.

PubMed

He, Yunqing; Xue, Ying

2010-09-02

The reaction mechanism of the cyanide-catalyzed benzoin condensation without protonic solvent assistance has been studied computationally for the first time employing the density functional theory (B3LYP) method in conjunction with 6-31+G(d,p) basis set. Four possible pathways have been investigated. A new proposed pathway on the basis of the Lapworth mechanism is determined to be the dominant pathway in aprotic solvent, in which the formation of the Lapworth's cyanohydrin intermediate is a sequence including three steps assisted by benzaldehyde, clearly manifesting that the reaction can take place in aprotic solvents such as DMSO. In this favorable pathway with six possible transition states located along the potential energy surface, the reaction of the cyanide/benzaldehyde complex with another benzaldehyde to afford an alpha-hydroxy ether is the rate-determining dynamically with the activation free energy barrier of 26.9 kcal/mol, and the step to form cyanohydrin intermediate from alpha-hydroxy ether is partially rate-determining for its relatively significant barrier 20.0 kcal/mol.

Communication: The description of strong correlation within self-consistent Green's function second-order perturbation theory

NASA Astrophysics Data System (ADS)

Phillips, Jordan J.; Zgid, Dominika

2014-06-01

We report an implementation of self-consistent Green's function many-body theory within a second-order approximation (GF2) for application with molecular systems. This is done by iterative solution of the Dyson equation expressed in matrix form in an atomic orbital basis, where the Green's function and self-energy are built on the imaginary frequency and imaginary time domain, respectively, and fast Fourier transform is used to efficiently transform these quantities as needed. We apply this method to several archetypical examples of strong correlation, such as a H32 finite lattice that displays a highly multireference electronic ground state even at equilibrium lattice spacing. In all cases, GF2 gives a physically meaningful description of the metal to insulator transition in these systems, without resorting to spin-symmetry breaking. Our results show that self-consistent Green's function many-body theory offers a viable route to describing strong correlations while remaining within a computationally tractable single-particle formalism.

A fast solver for the Helmholtz equation based on the generalized multiscale finite-element method

NASA Astrophysics Data System (ADS)

Fu, Shubin; Gao, Kai

2017-11-01

Conventional finite-element methods for solving the acoustic-wave Helmholtz equation in highly heterogeneous media usually require finely discretized mesh to represent the medium property variations with sufficient accuracy. Computational costs for solving the Helmholtz equation can therefore be considerably expensive for complicated and large geological models. Based on the generalized multiscale finite-element theory, we develop a novel continuous Galerkin method to solve the Helmholtz equation in acoustic media with spatially variable velocity and mass density. Instead of using conventional polynomial basis functions, we use multiscale basis functions to form the approximation space on the coarse mesh. The multiscale basis functions are obtained from multiplying the eigenfunctions of a carefully designed local spectral problem with an appropriate multiscale partition of unity. These multiscale basis functions can effectively incorporate the characteristics of heterogeneous media's fine-scale variations, thus enable us to obtain accurate solution to the Helmholtz equation without directly solving the large discrete system formed on the fine mesh. Numerical results show that our new solver can significantly reduce the dimension of the discrete Helmholtz equation system, and can also obviously reduce the computational time.

Stress-strain state on non-thin plates and shells. Generalized theory (survey)

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

Nemish, Yu.N.; Khoma, I.Yu.

1994-05-01

In the first part of this survey, we examined exact and approximate analytic solutions of specific problems for thick shells and plates obtained on the basis of three-dimensional equations of the mathematical theory of elasticity. The second part of the survey, presented here, is devoted to systematization and analysis of studies made in regard to a generalized theory of plates and shells based on expansion of the sought functions into Fourier series in Legendre polynomials of the thickness coordinate. Methods are described for constructing systems of differential equations in the coefficients of the expansions (as functions of two independent variablesmore » and time), along with the corresponding boundary and initial conditions. Matters relating to substantiation of the given approach and its generalizations are also discussed.« less

Auxiliary basis sets for density-fitting second-order Møller-Plesset perturbation theory: weighted core-valence correlation consistent basis sets for the 4d elements Y-Pd.

PubMed

Hill, J Grant

2013-09-30

Auxiliary basis sets (ABS) specifically matched to the cc-pwCVnZ-PP and aug-cc-pwCVnZ-PP orbital basis sets (OBS) have been developed and optimized for the 4d elements Y-Pd at the second-order Møller-Plesset perturbation theory level. Calculation of the core-valence electron correlation energies for small to medium sized transition metal complexes demonstrates that the error due to the use of these new sets in density fitting is three to four orders of magnitude smaller than that due to the OBS incompleteness, and hence is considered negligible. Utilizing the ABSs in the resolution-of-the-identity component of explicitly correlated calculations is also investigated, where it is shown that i-type functions are important to produce well-controlled errors in both integrals and correlation energy. Benchmarking at the explicitly correlated coupled cluster with single, double, and perturbative triple excitations level indicates impressive convergence with respect to basis set size for the spectroscopic constants of 4d monofluorides; explicitly correlated double-ζ calculations produce results close to conventional quadruple-ζ, and triple-ζ is within chemical accuracy of the complete basis set limit. Copyright © 2013 Wiley Periodicals, Inc.

Relevance of deterministic chaos theory to studies in functioning of dynamical systems

NASA Astrophysics Data System (ADS)

Glagolev, S. N.; Bukhonova, S. M.; Chikina, E. D.

2018-03-01

The paper considers chaotic behavior of dynamical systems typical for social and economic processes. Approaches to analysis and evaluation of system development processes are studies from the point of view of controllability and determinateness. Explanations are given for necessity to apply non-standard mathematical tools to explain states of dynamical social and economic systems on the basis of fractal theory. Features of fractal structures, such as non-regularity, self-similarity, dimensionality and fractionality are considered.

Configurational forces in electronic structure calculations using Kohn-Sham density functional theory

NASA Astrophysics Data System (ADS)

Motamarri, Phani; Gavini, Vikram

2018-04-01

We derive the expressions for configurational forces in Kohn-Sham density functional theory, which correspond to the generalized variational force computed as the derivative of the Kohn-Sham energy functional with respect to the position of a material point x . These configurational forces that result from the inner variations of the Kohn-Sham energy functional provide a unified framework to compute atomic forces as well as stress tensor for geometry optimization. Importantly, owing to the variational nature of the formulation, these configurational forces inherently account for the Pulay corrections. The formulation presented in this work treats both pseudopotential and all-electron calculations in a single framework, and employs a local variational real-space formulation of Kohn-Sham density functional theory (DFT) expressed in terms of the nonorthogonal wave functions that is amenable to reduced-order scaling techniques. We demonstrate the accuracy and performance of the proposed configurational force approach on benchmark all-electron and pseudopotential calculations conducted using higher-order finite-element discretization. To this end, we examine the rates of convergence of the finite-element discretization in the computed forces and stresses for various materials systems, and, further, verify the accuracy from finite differencing the energy. Wherever applicable, we also compare the forces and stresses with those obtained from Kohn-Sham DFT calculations employing plane-wave basis (pseudopotential calculations) and Gaussian basis (all-electron calculations). Finally, we verify the accuracy of the forces on large materials systems involving a metallic aluminum nanocluster containing 666 atoms and an alkane chain containing 902 atoms, where the Kohn-Sham electronic ground state is computed using a reduced-order scaling subspace projection technique [P. Motamarri and V. Gavini, Phys. Rev. B 90, 115127 (2014), 10.1103/PhysRevB.90.115127].

Site specific interaction between ZnO nanoparticles and tyrosine: A density functional theory study

NASA Astrophysics Data System (ADS)

Singh, Satvinder; Singh, Janpreet; Singh, Baljinder; Singh, Gurinder; Kaura, Aman; Tripathi, S. K.

2018-05-01

First Principles Calculations have been performed on ZnO/Tyrosine atomic complex to study site specific interaction of Tyrosine and ZnO nanoparticles. Calculated results shows that -COOH group present in Tyrosine is energetically more favorable than -NH2 group. Interactions show ionic bonding between ZnO and Tyrosine. All the calculations have been performed under the Density Functional Theory (DFT) framework. Structural and electronic properties of (ZnO)3/Tyrosine complex have been studied. Gaussian basis set approach has been adopted for the calculations. A ring type most stable (ZnO)3 atomic cluster has been modeled, analyzed and used for the calculations.

Gauge fields at finite temperatures—"Thermo field dynamics" and the KMS condition and their extension to gauge theories

NASA Astrophysics Data System (ADS)

Ojima, Izumi

1981-11-01

"Thermo field dynamics," allowing the Feynman diagram method to be applied to real-time causal Green's functions at finite temperatures ( not temperature Green's functions with imaginary times) expressed in the form of "vacuum" expectation values, is reconsidered in light of its connection with the algebraic formulation of statical machanics based upon the KMS condition. On the basis of so-obtained general basic formulae, the formalism is extended to the case of gauge theories, where the subsidiary condition specifying physical states, the notion of observables, and the structure of the physical subspace at finite temperatures are clarified.

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

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

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

2015-08-14

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

Using Density Functional Theory (DFT) for the Calculation of Atomization Energies

NASA Technical Reports Server (NTRS)

Bauschlicher, Charles W., Jr.; Partridge, Harry; Langhoff, Stephen R. (Technical Monitor)

1995-01-01

The calculation of atomization energies using density functional theory (DFT), using the B3LYP hybrid functional, is reported. The sensitivity of the atomization energy to basis set is studied and compared with the coupled cluster singles and doubles approach with a perturbational estimate of the triples (CCSD(T)). Merging the B3LYP results with the G2(MP2) approach is also considered. It is found that replacing the geometry optimization and calculation of the zero-point energy by the analogous quantities computed using the B3LYP approach reduces the maximum error in the G2(MP2) approach. In addition to the 55 G2 atomization energies, some results for transition metal containing systems will also be presented.

[Ionization energies and infrared spectra studies of histidine using density functional theory].

PubMed

Hu, Qiong; Wang, Guo-Ying; Liu, Gang; Ou, Jia-Ming; Wang, Rui-Li

2010-05-01

Histidines provide axial ligands to the primary electron donors in photosynthetic reaction centers (RCs) and play an important role in the protein environments of these donors. In this paper the authors present a systematic study of ionization energies and vibrational properties of histidine using hybrid density functional theory (DFT). All calculations were undertaken by using B3LYP method in combination with four basis sets: 6-31G(d), 6-31G(df, p), 6-31+G(d) and 6-311+G(2d, 2p) with the aim to investigate how the basis sets influence the calculation results. To investigate solvent effects and gain a detailed understanding of marker bands of histidine, the ionization energies of histidine and the vibrational frequencies of histidine which are unlabeled and 13C, 15N, and 2H labeled in the gas phase, CCl4, protein environment, THF and water solution, which span a wide range of dielectric constant, were also calculated. Our results showed that: (1) The main geometry parameters of histidine were impacted by basis sets and mediums, and C2-N3 and N3-C4 bond of imidazole ring of histidine side chain display the maximum bond lengths in the gas phase; (2) single point energies and frequencies calculated were decreased while ionization energies increased with the increasing level of basis sets and diffuse function applied in the same solvent; (3) with the same computational method, the higher the dielectric constant of the solvent used, the lower the ionization energy and vibrational frequency and the higher the intensity obtained. In addition, calculated ionization energy in the gas phase and marker bands of histidine as well as frequency shift upon 13C and 15N labeling at the computationally more expensive 6-311+G(2d, 2p) level are in good agreement with experimental observations available in literatures. All calculations indicated that the results calculated by using higher level basis set with diffuse function were more accurate and closer to the experimental value. In conclusion, the results provide useful information for the further studies of the functional and vibrational properties of chlorophyll-a ligated to histidine residue in photosynthetic reaction center.

FDE-vdW: A van der Waals inclusive subsystem density-functional theory.

PubMed

Kevorkyants, Ruslan; Eshuis, Henk; Pavanello, Michele

2014-07-28

We present a formally exact van der Waals inclusive electronic structure theory, called FDE-vdW, based on the Frozen Density Embedding formulation of subsystem Density-Functional Theory. In subsystem DFT, the energy functional is composed of subsystem additive and non-additive terms. We show that an appropriate definition of the long-range correlation energy is given by the value of the non-additive correlation functional. This functional is evaluated using the fluctuation-dissipation theorem aided by a formally exact decomposition of the response functions into subsystem contributions. FDE-vdW is derived in detail and several approximate schemes are proposed, which lead to practical implementations of the method. We show that FDE-vdW is Casimir-Polder consistent, i.e., it reduces to the generalized Casimir-Polder formula for asymptotic inter-subsystems separations. Pilot calculations of binding energies of 13 weakly bound complexes singled out from the S22 set show a dramatic improvement upon semilocal subsystem DFT, provided that an appropriate exchange functional is employed. The convergence of FDE-vdW with basis set size is discussed, as well as its dependence on the choice of associated density functional approximant.

FDE-vdW: A van der Waals inclusive subsystem density-functional theory

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

Kevorkyants, Ruslan; Pavanello, Michele, E-mail: m.pavanello@rutgers.edu; Eshuis, Henk

2014-07-28

We present a formally exact van der Waals inclusive electronic structure theory, called FDE-vdW, based on the Frozen Density Embedding formulation of subsystem Density-Functional Theory. In subsystem DFT, the energy functional is composed of subsystem additive and non-additive terms. We show that an appropriate definition of the long-range correlation energy is given by the value of the non-additive correlation functional. This functional is evaluated using the fluctuation–dissipation theorem aided by a formally exact decomposition of the response functions into subsystem contributions. FDE-vdW is derived in detail and several approximate schemes are proposed, which lead to practical implementations of the method.more » We show that FDE-vdW is Casimir-Polder consistent, i.e., it reduces to the generalized Casimir-Polder formula for asymptotic inter-subsystems separations. Pilot calculations of binding energies of 13 weakly bound complexes singled out from the S22 set show a dramatic improvement upon semilocal subsystem DFT, provided that an appropriate exchange functional is employed. The convergence of FDE-vdW with basis set size is discussed, as well as its dependence on the choice of associated density functional approximant.« less

Scanning tunneling microscopy image simulation of the rutile (110) TiO2 surface with hybrid functionals and the localized basis set approach

NASA Astrophysics Data System (ADS)

Di Valentin, Cristiana

2007-10-01

In this work we present a simplified procedure to use hybrid functionals and localized atomic basis sets to simulate scanning tunneling microscopy (STM) images of stoichiometric, reduced and hydroxylated rutile (110) TiO2 surface. For the two defective systems it is necessary to introduce some exact Hartree-Fock exchange in the exchange functional in order to correctly describe the details of the electronic structure. Results are compared to the standard density functional theory and planewave basis set approach. Both methods have advantages and drawbacks that are analyzed in detail. In particular, for the localized basis set approach, it is necessary to introduce a number of Gaussian function in the vacuum region above the surface in order to correctly describe the exponential decay of the integrated local density of states from the surface. In the planewave periodic approach, a thick vacuum region is required to achieve correct results. Simulated STM images are obtained for both the reduced and hydroxylated surface which nicely compare with experimental findings. A direct comparison of the two defects as displayed in the simulated STM images indicates that the OH groups should appear brighter than oxygen vacancies in perfect agreement with the experimental STM data.

Theory of nanoscale friction on chemically modified graphene

NASA Astrophysics Data System (ADS)

Ko, Jae-Hyeon; Kim, Yong-Hyun

2013-03-01

Recently, it is known from FFM experiments that friction force on graphene is significantly increased by chemical modification such as hydrogenation, oxidization, and fluorination, whereas adhesion properties are altered marginally. A novel nanotribological theory on two-dimensional materials is proposed on the basis of experimental results and first-principles density-functional theory (DFT) calculations. The proposed theory indicates that the total lateral stiffness that is the proportional constant of friction force is mostly associated with the out-of-plane bending stiffness of two-dimensional materials. This contrasts to the case of three-dimensional materials, in which the shear strength of materials determines nanoscale friction. We will discuss details of DFT calculations and how to generalize the current theory to three dimensional materials.

A comparison of the behavior of functional/basis set combinations for hydrogen-bonding in the water dimer with emphasis on basis set superposition error.

PubMed

Plumley, Joshua A; Dannenberg, J J

2011-06-01

We evaluate the performance of ten functionals (B3LYP, M05, M05-2X, M06, M06-2X, B2PLYP, B2PLYPD, X3LYP, B97D, and MPWB1K) in combination with 16 basis sets ranging in complexity from 6-31G(d) to aug-cc-pV5Z for the calculation of the H-bonded water dimer with the goal of defining which combinations of functionals and basis sets provide a combination of economy and accuracy for H-bonded systems. We have compared the results to the best non-density functional theory (non-DFT) molecular orbital (MO) calculations and to experimental results. Several of the smaller basis sets lead to qualitatively incorrect geometries when optimized on a normal potential energy surface (PES). This problem disappears when the optimization is performed on a counterpoise (CP) corrected PES. The calculated interaction energies (ΔEs) with the largest basis sets vary from -4.42 (B97D) to -5.19 (B2PLYPD) kcal/mol for the different functionals. Small basis sets generally predict stronger interactions than the large ones. We found that, because of error compensation, the smaller basis sets gave the best results (in comparison to experimental and high-level non-DFT MO calculations) when combined with a functional that predicts a weak interaction with the largest basis set. As many applications are complex systems and require economical calculations, we suggest the following functional/basis set combinations in order of increasing complexity and cost: (1) D95(d,p) with B3LYP, B97D, M06, or MPWB1k; (2) 6-311G(d,p) with B3LYP; (3) D95++(d,p) with B3LYP, B97D, or MPWB1K; (4) 6-311++G(d,p) with B3LYP or B97D; and (5) aug-cc-pVDZ with M05-2X, M06-2X, or X3LYP. Copyright © 2011 Wiley Periodicals, Inc.

Free Vibration Study of Anti-Symmetric Angle-Ply Laminated Plates under Clamped Boundary Conditions

NASA Astrophysics Data System (ADS)

Viswanathan, K. K.; Karthik, K.; Sanyasiraju, Y. V. S. S.; Aziz, Z. A.

2016-11-01

Two type of numerical approach namely, Radial Basis Function and Spline approximation, used to analyse the free vibration of anti-symmetric angle-ply laminated plates under clamped boundary conditions. The equations of motion are derived using YNS theory under first order shear deformation. By assuming the solution in separable form, coupled differential equations obtained in term of mid-plane displacement and rotational functions. The coupled differential is then approximated using Spline function and radial basis function to obtain the generalize eigenvalue problem and parametric studies are made to investigate the effect of aspect ratio, length-to-thickness ratio, number of layers, fibre orientation and material properties with respect to the frequency parameter. Some results are compared with the existing literature and other new results are given in tables and graphs.

Hybrid density-functional calculations of phonons in LaCoO3

NASA Astrophysics Data System (ADS)

Gryaznov, Denis; Evarestov, Robert A.; Maier, Joachim

2010-12-01

Phonon frequencies at Γ point in nonmagnetic rhombohedral phase of LaCoO3 were calculated using density-functional theory with hybrid exchange correlation functional PBE0. The calculations involved a comparison of results for two types of basis functions commonly used in ab initio calculations, namely, the plane-wave approach and linear combination of atomic orbitals, as implemented in VASP and CRYSTAL computer codes, respectively. A good qualitative, but also within an error margin of less than 30%, a quantitative agreement was observed not only between the two formalisms but also between theoretical and experimental phonon frequency predictions. Moreover, the correlation between the phonon symmetries in cubic and rhombohedral phases is discussed in detail on the basis of group-theoretical analysis. It is concluded that the hybrid PBE0 functional is able to predict correctly the phonon properties in LaCoO3 .

Time-dependent mean-field theory for x-ray near-edge spectroscopy

NASA Astrophysics Data System (ADS)

Bertsch, G. F.; Lee, A. J.

2014-02-01

We derive equations of motion for calculating the near-edge x-ray absorption spectrum in molecules and condensed matter, based on a two-determinant approximation and Dirac's variational principle. The theory provides an exact solution for the linear response when the Hamiltonian or energy functional has only diagonal interactions in some basis. We numerically solve the equations to compare with the Mahan-Nozières-De Dominicis theory of the edge singularity in metallic conductors. Our extracted power-law exponents are similar to those of the analytic theory, but are not in quantitative agreement. The calculational method can be readily generalized to treat Kohn-Sham Hamiltonians with electron-electron interactions derived from correlation-exchange potentials.

Ab Initio Theoretical Studies on the Kinetics of Hydrogen Abstraction Type Reactions of Hydroxyl Radicals with CH3CCl2F and CH3CClF2

NASA Astrophysics Data System (ADS)

Saheb, Vahid; Maleki, Samira

2018-03-01

The hydrogen abstraction reactions from CH3Cl2F (R-141b) and CH3CClF2 (R-142b) by OH radicals are studied theoretically by semi-classical transition state theory. The stationary points for the reactions are located by using KMLYP density functional method along with 6-311++G(2 d,2 p) basis set and MP2 method along with 6-311+G( d, p) basis set. Single-point energy calculations are performed by the CBS-Q and G4 combination methods on the geometries optimized at the KMLYP/6-311++G(2 d,2 p) level of theory. Vibrational anharmonicity coefficients, x ij , which are needed for semi-classical transition state theory calculations, are computed at the KMLYP/6-311++G(2 d,2 p) and MP2/6-311+G( d, p) levels of theory. The computed barrier heights are slightly sensitive to the quantum-chemical method. Thermal rate coefficients are computed over the temperature range from 200 to 2000 K and they are shown to be in accordance with available experimental data. On the basis of the computed rate coefficients, the tropospheric lifetime of the CH3CCl2F and CH3CClF2 are estimated to be about 6.5 and 12.0 years, respectively.

Vibrational spectroscopy investigation and density functional theory calculations on (E)-N‧-(4-methoxybenzylidene) benzohydrazide

NASA Astrophysics Data System (ADS)

Saleem, H.; Subashchandrabose, S.; Ramesh Babu, N.; Syed Ali Padusha, M.

2015-05-01

The FT-IR, FT-Raman and UV-Vis spectra of the Schiff base compound (E)-N‧-(4-methoxybenzylidene) benzohydrazide (MBBH) have been recorded and analyzed. The optimized geometrical parameters were calculated. The complete vibrational assignments were performed on the basis of TED of the vibrational modes, calculated with the help of SQM method. NBO analysis has been carried out to explore the hyperconjugative interactions and their second order stabilization energy within the molecule. The molecular orbitals (MO's) and its energy gap were studied. The first order hyperpolarizability (β0) and related properties (β, α0, Δα) of MBBH are also calculated. All theoretical calculations were performed on the basis of B3LYP/6-311++G(d,p) level of theory.

Group-theoretical analysis of two-dimensional hexagonal materials

NASA Astrophysics Data System (ADS)

Minami, Susumu; Sugita, Itaru; Tomita, Ryosuke; Oshima, Hiroyuki; Saito, Mineo

2017-10-01

Two-dimensional hexagonal materials such as graphene and silicene have highly symmetric crystal structures and Dirac cones at the K point, which induce novel electronic properties. In this report, we calculate their electronic structures by using density functional theory and analyze their band structures on the basis of the group theory. Dirac cones frequently appear when the symmetry at the K point is high; thus, two-dimensional irreducible representations are included. We discuss the relationship between symmetry and the appearance of the Dirac cone.

Chromosome territory relocation paradigm during DNA damage response: Some insights from molecular biology to physics.

PubMed

Fatakia, Sarosh N; Kulashreshtha, Mugdha; Mehta, Ishita S; Rao, Basuthkar J

2017-09-03

Among the many facets of DNA damage response (DDR), relocation of chromosome territories (CTs) is most intriguing. We have previously reported that cisplatin induced DDR in human dermal fibroblasts led to relocation of CTs 12, 15 from the nuclear periphery to its interior while CTs 19, 17 repositioned from the interior to its periphery. Studies of CT relocation remain nascent as we begin unraveling the role of key players in DDR to demonstrate its mechanistic basis. Consolidating our recent reports, we argue that γH2AX-signaling leads to enhanced recruitment of nuclear myosin 1 (NM1) to chromatin, which via its motor function, results in CT repositioning. Next, we invoke a novel systems-level theory that subsumed CTs as pairs, not solo entities, to present the physical basis for plasticity in interphase CT arrangement. Subsequently, we posited that our systems-level theory describes a unified physical basis for non-random positioning of CTs in interphase nuclei across disparate eukaryotes.

Linguistic Effects on the Neural Basis of Theory of Mind

PubMed Central

Frank, C. Kobayashi

2010-01-01

“Theory of mind” (ToM) has been described as the ability to attribute and understand other people’s desires and intentions as distinct from one’s own. There has been a debate about the extent to which language influences ToM development. Although very few studies directly examined linguistic influence on the neural basis of ToM, results from these studies indicate at least moderate influence of language on ToM. In this review both behavioral and neurological studies that examined the relationship between language and ToM are selectively discussed. This review focuses on cross-linguistic / cultural studies (especially Japanese vs. American / English) since my colleagues and I found evidence of significant linguistic influence on the neural basis of ToM through a series of functional brain imaging experiments. Evidence from both behavioral and neurological studies of ToM (including ours) suggests that the pragmatic (not the constitutive) aspects of language influence ToM understanding more significantly. PMID:21113278

Conceptual influences on category-based induction

PubMed Central

Gelman, Susan A.; Davidson, Natalie S.

2013-01-01

One important function of categories is to permit rich inductive inferences. Prior work shows that children use category labels to guide their inductive inferences. However, there are competing theories to explain this phenomenon, differing in the roles attributed to conceptual information versus perceptual similarity. Seven experiments with 4- to 5-year-old children and adults (N = 344) test these theories by teaching categories for which category membership and perceptual similarity are in conflict, and varying the conceptual basis of the novel categories. Results indicate that for non-natural kind categories that have little conceptual coherence, children make inferences based on perceptual similarity, whereas adults make inferences based on category membership. In contrast, for basic- and ontological-level categories that have a principled conceptual basis, children and adults alike make use of category membership more than perceptual similarity as the basis of their inferences. These findings provide evidence in favor of the role of conceptual information in preschoolers’ inferences, and further demonstrate that labeled categories are not all equivalent; they differ in their inductive potential. PMID:23517863

How to Generate Chaos at Home.

ERIC Educational Resources Information Center

Smith, Douglas

1992-01-01

Describes an electronic circuit that can function as a prototype for chaotic systems. Specific applied voltages produce chaotic signals that can be viewed with an oscilloscope or be made audible with a home stereo system. Provides directions for assembly with typical costs, mathematical basis of chaos theory, and experimental extensions. (JJK)

Calculation of electrostatic fields in periodic structures of complex shape

NASA Technical Reports Server (NTRS)

Kravchenko, V. F.

1978-01-01

A universal algorithm is presented for calculating electrostatic fields in an infinite periodic structure consisting of electrodes of arbitrary shape which are located in mirror-symmetrical manner along the axis of electron-beam propagation. The method is based on the theory of R-functions, and the differential operators which are derived on the basis of the functions. Numerical results are presented and the accuracy of the results is examined.

Ammonia-water cation and ammonia dimer cation.

PubMed

Kim, Hahn; Lee, Han Myoung

2009-06-25

We have investigated the structure, interaction energy, electronic properties, and IR spectra of the ammonia-water cation (NH(3)H(2)O)(+) using density functional theory (DFT) and high-level ab initio theory. The ammonia-water cation has three minimum-energy structures of (a) H(2)NH(+)...OH(2), (b) H(3)N(+)...OH(2), and (c) H(3)NH(+)...OH. The lowest-energy structure is (a), followed by (c) and (b). The ammonia dimer cation has two minimum-energy structures [the lowest H(3)NH(+)...NH(2) structure and the second lowest (H(3)N...NH(3))(+) structure]. The minimum transition barrier for the interconversion between (a), (b), and (c) is approximately 6 kcal/mol. Most DFT calculations with various functionals, except a few cases, overstabilize the N...O and N...N binding, predicting different structures from Moller-Plesset second-order perturbation (MP2) theory and the most reliable complete basis set (CBS) limit of coupled cluster theory with single, double, and perturbative triple excitations [CCSD(T)]. Thus, the validity test of the DFT functionals for these ionized molecular systems would be of importance.

A comparative study of DFT calculated and experimental UV/Visible spectra for thirty carboline and carbazole based compounds

NASA Astrophysics Data System (ADS)

Zara, Zeenat; Iqbal, Javed; Ayub, Khurshid; Irfan, Muhammad; Mahmood, Athar; Khera, Rasheed Ahmad; Eliasson, Bertil

2017-12-01

A comparative study of UV/Visible spectra of carboline and carbazole derivatives was conducted by employing the Density Functional Theory (DFT) approach. In this study, the geometries of ground and excited states, excitation energy and absorption spectra were estimated by using seven different DFT functional; CAM-B3LYP, B3LYP, MPW1PW91, PBE, B3PW91, WB97XD and HSE06 with 6-31G basis set. Moreover, five different basis sets 3-21G, 6-31G, DGDZVP, DGTZVP and SDD were also investigated with the CAM-B3LYP and WB97XD functional to take out the best combination of functional and basis set. CAM-B3LYP/6-31G and WB97XD/DGDZVP combination were found to have closest agreement with the experimental values of β-carboline derivatives and carbazole derivatives, respectively. This study provided an insight about the electronic characteristics of the selected compounds and provided an effective tool for developing and designing the better UV absorber compounds.

Adaptive critic autopilot design of bank-to-turn missiles using fuzzy basis function networks.

PubMed

Lin, Chuan-Kai

2005-04-01

A new adaptive critic autopilot design for bank-to-turn missiles is presented. In this paper, the architecture of adaptive critic learning scheme contains a fuzzy-basis-function-network based associative search element (ASE), which is employed to approximate nonlinear and complex functions of bank-to-turn missiles, and an adaptive critic element (ACE) generating the reinforcement signal to tune the associative search element. In the design of the adaptive critic autopilot, the control law receives signals from a fixed gain controller, an ASE and an adaptive robust element, which can eliminate approximation errors and disturbances. Traditional adaptive critic reinforcement learning is the problem faced by an agent that must learn behavior through trial-and-error interactions with a dynamic environment, however, the proposed tuning algorithm can significantly shorten the learning time by online tuning all parameters of fuzzy basis functions and weights of ASE and ACE. Moreover, the weight updating law derived from the Lyapunov stability theory is capable of guaranteeing both tracking performance and stability. Computer simulation results confirm the effectiveness of the proposed adaptive critic autopilot.

A Solution to the Fundamental Linear Fractional Order Differential Equation

NASA Technical Reports Server (NTRS)

Hartley, Tom T.; Lorenzo, Carl F.

1998-01-01

This paper provides a solution to the fundamental linear fractional order differential equation, namely, (sub c)d(sup q, sub t) + ax(t) = bu(t). The impulse response solution is shown to be a series, named the F-function, which generalizes the normal exponential function. The F-function provides the basis for a qth order "fractional pole". Complex plane behavior is elucidated and a simple example, the inductor terminated semi- infinite lossy line, is used to demonstrate the theory.

Invariant operators, orthogonal bases and correlators in general tensor models

NASA Astrophysics Data System (ADS)

Diaz, Pablo; Rey, Soo-Jong

2018-07-01

We study invariant operators in general tensor models. We show that representation theory provides an efficient framework to count and classify invariants in tensor models of (gauge) symmetry Gd = U (N1) ⊗ ⋯ ⊗ U (Nd). As a continuation and completion of our earlier work, we present two natural ways of counting invariants, one for arbitrary Gd and another valid for large rank of Gd. We construct bases of invariant operators based on the counting, and compute correlators of their elements. The basis associated with finite rank of Gd diagonalizes the two-point function of the free theory. It is analogous to the restricted Schur basis used in matrix models. We show that the constructions get almost identical as we swap the Littlewood-Richardson numbers in multi-matrix models with Kronecker coefficients in general tensor models. We explore the parallelism between matrix model and tensor model in depth from the perspective of representation theory and comment on several ideas for future investigation.

Exponentially accurate approximations to piece-wise smooth periodic functions

NASA Technical Reports Server (NTRS)

Greer, James; Banerjee, Saheb

1995-01-01

A family of simple, periodic basis functions with 'built-in' discontinuities are introduced, and their properties are analyzed and discussed. Some of their potential usefulness is illustrated in conjunction with the Fourier series representations of functions with discontinuities. In particular, it is demonstrated how they can be used to construct a sequence of approximations which converges exponentially in the maximum norm to a piece-wise smooth function. The theory is illustrated with several examples and the results are discussed in the context of other sequences of functions which can be used to approximate discontinuous functions.

Determination of a response function of a thermocouple using a short acoustic pulse.

PubMed

Tashiro, Yusuke; Biwa, Tetsushi; Yazaki, Taichi

2007-04-01

This paper reports on an experimental technique to determine a response function of a thermocouple using a short acoustic pulse wave. A pulse of 10 ms is generated in a tube filled with 1 bar helium gas. The temperature is measured using the thermocouple. The reference temperature is deduced from the measured pressure on the basis of a laminar oscillating flow theory. The response function of the thermocouple is obtained as a function of frequency below 50 Hz through a comparison between the measured and reference temperatures.

Heavy and Heavy-Light Mesons in the Covariant Spectator Theory

NASA Astrophysics Data System (ADS)

Stadler, Alfred; Leitão, Sofia; Peña, M. T.; Biernat, Elmar P.

2018-05-01

The masses and vertex functions of heavy and heavy-light mesons, described as quark-antiquark bound states, are calculated with the Covariant Spectator Theory (CST). We use a kernel with an adjustable mixture of Lorentz scalar, pseudoscalar, and vector linear confining interaction, together with a one-gluon-exchange kernel. A series of fits to the heavy and heavy-light meson spectrum were calculated, and we discuss what conclusions can be drawn from it, especially about the Lorentz structure of the kernel. We also apply the Brodsky-Huang-Lepage prescription to express the CST wave functions for heavy quarkonia in terms of light-front variables. They agree remarkably well with light-front wave functions obtained in the Hamiltonian basis light-front quantization approach, even in excited states.

Predicting vapor liquid equilibria using density functional theory: A case study of argon

NASA Astrophysics Data System (ADS)

Goel, Himanshu; Ling, Sanliang; Ellis, Breanna Nicole; Taconi, Anna; Slater, Ben; Rai, Neeraj

2018-06-01

Predicting vapor liquid equilibria (VLE) of molecules governed by weak van der Waals (vdW) interactions using the first principles approach is a significant challenge. Due to the poor scaling of the post Hartree-Fock wave function theory with system size/basis functions, the Kohn-Sham density functional theory (DFT) is preferred for systems with a large number of molecules. However, traditional DFT cannot adequately account for medium to long range correlations which are necessary for modeling vdW interactions. Recent developments in DFT such as dispersion corrected models and nonlocal van der Waals functionals have attempted to address this weakness with a varying degree of success. In this work, we predict the VLE of argon and assess the performance of several density functionals and the second order Møller-Plesset perturbation theory (MP2) by determining critical and structural properties via first principles Monte Carlo simulations. PBE-D3, BLYP-D3, and rVV10 functionals were used to compute vapor liquid coexistence curves, while PBE0-D3, M06-2X-D3, and MP2 were used for computing liquid density at a single state point. The performance of the PBE-D3 functional for VLE is superior to other functionals (BLYP-D3 and rVV10). At T = 85 K and P = 1 bar, MP2 performs well for the density and structural features of the first solvation shell in the liquid phase.

Nonperturbative light-front Hamiltonian methods

NASA Astrophysics Data System (ADS)

Hiller, J. R.

2016-09-01

We examine the current state-of-the-art in nonperturbative calculations done with Hamiltonians constructed in light-front quantization of various field theories. The language of light-front quantization is introduced, and important (numerical) techniques, such as Pauli-Villars regularization, discrete light-cone quantization, basis light-front quantization, the light-front coupled-cluster method, the renormalization group procedure for effective particles, sector-dependent renormalization, and the Lanczos diagonalization method, are surveyed. Specific applications are discussed for quenched scalar Yukawa theory, ϕ4 theory, ordinary Yukawa theory, supersymmetric Yang-Mills theory, quantum electrodynamics, and quantum chromodynamics. The content should serve as an introduction to these methods for anyone interested in doing such calculations and as a rallying point for those who wish to solve quantum chromodynamics in terms of wave functions rather than random samplings of Euclidean field configurations.

A new calibration of the semi-empirical photometric theory for Halley and other comets

NASA Technical Reports Server (NTRS)

Newburn, R. L., Jr.

1984-01-01

The semiempirical photometric theory of gas and dust production in comets (Newburn, 1979, 1981, and 1982) is recalibrated on the basis of the 17-comet compilation of spectrophotometric data of Newburn and Spinrad (1984). The results are presented in graphs and tables, and it is shown that no corrections are required for the constant R and the function delta, but that the mixing ratios (obtained as functions of heliocentric distance) can be improved, with implications for the visual-photometric comet model. Recently calculated light curves for comet Halley are compared, and the use of the nearly identical curves of Bortle and Morris (1984) and Marcus (1983) is recommended.

A density functional theory study of self-regenerating catalysts LaFe(1-x)M(x)O(3-y) (M = Pd, Rh, Pt).

PubMed

Hamada, Ikutaro; Uozumi, Akifumi; Morikawa, Yoshitada; Yanase, Akira; Katayama-Yoshida, Hiroshi

2011-11-23

Periodic density functional theory was used to investigate the stability and electronic structures of precious-metal atoms in the vicinity of LaFe(1-x)M(x)O(3) (M = Pd, Rh, Pt) perovskite catalyst surfaces. It was found that the surface segregation of Pd and Pt is significantly stabilized by the introduction of O vacancies, whereas the solid-solution phase is favorable for Rh, suggesting an important role of O vacancies in the self-regeneration of Pd and Pt. On the basis of the results, we propose a possible scenario for the self-regeneration of the precious metal in the perovskite catalyst.

Operator bases, S-matrices, and their partition functions

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

Henning, Brian; Lu, Xiaochuan; Melia, Tom

Relativistic quantum systems that admit scattering experiments are quantitatively described by effective field theories, where S-matrix kinematics and symmetry considerations are encoded in the operator spectrum of the EFT. Here in this paper we use the S-matrix to derive the structure of the EFT operator basis, providing complementary descriptions in (i) position space utilizing the conformal algebra and cohomology and (ii) momentum space via an algebraic formulation in terms of a ring of momenta with kinematics implemented as an ideal. These frameworks systematically handle redundancies associated with equations of motion (on-shell) and integration by parts (momentum conservation). We introduce amore » partition function, termed the Hilbert series, to enumerate the operator basis — correspondingly, the S-matrix — and derive a matrix integral expression to compute the Hilbert series. The expression is general, easily applied in any spacetime dimension, with arbitrary field content and (linearly realized) symmetries. In addition to counting, we discuss construction of the basis. Simple algorithms follow from the algebraic formulation in momentum space. We explicitly compute the basis for operators involving up to n = 5 scalar fields. This construction universally applies to fields with spin, since the operator basis for scalars encodes the momentum dependence of n-point amplitudes. We discuss in detail the operator basis for non-linearly realized symmetries. In the presence of massless particles, there is freedom to impose additional structure on the S- matrix in the form of soft limits. The most naÏve implementation for massless scalars leads to the operator basis for pions, which we confirm using the standard CCWZ formulation for non-linear realizations. Finally, although primarily discussed in the language of EFT, some of our results — conceptual and quantitative — may be of broader use in studying conformal field theories as well as the AdS/CFT correspondence.« less

Operator bases, S-matrices, and their partition functions

DOE PAGES

Henning, Brian; Lu, Xiaochuan; Melia, Tom; ...

2017-10-27

Relativistic quantum systems that admit scattering experiments are quantitatively described by effective field theories, where S-matrix kinematics and symmetry considerations are encoded in the operator spectrum of the EFT. Here in this paper we use the S-matrix to derive the structure of the EFT operator basis, providing complementary descriptions in (i) position space utilizing the conformal algebra and cohomology and (ii) momentum space via an algebraic formulation in terms of a ring of momenta with kinematics implemented as an ideal. These frameworks systematically handle redundancies associated with equations of motion (on-shell) and integration by parts (momentum conservation). We introduce amore » partition function, termed the Hilbert series, to enumerate the operator basis — correspondingly, the S-matrix — and derive a matrix integral expression to compute the Hilbert series. The expression is general, easily applied in any spacetime dimension, with arbitrary field content and (linearly realized) symmetries. In addition to counting, we discuss construction of the basis. Simple algorithms follow from the algebraic formulation in momentum space. We explicitly compute the basis for operators involving up to n = 5 scalar fields. This construction universally applies to fields with spin, since the operator basis for scalars encodes the momentum dependence of n-point amplitudes. We discuss in detail the operator basis for non-linearly realized symmetries. In the presence of massless particles, there is freedom to impose additional structure on the S- matrix in the form of soft limits. The most naÏve implementation for massless scalars leads to the operator basis for pions, which we confirm using the standard CCWZ formulation for non-linear realizations. Finally, although primarily discussed in the language of EFT, some of our results — conceptual and quantitative — may be of broader use in studying conformal field theories as well as the AdS/CFT correspondence.« less

Conceptual DFT: the chemical relevance of higher response functions.

PubMed

Geerlings, P; De Proft, F

2008-06-07

In recent years conceptual density functional theory offered a perspective for the interpretation/prediction of experimental/theoretical reactivity data on the basis of a series of response functions to perturbations in the number of electrons and/or external potential. This approach has enabled the sharp definition and computation, from first principles, of a series of well-known but sometimes vaguely defined chemical concepts such as electronegativity and hardness. In this contribution, a short overview of the shortcomings of the simplest, first order response functions is illustrated leading to a description of chemical bonding in a covalent interaction in terms of interacting atoms or groups, governed by electrostatics with the tendency to polarize bonds on the basis of electronegativity differences. The second order approach, well known until now, introduces the hardness/softness and Fukui function concepts related to polarizability and frontier MO theory, respectively. The introduction of polarizability/softness is also considered in a historical perspective in which polarizability was, with some exceptions, mainly put forward in non covalent interactions. A particular series of response functions, arising when the changes in the external potential are solely provoked by changes in nuclear configurations (the "R-analogues") are also systematically considered. The main part of the contribution is devoted to third order response functions which, at first sight, may be expected not to yield chemically significant information, as turns out to be for the hyperhardness. A counterexample is the dual descriptor and its R analogue, the initial hardness response, which turns out to yield a firm basis to regain the Woodward-Hoffmann rules for pericyclic reactions based on a density-only basis, i.e. without involving the phase, sign, symmetry of the wavefunction. Even the second order nonlinear response functions are shown possibly to bear interesting information, e.g. on the local and global polarizability. Its derivatives may govern the influence of charge on the polarizability, the R-analogues being the nuclear Fukui function and the quadratic and cubic force constants. Although some of the higher order derivatives may be difficult to evaluate a comparison with the energy expansion used in spectroscopy in terms of nuclear displacements, nuclear magnetic moments, electric and magnetic fields leads to the conjecture that, certainly cross terms may contain new, intricate information for understanding chemical reactivity.

Performance of NACA Eight-Stage Axial-Flow Compressor Designed on the Basis of Airfoil Theory

DTIC Science & Technology

1944-08-01

TEE BASIS OF AIRFOIL THEORY By John T. Slnnette, Jr., Oscar W. Schey, and J. Austin King Aircraft Engine Research Laboratory Cleveland, Ohio FILE...efficiency can he designed by the proper application of airfoil theory. Aircraft Engine Research laboratory, Hational Advisory Committee for Aeronautlos...Basis of Airfoil Theory AUTHORS): Sinnette, John T.; Schey, Oscar W.; and others ORIGINATING AGENCY: Aircraft Engine Research Laboratory, Cleveland

A high-order multiscale finite-element method for time-domain acoustic-wave modeling

NASA Astrophysics Data System (ADS)

Gao, Kai; Fu, Shubin; Chung, Eric T.

2018-05-01

Accurate and efficient wave equation modeling is vital for many applications in such as acoustics, electromagnetics, and seismology. However, solving the wave equation in large-scale and highly heterogeneous models is usually computationally expensive because the computational cost is directly proportional to the number of grids in the model. We develop a novel high-order multiscale finite-element method to reduce the computational cost of time-domain acoustic-wave equation numerical modeling by solving the wave equation on a coarse mesh based on the multiscale finite-element theory. In contrast to existing multiscale finite-element methods that use only first-order multiscale basis functions, our new method constructs high-order multiscale basis functions from local elliptic problems which are closely related to the Gauss-Lobatto-Legendre quadrature points in a coarse element. Essentially, these basis functions are not only determined by the order of Legendre polynomials, but also by local medium properties, and therefore can effectively convey the fine-scale information to the coarse-scale solution with high-order accuracy. Numerical tests show that our method can significantly reduce the computation time while maintain high accuracy for wave equation modeling in highly heterogeneous media by solving the corresponding discrete system only on the coarse mesh with the new high-order multiscale basis functions.

A high-order multiscale finite-element method for time-domain acoustic-wave modeling

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

Gao, Kai; Fu, Shubin; Chung, Eric T.

Accurate and efficient wave equation modeling is vital for many applications in such as acoustics, electromagnetics, and seismology. However, solving the wave equation in large-scale and highly heterogeneous models is usually computationally expensive because the computational cost is directly proportional to the number of grids in the model. We develop a novel high-order multiscale finite-element method to reduce the computational cost of time-domain acoustic-wave equation numerical modeling by solving the wave equation on a coarse mesh based on the multiscale finite-element theory. In contrast to existing multiscale finite-element methods that use only first-order multiscale basis functions, our new method constructsmore » high-order multiscale basis functions from local elliptic problems which are closely related to the Gauss–Lobatto–Legendre quadrature points in a coarse element. Essentially, these basis functions are not only determined by the order of Legendre polynomials, but also by local medium properties, and therefore can effectively convey the fine-scale information to the coarse-scale solution with high-order accuracy. Numerical tests show that our method can significantly reduce the computation time while maintain high accuracy for wave equation modeling in highly heterogeneous media by solving the corresponding discrete system only on the coarse mesh with the new high-order multiscale basis functions.« less

A high-order multiscale finite-element method for time-domain acoustic-wave modeling

DOE PAGES

Gao, Kai; Fu, Shubin; Chung, Eric T.

2018-02-04

Accurate and efficient wave equation modeling is vital for many applications in such as acoustics, electromagnetics, and seismology. However, solving the wave equation in large-scale and highly heterogeneous models is usually computationally expensive because the computational cost is directly proportional to the number of grids in the model. We develop a novel high-order multiscale finite-element method to reduce the computational cost of time-domain acoustic-wave equation numerical modeling by solving the wave equation on a coarse mesh based on the multiscale finite-element theory. In contrast to existing multiscale finite-element methods that use only first-order multiscale basis functions, our new method constructsmore » high-order multiscale basis functions from local elliptic problems which are closely related to the Gauss–Lobatto–Legendre quadrature points in a coarse element. Essentially, these basis functions are not only determined by the order of Legendre polynomials, but also by local medium properties, and therefore can effectively convey the fine-scale information to the coarse-scale solution with high-order accuracy. Numerical tests show that our method can significantly reduce the computation time while maintain high accuracy for wave equation modeling in highly heterogeneous media by solving the corresponding discrete system only on the coarse mesh with the new high-order multiscale basis functions.« less

Basis set limit and systematic errors in local-orbital based all-electron DFT

NASA Astrophysics Data System (ADS)

Blum, Volker; Behler, Jörg; Gehrke, Ralf; Reuter, Karsten; Scheffler, Matthias

2006-03-01

With the advent of efficient integration schemes,^1,2 numeric atom-centered orbitals (NAO's) are an attractive basis choice in practical density functional theory (DFT) calculations of nanostructured systems (surfaces, clusters, molecules). Though all-electron, the efficiency of practical implementations promises to be on par with the best plane-wave pseudopotential codes, while having a noticeably higher accuracy if required: Minimal-sized effective tight-binding like calculations and chemically accurate all-electron calculations are both possible within the same framework; non-periodic and periodic systems can be treated on equal footing; and the localized nature of the basis allows in principle for O(N)-like scaling. However, converging an observable with respect to the basis set is less straightforward than with competing systematic basis choices (e.g., plane waves). We here investigate the basis set limit of optimized NAO basis sets in all-electron calculations, using as examples small molecules and clusters (N2, Cu2, Cu4, Cu10). meV-level total energy convergence is possible using <=50 basis functions per atom in all cases. We also find a clear correlation between the errors which arise from underconverged basis sets, and the system geometry (interatomic distance). ^1 B. Delley, J. Chem. Phys. 92, 508 (1990), ^2 J.M. Soler et al., J. Phys.: Condens. Matter 14, 2745 (2002).

A first-principles examination of the asymmetric induction model in the binap/Rh(I)-catalysed 1,4-addition of phenylboronic acid to cyclic enones by density functional theory calculations.

PubMed

Qin, Hua-Li; Chen, Xiao-Qing; Huang, Yi-Zhen; Kantchev, Eric Assen B

2014-09-26

First-principles modelling of the diastereomeric transition states in the enantiodiscrimination stage of the catalytic cycle can reveal intimate details about the mechanism of enantioselection. This information can be invaluable for further improvement of the catalytic protocols by rational design. Herein, we present a density functional theory (IEFPCM/PBE0/DGDZVP level of theory) modelling of the carborhodation step for the asymmetric 1,4-arylation of cyclic α,β-unsaturated ketones mediated by a [(binap)Rh(I)] catalyst. The calculations completely support the older, qualitative, pictorial model predicting the sense of the asymmetric induction for both the chelating diphosphane (binap) and the more recent chiral diene (Phbod) ligands, while also permitting quantification of the enantiomeric excess (ee). The effect of dispersion interaction correction and basis sets has been also investigated. Dispersion-corrected functionals and solvation models significantly improve the predicted ee values. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A density functional theory study of the magnetic exchange coupling in dinuclear manganese(II) inverse crown structures.

PubMed

Vélez, Ederley; Alberola, Antonio; Polo, Víctor

2009-12-17

The magnetic exchange coupling constants between two Mn(II) centers for a set of five inverse crown structures have been investigated by means of a methodology based on broken-symmetry unrestricted density functional theory. These novel and highly unstable compounds present superexchange interactions between two Mn centers, each one with S = 5/2 through anionic "guests" such as oxygen, benzene, or hydrides or through the cationic ring formed by amide ligands and alkali metals (Na, Li). Magnetic exchange couplings calculated at B3LYP/6-31G(d,p) level yield strong antiferromagnetic couplings for compounds linked via an oxygen atom or hydride and very small antiferromagnetic couplings for those linked via a benzene molecule, deprotonated in either 1,4- or 1,3- positions. Analysis of the magnetic orbitals and spin polarization maps provide an understanding of the exchange mechanism between the Mn centers. The dependence of J with respect to 10 different density functional theory potentials employed and the basis set has been analyzed.

Beyond statistical inference: A decision theory for science

PubMed Central

KILLEEN, PETER R.

2008-01-01

Traditional null hypothesis significance testing does not yield the probability of the null or its alternative and, therefore, cannot logically ground scientific decisions. The decision theory proposed here calculates the expected utility of an effect on the basis of (1) the probability of replicating it and (2) a utility function on its size. It takes significance tests—which place all value on the replicability of an effect and none on its magnitude—as a special case, one in which the cost of a false positive is revealed to be an order of magnitude greater than the value of a true positive. More realistic utility functions credit both replicability and effect size, integrating them for a single index of merit. The analysis incorporates opportunity cost and is consistent with alternate measures of effect size, such as r2 and information transmission, and with Bayesian model selection criteria. An alternate formulation is functionally equivalent to the formal theory, transparent, and easy to compute. PMID:17201351

Beyond statistical inference: a decision theory for science.

PubMed

Killeen, Peter R

2006-08-01

Traditional null hypothesis significance testing does not yield the probability of the null or its alternative and, therefore, cannot logically ground scientific decisions. The decision theory proposed here calculates the expected utility of an effect on the basis of (1) the probability of replicating it and (2) a utility function on its size. It takes significance tests--which place all value on the replicability of an effect and none on its magnitude--as a special case, one in which the cost of a false positive is revealed to be an order of magnitude greater than the value of a true positive. More realistic utility functions credit both replicability and effect size, integrating them for a single index of merit. The analysis incorporates opportunity cost and is consistent with alternate measures of effect size, such as r2 and information transmission, and with Bayesian model selection criteria. An alternate formulation is functionally equivalent to the formal theory, transparent, and easy to compute.

A new class of methods for functional connectivity estimation

NASA Astrophysics Data System (ADS)

Lin, Wutu

Measuring functional connectivity from neural recordings is important in understanding processing in cortical networks. The covariance-based methods are the current golden standard for functional connectivity estimation. However, the link between the pair-wise correlations and the physiological connections inside the neural network is unclear. Therefore, the power of inferring physiological basis from functional connectivity estimation is limited. To build a stronger tie and better understand the relationship between functional connectivity and physiological neural network, we need (1) a realistic model to simulate different types of neural recordings with known ground truth for benchmarking; (2) a new functional connectivity method that produce estimations closely reflecting the physiological basis. In this thesis, (1) I tune a spiking neural network model to match with human sleep EEG data, (2) introduce a new class of methods for estimating connectivity from different kinds of neural signals and provide theory proof for its superiority, (3) apply it to simulated fMRI data as an application.

The application of trigonal curve to the Mikhailov-Shabat-Sokolov flows

NASA Astrophysics Data System (ADS)

He, Guoliang; Geng, Xianguo; Wu, Lihua

2016-08-01

Resorting to the characteristic polynomial of Lax matrix for the Mikhailov-Shabat-Sokolov hierarchy associated with a {3 × 3} matrix spectral problem, we introduce a trigonal curve, from which we deduce the associated Baker-Akhiezer function, meromorphic functions and Dubrovin-type equations. The straightening out of the Mikhailov-Shabat-Sokolov flows is exactly given through the Abel map. On the basis of these results and the theory of trigonal curve, we obtain the explicit theta function representations of the Baker-Akhiezer function, the meromorphic functions, and in particular, that of solutions for the entire Mikhailov-Shabat-Sokolov hierarchy.

Modeling L2,3-Edge X-ray Absorption Spectroscopy with Real-Time Exact Two-Component Relativistic Time-Dependent Density Functional Theory.

PubMed

Kasper, Joseph M; Lestrange, Patrick J; Stetina, Torin F; Li, Xiaosong

2018-04-10

X-ray absorption spectroscopy is a powerful technique to probe local electronic and nuclear structure. There has been extensive theoretical work modeling K-edge spectra from first principles. However, modeling L-edge spectra directly with density functional theory poses a unique challenge requiring further study. Spin-orbit coupling must be included in the model, and a noncollinear density functional theory is required. Using the real-time exact two-component method, we are able to variationally include one-electron spin-orbit coupling terms when calculating the absorption spectrum. The abilities of different basis sets and density functionals to model spectra for both closed- and open-shell systems are investigated using SiCl 4 and three transition metal complexes, TiCl 4 , CrO 2 Cl 2 , and [FeCl 6 ] 3- . Although we are working in the real-time framework, individual molecular orbital transitions can still be recovered by projecting the density onto the ground state molecular orbital space and separating contributions to the time evolving dipole moment.

Orientation-dependent integral equation theory for a two-dimensional model of water

NASA Astrophysics Data System (ADS)

Urbič, T.; Vlachy, V.; Kalyuzhnyi, Yu. V.; Dill, K. A.

2003-03-01

We develop an integral equation theory that applies to strongly associating orientation-dependent liquids, such as water. In an earlier treatment, we developed a Wertheim integral equation theory (IET) that we tested against NPT Monte Carlo simulations of the two-dimensional Mercedes Benz model of water. The main approximation in the earlier calculation was an orientational averaging in the multidensity Ornstein-Zernike equation. Here we improve the theory by explicit introduction of an orientation dependence in the IET, based upon expanding the two-particle angular correlation function in orthogonal basis functions. We find that the new orientation-dependent IET (ODIET) yields a considerable improvement of the predicted structure of water, when compared to the Monte Carlo simulations. In particular, ODIET predicts more long-range order than the original IET, with hexagonal symmetry, as expected for the hydrogen bonded ice in this model. The new theoretical approximation still errs in some subtle properties; for example, it does not predict liquid water's density maximum with temperature or the negative thermal expansion coefficient.

Transition operators in electromagnetic-wave diffraction theory. II - Applications to optics

NASA Technical Reports Server (NTRS)

Hahne, G. E.

1993-01-01

The theory developed by Hahne (1992) for the diffraction of time-harmonic electromagnetic waves from fixed obstacles is briefly summarized and extended. Applications of the theory are considered which comprise, first, a spherical harmonic expansion of the so-called radiation impedance operator in the theory, for a spherical surface, and second, a reconsideration of familiar short-wavelength approximation from the new standpoint, including a derivation of the so-called physical optics method on the basis of quasi-planar approximation to the radiation impedance operator, augmented by the method of stationary phase. The latter includes a rederivation of the geometrical optics approximation for the complete Green's function for the electromagnetic field in the presence of a smooth- and a convex-surfaced perfectly electrically conductive obstacle.

Extending the Functional Cerebral Systems Theory of Emotion to the Vestibular Modality: A Systematic and Integrative Approach

ERIC Educational Resources Information Center

Carmona, Joseph E.; Holland, Alissa K.; Harrison, David W.

2009-01-01

Throughout history, vestibular and emotional dysregulation have often manifested together in clinical settings, with little consideration that they may have a common basis. Regarding vestibular mechanisms, the role of brainstem and cerebellar structures has been emphasized in the neurological literature, whereas emotion processing in the cerebral…

27ps DFTMD Simulations of Maltose using a Reduced Basis Set

USDA-ARS?s Scientific Manuscript database

The disaccharide, a-maltose, has been studied using constant energy density functional molecular dynamics (DFTMD) at the B3LYP/6-31+G*/4-31G+COSMO (solvent) level of theory. Maltose is of particular interest as the variation in glycosidic dihedral angles has been found to be dependent upon the star...

The addictive brain: all roads lead to dopamine.

PubMed

Blum, Kenneth; Chen, Amanda L C; Giordano, John; Borsten, Joan; Chen, Thomas J H; Hauser, Mary; Simpatico, Thomas; Femino, John; Braverman, Eric R; Barh, Debmalya

2012-01-01

This article will touch on theories, scientific research and conjecture about the evolutionary genetics of the brain function and the impact of genetic variants called polymorphisms on drug-seeking behavior. It will cover the neurological basis of pleasure-seeking and addiction, which affects multitudes in a global atmosphere where people are seeking "pleasure states".

Rapidly calculated density functional theory (DFT) relaxed Iso-potential Phi Si Maps: Beta-cellobiose

USDA-ARS?s Scientific Manuscript database

New cellobiose Phi-H/Si-H maps are rapidly generated using a mixed basis set DFT method, found to achieve a high level of confidence while reducing computer resources dramatically. Relaxed iso-potential maps are made for different conformational states of cellobiose, showing how glycosidic bond dihe...

Study on conformational stability, molecular structure, vibrational spectra, NBO, TD-DFT, HOMO and LUMO analysis of 3,5-dinitrosalicylic acid by DFT techniques

NASA Astrophysics Data System (ADS)

Sebastian, S.; Sylvestre, S.; Jayabharathi, J.; Ayyapan, S.; Amalanathan, M.; Oudayakumar, K.; Herman, Ignatius A.

2015-02-01

In this work we analyzed the vibrational spectra of 3,5-dinitrosalicylic acid (3,5DNSA) molecule. The total energy of eight possible conformers can be calculated by Density Functional Theory with 6-31G(d,p) as basis set to find the most stable conformer. Computational result identify the most stable conformer of 3,5DNSA is C6. The assignments of the vibrational spectra have been carried out by computing Total Energy Distribution (TED). The molecular geometry, second order perturbation energies and Electron Density (ED) transfer from filled lone pairs of Lewis base to unfilled Lewis acid sites for 3,5-DNSA molecular analyzed on the basis of Natural Bond Orbital (NBO) analysis. The formation of inter and intramolecular hydrogen bonding between sbnd OH and sbnd COOH group gave the evidence for the formation of dimer formation for 3,5-DNSA molecule. The energy and oscillator strength calculated by Time-Dependent Density Functional Theory (TD-DFT) complements with the experimental findings. The simulated spectra satisfactorily coincides with the experimental spectra.

Electronic structure and electric polarity of edge-functionalized graphene nanoribbons

NASA Astrophysics Data System (ADS)

Taira, Remi; Yamanaka, Ayaka; Okada, Susumu

2017-08-01

On the basis of the density functional theory combined with the effective screening medium method, we studied the electronic structure of graphene nanoribbons with zigzag edges, which are terminated by functional groups. The work function of the nanoribbons is sensitive to the functional groups. The edge state inherent in the zigzag edges is robust against edge functionalization. OH termination causes the injection of electrons into the nearly free electron states situated alongside the nanoribbons, resulting in the formation of free electron channels outside the nanoribbons. We also demonstrated that the polarity of zigzag graphene nanoribbons is controllable by the asymmetrical functionalization of their edges.

Vibrational spectroscopic study of fluticasone propionate

NASA Astrophysics Data System (ADS)

Ali, H. R. H.; Edwards, H. G. M.; Kendrick, J.; Scowen, I. J.

2009-03-01

Fluticasone propionate is a synthetic glucocorticoid with potent anti-inflammatory activity that has been used effectively in the treatment of chronic asthma. The present work reports a vibrational spectroscopic study of fluticasone propionate and gives proposed molecular assignments on the basis of ab initio calculations using BLYP density functional theory with a 6-31G* basis set and vibrational frequencies predicted within the quasi-harmonic approximation. Several spectral features and band intensities are explained. This study generated a library of information that can be employed to aid the process monitoring of fluticasone propionate.

Atypical frontal-posterior synchronization of Theory of Mind regions in autism during mental state attribution

PubMed Central

Kana, Rajesh K.; Keller, Timothy A.; Cherkassky, Vladimir L.; Minshew, Nancy J.; Just, Marcel Adam

2011-01-01

This study used fMRI to investigate the functioning of the Theory of Mind (ToM) cortical network in autism during the viewing of animations that in some conditions entailed the attribution of a mental state to animated geometric figures. At the cortical level, mentalizing (attribution of metal states) is underpinned by the coordination and integration of the components of the ToM network, which include the medial frontal gyrus, the anterior paracingulate, and the right temporoparietal junction. The pivotal new finding was a functional underconnectivity (a lower degree of synchronization) in autism, especially in the connections between frontal and posterior areas during the attribution of mental states. In addition, the frontal Theory of Mind regions activated less in participants with autism relative to control participants. In the autism group, an independent psychometric assessment of Theory of Mind ability and the activation in the right temporoparietal junction were reliably correlated. The results together provide new evidence for the biological basis of atypical processing of Theory of Mind in autism, implicating the underconnectivity between frontal regions and more posterior areas. PMID:18633829

Sociological analysis and comparative education

NASA Astrophysics Data System (ADS)

Woock, Roger R.

1981-12-01

It is argued that comparative education is essentially a derivative field of study, in that it borrows theories and methods from academic disciplines. After a brief humanistic phase, in which history and philosophy were central for comparative education, sociology became an important source. In the mid-50's and 60's, sociology in the United States was characterised by Structural Functionalism as a theory, and Social Survey as a dominant methodology. Both were incorporated into the development of comparative education. Increasingly in the 70's, and certainly today, the new developments in sociology are characterised by an attack on Positivism, which is seen as the philosophical position underlying both functionalism and survey methods. New or re-discovered theories with their attendant methodologies included Marxism, Phenomenological Sociology, Critical Theory, and Historical Social Science. The current relationship between comparative education and social science is one of uncertainty, but since social science is seen to be returning to its European roots, the hope is held out for the development of an integrated social theory and method which will provide a much stronger basis for developments in comparative education.

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.

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

Nakatsuji, Hiroshi, E-mail: h.nakatsuji@qcri.or.jp; Nakashima, Hiroyuki

The Schrödinger equation (SE) and the antisymmetry principle constitute the governing principle of chemistry. A general method of solving the SE was presented before as the free complement (FC) theory, which gave highly accurate solutions for small atoms and molecules. We assume here to use the FC theory starting from the local valence bond wave function. When this theory is applied to larger molecules, antisymmetrizations of electronic wave functions become time-consuming and therefore, an additional breakthrough is necessary concerning the antisymmetry principle. Usually, in molecular calculations, we first construct the wave function to satisfy the antisymmetry rule, “electronic wave functionsmore » must be prescribed to be antisymmetric for all exchanges of electrons, otherwise bosonic interference may disturb the basis of the science.” Starting from determinantal wave functions is typical. Here, we give an antisymmetrization theory, called inter-exchange (iExg) theory, by dividing molecular antisymmetrizations to those within atoms and between atoms. For the electrons belonging to distant atoms in a molecule, only partial antisymmetrizations or even no antisymmetrizations are necessary, depending on the distance between the atoms. So, the above antisymmetry rule is not necessarily followed strictly to get the results of a desired accuracy. For this and other reasons, the necessary parts of the antisymmetrization operations become very small as molecules become larger, leading finally to the operation counts of lower orders of N, the number of electrons. This theory creates a natural antisymmetrization method that is useful for large molecules.« less

Implementation of Two-Component Time-Dependent Density Functional Theory in TURBOMOLE.

PubMed

Kühn, Michael; Weigend, Florian

2013-12-10

We report the efficient implementation of a two-component time-dependent density functional theory proposed by Wang et al. (Wang, F.; Ziegler, T.; van Lenthe, E.; van Gisbergen, S.; Baerends, E. J. J. Chem. Phys. 2005, 122, 204103) that accounts for spin-orbit effects on excitations of closed-shell systems by employing a noncollinear exchange-correlation kernel. In contrast to the aforementioned implementation, our method is based on two-component effective core potentials as well as Gaussian-type basis functions. It is implemented in the TURBOMOLE program suite for functionals of the local density approximation and the generalized gradient approximation. Accuracy is assessed by comparison of two-component vertical excitation energies of heavy atoms and ions (Cd, Hg, Au(+)) and small molecules (I2, TlH) to other two- and four-component approaches. Efficiency is demonstrated by calculating the electronic spectrum of Au20.

Exploring the surface reactivity of 3d metal endofullerenes: a density-functional theory study.

PubMed

Estrada-Salas, Rubén E; Valladares, Ariel A

2009-09-24

Changes in the preferential sites of electrophilic, nucleophilic, and radical attacks on the pristine C60 surface with endohedral doping using 3d transition metal atoms were studied via two useful reactivity indices, namely the Fukui functions and the molecular electrostatic potential. Both of these were calculated at the density functional BPW91 level of theory with the DNP basis set. Our results clearly show changes in the preferential reactivity sites on the fullerene surface when it is doped with Mn, Fe, Co, or Ni atoms, whereas there are no significant changes in the preferential reactivity sites on the C60 surface upon endohedral doping with Cu and Zn atoms. Electron affinities (EA), ionization potentials (IP), and HOMO-LUMO gaps (Eg) were also calculated to complete the study of the endofullerene's surface reactivity. These findings provide insight into endofullerene functionalization, an important issue in their application.

Game Theory of Mind

PubMed Central

Yoshida, Wako; Dolan, Ray J.; Friston, Karl J.

2008-01-01

This paper introduces a model of ‘theory of mind’, namely, how we represent the intentions and goals of others to optimise our mutual interactions. We draw on ideas from optimum control and game theory to provide a ‘game theory of mind’. First, we consider the representations of goals in terms of value functions that are prescribed by utility or rewards. Critically, the joint value functions and ensuing behaviour are optimised recursively, under the assumption that I represent your value function, your representation of mine, your representation of my representation of yours, and so on ad infinitum. However, if we assume that the degree of recursion is bounded, then players need to estimate the opponent's degree of recursion (i.e., sophistication) to respond optimally. This induces a problem of inferring the opponent's sophistication, given behavioural exchanges. We show it is possible to deduce whether players make inferences about each other and quantify their sophistication on the basis of choices in sequential games. This rests on comparing generative models of choices with, and without, inference. Model comparison is demonstrated using simulated and real data from a ‘stag-hunt’. Finally, we note that exactly the same sophisticated behaviour can be achieved by optimising the utility function itself (through prosocial utility), producing unsophisticated but apparently altruistic agents. This may be relevant ethologically in hierarchal game theory and coevolution. PMID:19112488

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.

Møller-Plesset perturbation energies and distances for HeC(20) extrapolated to the complete basis set limit.

PubMed

Varandas, A J C

2009-02-01

The potential energy surface for the C(20)-He interaction is extrapolated for three representative cuts to the complete basis set limit using second-order Møller-Plesset perturbation calculations with correlation consistent basis sets up to the doubly augmented variety. The results both with and without counterpoise correction show consistency with each other, supporting that extrapolation without such a correction provides a reliable scheme to elude the basis-set-superposition error. Converged attributes are obtained for the C(20)-He interaction, which are used to predict the fullerene dimer ones. Time requirements show that the method can be drastically more economical than the counterpoise procedure and even competitive with Kohn-Sham density functional theory for the title system.

Four-Component Relativistic Density-Functional Theory Calculations of Nuclear Spin-Rotation Constants: Relativistic Effects in p-Block Hydrides.

PubMed

Komorovsky, Stanislav; Repisky, Michal; Malkin, Elena; Demissie, Taye B; Ruud, Kenneth

2015-08-11

We present an implementation of the nuclear spin-rotation (SR) constants based on the relativistic four-component Dirac-Coulomb Hamiltonian. This formalism has been implemented in the framework of the Hartree-Fock and Kohn-Sham theory, allowing assessment of both pure and hybrid exchange-correlation functionals. In the density-functional theory (DFT) implementation of the response equations, a noncollinear generalized gradient approximation (GGA) has been used. The present approach enforces a restricted kinetic balance condition for the small-component basis at the integral level, leading to very efficient calculations of the property. We apply the methodology to study relativistic effects on the spin-rotation constants by performing calculations on XHn (n = 1-4) for all elements X in the p-block of the periodic table and comparing the effects of relativity on the nuclear SR tensors to that observed for the nuclear magnetic shielding tensors. Correlation effects as described by the density-functional theory are shown to be significant for the spin-rotation constants, whereas the differences between the use of GGA and hybrid density functionals are much smaller. Our calculated relativistic spin-rotation constants at the DFT level of theory are only in fair agreement with available experimental data. It is shown that the scaling of the relativistic effects for the spin-rotation constants (varying between Z(3.8) and Z(4.5)) is as strong as for the chemical shieldings but with a much smaller prefactor.

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.

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

Bazante, Alexandre P., E-mail: abazante@chem.ufl.edu; Bartlett, Rodney J.; Davidson, E. R.

The benzene radical anion is studied with ab initio coupled-cluster theory in large basis sets. Unlike the usual assumption, we find that, at the level of theory investigated, the minimum energy geometry is non-planar with tetrahedral distortion at two opposite carbon atoms. The anion is well known for its instability to auto-ionization which poses computational challenges to determine its properties. Despite the importance of the benzene radical anion, the considerable attention it has received in the literature so far has failed to address the details of its structure and shape-resonance character at a high level of theory. Here, we examinemore » the dynamic Jahn-Teller effect and its impact on the anion potential energy surface. We find that a minimum energy geometry of C{sub 2} symmetry is located below one D{sub 2h} stationary point on a C{sub 2h} pseudo-rotation surface. The applicability of standard wave function methods to an unbound anion is assessed with the stabilization method. The isotropic hyperfine splitting constants (A{sub iso}) are computed and compared to data obtained from experimental electron spin resonance experiments. Satisfactory agreement with experiment is obtained with coupled-cluster theory and large basis sets such as cc-pCVQZ.« less

Density functional theory study on the ionic liquid pyridinium hydrogen sulfate

NASA Astrophysics Data System (ADS)

Tankov, Ivaylo; Yankova, Rumyana; Genieva, Svetlana; Mitkova, Magdalena; Stratiev, Dicho

2017-07-01

The geometry, electronic structure and chemical reactivity of a pyridinium-based ionic liquid, pyridinium hydrogen sulfate ([H-Pyr]+[HSO4]-), have been discussed on the basis of quantum chemical density functional theory calculations using B3LYP/6-311+G(d,p) and B3LYP/6-311++G(2d,2p) approaches. The calculations indicated that [H-Pyr]+[HSO4]- exists in the form of an ion pair. A large electropositive potential was found on the pyridinium ring, while the regions of a negative electrostatic potential is linked with the lone pair of electronegative oxygen atoms in hydrogen sulfate anion ([HSO4]-). Electron transfer both within the anion, and between the anion and cation of an ion pair were described using natural bond orbital theory. The energy values of -7.1375 and -2.8801 eV were related to HOMO and LUMO orbitals, respectively.

Perturbative Out of Equilibrium Quantum Field Theory beyond the Gradient Approximation and Generalized Boltzmann Equation

NASA Astrophysics Data System (ADS)

Ozaki, H.

2004-01-01

Using the closed-time-path formalism, we construct perturbative frameworks, in terms of quasiparticle picture, for studying quasiuniform relativistic quantum field systems near equilibrium and non-equilibrium quasistationary systems. We employ the derivative expansion and take in up to the second-order term, i.e., one-order higher than the gradient approximation. After constructing self-energy resummed propagator, we formulated two kinds of mutually equivalent perturbative frameworks: The first one is formulated on the basis of the ``bare'' number density function, and the second one is formulated on the basis of ``physical'' number density function. In the course of construction of the second framework, the generalized Boltzmann equations directly come out, which describe the evolution of the system.

Water adsorption on a copper formate paddlewheel model of CuBTC: A comparative MP2 and DFT study

NASA Astrophysics Data System (ADS)

Toda, Jordi; Fischer, Michael; Jorge, Miguel; Gomes, José R. B.

2013-11-01

Simultaneous adsorption of two water molecules on open metal sites of the HKUST-1 metal-organic framework (MOF), modeled with a Cu2(HCOO)4 cluster, was studied by means of density functional theory (DFT) and second-order Moller-Plesset (MP2) approaches together with correlation consistent basis sets. Experimental geometries and MP2 energetic data extrapolated to the complete basis set limit were used as benchmarks for testing the accuracy of several different exchange-correlation functionals in the correct description of the water-MOF interaction. M06-L and some LC-DFT methods arise as the most appropriate in terms of the quality of geometrical data, energetic data and computational resources needed.

On the importance of local orbitals using second energy derivatives for d and f electrons

NASA Astrophysics Data System (ADS)

Karsai, Ferenc; Tran, Fabien; Blaha, Peter

2017-11-01

The all-electron linearized augmented plane wave (LAPW) methods are among the most accurate to solve the Kohn-Sham equations of density functional theory for periodic solids. In the LAPW methods, the unit cell is partitioned into spheres surrounding the atoms, inside which the wave functions are expanded into spherical harmonics, and the interstitial region, where the wave functions are expanded in Fourier series. Recently, Michalicek et al. (2013) reported an analysis of the so-called linearization error, which is inherent to the basis functions inside the spheres, and advocated the use of local orbital basis functions involving the second energy derivative of the radial part (HDLO). In the present work, we report the implementation of such basis functions into the WIEN2k code, and discuss in detail the improvement in terms of accuracy. From our tests, which involve atoms from the whole periodic table, it is concluded that for ground-state properties (e.g., equilibrium volume) the use of HDLO is necessary only for atoms with d or f electrons in the valence and large atomic spheres. For unoccupied states which are not too high above the Fermi energy, HDLO systematically improve the band structure, which may be of importance for the calculation of optical properties.

Curvature and frontier orbital energies in density functional theory

NASA Astrophysics Data System (ADS)

Kronik, Leeor; Stein, Tamar; Autschbach, Jochen; Govind, Niranjan; Baer, Roi

2013-03-01

Perdew et al. [Phys. Rev. Lett 49, 1691 (1982)] discovered and proved two different properties of exact Kohn-Sham density functional theory (DFT): (i) The exact total energy versus particle number is a series of linear segments between integer electron points; (ii) Across an integer number of electrons, the exchange-correlation potential may ``jump'' by a constant, known as the derivative discontinuity (DD). Here, we show analytically that in both the original and the generalized Kohn-Sham formulation of DFT, the two are in fact two sides of the same coin. Absence of a derivative discontinuity necessitates deviation from piecewise linearity, and the latter can be used to correct for the former, thereby restoring the physical meaning of the orbital energies. Using selected small molecules, we show that this results in a simple correction scheme for any underlying functional, including semi-local and hybrid functionals as well as Hartree-Fock theory, suggesting a practical correction for the infamous gap problem of DFT. Moreover, we show that optimally-tuned range-separated hybrid functionals can inherently minimize both DD and curvature, thus requiring no correction, and show that this can be used as a sound theoretical basis for novel tuning strategies.

Optimal stimulation as theoretical basis of hyperactivity.

PubMed

Zentall, Sydney

1975-07-01

Current theory and practice in the clinical and educational management of hyperactive children recommend reduction of environmental stimulation, assuming hyperactive and distractable behaviors to be due to overstimulation. This paper reviews research suggesting that hyperactive behavior may result from a homeostatic mechanism that functions to increase stimulation for a child experienceing insufficient sensory stimulation. It is suggested that the effectiveness of drug and behavior therapies, as well as evidence from the field of sensory deprivation, further support the theory of a homeostatic mechanism that attempts to optimize sensory input.

The theory precision analyse of RFM localization of satellite remote sensing imagery

NASA Astrophysics Data System (ADS)

Zhang, Jianqing; Xv, Biao

2009-11-01

The tradition method of detecting precision of Rational Function Model(RFM) is to make use of a great deal check points, and it calculates mean square error through comparing calculational coordinate with known coordinate. This method is from theory of probability, through a large number of samples to statistic estimate value of mean square error, we can think its estimate value approaches in its true when samples are well enough. This paper is from angle of survey adjustment, take law of propagation of error as the theory basis, and it calculates theory precision of RFM localization. Then take the SPOT5 three array imagery as experiment data, and the result of traditional method and narrated method in the paper are compared, while has confirmed tradition method feasible, and answered its theory precision question from the angle of survey adjustment.

Beta-decay rate and beta-delayed neutron emission probability of improved gross theory

NASA Astrophysics Data System (ADS)

Koura, Hiroyuki

2014-09-01

A theoretical study has been carried out on beta-decay rate and beta-delayed neutron emission probability. The gross theory of the beta decay is based on an idea of the sum rule of the beta-decay strength function, and has succeeded in describing beta-decay half-lives of nuclei overall nuclear mass region. The gross theory includes not only the allowed transition as the Fermi and the Gamow-Teller, but also the first-forbidden transition. In this work, some improvements are introduced as the nuclear shell correction on nuclear level densities and the nuclear deformation for nuclear strength functions, those effects were not included in the original gross theory. The shell energy and the nuclear deformation for unmeasured nuclei are adopted from the KTUY nuclear mass formula, which is based on the spherical-basis method. Considering the properties of the integrated Fermi function, we can roughly categorized energy region of excited-state of a daughter nucleus into three regions: a highly-excited energy region, which fully affect a delayed neutron probability, a middle energy region, which is estimated to contribute the decay heat, and a region neighboring the ground-state, which determines the beta-decay rate. Some results will be given in the presentation. A theoretical study has been carried out on beta-decay rate and beta-delayed neutron emission probability. The gross theory of the beta decay is based on an idea of the sum rule of the beta-decay strength function, and has succeeded in describing beta-decay half-lives of nuclei overall nuclear mass region. The gross theory includes not only the allowed transition as the Fermi and the Gamow-Teller, but also the first-forbidden transition. In this work, some improvements are introduced as the nuclear shell correction on nuclear level densities and the nuclear deformation for nuclear strength functions, those effects were not included in the original gross theory. The shell energy and the nuclear deformation for unmeasured nuclei are adopted from the KTUY nuclear mass formula, which is based on the spherical-basis method. Considering the properties of the integrated Fermi function, we can roughly categorized energy region of excited-state of a daughter nucleus into three regions: a highly-excited energy region, which fully affect a delayed neutron probability, a middle energy region, which is estimated to contribute the decay heat, and a region neighboring the ground-state, which determines the beta-decay rate. Some results will be given in the presentation. This work is a result of Comprehensive study of delayed-neutron yields for accurate evaluation of kinetics of high-burn up reactors entrusted to Tokyo Institute of Technology by the Ministry of Education, Culture, Sports, Science and Technology of Japan.

DGDFT: A massively parallel method for large scale density functional theory calculations.

PubMed

Hu, Wei; Lin, Lin; Yang, Chao

2015-09-28

We describe a massively parallel implementation of the recently developed discontinuous Galerkin density functional theory (DGDFT) method, for efficient large-scale Kohn-Sham DFT based electronic structure calculations. The DGDFT method uses adaptive local basis (ALB) functions generated on-the-fly during the self-consistent field iteration to represent the solution to the Kohn-Sham equations. The use of the ALB set provides a systematic way to improve the accuracy of the approximation. By using the pole expansion and selected inversion technique to compute electron density, energy, and atomic forces, we can make the computational complexity of DGDFT scale at most quadratically with respect to the number of electrons for both insulating and metallic systems. We show that for the two-dimensional (2D) phosphorene systems studied here, using 37 basis functions per atom allows us to reach an accuracy level of 1.3 × 10(-4) Hartree/atom in terms of the error of energy and 6.2 × 10(-4) Hartree/bohr in terms of the error of atomic force, respectively. DGDFT can achieve 80% parallel efficiency on 128,000 high performance computing cores when it is used to study the electronic structure of 2D phosphorene systems with 3500-14 000 atoms. This high parallel efficiency results from a two-level parallelization scheme that we will describe in detail.

The Oscillating Circular Airfoil on the Basis of Potential Theory

NASA Technical Reports Server (NTRS)

Schade, T.; Krienes, K.

1947-01-01

Proceeding from the thesis by W. Kinner the present report treats the problem of the circular airfoil in uniform airflow executing small oscillations, the amplitudes of which correspond to whole functions of the second degree in x and y. The pressure distribution is secured by means of Prandtl's acceleration potential. It results in a system of linear equations the coefficients of which can be calculated exactly with the aid of exponential functions and Hankel's functions. The equations necessary are derived in part I; the numerical calculation follows in part II.

Solvatochromic shifts from coupled-cluster theory embedded in density functional theory

NASA Astrophysics Data System (ADS)

Höfener, Sebastian; Gomes, André Severo Pereira; Visscher, Lucas

2013-09-01

Building on the framework recently reported for determining general response properties for frozen-density embedding [S. Höfener, A. S. P. Gomes, and L. Visscher, J. Chem. Phys. 136, 044104 (2012)], 10.1063/1.3675845, in this work we report a first implementation of an embedded coupled-cluster in density-functional theory (CC-in-DFT) scheme for electronic excitations, where only the response of the active subsystem is taken into account. The formalism is applied to the calculation of coupled-cluster excitation energies of water and uracil in aqueous solution. We find that the CC-in-DFT results are in good agreement with reference calculations and experimental results. The accuracy of calculations is mainly sensitive to factors influencing the correlation treatment (basis set quality, truncation of the cluster operator) and to the embedding treatment of the ground-state (choice of density functionals). This allows for efficient approximations at the excited state calculation step without compromising the accuracy. This approximate scheme makes it possible to use a first principles approach to investigate environment effects with specific interactions at coupled-cluster level of theory at a cost comparable to that of calculations of the individual subsystems in vacuum.

Benchmarking fully analytic DFT force fields for vibrational spectroscopy: A study on halogenated compounds

NASA Astrophysics Data System (ADS)

Pietropolli Charmet, Andrea; Cornaton, Yann

2018-05-01

This work presents an investigation of the theoretical predictions yielded by anharmonic force fields having the cubic and quartic force constants are computed analytically by means of density functional theory (DFT) using the recursive scheme developed by M. Ringholm et al. (J. Comput. Chem. 35 (2014) 622). Different functionals (namely B3LYP, PBE, PBE0 and PW86x) and basis sets were used for calculating the anharmonic vibrational spectra of two halomethanes. The benchmark analysis carried out demonstrates the reliability and overall good performances offered by hybrid approaches, where the harmonic data obtained at the coupled cluster with single and double excitations level of theory augmented by a perturbational estimate of the effects of connected triple excitations, CCSD(T), are combined with the fully analytic higher order force constants yielded by DFT functionals. These methods lead to reliable and computationally affordable calculations of anharmonic vibrational spectra with an accuracy comparable to that yielded by hybrid force fields having the anharmonic force fields computed at second order Møller-Plesset perturbation theory (MP2) level of theory using numerical differentiation but without the corresponding potential issues related to computational costs and numerical errors.

Vibrational spectroscopic studies, NLO, HOMO-LUMO and electronic structure calculations of α,α,α-trichlorotoluene using HF and DFT.

PubMed

Govindarajan, M; Karabacak, M; Periandy, S; Xavier, S

2012-08-01

FT-IR and FT-Raman spectra of α,α,α-trichlorotoluene have been recorded and analyzed. The geometry, fundamental vibrational frequencies are interpreted with the aid of structure optimizations and normal coordinate force field calculations based on density functional theory (DFT) B3LYP/6-311++G(d,p) method and a comparative study between HF level and various basis sets combination. The fundamental vibrational wavenumbers as well as their intensities were calculated and a good agreement between observed and scaled calculated wavenumbers has been achieved. The complete vibrational assignments of wavenumbers are made on the basis of potential energy distribution (PED). The effects due to the substitutions of methyl group and halogen were investigated. The absorption energy and oscillator strength are calculated by time-dependent density functional theory (TD-DFT). The electric dipole moment, polarizability and the first hyperpolarizability values of the α,α,α-trichlorotoluene have been calculated. (1)H NMR chemical shifts were calculated by using the gauge independent atomic orbital (GIAO) method with HF and B3LYP methods with 6-311++G(d,p) basis set. Moreover, molecular electrostatic potential (MEP) and thermodynamic properties were performed. Mulliken and natural charges of the title molecule were also calculated and interpreted. Copyright © 2012 Elsevier B.V. All rights reserved.

First-principle modelling of forsterite surface properties: Accuracy of methods and basis sets.

PubMed

Demichelis, Raffaella; Bruno, Marco; Massaro, Francesco R; Prencipe, Mauro; De La Pierre, Marco; Nestola, Fabrizio

2015-07-15

The seven main crystal surfaces of forsterite (Mg2 SiO4 ) were modeled using various Gaussian-type basis sets, and several formulations for the exchange-correlation functional within the density functional theory (DFT). The recently developed pob-TZVP basis set provides the best results for all properties that are strongly dependent on the accuracy of the wavefunction. Convergence on the structure and on the basis set superposition error-corrected surface energy can be reached also with poorer basis sets. The effect of adopting different DFT functionals was assessed. All functionals give the same stability order for the various surfaces. Surfaces do not exhibit any major structural differences when optimized with different functionals, except for higher energy orientations where major rearrangements occur around the Mg sites at the surface or subsurface. When dispersions are not accounted for, all functionals provide similar surface energies. The inclusion of empirical dispersions raises the energy of all surfaces by a nearly systematic value proportional to the scaling factor s of the dispersion formulation. An estimation for the surface energy is provided through adopting C6 coefficients that are more suitable than the standard ones to describe O-O interactions in minerals. A 2 × 2 supercell of the most stable surface (010) was optimized. No surface reconstruction was observed. The resulting structure and surface energy show no difference with respect to those obtained when using the primitive cell. This result validates the (010) surface model here adopted, that will serve as a reference for future studies on adsorption and reactivity of water and carbon dioxide at this interface. © 2015 Wiley Periodicals, Inc.

Symmetry analysis of a model for the exercise of a barrier option

NASA Astrophysics Data System (ADS)

O'Hara, J. G.; Sophocleous, C.; Leach, P. G. L.

2013-09-01

A barrier option takes into account the possibility of an unacceptable change in the price of the underlying stock. Such a change could carry considerable financial loss. We examine one model based upon the Black-Scholes-Merton Equation and determine the functional forms of the barrier function and rebate function which are consistent with a solution of the underlying evolution partial differential equation using the Lie Theory of Extended Groups. The solution is consistent with the possibility of no rebate and the barrier function is very similar to one adopted on an heuristic basis.

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.

Absorption and resonance Raman study of the pyromellitic diahydride anion via density functional theory

NASA Astrophysics Data System (ADS)

Andruniow, T.; Pawlikowski, M.

2000-05-01

The electronic structure of the low-energy states of the pyromellitic diahydride (PMDA) anion is investigated in terms of the VWN (Vosco-Wilk-Nusair) the BP (Becke-Perdew) and the B3LYP density functional (DF) methods employed with 6-31G * basis sets. All the methods are shown to reproduce correctly the absorption and resonance Raman spectra in the region corresponding to the low-energy 1 2Au→1 2B3g transition. The discrepancies between the theory and experiment are attributed to a (weak) Dushinsky effect predominately due to a mixing of the ν3=1593 cm -1 and ν4=1342 cm -1 vibrations in the 1 2B3 g state of the PMDA radical.

An intangible energy in the functioning biosystem. II: Useful parallels with circuit theory and with non-linear optics.

PubMed

Reid, B L

1995-06-01

The argument is developed that a structure and function already exists in selected inanimate systems for an intangible energy dissipating these systems and that, in so doing, this energy exhibits certain properties, readily recognised in the functioning biosystem. The central thesis is that, during dissipation, the structure of the biosystem affords opportunity for an enhanced display of these properties, so that this structure can be rationally recognised as obligatory in the transition, inanimate to animate matter. The systems chosen are those of reactance in linear circuit theory of electronics, and some recent developments in non-linear optics, both of which rely on imaginary or quantal force to display observable effects. Discussion occurs on the fashion which the development of a statistical formalism as a basis for the study of squeezed states of light in these non-linear systems, has, at the same time, overcome a long standing veto on the practical use of quantal energy associated with the Uncertainty Principle of Heisenberg. These ideas are used to vindicate the suggestion that a theoretical basis is presently available for an engineering type approach, toward an intangible force as it exists in the biosystem. The origins and properties of such a force continue to be considered by many as immersed in mysticism.

Executive function depletion in children and its impact on theory of mind.

PubMed

Powell, Lindsey J; Carey, Susan

2017-07-01

The current studies provide an experimental, rather than correlational, method for testing hypotheses about the role of executive function (EF) in conceptual development. Previous research has established that adults' tendency to deploy EF can be temporarily diminished by use. Exercising self-control in one context decreases adults' performance on other EF demanding tasks immediately thereafter. Using two different depletion methods, Experiments 1 and 3 extend this finding to preschool-aged children. Experiments 2 and 4 make use of these EF depletion methods to elucidate the role of EF in children's theory of mind reasoning. Experiment 2 shows that EF depletion affects 5-year-olds' ability to predict another's behavior on the basis of that person's false belief, and Experiment 4 shows that this negative effect of depletion extends to 4- and 5-year-olds' ability to explain others' behavior on the basis of their false beliefs. These findings provide direct evidence that EF is required for the expression of an understanding of others' false beliefs across a variety of task demands, even in children who clearly have the capacity to construct such representations. We suggest ways in which depletion may be used as a tool for further investigating the role of executive function in cognitive development. Copyright © 2017. Published by Elsevier B.V.

Vibration control of uncertain multiple launch rocket system using radial basis function neural network

NASA Astrophysics Data System (ADS)

Li, Bo; Rui, Xiaoting

2018-01-01

Poor dispersion characteristics of rockets due to the vibration of Multiple Launch Rocket System (MLRS) have always restricted the MLRS development for several decades. Vibration control is a key technique to improve the dispersion characteristics of rockets. For a mechanical system such as MLRS, the major difficulty in designing an appropriate control strategy that can achieve the desired vibration control performance is to guarantee the robustness and stability of the control system under the occurrence of uncertainties and nonlinearities. To approach this problem, a computed torque controller integrated with a radial basis function neural network is proposed to achieve the high-precision vibration control for MLRS. In this paper, the vibration response of a computed torque controlled MLRS is described. The azimuth and elevation mechanisms of the MLRS are driven by permanent magnet synchronous motors and supposed to be rigid. First, the dynamic model of motor-mechanism coupling system is established using Lagrange method and field-oriented control theory. Then, in order to deal with the nonlinearities, a computed torque controller is designed to control the vibration of the MLRS when it is firing a salvo of rockets. Furthermore, to compensate for the lumped uncertainty due to parametric variations and un-modeled dynamics in the design of the computed torque controller, a radial basis function neural network estimator is developed to adapt the uncertainty based on Lyapunov stability theory. Finally, the simulated results demonstrate the effectiveness of the proposed control system and show that the proposed controller is robust with regard to the uncertainty.

Frequency and zero-point vibrational energy scale factors for double-hybrid density functionals (and other selected methods): can anharmonic force fields be avoided?

PubMed

Kesharwani, Manoj K; Brauer, Brina; Martin, Jan M L

2015-03-05

We have obtained uniform frequency scaling factors λ(harm) (for harmonic frequencies), λ(fund) (for fundamentals), and λ(ZPVE) (for zero-point vibrational energies (ZPVEs)) for the Weigend-Ahlrichs and other selected basis sets for MP2, SCS-MP2, and a variety of DFT functionals including double hybrids. For selected levels of theory, we have also obtained scaling factors for true anharmonic fundamentals and ZPVEs obtained from quartic force fields. For harmonic frequencies, the double hybrids B2PLYP, B2GP-PLYP, and DSD-PBEP86 clearly yield the best performance at RMSD = 10-12 cm(-1) for def2-TZVP and larger basis sets, compared to 5 cm(-1) at the CCSD(T) basis set limit. For ZPVEs, again, the double hybrids are the best performers, reaching root-mean-square deviations (RMSDs) as low as 0.05 kcal/mol, but even mainstream functionals like B3LYP can get down to 0.10 kcal/mol. Explicitly anharmonic ZPVEs only are marginally more accurate. For fundamentals, however, simple uniform scaling is clearly inadequate.

A DFT and ab initio benchmarking study of metal-alkane interactions and the activation of carbon-hydrogen bonds.

PubMed

Flener-Lovitt, Charity; Woon, David E; Dunning, Thom H; Girolami, Gregory S

2010-02-04

Density functional theory and ab initio methods have been used to calculate the structures and energies of minima and transition states for the reactions of methane coordinated to a transition metal. The reactions studied are reversible C-H bond activation of the coordinated methane ligand to form a transition metal methyl hydride complex and dissociation of the coordinated methane ligand. The reaction sequence can be summarized as L(x)M(CH(3))H <==> L(x)M(CH(4)) <==> L(x)M + CH(4), where L(x)M is the osmium-containing fragment (C(5)H(5))Os(R(2)PCH(2)PR(2))(+) and R is H or CH(3). Three-center metal-carbon-hydrogen interactions play an important role in this system. Both basis sets and functionals have been benchmarked in this work, including new correlation consistent basis sets for a third transition series element, osmium. Double zeta quality correlation consistent basis sets yield energies close to those from calculations with quadruple-zeta basis sets, with variations that are smaller than the differences between functionals. The energies of important species on the potential energy surface, calculated by using 10 DFT functionals, are compared both to experimental values and to CCSD(T) single point calculations. Kohn-Sham natural bond orbital descriptions are used to understand the differences between functionals. Older functionals favor electrostatic interactions over weak donor-acceptor interactions and, therefore, are not particularly well suited for describing systems--such as sigma-complexes--in which the latter are dominant. Newer kinetic and dispersion-corrected functionals such as MPW1K and M05-2X provide significantly better descriptions of the bonding interactions, as judged by their ability to predict energies closer to CCSD(T) values. Kohn-Sham and natural bond orbitals are used to differentiate between bonding descriptions. Our evaluations of these basis sets and DFT functionals lead us to recommend the use of dispersion corrected functionals in conjunction with double-zeta or larger basis sets with polarization functions for calculations involving weak interactions, such as those found in sigma-complexes with transition metals.

Appropriate description of intermolecular interactions in the methane hydrates: an assessment of DFT methods.

PubMed

Liu, Yuan; Zhao, Jijun; Li, Fengyu; Chen, Zhongfang

2013-01-15

Accurate description of hydrogen-bonding energies between water molecules and van der Waals interactions between guest molecules and host water cages is crucial for study of methane hydrates (MHs). Using high-level ab initio MP2 and CCSD(T) results as the reference, we carefully assessed the performance of a variety of exchange-correlation functionals and various basis sets in describing the noncovalent interactions in MH. The functionals under investigation include the conventional GGA, meta-GGA, and hybrid functionals (PBE, PW91, TPSS, TPSSh, B3LYP, and X3LYP), long-range corrected functionals (ωB97X, ωB97, LC-ωPBE, CAM-B3LYP, and LC-TPSS), the newly developed Minnesota class functionals (M06-L, M06-HF, M06, and M06-2X), and the dispersion-corrected density functional theory (DFT) (DFT-D) methods (B97-D, ωB97X-D, PBE-TS, PBE-Grimme, and PW91-OBS). We found that the conventional functionals are not suitable for MH, notably, the widely used B3LYP functional even predicts repulsive interaction between CH(4) and (H(2)O)(6) cluster. M06-2X is the best among the M06-Class functionals. The ωB97X-D outperforms the other DFT-D methods and is recommended for accurate first-principles calculations of MH. B97-D is also acceptable as a compromise of computational cost and precision. Considering both accuracy and efficiency, B97-D, ωB97X-D, and M06-2X functional with 6-311++G(2d,2p) basis set without basis set superposition error (BSSE) correction are recommended. Though a fairly large basis set (e.g., aug-cc-pVTZ) and BSSE correction are necessary for a reliable MP2 calculation, DFT methods are less sensitive to the basis set and BSSE correction if the basis set is sufficient (e.g., 6-311++G(2d,2p)). These assessments provide useful guidance for choosing appropriate methodology of first-principles simulation of MH and related systems. © 2012 Wiley Periodicals, Inc. Copyright © 2012 Wiley Periodicals, Inc.

C2 Fragmentation Energy of C60 Revisited: Theory Disagrees with Most Experiments

NASA Technical Reports Server (NTRS)

Boese, A. Daniel; Scuseria, Gustavo E.

1998-01-01

Following our earlier work on the subject, we have carried out density functional theory (DFT) and second-order Moller-Plesset perturbation theory (MP2) calculations of the dissociation energy of the reaction C60 yields C58 + C2 using polarized basis sets and geometries optimized with DFT methods. The present theoretical results support an electronic fragmentation energy D(sub e) around 10-11 eV in disagreement with most experimental results that place the dissociation energy D(sub o) (including zero point energy) around 7-8 eV. The plausible errors remaining in the theoretical calculations are unlikely to account for this big difference (2-4 eV).

Marine and Maritime Sector Skills Shortages in the South West of England: Developing Regional Training Provision

ERIC Educational Resources Information Center

Beer, Julian; Meethan, Kevin

2007-01-01

Clustering theory assumes that companies gravitate towards each other on the basis of locally and regionally specific resources and supply chain characteristics, which lead in turn to innovation and high-value economic development. In line with such thinking, UK government policy has devolved certain functions to regional development agencies such…

Comment on "Nonuniqueness of algebraic first-order density-matrix functionals"

NASA Astrophysics Data System (ADS)

Gritsenko, O. V.

2018-02-01

Wang and Knowles (WK) [Phys. Rev. A 92, 012520 (2015), 10.1103/PhysRevA.92.012520] have given a counterexample to the conventional in reduced density-matrix functional theory representation of the second-order reduced density matrix (2RDM) Γi j ,k l in the basis of the natural orbitals as a function Γi j ,k l(n ) of the orbital occupation numbers (ONs) ni. The observed nonuniqueness of Γi j ,k l for prototype systems of different symmetry has been interpreted as the inherent inability of ON functions to reproduce the 2RDM, due to the insufficient information contained in the 1RDM spectrum. In this Comment, it is argued that, rather than totally invalidating Γi j ,k l(n ) , the WK example exposes its symmetry dependence which, as well as the previously established analogous dependence in density functional theory, is demonstrated with a general formulation based on the Levy constrained search.

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

Azadi, Sam, E-mail: s.azadi@ucl.ac.uk; Cohen, R. E.

We report an accurate study of interactions between benzene molecules using variational quantum Monte Carlo (VMC) and diffusion quantum Monte Carlo (DMC) methods. We compare these results with density functional theory using different van der Waals functionals. In our quantum Monte Carlo (QMC) calculations, we use accurate correlated trial wave functions including three-body Jastrow factors and backflow transformations. We consider two benzene molecules in the parallel displaced geometry, and find that by highly optimizing the wave function and introducing more dynamical correlation into the wave function, we compute the weak chemical binding energy between aromatic rings accurately. We find optimalmore » VMC and DMC binding energies of −2.3(4) and −2.7(3) kcal/mol, respectively. The best estimate of the coupled-cluster theory through perturbative triplets/complete basis set limit is −2.65(2) kcal/mol [Miliordos et al., J. Phys. Chem. A 118, 7568 (2014)]. Our results indicate that QMC methods give chemical accuracy for weakly bound van der Waals molecular interactions, comparable to results from the best quantum chemistry methods.« less

Carcinogenesis: alterations in reciprocal interactions of normal functional structure of biologic systems.

PubMed

Davydyan, Garri

2015-12-01

The evolution of biologic systems (BS) includes functional mechanisms that in some conditions may lead to the development of cancer. Using mathematical group theory and matrix analysis, previously, it was shown that normally functioning BS are steady functional structures regulated by three basis regulatory components: reciprocal links (RL), negative feedback (NFB) and positive feedback (PFB). Together, they form an integrative unit maintaining system's autonomy and functional stability. It is proposed that phylogenetic development of different species is implemented by the splitting of "rudimentary" characters into two relatively independent functional parts that become encoded in chromosomes. The functional correlate of splitting mechanisms is RL. Inversion of phylogenetic mechanisms during ontogenetic development leads cell differentiation until cells reach mature states. Deterioration of reciprocal structure in the genome during ontogenesis gives rise of pathological conditions characterized by unsteadiness of the system. Uncontrollable cell proliferation and invasive cell growth are the leading features of the functional outcomes of malfunctioning systems. The regulatory element responsible for these changes is RL. In matrix language, pathological regulation is represented by matrices having positive values of diagonal elements ( TrA  > 0) and also positive values of matrix determinant ( detA  > 0). Regulatory structures of that kind can be obtained if the negative entry of the matrix corresponding to RL is replaced with the positive one. To describe not only normal but also pathological states of BS, a unit matrix should be added to the basis matrices representing RL, NFB and PFB. A mathematical structure corresponding to the set of these four basis functional patterns (matrices) is a split quaternion (coquaternion). The structure and specific role of basis elements comprising four-dimensional linear space of split quaternions help to understand what changes in mechanism of cell differentiation may lead to cancer development.

Study on evaluation of construction reliability for engineering project based on fuzzy language operator

NASA Astrophysics Data System (ADS)

Shi, Yu-Fang; Ma, Yi-Yi; Song, Ping-Ping

2018-03-01

System Reliability Theory is a research hotspot of management science and system engineering in recent years, and construction reliability is useful for quantitative evaluation of project management level. According to reliability theory and target system of engineering project management, the defination of construction reliability appears. Based on fuzzy mathematics theory and language operator, value space of construction reliability is divided into seven fuzzy subsets and correspondingly, seven membership function and fuzzy evaluation intervals are got with the operation of language operator, which provides the basis of corresponding method and parameter for the evaluation of construction reliability. This method is proved to be scientific and reasonable for construction condition and an useful attempt for theory and method research of engineering project system reliability.

Ideal flow theory for the double - shearing model as a basis for metal forming design

NASA Astrophysics Data System (ADS)

Alexandrov, S.; Trung, N. T.

2018-02-01

In the case of Tresca’ solids (i.e. solids obeying the Tresca yield criterion and its associated flow rule) ideal flows have been defined elsewhere as solenoidal smooth deformations in which an eigenvector field associated everywhere with the greatest principal stress (and strain rate) is fixed in the material. Under such conditions all material elements undergo paths of minimum plastic work, a condition which is often advantageous for metal forming processes. Therefore, the ideal flow theory is used as the basis of a procedure for the preliminary design of such processes. The present paper extends the theory of stationary planar ideal flow to pressure dependent materials obeying the double shearing model and the double slip and rotation model. It is shown that the original problem of plasticity reduces to a purely geometric problem. The corresponding system of equations is hyperbolic. The characteristic relations are integrated in elementary functions. In regions where one family of characteristics is straight, mapping between the principal lines and Cartesian coordinates is determined by linear ordinary differential equations. An illustrative example is provided.

molgw 1: Many-body perturbation theory software for atoms, molecules, and clusters

DOE PAGES

Bruneval, Fabien; Rangel, Tonatiuh; Hamed, Samia M.; ...

2016-07-12

Here, we summarize the MOLGW code that implements density-functional theory and many-body perturbation theory in a Gaussian basis set. The code is dedicated to the calculation of the many-body self-energy within the GW approximation and the solution of the Bethe–Salpeter equation. These two types of calculations allow the user to evaluate physical quantities that can be compared to spectroscopic experiments. Quasiparticle energies, obtained through the calculation of the GW self-energy, can be compared to photoemission or transport experiments, and neutral excitation energies and oscillator strengths, obtained via solution of the Bethe–Salpeter equation, are measurable by optical absorption. The implementation choicesmore » outlined here have aimed at the accuracy and robustness of calculated quantities with respect to measurements. Furthermore, the algorithms implemented in MOLGW allow users to consider molecules or clusters containing up to 100 atoms with rather accurate basis sets, and to choose whether or not to apply the resolution-of-the-identity approximation. Finally, we demonstrate the parallelization efficacy of the MOLGW code over several hundreds of processors.« less

Do Practical Standard Coupled Cluster Calculations Agree Better than Kohn–Sham Calculations with Currently Available Functionals When Compared to the Best Available Experimental Data for Dissociation Energies of Bonds to 3d Transition Metals?

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

Xu, Xuefei; Zhang, Wenjing; Tang, Mingsheng

2015-05-12

Coupled-cluster (CC) methods have been extensively used as the high-level approach in quantum electronic structure theory to predict various properties of molecules when experimental results are unavailable. It is often assumed that CC methods, if they include at least up to connected-triple-excitation quasiperturbative corrections to a full treatment of single and double excitations (in particular, CCSD(T)), and a very large basis set, are more accurate than Kohn–Sham (KS) density functional theory (DFT). In the present work, we tested and compared the performance of standard CC and KS methods on bond energy calculations of 20 3d transition metal-containing diatomic molecules againstmore » the most reliable experimental data available, as collected in a database called 3dMLBE20. It is found that, although the CCSD(T) and higher levels CC methods have mean unsigned deviations from experiment that are smaller than most exchange-correlation functionals for metal–ligand bond energies of transition metals, the improvement is less than one standard deviation of the mean unsigned deviation. Furthermore, on average, almost half of the 42 exchange-correlation functionals that we tested are closer to experiment than CCSD(T) with the same extended basis set for the same molecule. The results show that, when both relativistic and core–valence correlation effects are considered, even the very high-level (expensive) CC method with single, double, triple, and perturbative quadruple cluster operators, namely, CCSDT(2)Q, averaged over 20 bond energies, gives a mean unsigned deviation (MUD(20) = 4.7 kcal/mol when one correlates only valence, 3p, and 3s electrons of transition metals and only valence electrons of ligands, or 4.6 kcal/mol when one correlates all core electrons except for 1s shells of transition metals, S, and Cl); and that is similar to some good xc functionals (e.g., B97-1 (MUD(20) = 4.5 kcal/mol) and PW6B95 (MUD(20) = 4.9 kcal/mol)) when the same basis set is used. We found that, for both coupled cluster calculations and KS calculations, the T1 diagnostics correlate the errors better than either the M diagnostics or the B1 DFT-based diagnostics. The potential use of practical standard CC methods as a benchmark theory is further confounded by the finding that CC and DFT methods usually have different signs of the error. We conclude that the available experimental data do not provide a justification for using conventional single-reference CC theory calculations to validate or test xc functionals for systems involving 3d transition metals.« less

An unscaled quantum mechanical harmonic force field for p-benzoquinone

NASA Astrophysics Data System (ADS)

Nonella, Marco; Tavan, Paul

1995-10-01

Structure and harmonic vibrational frequencies of p-benzoquinone have been calculated using quantum chemical ab initio and density functional methods. Our calculations show that a satisfactory description of fundamentals and normal mode compositions is achieved upon consideration of correlation effects by means of Møller-Plesset perturbation expansion (MP2) or by density functional theory (DFT). Furthermore, for correct prediction of CO bondlength and force constant, basis sets augmented by polarization functions are required. Applying such basis sets, MP2 and DFT calculations both give results which are generally in reasonable agreement with experimental data. The quantitatively better agreement, however, is achieved with the computationally less demanding DFT method. This method particularly allows very precise prediction of the experimentally important absorptions in the frequency region between 1500 and 1800 cm -1 and of the isotopic shifts of these vibrations due to 13C or 18O substitution.

The advantage of flexible neuronal tunings in neural network models for motor learning

PubMed Central

Marongelli, Ellisha N.; Thoroughman, Kurt A.

2013-01-01

Human motor adaptation to novel environments is often modeled by a basis function network that transforms desired movement properties into estimated forces. This network employs a layer of nodes that have fixed broad tunings that generalize across the input domain. Learning is achieved by updating the weights of these nodes in response to training experience. This conventional model is unable to account for rapid flexibility observed in human spatial generalization during motor adaptation. However, added plasticity in the widths of the basis function tunings can achieve this flexibility, and several neurophysiological experiments have revealed flexibility in tunings of sensorimotor neurons. We found a model, Locally Weighted Projection Regression (LWPR), which uniquely possesses the structure of a basis function network in which both the weights and tuning widths of the nodes are updated incrementally during adaptation. We presented this LWPR model with training functions of different spatial complexities and monitored incremental updates to receptive field widths. An inverse pattern of dependence of receptive field adaptation on experienced error became evident, underlying both a relationship between generalization and complexity, and a unique behavior in which generalization always narrows after a sudden switch in environmental complexity. These results implicate a model that is flexible in both basis function widths and weights, like LWPR, as a viable alternative model for human motor adaptation that can account for previously observed plasticity in spatial generalization. This theory can be tested by using the behaviors observed in our experiments as novel hypotheses in human studies. PMID:23888141

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.

STM contrast of a CO dimer on a Cu(1 1 1) surface: a wave-function analysis.

PubMed

Gustafsson, Alexander; Paulsson, Magnus

2017-12-20

We present a method used to intuitively interpret the scanning tunneling microscopy (STM) contrast by investigating individual wave functions originating from the substrate and tip side. We use localized basis orbital density functional theory, and propagate the wave functions into the vacuum region at a real-space grid, including averaging over the lateral reciprocal space. Optimization by means of the method of Lagrange multipliers is implemented to perform a unitary transformation of the wave functions in the middle of the vacuum region. The method enables (i) reduction of the number of contributing tip-substrate wave function combinations used in the corresponding transmission matrix, and (ii) to bundle up wave functions with similar symmetry in the lateral plane, so that (iii) an intuitive understanding of the STM contrast can be achieved. The theory is applied to a CO dimer adsorbed on a Cu(1 1 1) surface scanned by a single-atom Cu tip, whose STM image is discussed in detail by the outlined method.

STM contrast of a CO dimer on a Cu(1 1 1) surface: a wave-function analysis

NASA Astrophysics Data System (ADS)

Gustafsson, Alexander; Paulsson, Magnus

2017-12-01

We present a method used to intuitively interpret the scanning tunneling microscopy (STM) contrast by investigating individual wave functions originating from the substrate and tip side. We use localized basis orbital density functional theory, and propagate the wave functions into the vacuum region at a real-space grid, including averaging over the lateral reciprocal space. Optimization by means of the method of Lagrange multipliers is implemented to perform a unitary transformation of the wave functions in the middle of the vacuum region. The method enables (i) reduction of the number of contributing tip-substrate wave function combinations used in the corresponding transmission matrix, and (ii) to bundle up wave functions with similar symmetry in the lateral plane, so that (iii) an intuitive understanding of the STM contrast can be achieved. The theory is applied to a CO dimer adsorbed on a Cu(1 1 1) surface scanned by a single-atom Cu tip, whose STM image is discussed in detail by the outlined method.

Accurate calculation and modeling of the adiabatic connection in density functional theory

NASA Astrophysics Data System (ADS)

Teale, A. M.; Coriani, S.; Helgaker, T.

2010-04-01

Using a recently implemented technique for the calculation of the adiabatic connection (AC) of density functional theory (DFT) based on Lieb maximization with respect to the external potential, the AC is studied for atoms and molecules containing up to ten electrons: the helium isoelectronic series, the hydrogen molecule, the beryllium isoelectronic series, the neon atom, and the water molecule. The calculation of AC curves by Lieb maximization at various levels of electronic-structure theory is discussed. For each system, the AC curve is calculated using Hartree-Fock (HF) theory, second-order Møller-Plesset (MP2) theory, coupled-cluster singles-and-doubles (CCSD) theory, and coupled-cluster singles-doubles-perturbative-triples [CCSD(T)] theory, expanding the molecular orbitals and the effective external potential in large Gaussian basis sets. The HF AC curve includes a small correlation-energy contribution in the context of DFT, arising from orbital relaxation as the electron-electron interaction is switched on under the constraint that the wave function is always a single determinant. The MP2 and CCSD AC curves recover the bulk of the dynamical correlation energy and their shapes can be understood in terms of a simple energy model constructed from a consideration of the doubles-energy expression at different interaction strengths. Differentiation of this energy expression with respect to the interaction strength leads to a simple two-parameter doubles model (AC-D) for the AC integrand (and hence the correlation energy of DFT) as a function of the interaction strength. The structure of the triples-energy contribution is considered in a similar fashion, leading to a quadratic model for the triples correction to the AC curve (AC-T). From a consideration of the structure of a two-level configuration-interaction (CI) energy expression of the hydrogen molecule, a simple two-parameter CI model (AC-CI) is proposed to account for the effects of static correlation on the AC. When parametrized in terms of the same input data, the AC-CI model offers improved performance over the corresponding AC-D model, which is shown to be the lowest-order contribution to the AC-CI model. The utility of the accurately calculated AC curves for the analysis of standard density functionals is demonstrated for the BLYP exchange-correlation functional and the interaction-strength-interpolation (ISI) model AC integrand. From the results of this analysis, we investigate the performance of our proposed two-parameter AC-D and AC-CI models when a simple density functional for the AC at infinite interaction strength is employed in place of information at the fully interacting point. The resulting two-parameter correlation functionals offer a qualitatively correct behavior of the AC integrand with much improved accuracy over previous attempts. The AC integrands in the present work are recommended as a basis for further work, generating functionals that avoid spurious error cancellations between exchange and correlation energies and give good accuracy for the range of densities and types of correlation contained in the systems studied here.

Theoretical study on the spectroscopic properties of CO3(*-).nH2O clusters: extrapolation to bulk.

PubMed

Pathak, Arup K; Mukherjee, Tulsi; Maity, Dilip K

2008-10-24

Vertical detachment energies (VDE) and UV/Vis absorption spectra of hydrated carbonate radical anion clusters, CO(3)(*-).nH(2)O (n=1-8), are determined by means of ab initio electronic structure theory. The VDE values of the hydrated clusters are calculated with second-order Moller-Plesset perturbation (MP2) and coupled cluster theory using the 6-311++G(d,p) set of basis functions. The bulk VDE value of an aqueous carbonate radical anion solution is predicted to be 10.6 eV from the calculated weighted average VDE values of the CO(3)(*-).nH(2)O clusters. UV/Vis absorption spectra of the hydrated clusters are calculated by means of time-dependent density functional theory using the Becke three-parameter nonlocal exchange and the Lee-Yang-Parr nonlocal correlation functional (B3LYP). The simulated UV/Vis spectrum of the CO(3)(*-).8H(2)O cluster is in excellent agreement with the reported experimental spectrum for CO(3)(*-) (aq), obtained based on pulse radiolysis experiments.

Density functional calculations of multiphonon capture cross sections at defects in semiconductors

NASA Astrophysics Data System (ADS)

Barmparis, Georgios D.; Puzyrev, Yevgeniy S.; Zhang, X.-G.; Pantelides, Sokrates T.

2014-03-01

The theory of electron capture cross sections by multiphonon processes in semiconductors has a long and controversial history. Here we present a comprehensive theory and describe its implementation for realistic calculations. The Born-Oppenheimer and the Frank-Condon approximations are employed. The transition probability of an incoming electron is written as a product of an instantaneous electronic transition in the initial defect configuration and the line shape function (LSF) that describes the multiphonon processes that lead to lattice relaxation. The electronic matrix elements are calculated using the Projector Augmented Wave (PAW) method which yields the true wave functions while still employing a plane-wave basis. The LSF is calculated by employing a Monte Carlo method and the real phonon modes of the defect, calculated using density functional theory in the PAW scheme. Initial results of the capture cross section for a prototype system, namely a triply hydrogenated vacancy in Si are presented. The results are relevant for modeling device degradation by hot electron effects. This work is supported in part by the Samsung Advanced Institute of Technology (SAIT)'s Global Research Outreach (GRO) Program and by the LDRD program at ORNL.

A Finite Element Theory for Predicting the Attenuation of Extended-Reacting Liners

NASA Technical Reports Server (NTRS)

Watson, W. R.; Jones, M. G.

2009-01-01

A non-modal finite element theory for predicting the attenuation of an extended-reacting liner containing a porous facesheet and located in a no-flow duct is presented. The mathematical approach is to solve separate wave equations in the liner and duct airway and to couple these two solutions by invoking kinematic constraints at the facesheet that are consistent with a continuum theory of fluid motion. Given the liner intrinsic properties, a weak Galerkin finite element formulation with cubic polynomial basis functions is used as the basis for generating a discrete system of acoustic equations that are solved to obtain the coupled acoustic field. A state-of-the-art, asymmetric, parallel, sparse equation solver is implemented that allows tens of thousands of grid points to be analyzed. A grid refinement study is presented to show that the predicted attenuation converges. Excellent comparison of the numerically predicted attenuation to that of a mode theory (using a Haynes 25 metal foam liner) is used to validate the computational approach. Simulations are also presented for fifteen porous plate, extended-reacting liners. The construction of some of the porous plate liners suggest that they should behave as resonant liners while the construction of others suggest that they should behave as broadband attenuators. In each case the finite element theory is observed to predict the proper attenuation trend.

Fermionic Approach to Weighted Hurwitz Numbers and Topological Recursion

NASA Astrophysics Data System (ADS)

Alexandrov, A.; Chapuy, G.; Eynard, B.; Harnad, J.

2017-12-01

A fermionic representation is given for all the quantities entering in the generating function approach to weighted Hurwitz numbers and topological recursion. This includes: KP and 2D Toda {τ} -functions of hypergeometric type, which serve as generating functions for weighted single and double Hurwitz numbers; the Baker function, which is expanded in an adapted basis obtained by applying the same dressing transformation to all vacuum basis elements; the multipair correlators and the multicurrent correlators. Multiplicative recursion relations and a linear differential system are deduced for the adapted bases and their duals, and a Christoffel-Darboux type formula is derived for the pair correlator. The quantum and classical spectral curves linking this theory with the topological recursion program are derived, as well as the generalized cut-and-join equations. The results are detailed for four special cases: the simple single and double Hurwitz numbers, the weakly monotone case, corresponding to signed enumeration of coverings, the strongly monotone case, corresponding to Belyi curves and the simplest version of quantum weighted Hurwitz numbers.

Fermionic Approach to Weighted Hurwitz Numbers and Topological Recursion

NASA Astrophysics Data System (ADS)

Alexandrov, A.; Chapuy, G.; Eynard, B.; Harnad, J.

2018-06-01

A fermionic representation is given for all the quantities entering in the generating function approach to weighted Hurwitz numbers and topological recursion. This includes: KP and 2 D Toda {τ} -functions of hypergeometric type, which serve as generating functions for weighted single and double Hurwitz numbers; the Baker function, which is expanded in an adapted basis obtained by applying the same dressing transformation to all vacuum basis elements; the multipair correlators and the multicurrent correlators. Multiplicative recursion relations and a linear differential system are deduced for the adapted bases and their duals, and a Christoffel-Darboux type formula is derived for the pair correlator. The quantum and classical spectral curves linking this theory with the topological recursion program are derived, as well as the generalized cut-and-join equations. The results are detailed for four special cases: the simple single and double Hurwitz numbers, the weakly monotone case, corresponding to signed enumeration of coverings, the strongly monotone case, corresponding to Belyi curves and the simplest version of quantum weighted Hurwitz numbers.

Computation of indirect nuclear spin-spin couplings with reduced complexity in pure and hybrid density functional approximations.

PubMed

Luenser, Arne; Kussmann, Jörg; Ochsenfeld, Christian

2016-09-28

We present a (sub)linear-scaling algorithm to determine indirect nuclear spin-spin coupling constants at the Hartree-Fock and Kohn-Sham density functional levels of theory. Employing efficient integral algorithms and sparse algebra routines, an overall (sub)linear scaling behavior can be obtained for systems with a non-vanishing HOMO-LUMO gap. Calculations on systems with over 1000 atoms and 20 000 basis functions illustrate the performance and accuracy of our reference implementation. Specifically, we demonstrate that linear algebra dominates the runtime of conventional algorithms for 10 000 basis functions and above. Attainable speedups of our method exceed 6 × in total runtime and 10 × in the linear algebra steps for the tested systems. Furthermore, a convergence study of spin-spin couplings of an aminopyrazole peptide upon inclusion of the water environment is presented: using the new method it is shown that large solvent spheres are necessary to converge spin-spin coupling values.

Density Functional Theory (DFT) Study of Molecularly Imprinted Polymer (MIP) Methacrylic Acid (MAA) with D-Glucose

NASA Astrophysics Data System (ADS)

Wungu, T. D. K.; Marsha, S. E.; Widayani; Suprijadi

2017-07-01

In order to find an alternative biosensor material which enables to detect the glucose level, therefore in this study, the interaction between Methacrylic Acid (MAA) based Molecularly Imprinted Polymer (MIP) with D-Glucose is investigated using the Density Functional Theory (DFT). The aim of this study is to determine whether a molecule of the MAA can be functioned as a bio-sensing of glucose. In this calculation, the Gaussian 09 with B3LYP and 631+G(d) basis sets is used to calculate all electronic properties. It is found that the interaction between a molecule of MAA and a molecule of D-Glucose was observed through the shortened distance between the two molecules. The binding energy of MAA/D-glucose and the Mulliken population analysis are investigated for checking possible interaction. From analysis, the MAA based MIP can be used as a bio-sensing material.

DFT based vibrational spectroscopic investigations and biological activity of toxic material monocrotophos

NASA Astrophysics Data System (ADS)

Nimmi, D. E.; Sam, S. P. Chandhini; Praveen, S. G.; Binoy, J.

2018-05-01

Many organophosphate compounds exhibiting toxicity are widely used as pesticides and insecticides whose structural features can be explained excellently using geometric simulation using density functional theory and vibrational spectrum. In this work, the molecular structural parameters and vibrational frequencies of the fundamental modes of Monocrotophoshave been obtained using Density functional theory (DFT), using B3LYP functional with 6-311++G(d, p) basis sets and the detailed vibrational analysis of FT-IR and FT-Ramanspectral bands have been carried out using potential energy distribution (PED). The deviation from the resonance structure of phosphate group due to `bridging of oxygen' and π-resonance of amides has been investigated based on the spectral and geometric data. The molecular docking simulation of Monocrotophos with BSA and DNA has been performed to find the mode of binding and the interactions with BSA has been investigated with UV-Visible spectroscopic method, to assess the strength of binding.

Vibrational, spectroscopic, molecular docking and density functional theory studies on N-(5-aminopyridin-2-yl)acetamide

NASA Astrophysics Data System (ADS)

Asath, R. Mohamed; Rekha, T. N.; Premkumar, S.; Mathavan, T.; Benial, A. Milton Franklin

2016-12-01

Conformational analysis was carried out for N-(5-aminopyridin-2-yl)acetamide (APA) molecule. The most stable, optimized structure was predicted by the density functional theory calculations using the B3LYP functional with cc-pVQZ basis set. The optimized structural parameters and vibrational frequencies were calculated. The experimental and theoretical vibrational frequencies were assigned and compared. Ultraviolet-visible spectrum was simulated and validated experimentally. The molecular electrostatic potential surface was simulated. Frontier molecular orbitals and related molecular properties were computed, which reveals that the higher molecular reactivity and stability of the APA molecule and further density of states spectrum was simulated. The natural bond orbital analysis was also performed to confirm the bioactivity of the APA molecule. Antidiabetic activity was studied based on the molecular docking analysis and the APA molecule was identified that it can act as a good inhibitor against diabetic nephropathy.

G3//BMK and Its Application to Calculation of Bond Dissociation Enthalpies.

PubMed

Zheng, Wen-Rui; Fu, Yao; Guo, Qing-Xiang

2008-08-01

On the basis of systematic examinations it was found that the BMK functional significantly outperformed the other popular density functional theory methods including B3LYP, B3P86, KMLYP, MPW1P86, O3LYP, and X3LYP for the calculation of bond dissociation enthalpies (BDEs). However, it was also found that even the BMK functional might dramatically fail in predicting the BDEs of some chemical bonds. To solve this problem, a new composite ab initio method named G3//BMK was developed by combining the strengths of both the G3 theory and BMK. G3//BMK was found to outperform the G3 and G3//B3LYP methods. It could accurately predict the BDEs of diverse types of chemical bonds in various organic molecules within a precision of ca. 1.2 kcal/mol.

Determination of the absolute configurations of synthetic daunorubicin analogues using vibrational circular dichroism spectroscopy and density functional theory.

PubMed

Yang, Guochun; Tran, Ha; Fan, Eric; Shi, Wei; Lowary, Todd L; Xu, Yunjie

2010-08-01

The absolute configurations of three synthesized anthracycline analogues have been determined using vibrational circular dichroism (VCD) spectroscopy and the density functional theory (DFT) calculations. The experimental VCD spectra of the three compounds have been measured for the first time in the film state, prepared from their CDCl(3) solutions. Conformational searches for the monomers and some dimers of the three compounds have been performed at the DFT level using the B3LYP functional and the 6-311G** and 6-311++G** basis sets. The corresponding vibrational absorption and VCD spectra have been calculated. The good agreement between the experimental and the calculated spectra allows one to assign the absolute configurations of the three compounds with high confidence. In addition, the dominant conformers of the three compounds have also been identified. Copyright 2010 Wiley-Liss, Inc.

[The relevance of ethology for psychiatry].

PubMed

Brüne, M

1998-07-01

Darwin's evolutionary theory was the starting point for ethology, associated with an impact on scientific psychiatry. Psychiatry and ethology have common scientific and methodological prerequisites: inductive and deductive methods and "gestalt theory" as a basis for observing and describing behaviour patterns with subsequent causal analysis. There have been early endeavours to anchor ethological thinking in psychiatry but this tendency did not prevail for the following reasons: on the one hand, the methodology of ethology was immature or not applicable to man, whereas on the other hand the dominating experiential phenomenological school of Karl Jaspers and Kurt Schneider stressed the privileged position of human thinking, perception, and feeling. These fundamental categories of human existence did not appear amenable to any causal ethological analysis. Psychiatry and evolutionary biology were linked in an atrocious manner during the Nazi regime, both being abused for propaganda purposes and genocide. More recently, there is a "reconciliation" of both disciplines. In psychiatric nosology, operational, behaviour-oriented diagnostic systems have been introduced; ethology has opened up for theories of learning; new subsections like human ethology and sociobiology have evolved. The seeming incompatibility of (behavioural) biological psychiatry and experiential phenomenological psychopathology may be overcome on the basis of Konrad Lorenz' evolutionary epistemology. The functional analysis of human feeling and behaviour in psychotic disorders on the basis of Jackson's theory of the evolution and dissolution of the nervous system may serve as an example. The significance of an "ethological psychiatry" for diagnostic and therapeutical processes of psychiatric disorders derive from prognostic possibilities and the analysis of non-verbal communication in therapist-patient-interactions, but have not yet been systematically investigated.

State-of-the-art ab initio potential energy curve for the krypton atom pair and thermophysical properties of dilute krypton gas

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

Jäger, Benjamin, E-mail: benjamin.jaeger@uni-rostock.de; Hellmann, Robert, E-mail: robert.hellmann@uni-rostock.de; Bich, Eckard

2016-03-21

A new reference krypton-krypton interatomic potential energy curve was developed by means of quantum-chemical ab initio calculations for 36 interatomic separations. Highly accurate values for the interaction energies at the complete basis set limit were obtained using the coupled-cluster method with single, double, and perturbative triple excitations as well as t-aug-cc-pV5Z and t-aug-cc-pV6Z basis sets including mid-bond functions, with the 6Z basis set being newly constructed for this study. Higher orders of coupled-cluster terms were considered in a successive scheme up to full quadruple excitations. Core-core and core-valence correlation effects were included. Furthermore, relativistic effects were studied not only atmore » a scalar relativistic level using second-order direct perturbation theory, but also utilizing full four-component and Gaunt-effect computations. An analytical pair potential function was fitted to the interaction energies, which is characterized by a depth of 200.88 K with an estimated standard uncertainty of 0.51 K. Thermophysical properties of low-density krypton were calculated for temperatures up to 5000 K. Second and third virial coefficients were obtained from statistical thermodynamics. Viscosity and thermal conductivity as well as the self-diffusion coefficient were computed using the kinetic theory of gases. The theoretical results are compared with experimental data and with results for other pair potential functions from the literature, especially with those calculated from the recently developed ab initio potential of Waldrop et al. [J. Chem. Phys. 142, 204307 (2015)]. Highly accurate experimental viscosity data indicate that both the present ab initio pair potential and the one of Waldrop et al. can be regarded as reference potentials, even though the quantum-chemical methods and basis sets differ. However, the uncertainties of the present potential and of the derived properties are estimated to be considerably lower.« less

State-of-the-art ab initio potential energy curve for the krypton atom pair and thermophysical properties of dilute krypton gas.

PubMed

Jäger, Benjamin; Hellmann, Robert; Bich, Eckard; Vogel, Eckhard

2016-03-21

A new reference krypton-krypton interatomic potential energy curve was developed by means of quantum-chemical ab initio calculations for 36 interatomic separations. Highly accurate values for the interaction energies at the complete basis set limit were obtained using the coupled-cluster method with single, double, and perturbative triple excitations as well as t-aug-cc-pV5Z and t-aug-cc-pV6Z basis sets including mid-bond functions, with the 6Z basis set being newly constructed for this study. Higher orders of coupled-cluster terms were considered in a successive scheme up to full quadruple excitations. Core-core and core-valence correlation effects were included. Furthermore, relativistic effects were studied not only at a scalar relativistic level using second-order direct perturbation theory, but also utilizing full four-component and Gaunt-effect computations. An analytical pair potential function was fitted to the interaction energies, which is characterized by a depth of 200.88 K with an estimated standard uncertainty of 0.51 K. Thermophysical properties of low-density krypton were calculated for temperatures up to 5000 K. Second and third virial coefficients were obtained from statistical thermodynamics. Viscosity and thermal conductivity as well as the self-diffusion coefficient were computed using the kinetic theory of gases. The theoretical results are compared with experimental data and with results for other pair potential functions from the literature, especially with those calculated from the recently developed ab initio potential of Waldrop et al. [J. Chem. Phys. 142, 204307 (2015)]. Highly accurate experimental viscosity data indicate that both the present ab initio pair potential and the one of Waldrop et al. can be regarded as reference potentials, even though the quantum-chemical methods and basis sets differ. However, the uncertainties of the present potential and of the derived properties are estimated to be considerably lower.

Consistent structures and interactions by density functional theory with small atomic orbital basis sets.

PubMed

Grimme, Stefan; Brandenburg, Jan Gerit; Bannwarth, Christoph; Hansen, Andreas

2015-08-07

A density functional theory (DFT) based composite electronic structure approach is proposed to efficiently compute structures and interaction energies in large chemical systems. It is based on the well-known and numerically robust Perdew-Burke-Ernzerhoff (PBE) generalized-gradient-approximation in a modified global hybrid functional with a relatively large amount of non-local Fock-exchange. The orbitals are expanded in Ahlrichs-type valence-double zeta atomic orbital (AO) Gaussian basis sets, which are available for many elements. In order to correct for the basis set superposition error (BSSE) and to account for the important long-range London dispersion effects, our well-established atom-pairwise potentials are used. In the design of the new method, particular attention has been paid to an accurate description of structural parameters in various covalent and non-covalent bonding situations as well as in periodic systems. Together with the recently proposed three-fold corrected (3c) Hartree-Fock method, the new composite scheme (termed PBEh-3c) represents the next member in a hierarchy of "low-cost" electronic structure approaches. They are mainly free of BSSE and account for most interactions in a physically sound and asymptotically correct manner. PBEh-3c yields good results for thermochemical properties in the huge GMTKN30 energy database. Furthermore, the method shows excellent performance for non-covalent interaction energies in small and large complexes. For evaluating its performance on equilibrium structures, a new compilation of standard test sets is suggested. These consist of small (light) molecules, partially flexible, medium-sized organic molecules, molecules comprising heavy main group elements, larger systems with long bonds, 3d-transition metal systems, non-covalently bound complexes (S22 and S66×8 sets), and peptide conformations. For these sets, overall deviations from accurate reference data are smaller than for various other tested DFT methods and reach that of triple-zeta AO basis set second-order perturbation theory (MP2/TZ) level at a tiny fraction of computational effort. Periodic calculations conducted for molecular crystals to test structures (including cell volumes) and sublimation enthalpies indicate very good accuracy competitive to computationally more involved plane-wave based calculations. PBEh-3c can be applied routinely to several hundreds of atoms on a single processor and it is suggested as a robust "high-speed" computational tool in theoretical chemistry and physics.

Vibrational assignment and structure of trinuclear oxo-centered of basic formate iron(III) and chromium(III) complexes: A density functional theory study

NASA Astrophysics Data System (ADS)

Kiana, Samaneh; Yazdanbakhsh, Mohammad; Jamialahmadi, Mina; Tayyari, Sayyed Faramarz

2014-09-01

[Fe3O(OOCH)6(H2O)3]OOCH·HCOOH, and [Cr3O(OOCH)6(H2O)3]OOCH·2.5HNO3 were synthesized and the molecular structure and vibrational assignments of their cations were investigated by means of density functional theory (DFT) calculations. The harmonic vibrational frequencies of [Fe3O(OOCH)6(H2O)3]+ and [Cr3O(OOCH)6(H2O)3]+ were obtained at the UB3LYP level using a series of basis sets. The topological properties of the charge distribution of both cations in their ground states are discussed in detail by means of natural bond orbital (NBO) theory and of [Fe3O(OOCH)6(H2O)3]+ by the quantum theory of atoms in molecules (AIM). The calculated geometrical parameters and vibrational frequencies were compared with the experimental results. The scaled theoretical frequencies and the structural parameters were found to be in good agreement with the experimental data.

Reaction mechanisms and kinetics of the elimination processes of 2-chloroethylsilane and derivatives: A DFT study using CTST, RRKM, and BET theories

NASA Astrophysics Data System (ADS)

Shiroudi, Abolfazl; Zahedi, Ehsan; Oliaey, Ahmad Reza; Deleuze, Michael S.

2017-03-01

The thermal decomposition kinetics of 2-chloroethylsilane and derivatives in the gas phase has been studied computationally using density functional theory, along with various exchange-correlation functionals (UM06-2x and ωB97XD) and the aug-cc-pVTZ basis set. The calculated energy profile has been supplemented with calculations of kinetic rate constants under atmospheric pressure and in the fall-off regime, using transition state theory (TST) and statistical Rice-Ramsperger-Kassel-Marcus (RRKM) theory. Activation energies and rate constants obtained using the UM06-2x/aug-cc-pVTZ approach are in good agreement with the experimental data. The decomposition of 2-chloroethyltriethylsilane species into the related products [C2H4 + Et3SiCl] is characterized by 6 successive structural stability domains associated to the sequence of catastrophes C8H19SiCl: 6-C†FCC†[FF]-0: C6H15SiCl + C2H4. Breaking of Si-C bonds and formation of Si-Cl bonds occur in the vicinity of the transition state.

A density functional theory (DFT) and time-dependent density functional theory (TDDFT) study on optical transitions in oligo(p-phenylenevinylene)-fullerene dyads and the applicability to resonant energy transfer.

PubMed

Toivonen, Teemu L J; Hukka, Terttu I

2007-06-07

The optical transitions of three different size oligo(p-phenylenevinylene)-fullerene dyads (OPV(n)-MPC(60); n = 2-4) and of the corresponding separate molecules are studied using density functional theory (DFT) and time-dependent density functional theory. The DFT is used to determine the geometries and the electronic structures of the ground states. Transition energies and excited-state structures are obtained from the TDDFT calculations. Resonant energy transfer from OPV(n) to MPC(60) is also studied and the Fermi golden rule is used, along with two simple models to describe the electronic coupling to calculate the energy transfer rates. The hybrid-type PBE0 functional is used with a split-valence basis set augmented with a polarization function (SV(P)) in calculations and the calculated results are compared to the corresponding experimental results. The calculated PBE0 spectra of the OPV(n)-MPC(60) dyads correspond to the experimental spectra very well and are approximately sums of the absorption spectra of the separate OPV(n) and MPC(60) molecules. Also, the absorption energies of OPV(n) and MPC(60) and the emission energies of OPV(n) are predicted well with the PBE0 functional. The PBE0 calculated resonant energy transfer rates are in a good agreement with the experimental rates and show the existence of many possible pathways for energy transfer from the first excited singlet states of the OPV(n) molecules to the MPC(60) molecule.

Teaching the English Active and Passive Voice with the Help of Cognitive Grammar: An Empirical Study

ERIC Educational Resources Information Center

Bielak, Jakub; Pawlak, Mirosuaw; Mystkowska-Wiertelak, Anna

2013-01-01

Functionally-oriented linguistic theories, such as cognitive grammar (CG), offer nuanced descriptions of the meanings and uses of grammatical features. A simplified characterization of the semantics of the English active and passive voice grounded in CG terms and based on the reference point model is presented, as it is the basis of the…

Computational study of frontier orbitals, moments, chemical reactivity and thermodynamic parameters of sildenafil

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

Sachdeva, Ritika, E-mail: ritika.sachdeva21@gmail.com; Kaur, Prabhjot; Singh, V. P.

2016-05-06

Analysis of frontier orbitals of sildenafil has been carried using Density Functional Theory. On the basis of HOMO-LUMO energy, values of global chemical reactivity descriptors such as electronegativity, chemical hardness, softness, chemical potential, electrophilicity index have been calculated. Calculated values of dipole moment, polarizability, hyperpolarizability have also been reported for sildenafil along with its thermodynamic parameters.

Molecular conformational analysis, vibrational spectra and normal coordinate analysis of trans-1,2-bis(3,5-dimethoxy phenyl)-ethene based on density functional theory calculations.

PubMed

Joseph, Lynnette; Sajan, D; Chaitanya, K; Isac, Jayakumary

2014-03-25

The conformational behavior and structural stability of trans-1,2-bis(3,5-dimethoxy phenyl)-ethene (TDBE) were investigated by using density functional theory (DFT) method with the B3LYP/6-311++G(d,p) basis set combination. The vibrational wavenumbers of TDBE were computed at DFT level and complete vibrational assignments were made on the basis of normal coordinate analysis calculations (NCA). The DFT force field transformed to natural internal coordinates was corrected by a well-established set of scale factors that were found to be transferable to the title compound. The infrared and Raman spectra were also predicted from the calculated intensities. The observed Fourier transform infrared (FTIR) and Fourier transform (FT) Raman vibrational wavenumbers were analyzed and compared with the theoretically predicted vibrational spectra. Comparison of the simulated spectra with the experimental spectra provides important information about the ability of the computational method to describe the vibrational modes. Information about the size, shape, charge density distribution and site of chemical reactivity of the molecules has been obtained by mapping electron density isosurface with electrostatic potential surfaces (ESP). Copyright © 2013 Elsevier B.V. All rights reserved.

Stochastic theory of polarized light in nonlinear birefringent media: An application to optical rotation

NASA Astrophysics Data System (ADS)

Tsuchida, Satoshi; Kuratsuji, Hiroshi

2018-05-01

A stochastic theory is developed for the light transmitting the optical media exhibiting linear and nonlinear birefringence. The starting point is the two-component nonlinear Schrödinger equation (NLSE). On the basis of the ansatz of “soliton” solution for the NLSE, the evolution equation for the Stokes parameters is derived, which turns out to be the Langevin equation by taking account of randomness and dissipation inherent in the birefringent media. The Langevin equation is converted to the Fokker-Planck (FP) equation for the probability distribution by employing the technique of functional integral on the assumption of the Gaussian white noise for the random fluctuation. The specific application is considered for the optical rotation, which is described by the ellipticity (third component of the Stokes parameters) alone: (i) The asymptotic analysis is given for the functional integral, which leads to the transition rate on the Poincaré sphere. (ii) The FP equation is analyzed in the strong coupling approximation, by which the diffusive behavior is obtained for the linear and nonlinear birefringence. These would provide with a basis of statistical analysis for the polarization phenomena in nonlinear birefringent media.

Vibrational analysis, NBO analysis, NMR, UV-VIS, hyperpolarizability analysis of Trimethadione by density functional theory

NASA Astrophysics Data System (ADS)

Vijayachamundeeswari, S. P.; Yagna Narayana, B.; Jone Pradeepa, S.; Sundaraganesan, N.

2015-11-01

Trimethadione (TMD) is an anticonvulsant drug widely used against absences seizures. We have characterised the TMD by various spectra including UV-VIS, IR, Raman, GC-MS and NMR. In this work, we made use of Density Functional Theory (DFT) B3LYP method with 6-31G (d, p) basis set, to calculate the molecular structure of TMD, and predicted its infrared, Raman and ultraviolet spectra for the first time. FT-IR and FT-Raman spectra were recorded in the region 4000-400 cm-1 and 3500-50 cm-1, respectively. The vibrational frequencies were calculated and scaled values were compared with the experimental FT-IR and FT-Raman spectra. The observed and calculated frequencies are found to be in good agreement. The complete assignments were performed on the basis of the total energy distribution (TED) of the vibrational modes. The optimized geometry parameters were calculated. NMR chemical shifts of the molecule were calculated using the gauge independent atomic orbital (GIAO) method. The predicted first hyperpolarizibility also shows that the molecule might have convincingly good nonlinear optical (NLO) activities. The calculated HOMO-LUMO energy gap discloses that charge transfer occurs within the molecule.

Experimental and theoretical studies of (FT-IR, FT-Raman, UV-Visible and DFT) 4-(6-methoxynaphthalen-2-yl) butan-2-one.

PubMed

Govindasamy, P; Gunasekaran, S

2015-01-01

In this work, the vibrational spectral analysis was carried out by using FT-Raman and FT-IR spectroscopy in the range 4000-50 cm(-1) and 4000-450 cm(-1) respectively for 4-(6-methoxynaphthalen-2-yl) butan-2-one (abbreviated as 4MNBO) molecule. Theoretical calculations were performed by density functional theory (DFT/B3LYP) method using 6-311G(d,p) and 6-311++G(d,p) basis sets. The difference between the observed and calculated wavenumber value of most of the fundamentals were very small. The complete vibrational assignments of wavenumbers were made on the basis of potential energy distribution (PED). The UV-Vis spectrum was recorded in the methanol solution. The energy, wavelength and oscillator's strength were calculated by Time Dependent Density Functional Theory (TD-DFT) and matched to the experimental findings. The intramolecular contacts have been interpreted using natural bond orbital (NBO) and natural localized molecular orbital (NLMO) analysis. Thermodynamic properties of 4MNBO at different temperature have been calculated. The molecular electrostatic potential surface (MESP) and Frontier molecular orbital's (FMO's) analysis were investigated using theoretical calculations. Copyright © 2015 Elsevier B.V. All rights reserved.

Molecular structure, vibrational spectra, NBO analysis and molecular packing prediction of 3-nitroacetanilide by ab initio HF and density functional theory.

PubMed

Li, Xiao-Hong; Li, Tong-Wei; Ju, Wei-Wei; Yong, Yong-Liang; Zhang, Xian-Zhou

2014-01-24

Quantum chemical calculations of geometries and vibrational wavenumbers of 3-nitroacetanilide (C8H8N2O3) in the ground state were carried out by using ab initio HF and density functional theory (DFT/B3LYP) methods with 6-31+G(*) basis set. The -311++G(**) basis set is also used for B3LYP level. The scaled harmonic vibrational frequencies have been compared with experimental FT-IR spectra. Theoretical vibrational spectra of the title compound were interpreted by means of potential energies distributions (PEDs) using MOLVIB program. The theoretical spectrograms for IR spectra of the title compound have been constructed. The shortening of C-H bond length and the elongation of N-H bond length suggest the existence of weak C-H⋯O and N-H⋯O hydrogen bonds, which is confirmed by the natural bond orbital analysis. In addition, the crystal structure obtained by molecular mechanics belongs to the P2(1) space group, with lattice parameters Z=4, a=14.9989 Å, b=4.0367 Å, c=12.9913 Å, ρ=0.998 g cm(-3). Copyright © 2013 Elsevier B.V. All rights reserved.

Molecular structure, vibrational spectra, NBO analysis and molecular packing prediction of 3-nitroacetanilide by ab initio HF and density functional theory

NASA Astrophysics Data System (ADS)

Li, Xiao-Hong; Li, Tong-Wei; Ju, Wei-Wei; Yong, Yong-Liang; Zhang, Xian-Zhou

2014-01-01

Quantum chemical calculations of geometries and vibrational wavenumbers of 3-nitroacetanilide (C8H8N2O3) in the ground state were carried out by using ab initio HF and density functional theory (DFT/B3LYP) methods with 6-31+G* basis set. The -311++G** basis set is also used for B3LYP level. The scaled harmonic vibrational frequencies have been compared with experimental FT-IR spectra. Theoretical vibrational spectra of the title compound were interpreted by means of potential energies distributions (PEDs) using MOLVIB program. The theoretical spectrograms for IR spectra of the title compound have been constructed. The shortening of Csbnd H bond length and the elongation of Nsbnd H bond length suggest the existence of weak Csbnd H⋯O and Nsbnd H⋯O hydrogen bonds, which is confirmed by the natural bond orbital analysis. In addition, the crystal structure obtained by molecular mechanics belongs to the P21 space group, with lattice parameters Z = 4, a = 14.9989 Å, b = 4.0367 Å, c = 12.9913 Å, ρ = 0.998 g cm-3.

[Density functional theory studies on structure and spectrum of Cu3 Ti cluster].

PubMed

Wei, Yong-Hui; Cheng, Jian-Bo; Zhao, Bing; Lombardi, John R

2008-07-01

Bulk intermetallic Ti-Cu compounds have been found to possess special properties, including increased hardness, as well as displaying enhanced sound absorption and e shape memory. Since only one Raman progression is observed, there is not sufficient information to determine the structure of TiCu3. The different structures and vibrational frequencies of the Cu3 Ti cluster were studied by means of the density functional theory with SVWN5, B3LYP and BPW91 methods at basis sets of lanl2dz, 6-31g, 6-311g, 6-311g(d), 6-311 +/- g(2df) and 6-311 +/- g(3d2f). The calculated results show that the ground state of the Cu3 Ti cluster is a e-type structure with the C2v point group symmetry, and the bond lengths and vibrational frequencies of Cu3 T are considerably dependent on the variation of basis sets. We observed only a single Raman progression in approximately 300 cm(-1). This progression is most likely the totally symmetric stretch. The computed and observed Raman spectra were also compared with each other.

A Mathematical Basis for the Safety Analysis of Conflict Prevention Algorithms

NASA Technical Reports Server (NTRS)

Maddalon, Jeffrey M.; Butler, Ricky W.; Munoz, Cesar A.; Dowek, Gilles

2009-01-01

In air traffic management systems, a conflict prevention system examines the traffic and provides ranges of guidance maneuvers that avoid conflicts. This guidance takes the form of ranges of track angles, vertical speeds, or ground speeds. These ranges may be assembled into prevention bands: maneuvers that should not be taken. Unlike conflict resolution systems, which presume that the aircraft already has a conflict, conflict prevention systems show conflicts for all maneuvers. Without conflict prevention information, a pilot might perform a maneuver that causes a near-term conflict. Because near-term conflicts can lead to safety concerns, strong verification of correct operation is required. This paper presents a mathematical framework to analyze the correctness of algorithms that produce conflict prevention information. This paper examines multiple mathematical approaches: iterative, vector algebraic, and trigonometric. The correctness theories are structured first to analyze conflict prevention information for all aircraft. Next, these theories are augmented to consider aircraft which will create a conflict within a given lookahead time. Certain key functions for a candidate algorithm, which satisfy this mathematical basis are presented; however, the proof that a full algorithm using these functions completely satisfies the definition of safety is not provided.

The molecular gradient using the divide-expand-consolidate resolution of the identity second-order Møller-Plesset perturbation theory: The DEC-RI-MP2 gradient

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

Bykov, Dmytro; Kristensen, Kasper; Kjærgaard, Thomas

We report an implementation of the molecular gradient using the divide-expand-consolidate resolution of the identity second-order Møller-Plesset perturbation theory (DEC-RI-MP2). The new DEC-RI-MP2 gradient method combines the precision control as well as the linear-scaling and massively parallel features of the DEC scheme with efficient evaluations of the gradient contributions using the RI approximation. We further demonstrate that the DEC-RI-MP2 gradient method is capable of calculating molecular gradients for very large molecular systems. A test set of supramolecular complexes containing up to 158 atoms and 1960 contracted basis functions has been employed to demonstrate the general applicability of the DEC-RI-MP2 methodmore » and to analyze the errors of the DEC approximation. Moreover, the test set contains molecules of complicated electronic structures and is thus deliberately chosen to stress test the DEC-RI-MP2 gradient implementation. Additionally, as a showcase example the full molecular gradient for insulin (787 atoms and 7604 contracted basis functions) has been evaluated.« less

Perturbation theory of nuclear matter with a microscopic effective interaction

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

Benhar, Omar; Lovato, Alessandro

Here, an updated and improved version of the effective interaction based on the Argonne-Urbana nuclear Hamiltonian, derived using the formalism of correlated basis functions and the cluster expansion technique, is employed to obtain a number of properties of cold nuclear matter at arbitrary neutron excess within the formalism of many-body perturbation theory. The numerical results, including the ground-state energy per nucleon, the symmetry energy, the pressure, the compressibility, and the single-particle spectrum, are discussed in the context of the available empirical information, obtained from measured nuclear properties and heavy-ion collisions.

Perturbation theory of nuclear matter with a microscopic effective interaction

DOE PAGES

Benhar, Omar; Lovato, Alessandro

2017-11-01

Here, an updated and improved version of the effective interaction based on the Argonne-Urbana nuclear Hamiltonian, derived using the formalism of correlated basis functions and the cluster expansion technique, is employed to obtain a number of properties of cold nuclear matter at arbitrary neutron excess within the formalism of many-body perturbation theory. The numerical results, including the ground-state energy per nucleon, the symmetry energy, the pressure, the compressibility, and the single-particle spectrum, are discussed in the context of the available empirical information, obtained from measured nuclear properties and heavy-ion collisions.

Magic bases, metric ansaetze and generalized graph theories in the Virasoro master equation

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

Halpern, M.B.; Obers, N.A.

1991-11-15

The authors define a class of magic Lie group bases in which the Virasoro master equation admits a class of simple metric ansaetze (g{sub metric}), whose structure is visible in the high-level expansion. When a magic basis is real on compact g, the corresponding g{sub metric} is a large system of unitary, generically irrational conformal field theories. Examples in this class include the graph-theory ansatz SO(n){sub diag} in the Cartesian basis of So(n) and the ansatz SU(n){sub metric} in the Pauli-like basis of SU(n). A new phenomenon is observed in the high-level comparison of SU(n){sub metric}: Due to the trigonometricmore » structure constants of the Pauli-like basis, irrational central charge is clearly visible at finite order of the expansion. They also define the sine-area graphs of SU(n), which label the conformal field theories of SU(n){sub metric} and note that, in a similar fashion, each magic basis of g defines a generalize graph theory on g which labels the conformal field theories of g{sub metric}.« less

Vibrational spectroscopy and density functional theory analysis of 3-O-caffeoylquinic acid

NASA Astrophysics Data System (ADS)

Mishra, Soni; Tandon, Poonam; Eravuchira, Pinkie J.; El-Abassy, Rasha M.; Materny, Arnulf

2013-03-01

Density functional theory (DFT) calculations are being performed to investigate the geometric, vibrational, and electronic properties of the chlorogenic acid isomer 3-CQA (1R,3R,4S,5R)-3-{[(2E)-3-(3,4-dihydroxyphenyl)prop-2-enoyl]oxy}-1,4,5-trihydroxycyclohexanecarboxylic acid), a major phenolic compound in coffee. DFT calculations with the 6-311G(d,p) basis set produce very good results. The electrostatic potential mapped onto an isodensity surface has been obtained. A natural bond orbital analysis (NBO) has been performed in order to study intramolecular bonding, interactions among bonds, and delocalization of unpaired electrons. HOMO-LUMO studies give insights into the interaction of the molecule with other species. The calculated HOMO and LUMO energies indicate that a charge transfer occurs within the molecule.

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.

A quantitative relationship for the shock sensitivities of energetic compounds based on X-NO(2) (X=C, N, O) bond dissociation energy.

PubMed

Li, Jinshan

2010-08-15

The ZPE-corrected X-NO(2) (X=C, N, O) bond dissociation energies (BDEs(ZPE)) of 11 energetic nitrocompounds of different types have been calculated employing density functional theory methods. Computed results show that using the 6-31G** basis set the UB3LYP calculated BDE(ZPE) is less than the UB3P86. For these typical energetic nitrocompounds the shock-initiated pressure (P(98)) is strongly related to the BDE(ZPE) indeed, and a polynomial correlation of ln(P(98)) with the BDE(ZPE) has been established successfully at different density functional theory levels, which provides a method to address the shock sensitivity problem. Copyright 2010 Elsevier B.V. All rights reserved.

Vibrational study and Natural Bond Orbital analysis of serotonin in monomer and dimer states by density functional theory

NASA Astrophysics Data System (ADS)

Borah, Mukunda Madhab; Devi, Th. Gomti

2018-06-01

The vibrational spectral analysis of Serotonin and its dimer were carried out using the Fourier Transform Infrared (FTIR) and Raman techniques. The equilibrium geometrical parameters, harmonic vibrational wavenumbers, Frontier orbitals, Mulliken atomic charges, Natural Bond orbitals, first order hyperpolarizability and some optimized energy parameters were computed by density functional theory with 6-31G(d,p) basis set. The detailed analysis of the vibrational spectra have been carried out by computing Potential Energy Distribution (PED, %) with the help of Vibrational Energy Distribution Analysis (VEDA) program. The second order delocalization energies E(2) confirms the occurrence of intramolecular Charge Transfer (ICT) within the molecule. The computed wavenumbers of Serotonin monomer and dimer were found in good agreement with the experimental Raman and IR values.

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.

Theory of correlation in a network with synaptic depression

NASA Astrophysics Data System (ADS)

Igarashi, Yasuhiko; Oizumi, Masafumi; Okada, Masato

2012-01-01

Synaptic depression affects not only the mean responses of neurons but also the correlation of response variability in neural populations. Although previous studies have constructed a theory of correlation in a spiking neuron model by using the mean-field theory framework, synaptic depression has not been taken into consideration. We expanded the previous theoretical framework in this study to spiking neuron models with short-term synaptic depression. On the basis of this theory we analytically calculated neural correlations in a ring attractor network with Mexican-hat-type connectivity, which was used as a model of the primary visual cortex. The results revealed that synaptic depression reduces neural correlation, which could be beneficial for sensory coding. Furthermore, our study opens the way for theoretical studies on the effect of interaction change on the linear response function in large stochastic networks.

Quantitative molecular orbital energies within a G0W0 approximation

NASA Astrophysics Data System (ADS)

Sharifzadeh, S.; Tamblyn, I.; Doak, P.; Darancet, P. T.; Neaton, J. B.

2012-09-01

Using many-body perturbation theory within a G 0 W 0 approximation, with a plane wave basis set and using a starting point based on density functional theory within the generalized gradient approximation, we explore routes for computing the ionization potential (IP), electron affinity (EA), and fundamental gap of three gas-phase molecules — benzene, thiophene, and (1,4) diamino-benzene — and compare with experiments. We examine the dependence of the IP and fundamental gap on the number of unoccupied states used to represent the dielectric function and the self energy, as well as the dielectric function plane-wave cutoff. We find that with an effective completion strategy for approximating the unoccupied subspace, and a well converged dielectric function kinetic energy cutoff, the computed IPs and EAs are in excellent quantitative agreement with available experiment (within 0.2 eV), indicating that a one-shot G 0 W 0 approach can be very accurate for calculating addition/removal energies of small organic molecules.

Kubo formulas for the shear and bulk viscosity relaxation times and the scalar field theory shear τπ calculation

NASA Astrophysics Data System (ADS)

Czajka, Alina; Jeon, Sangyong

2017-06-01

In this paper we provide a quantum field theoretical study on the shear and bulk relaxation times. First, we find Kubo formulas for the shear and the bulk relaxation times, respectively. They are found by examining response functions of the stress-energy tensor. We use general properties of correlation functions and the gravitational Ward identity to parametrize analytical structures of the Green functions describing both sound and diffusion mode. We find that the hydrodynamic limits of the real parts of the respective energy-momentum tensor correlation functions provide us with the method of computing both the shear and bulk viscosity relaxation times. Next, we calculate the shear viscosity relaxation time using the diagrammatic approach in the Keldysh basis for the massless λ ϕ4 theory. We derive a respective integral equation which enables us to compute η τπ and then we extract the shear relaxation time. The relaxation time is shown to be inversely related to the thermal width as it should be.

Oxygen reduction on a Pt(111) catalyst in HT-PEM fuel cells by density functional theory

NASA Astrophysics Data System (ADS)

Sun, Hong; Li, Jie; Almheiri, Saif; Xiao, Jianyu

2017-08-01

The oxygen reduction reaction plays an important role in the performance of high-temperature proton exchange membrane (HT-PEM) fuel cells. In this study, a molecular dynamics model, which is based on the density functional theory and couples the system's energy, the exchange-correlation energy functional, the charge density distribution function, and the simplified Kohn-Sham equation, was developed to simulate the oxygen reduction reaction on a Pt(111) surface. Additionally, an electrochemical reaction system on the basis of a four-electron reaction mechanism was also developed for this simulation. The reaction path of the oxygen reduction reaction, the product structure of each reaction step and the system's energy were simulated. It is found that the first step reaction of the first hydrogen ion with the oxygen molecule is the controlling step of the overall reaction. Increasing the operating temperature speeds up the first step reaction rate and slightly decreases its reaction energy barrier. Our results provide insight into the working principles of HT-PEM fuel cells.

The relationship of self-regulation and aggression: an empirical test of personality systems interaction theory.

PubMed

Ross, Thomas; Fontao, María Isabel

2008-10-01

On the basis of personality systems interaction (PSI) theory, the authors examine self-regulation, conflict behaviour, behavioural resources, and personality disorders in a sample of 83 male offenders and explore the role self-regulatory variables play with respect to aggressive behaviour. Although substantial correlations between self-regulatory functions and aggressive behaviour were found, these variables did not predict aggression in a subsequent regression analysis with measures of self-regulation, conflict behaviour, and personality disorders as independent variables. Antisocial behaviour, behavioural self-control, and affect were among the strongest predictors of aggression. Specific predictions based on PSI theory could not be confirmed. Theoretical implications of the findings are discussed and put into relation with treatment issues of offenders.

Conformational analysis, spectroscopic study (FT-IR, FT-Raman, UV, 1H and 13C NMR), molecular orbital energy and NLO properties of 5-iodosalicylic acid

NASA Astrophysics Data System (ADS)

Karaca, Caglar; Atac, Ahmet; Karabacak, Mehmet

2015-02-01

In this study, 5-iodosalicylic acid (5-ISA, C7H5IO3) is structurally characterized by FT-IR, FT-Raman, NMR and UV spectroscopies. There are eight conformers, Cn, n = 1-8 for this molecule therefore the molecular geometry for these eight conformers in the ground state are calculated by using the ab-initio density functional theory (DFT) B3LYP method approach with the aug-cc-pVDZ-PP basis set for iodine and the aug-cc-pVDZ basis set for the other elements. The computational results identified that the most stable conformer of 5-ISA is the C1 form. The vibrational spectra are calculated DFT method invoking the same basis sets and fundamental vibrations are assigned on the basis of the total energy distribution (TED) of the vibrational modes, calculated with scaled quantum mechanics (SQM) method with PQS program. Total density of state (TDOS) and partial density of state (PDOS) and also overlap population density of state (COOP or OPDOS) diagrams analysis for C1 conformer were calculated using the same method. The energy and oscillator strength are calculated by time-dependent density functional theory (TD-DFT) results complement with the experimental findings. Besides, charge transfer occurring in the molecule between HOMO and LUMO energies, frontier energy gap, molecular electrostatic potential (MEP) are calculated and presented. The NMR chemical shifts (1H and 13C) spectra are recorded and calculated using the gauge independent atomic orbital (GIAO) method. Mulliken atomic charges of the title molecule are also calculated, interpreted and compared with salicylic acid. The optimized bond lengths, bond angles and calculated NMR and UV, vibrational wavenumbers showed the best agreement with the experimental results.

From plane waves to local Gaussians for the simulation of correlated periodic systems

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

Booth, George H., E-mail: george.booth@kcl.ac.uk; Tsatsoulis, Theodoros; Grüneis, Andreas, E-mail: a.grueneis@fkf.mpg.de

2016-08-28

We present a simple, robust, and black-box approach to the implementation and use of local, periodic, atom-centered Gaussian basis functions within a plane wave code, in a computationally efficient manner. The procedure outlined is based on the representation of the Gaussians within a finite bandwidth by their underlying plane wave coefficients. The core region is handled within the projected augment wave framework, by pseudizing the Gaussian functions within a cutoff radius around each nucleus, smoothing the functions so that they are faithfully represented by a plane wave basis with only moderate kinetic energy cutoff. To mitigate the effects of themore » basis set superposition error and incompleteness at the mean-field level introduced by the Gaussian basis, we also propose a hybrid approach, whereby the complete occupied space is first converged within a large plane wave basis, and the Gaussian basis used to construct a complementary virtual space for the application of correlated methods. We demonstrate that these pseudized Gaussians yield compact and systematically improvable spaces with an accuracy comparable to their non-pseudized Gaussian counterparts. A key advantage of the described method is its ability to efficiently capture and describe electronic correlation effects of weakly bound and low-dimensional systems, where plane waves are not sufficiently compact or able to be truncated without unphysical artifacts. We investigate the accuracy of the pseudized Gaussians for the water dimer interaction, neon solid, and water adsorption on a LiH surface, at the level of second-order Møller–Plesset perturbation theory.« less

Effective scheme for partitioning covalent bonds in density-functional embedding theory: From molecules to extended covalent systems.

PubMed

Huang, Chen; Muñoz-García, Ana Belén; Pavone, Michele

2016-12-28

Density-functional embedding theory provides a general way to perform multi-physics quantum mechanics simulations of large-scale materials by dividing the total system's electron density into a cluster's density and its environment's density. It is then possible to compute the accurate local electronic structures and energetics of the embedded cluster with high-level methods, meanwhile retaining a low-level description of the environment. The prerequisite step in the density-functional embedding theory is the cluster definition. In covalent systems, cutting across the covalent bonds that connect the cluster and its environment leads to dangling bonds (unpaired electrons). These represent a major obstacle for the application of density-functional embedding theory to study extended covalent systems. In this work, we developed a simple scheme to define the cluster in covalent systems. Instead of cutting covalent bonds, we directly split the boundary atoms for maintaining the valency of the cluster. With this new covalent embedding scheme, we compute the dehydrogenation energies of several different molecules, as well as the binding energy of a cobalt atom on graphene. Well localized cluster densities are observed, which can facilitate the use of localized basis sets in high-level calculations. The results are found to converge faster with the embedding method than the other multi-physics approach ONIOM. This work paves the way to perform the density-functional embedding simulations of heterogeneous systems in which different types of chemical bonds are present.

Scalar relativistic computations of nuclear magnetic shielding and g-shifts with the zeroth-order regular approximation and range-separated hybrid density functionals

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

Aquino, Fredy W.; Govind, Niranjan; Autschbach, Jochen

2011-10-01

Density functional theory (DFT) calculations of NMR chemical shifts and molecular g-tensors with Gaussian-type orbitals are implemented via second-order energy derivatives within the scalar relativistic zeroth order regular approximation (ZORA) framework. Nonhybrid functionals, standard (global) hybrids, and range-separated (Coulomb-attenuated, long-range corrected) hybrid functionals are tested. Origin invariance of the results is ensured by use of gauge-including atomic orbital (GIAO) basis functions. The new implementation in the NWChem quantum chemistry package is verified by calculations of nuclear shielding constants for the heavy atoms in HX (X=F, Cl, Br, I, At) and H2X (X = O, S, Se, Te, Po), and Temore » chemical shifts in a number of tellurium compounds. The basis set and functional dependence of g-shifts is investigated for 14 radicals with light and heavy atoms. The problem of accurately predicting F NMR shielding in UF6-nCln, n = 1 to 6, is revisited. The results are sensitive to approximations in the density functionals, indicating a delicate balance of DFT self-interaction vs. correlation. For the uranium halides, the results with the range-separated functionals are mixed.« less

Studies of dispersion energy in hydrogen-bonded systems. H2O-HOH, H2O-HF, H3N-HF, HF-HF

NASA Astrophysics Data System (ADS)

Szcześniak, M. M.; Scheiner, Steve

1984-02-01

Dispersion energy is calculated in the systems H2O-HOH, H2O-HF, H3N-HF, and HF-HF as a function of the intermolecular separation using a variety of methods. M≂ller-Plesset perturbation theory to second and third orders is applied in conjunction with polarized basis sets of 6-311G** type and with an extended basis set including a second set of polarization functions (DZ+2P). These results are compared to a multipole expansion of the dispersion energy, based on the Unsöld approximation, carried out to the inverse tenth power of the intermolecular distance. Pairwise evaluation is also carried out using both atom-atom and bond-bond formulations. The MP3/6-311G** results are in generally excellent accord with the leading R-6 term of the multipole expansion. This expansion, if carried out to the R-10 term, reproduces extremely well previously reported dispersion energies calculated via variation-perturbation theory. Little damping of the expansion is required for intermolecular distances equal to or greater than the equilibrium separation. Although the asymptotic behavior of the MP2 dispersion energy is somewhat different than that of the other methods, augmentation of the basis set by a second diffuse set of d functions leads to quite good agreement in the vicinity of the minima. Both the atom-atom and bond-bond parametrization schemes are in good qualitative agreement with the other methods tested. All approaches produce similar dependence of the dispersion energy upon the angular orientation between the two molecules involved in the H bond.

Psi4 1.1: An Open-Source Electronic Structure Program Emphasizing Automation, Advanced Libraries, and Interoperability.

PubMed

Parrish, Robert M; Burns, Lori A; Smith, Daniel G A; Simmonett, Andrew C; DePrince, A Eugene; Hohenstein, Edward G; Bozkaya, Uğur; Sokolov, Alexander Yu; Di Remigio, Roberto; Richard, Ryan M; Gonthier, Jérôme F; James, Andrew M; McAlexander, Harley R; Kumar, Ashutosh; Saitow, Masaaki; Wang, Xiao; Pritchard, Benjamin P; Verma, Prakash; Schaefer, Henry F; Patkowski, Konrad; King, Rollin A; Valeev, Edward F; Evangelista, Francesco A; Turney, Justin M; Crawford, T Daniel; Sherrill, C David

2017-07-11

Psi4 is an ab initio electronic structure program providing methods such as Hartree-Fock, density functional theory, configuration interaction, and coupled-cluster theory. The 1.1 release represents a major update meant to automate complex tasks, such as geometry optimization using complete-basis-set extrapolation or focal-point methods. Conversion of the top-level code to a Python module means that Psi4 can now be used in complex workflows alongside other Python tools. Several new features have been added with the aid of libraries providing easy access to techniques such as density fitting, Cholesky decomposition, and Laplace denominators. The build system has been completely rewritten to simplify interoperability with independent, reusable software components for quantum chemistry. Finally, a wide range of new theoretical methods and analyses have been added to the code base, including functional-group and open-shell symmetry adapted perturbation theory, density-fitted coupled cluster with frozen natural orbitals, orbital-optimized perturbation and coupled-cluster methods (e.g., OO-MP2 and OO-LCCD), density-fitted multiconfigurational self-consistent field, density cumulant functional theory, algebraic-diagrammatic construction excited states, improvements to the geometry optimizer, and the "X2C" approach to relativistic corrections, among many other improvements.

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

Saperstein, E. E., E-mail: saper@mbslab.kiae.ru; Tolokonnikov, S. V.

Recent results obtained on the basis of the self-consistent theory of finite Fermi systems by employing the energy density functional proposed by Fayans and his coauthors are surveyed. These results are compared with the predictions of Skyrme–Hartree–Fock theory involving several popular versions of the Skyrme energy density functional. Spherical nuclei are predominantly considered. The charge radii of even and odd nuclei and features of low-lying 2{sup +} excitations in semimagic nuclei are discussed briefly. The single-particle energies ofmagic nuclei are examined inmore detail with allowance for corrections to mean-field theory that are induced by particle coupling to low-lying collective surfacemore » excitations (phonons). The importance of taking into account, in this problem, nonpole (tadpole) diagrams, which are usually disregarded, is emphasized. The spectroscopic factors of magic and semimagic nuclei are also considered. In this problem, only the surface term stemming from the energy dependence induced in the mass operator by the exchange of surface phonons is usually taken into account. The volume contribution associated with the energy dependence initially present in the mass operator within the self-consistent theory of finite Fermi systems because of the exchange of high-lying particle–hole excitations is also included in the spectroscopic factor. The results of the first studies that employed the Fayans energy density functional for deformed nuclei are also presented.« less

Applications of fuzzy theories to multi-objective system optimization

NASA Technical Reports Server (NTRS)

Rao, S. S.; Dhingra, A. K.

1991-01-01

Most of the computer aided design techniques developed so far deal with the optimization of a single objective function over the feasible design space. However, there often exist several engineering design problems which require a simultaneous consideration of several objective functions. This work presents several techniques of multiobjective optimization. In addition, a new formulation, based on fuzzy theories, is also introduced for the solution of multiobjective system optimization problems. The fuzzy formulation is useful in dealing with systems which are described imprecisely using fuzzy terms such as, 'sufficiently large', 'very strong', or 'satisfactory'. The proposed theory translates the imprecise linguistic statements and multiple objectives into equivalent crisp mathematical statements using fuzzy logic. The effectiveness of all the methodologies and theories presented is illustrated by formulating and solving two different engineering design problems. The first one involves the flight trajectory optimization and the main rotor design of helicopters. The second one is concerned with the integrated kinematic-dynamic synthesis of planar mechanisms. The use and effectiveness of nonlinear membership functions in fuzzy formulation is also demonstrated. The numerical results indicate that the fuzzy formulation could yield results which are qualitatively different from those provided by the crisp formulation. It is felt that the fuzzy formulation will handle real life design problems on a more rational basis.

Spin-orbit ZORA and four-component Dirac-Coulomb estimation of relativistic corrections to isotropic nuclear shieldings and chemical shifts of noble gas dimers.

PubMed

Jankowska, Marzena; Kupka, Teobald; Stobiński, Leszek; Faber, Rasmus; Lacerda, Evanildo G; Sauer, Stephan P A

2016-02-05

Hartree-Fock and density functional theory with the hybrid B3LYP and general gradient KT2 exchange-correlation functionals were used for nonrelativistic and relativistic nuclear magnetic shielding calculations of helium, neon, argon, krypton, and xenon dimers and free atoms. Relativistic corrections were calculated with the scalar and spin-orbit zeroth-order regular approximation Hamiltonian in combination with the large Slater-type basis set QZ4P as well as with the four-component Dirac-Coulomb Hamiltonian using Dyall's acv4z basis sets. The relativistic corrections to the nuclear magnetic shieldings and chemical shifts are combined with nonrelativistic coupled cluster singles and doubles with noniterative triple excitations [CCSD(T)] calculations using the very large polarization-consistent basis sets aug-pcSseg-4 for He, Ne and Ar, aug-pcSseg-3 for Kr, and the AQZP basis set for Xe. For the dimers also, zero-point vibrational (ZPV) corrections are obtained at the CCSD(T) level with the same basis sets were added. Best estimates of the dimer chemical shifts are generated from these nuclear magnetic shieldings and the relative importance of electron correlation, ZPV, and relativistic corrections for the shieldings and chemical shifts is analyzed. © 2015 Wiley Periodicals, Inc.

Consistent multiphase-field theory for interface driven multidomain dynamics

NASA Astrophysics Data System (ADS)

Tóth, Gyula I.; Pusztai, Tamás; Gránásy, László

2015-11-01

We present a multiphase-field theory for describing pattern formation in multidomain and/or multicomponent systems. The construction of the free energy functional and the dynamic equations is based on criteria that ensure mathematical and physical consistency. We first analyze previous multiphase-field theories and identify their advantageous and disadvantageous features. On the basis of this analysis, we introduce a way of constructing the free energy surface and derive a generalized multiphase description for arbitrary number of phases (or domains). The presented approach retains the variational formalism, reduces (or extends) naturally to lower (or higher) number of fields on the level of both the free energy functional and the dynamic equations, enables the use of arbitrary pairwise equilibrium interfacial properties, penalizes multiple junctions increasingly with the number of phases, ensures non-negative entropy production and the convergence of the dynamic solutions to the equilibrium solutions, and avoids the appearance of spurious phases on binary interfaces. The approach is tested for multicomponent phase separation and grain coarsening.

Variational treatment of electron-polyatomic-molecule scattering calculations using adaptive overset grids

NASA Astrophysics Data System (ADS)

Greenman, Loren; Lucchese, Robert R.; McCurdy, C. William

2017-11-01

The complex Kohn variational method for electron-polyatomic-molecule scattering is formulated using an overset-grid representation of the scattering wave function. The overset grid consists of a central grid and multiple dense atom-centered subgrids that allow the simultaneous spherical expansions of the wave function about multiple centers. Scattering boundary conditions are enforced by using a basis formed by the repeated application of the free-particle Green's function and potential Ĝ0+V ̂ on the overset grid in a Born-Arnoldi solution of the working equations. The theory is shown to be equivalent to a specific Padé approximant to the T matrix and has rapid convergence properties, in both the number of numerical basis functions employed and the number of partial waves employed in the spherical expansions. The method is demonstrated in calculations on methane and CF4 in the static-exchange approximation and compared in detail with calculations performed with the numerical Schwinger variational approach based on single-center expansions. An efficient procedure for operating with the free-particle Green's function and exchange operators (to which no approximation is made) is also described.

On the truncation of the number of excited states in density functional theory sum-over-states calculations of indirect spin spin coupling constants

NASA Astrophysics Data System (ADS)

Zarycz, M. Natalia C.; Provasi, Patricio F.; Sauer, Stephan P. A.

2015-12-01

It is investigated, whether the number of excited (pseudo)states can be truncated in the sum-over-states expression for indirect spin-spin coupling constants (SSCCs), which is used in the Contributions from Localized Orbitals within the Polarization Propagator Approach and Inner Projections of the Polarization Propagator (IPPP-CLOPPA) approach to analyzing SSCCs in terms of localized orbitals. As a test set we have studied the nine simple compounds, CH4, NH3, H2O, SiH4, PH3, SH2, C2H2, C2H4, and C2H6. The excited (pseudo)states were obtained from time-dependent density functional theory (TD-DFT) calculations with the B3LYP exchange-correlation functional and the specialized core-property basis set, aug-cc-pVTZ-J. We investigated both how the calculated coupling constants depend on the number of (pseudo)states included in the summation and whether the summation can be truncated in a systematic way at a smaller number of states and extrapolated to the total number of (pseudo)states for the given one-electron basis set. We find that this is possible and that for some of the couplings it is sufficient to include only about 30% of the excited (pseudo)states.

A numerical homogenization method for heterogeneous, anisotropic elastic media based on multiscale theory

DOE PAGES

Gao, Kai; Chung, Eric T.; Gibson, Richard L.; ...

2015-06-05

The development of reliable methods for upscaling fine scale models of elastic media has long been an important topic for rock physics and applied seismology. Several effective medium theories have been developed to provide elastic parameters for materials such as finely layered media or randomly oriented or aligned fractures. In such cases, the analytic solutions for upscaled properties can be used for accurate prediction of wave propagation. However, such theories cannot be applied directly to homogenize elastic media with more complex, arbitrary spatial heterogeneity. We therefore propose a numerical homogenization algorithm based on multiscale finite element methods for simulating elasticmore » wave propagation in heterogeneous, anisotropic elastic media. Specifically, our method used multiscale basis functions obtained from a local linear elasticity problem with appropriately defined boundary conditions. Homogenized, effective medium parameters were then computed using these basis functions, and the approach applied a numerical discretization that is similar to the rotated staggered-grid finite difference scheme. Comparisons of the results from our method and from conventional, analytical approaches for finely layered media showed that the homogenization reliably estimated elastic parameters for this simple geometry. Additional tests examined anisotropic models with arbitrary spatial heterogeneity where the average size of the heterogeneities ranged from several centimeters to several meters, and the ratio between the dominant wavelength and the average size of the arbitrary heterogeneities ranged from 10 to 100. Comparisons to finite-difference simulations proved that the numerical homogenization was equally accurate for these complex cases.« less

Density-functional approaches to noncovalent interactions: a comparison of dispersion corrections (DFT-D), exchange-hole dipole moment (XDM) theory, and specialized functionals.

PubMed

Burns, Lori A; Vázquez-Mayagoitia, Alvaro; Sumpter, Bobby G; Sherrill, C David

2011-02-28

A systematic study of techniques for treating noncovalent interactions within the computationally efficient density functional theory (DFT) framework is presented through comparison to benchmark-quality evaluations of binding strength compiled for molecular complexes of diverse size and nature. In particular, the efficacy of functionals deliberately crafted to encompass long-range forces, a posteriori DFT+dispersion corrections (DFT-D2 and DFT-D3), and exchange-hole dipole moment (XDM) theory is assessed against a large collection (469 energy points) of reference interaction energies at the CCSD(T) level of theory extrapolated to the estimated complete basis set limit. The established S22 [revised in J. Chem. Phys. 132, 144104 (2010)] and JSCH test sets of minimum-energy structures, as well as collections of dispersion-bound (NBC10) and hydrogen-bonded (HBC6) dissociation curves and a pairwise decomposition of a protein-ligand reaction site (HSG), comprise the chemical systems for this work. From evaluations of accuracy, consistency, and efficiency for PBE-D, BP86-D, B97-D, PBE0-D, B3LYP-D, B970-D, M05-2X, M06-2X, ωB97X-D, B2PLYP-D, XYG3, and B3LYP-XDM methodologies, it is concluded that distinct, often contrasting, groups of these elicit the best performance within the accessible double-ζ or robust triple-ζ basis set regimes and among hydrogen-bonded or dispersion-dominated complexes. For overall results, M05-2X, B97-D3, and B970-D2 yield superior values in conjunction with aug-cc-pVDZ, for a mean absolute deviation of 0.41 - 0.49 kcal/mol, and B3LYP-D3, B97-D3, ωB97X-D, and B2PLYP-D3 dominate with aug-cc-pVTZ, affording, together with XYG3/6-311+G(3df,2p), a mean absolute deviation of 0.33 - 0.38 kcal/mol.

Predictive coupled-cluster isomer orderings for some Si{sub n}C{sub m} (m, n ≤ 12) clusters: A pragmatic comparison between DFT and complete basis limit coupled-cluster benchmarks

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

Byrd, Jason N., E-mail: byrd.jason@ensco.com; ENSCO, Inc., 4849 North Wickham Road, Melbourne, Florida 32940; Lutz, Jesse J., E-mail: jesse.lutz.ctr@afit.edu

The accurate determination of the preferred Si{sub 12}C{sub 12} isomer is important to guide experimental efforts directed towards synthesizing SiC nano-wires and related polymer structures which are anticipated to be highly efficient exciton materials for the opto-electronic devices. In order to definitively identify preferred isomeric structures for silicon carbon nano-clusters, highly accurate geometries, energies, and harmonic zero point energies have been computed using coupled-cluster theory with systematic extrapolation to the complete basis limit for set of silicon carbon clusters ranging in size from SiC{sub 3} to Si{sub 12}C{sub 12}. It is found that post-MBPT(2) correlation energy plays a significant rolemore » in obtaining converged relative isomer energies, suggesting that predictions using low rung density functional methods will not have adequate accuracy. Utilizing the best composite coupled-cluster energy that is still computationally feasible, entailing a 3-4 SCF and coupled-cluster theory with singles and doubles extrapolation with triple-ζ (T) correlation, the closo Si{sub 12}C{sub 12} isomer is identified to be the preferred isomer in the support of previous calculations [X. F. Duan and L. W. Burggraf, J. Chem. Phys. 142, 034303 (2015)]. Additionally we have investigated more pragmatic approaches to obtaining accurate silicon carbide isomer energies, including the use of frozen natural orbital coupled-cluster theory and several rungs of standard and double-hybrid density functional theory. Frozen natural orbitals as a way to compute post-MBPT(2) correlation energy are found to be an excellent balance between efficiency and accuracy.« less

Accelerating wavefunction in density-functional-theory embedding by truncating the active basis set

NASA Astrophysics Data System (ADS)

Bennie, Simon J.; Stella, Martina; Miller, Thomas F.; Manby, Frederick R.

2015-07-01

Methods where an accurate wavefunction is embedded in a density-functional description of the surrounding environment have recently been simplified through the use of a projection operator to ensure orthogonality of orbital subspaces. Projector embedding already offers significant performance gains over conventional post-Hartree-Fock methods by reducing the number of correlated occupied orbitals. However, in our first applications of the method, we used the atomic-orbital basis for the full system, even for the correlated wavefunction calculation in a small, active subsystem. Here, we further develop our method for truncating the atomic-orbital basis to include only functions within or close to the active subsystem. The number of atomic orbitals in a calculation on a fixed active subsystem becomes asymptotically independent of the size of the environment, producing the required O ( N 0 ) scaling of cost of the calculation in the active subsystem, and accuracy is controlled by a single parameter. The applicability of this approach is demonstrated for the embedded many-body expansion of binding energies of water hexamers and calculation of reaction barriers of SN2 substitution of fluorine by chlorine in α-fluoroalkanes.

Infinite occupation number basis of bosons: Solving a numerical challenge

NASA Astrophysics Data System (ADS)

Geißler, Andreas; Hofstetter, Walter

2017-06-01

In any bosonic lattice system, which is not dominated by local interactions and thus "frozen" in a Mott-type state, numerical methods have to cope with the infinite size of the corresponding Hilbert space even for finite lattice sizes. While it is common practice to restrict the local occupation number basis to Nc lowest occupied states, the presence of a finite condensate fraction requires the complete number basis for an exact representation of the many-body ground state. In this work we present a truncation scheme to account for contributions from higher number states. By simply adding a single coherent-tail state to this common truncation, we demonstrate increased numerical accuracy and the possible increase in numerical efficiency of this method for the Gutzwiller variational wave function and within dynamical mean-field theory.

Many-body calculations of molecular electric polarizabilities in asymptotically complete basis sets

NASA Astrophysics Data System (ADS)

Monten, Ruben; Hajgató, Balázs; Deleuze, Michael S.

2011-10-01

The static dipole polarizabilities of Ne, CO, N2, F2, HF, H2O, HCN, and C2H2 (acetylene) have been determined close to the Full-CI limit along with an asymptotically complete basis set (CBS), according to the principles of a Focal Point Analysis. For this purpose the results of Finite Field calculations up to the level of Coupled Cluster theory including Single, Double, Triple, Quadruple and perturbative Pentuple excitations [CCSDTQ(P)] were used, in conjunction with suited extrapolations of energies obtained using augmented and doubly-augmented Dunning's correlation consistent polarized valence basis sets of improving quality. The polarizability characteristics of C2H4 (ethylene) and C2H6 (ethane) have been determined on the same grounds at the CCSDTQ level in the CBS limit. Comparison is made with results obtained using lower levels in electronic correlation, or taking into account the relaxation of the molecular structure due to an adiabatic polarization process. Vibrational corrections to electronic polarizabilities have been empirically estimated according to Born-Oppenheimer Molecular Dynamical simulations employing Density Functional Theory. Confrontation with experiment ultimately indicates relative accuracies of the order of 1 to 2%.

[From Descartes to fMRI. Pain theories and pain concepts].

PubMed

Handwerker, H O

2007-08-01

In the seventeenth century the philosopher Rene Descartes was the forerunner by establishing a scientific hypothesis on the origin of pain. Much later, in the nineteenth century, pain hypotheses emerged which explained the pain sensation either on the basis of intense stimulation of any kind of nerve fibers (intensity hypothesis) or on the basis of specific nociceptors (specificity hypothesis). The "gate control theory" established by Melzack and Wall (1964) offered an explanation of modulations of pain sensation by the interaction between nociceptive and non-nociceptive nerve fibers and by descending control in the central nervous system. Though this hypothesis is outdated in its original form, it had - in a more common formulation - a great influence on our understanding of pain. For building a bridge to our present knowledge, the molecular structure of the nociceptor membrane is of particular importance. On this basis also new pain therapies have been developed. On the other hand, the methods of functional imaging allow the identification of brain regions related to pain processing at a macroscopic level. This new technology opened up new ways of understanding chronic pain processes and new possibilities for the control of therapeutic effects.

Calculating Interaction Energies Using First Principle Theories: Consideration of Basis Set Superposition Error and Fragment Relaxation

ERIC Educational Resources Information Center

Bowen, J. Philip; Sorensen, Jennifer B.; Kirschner, Karl N.

2007-01-01

The analysis explains the basis set superposition error (BSSE) and fragment relaxation involved in calculating the interaction energies using various first principle theories. Interacting the correlated fragment and increasing the size of the basis set can help in decreasing the BSSE to a great extent.

A Study of the Speed of Understanding Sentences as a Function of Sentence Structure. Final Report.

ERIC Educational Resources Information Center

Halamandaris, Pandelis G.

On the basis of the grammatical theory developed by Noam Chomsky, it is reasonable to presume that the different parts of a sentence may not all be understood with equal facility and speed. One purpose of this study was to determine whether some of the grammatical relations within a sentence were understood more readily than others. Sentences of…

Finite Element Based Structural Damage Detection Using Artificial Boundary Conditions

DTIC Science & Technology

2007-09-01

C. (2005). Elementary Linear Algebra . New York: John Wiley and Sons. Avitable, Peter (2001, January) Experimental Modal Analysis, A Simple Non...variables under consideration. 3 Frequency sensitivities are the basis for a linear approximation to compute the change in the natural frequencies of a...THEORY The general problem statement for a non- linear constrained optimization problem is: To minimize ( )f x Objective Function Subject to

Accuracy of Td-DFT in the Ultraviolet and Circular Dichroism Spectra of Deoxyguanosine and Uridine.

PubMed

Miyahara, Tomoo; Nakatsuji, Hiroshi

2018-01-11

Accuracy of the time-dependent density functional theory (Td-DFT) was examined for the ultraviolet (UV) and circular dichroism (CD) spectra of deoxyguanosine (dG) and uridine, using 11 different DFT functionals and two different basis sets. The Td-DFT results of the UV and CD spectra were strongly dependent on the functionals used. The basis-set dependence was observed only for the CD spectral calculations. For the UV spectra, the B3LYP and PBE0 functionals gave relatively good results. For the CD spectra, the B3LYP and PBE0 with 6-311G(d,p) basis gave relatively permissible result only for dG. The results of other functionals were difficult to be used for the studies of the UV and CD spectra, though the symmetry adapted cluster-configuration interaction (SAC-CI) method reproduced well the experimental spectra of these molecules. To obtain valuable information from the theoretical calculations of the UV and CD spectra, the theoretical tool must be able to reproduce correctly both of the intensities and peak positions of the UV and CD spectra. Then, we can analyze the reasons of the changes of the intensity and/or the peak position to clarify the chemistry involved. It is difficult to recommend Td-DFT as such tools of science, at least from the examinations using dG and uridine.

Weak solution concept and Galerkin's matrix for the exterior of an oblate ellipsoid of revolution in the representation of the Earth's gravity potential by buried masses

NASA Astrophysics Data System (ADS)

Holota, Petr; Nesvadba, Otakar

2017-04-01

The paper is motivated by the role of boundary value problems in Earth's gravity field studies. The discussion focuses on Neumann's problem formulated for the exterior of an oblate ellipsoid of revolution as this is considered a basis for an iteration solution of the linear gravimetric boundary value problem in the determination of the disturbing potential. The approach follows the concept of the weak solution and Galerkin's approximations are applied. This means that the solution of the problem is approximated by linear combinations of basis functions with scalar coefficients. The construction of Galerkin's matrix for basis functions generated by elementary potentials (point masses) is discussed. Ellipsoidal harmonics are used as a natural tool and the elementary potentials are expressed by means of series of ellipsoidal harmonics. The problem, however, is the summation of the series that represent the entries of Galerkin's matrix. It is difficult to reduce the number of summation indices since in the ellipsoidal case there is no analogue to the addition theorem known for spherical harmonics. Therefore, the straightforward application of series of ellipsoidal harmonics is complemented by deeper relations contained in the theory of ordinary differential equations of second order and in the theory of Legendre's functions. Subsequently, also hypergeometric functions and series are used. Moreover, within some approximations the entries are split into parts. Some of the resulting series may be summed relatively easily, apart from technical tricks. For the remaining series the summation was converted to elliptic integrals. The approach made it possible to deduce a closed (though approximate) form representation of the entries in Galerkin's matrix. The result rests on concepts and methods of mathematical analysis. In the paper it is confronted with a direct numerical approach applied for the implementation of Legendre's functions. The computation of the entries is more demanding in this case, but conceptually it avoids approximations. Finally, some specific features associated with function bases generated by elementary potentials in case the ellipsoidal solution domain are illustrated and discussed.

Chemical accuracy from quantum Monte Carlo for the benzene dimer.

PubMed

Azadi, Sam; Cohen, R E

2015-09-14

We report an accurate study of interactions between benzene molecules using variational quantum Monte Carlo (VMC) and diffusion quantum Monte Carlo (DMC) methods. We compare these results with density functional theory using different van der Waals functionals. In our quantum Monte Carlo (QMC) calculations, we use accurate correlated trial wave functions including three-body Jastrow factors and backflow transformations. We consider two benzene molecules in the parallel displaced geometry, and find that by highly optimizing the wave function and introducing more dynamical correlation into the wave function, we compute the weak chemical binding energy between aromatic rings accurately. We find optimal VMC and DMC binding energies of -2.3(4) and -2.7(3) kcal/mol, respectively. The best estimate of the coupled-cluster theory through perturbative triplets/complete basis set limit is -2.65(2) kcal/mol [Miliordos et al., J. Phys. Chem. A 118, 7568 (2014)]. Our results indicate that QMC methods give chemical accuracy for weakly bound van der Waals molecular interactions, comparable to results from the best quantum chemistry methods.

A roadmap for the study of conscious audition and its neural basis

PubMed Central

Cariani, Peter A.; Gutschalk, Alexander

2017-01-01

How and which aspects of neural activity give rise to subjective perceptual experience—i.e. conscious perception—is a fundamental question of neuroscience. To date, the vast majority of work concerning this question has come from vision, raising the issue of generalizability of prominent resulting theories. However, recent work has begun to shed light on the neural processes subserving conscious perception in other modalities, particularly audition. Here, we outline a roadmap for the future study of conscious auditory perception and its neural basis, paying particular attention to how conscious perception emerges (and of which elements or groups of elements) in complex auditory scenes. We begin by discussing the functional role of the auditory system, particularly as it pertains to conscious perception. Next, we ask: what are the phenomena that need to be explained by a theory of conscious auditory perception? After surveying the available literature for candidate neural correlates, we end by considering the implications that such results have for a general theory of conscious perception as well as prominent outstanding questions and what approaches/techniques can best be used to address them. This article is part of the themed issue ‘Auditory and visual scene analysis’. PMID:28044014

Receptive fields and the theory of discriminant operators

NASA Astrophysics Data System (ADS)

Gupta, Madan M.; Hungenahally, Suresh K.

1991-02-01

Biological basis for machine vision is a notion which is being used extensively for the development of machine vision systems for various applications. In this paper we have made an attempt to emulate the receptive fields that exist in the biological visual channels. In particular we have exploited the notion of receptive fields for developing the mathematical functions named as discriminantfunctions for the extraction of transition information from signals and multi-dimensional signals and images. These functions are found to be useful for the development of artificial receptive fields for neuro-vision systems. 1.

NMR shieldings from density functional perturbation theory: GIPAW versus all-electron calculations

NASA Astrophysics Data System (ADS)

de Wijs, G. A.; Laskowski, R.; Blaha, P.; Havenith, R. W. A.; Kresse, G.; Marsman, M.

2017-02-01

We present a benchmark of the density functional linear response calculation of NMR shieldings within the gauge-including projector-augmented-wave method against all-electron augmented-plane-wave+local-orbital and uncontracted Gaussian basis set results for NMR shieldings in molecular and solid state systems. In general, excellent agreement between the aforementioned methods is obtained. Scalar relativistic effects are shown to be quite large for nuclei in molecules in the deshielded limit. The small component makes up a substantial part of the relativistic corrections.

NMR shieldings from density functional perturbation theory: GIPAW versus all-electron calculations.

PubMed

de Wijs, G A; Laskowski, R; Blaha, P; Havenith, R W A; Kresse, G; Marsman, M

2017-02-14

We present a benchmark of the density functional linear response calculation of NMR shieldings within the gauge-including projector-augmented-wave method against all-electron augmented-plane-wave+local-orbital and uncontracted Gaussian basis set results for NMR shieldings in molecular and solid state systems. In general, excellent agreement between the aforementioned methods is obtained. Scalar relativistic effects are shown to be quite large for nuclei in molecules in the deshielded limit. The small component makes up a substantial part of the relativistic corrections.

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

Shirkov, Leonid; Makarewicz, Jan, E-mail: jama@amu.edu.pl

An ab initio intermolecular potential energy surface (PES) has been constructed for the benzene-krypton (BKr) van der Waals (vdW) complex. The interaction energy has been calculated at the coupled cluster level of theory with single, double, and perturbatively included triple excitations using different basis sets. As a result, a few analytical PESs of the complex have been determined. They allowed a prediction of the complex structure and its vibrational vdW states. The vibrational energy level pattern exhibits a distinct polyad structure. Comparison of the equilibrium structure, the dipole moment, and vibrational levels of BKr with their experimental counterparts has allowedmore » us to design an optimal basis set composed of a small Dunning’s basis set for the benzene monomer, a larger effective core potential adapted basis set for Kr and additional midbond functions. Such a basis set yields vibrational energy levels that agree very well with the experimental ones as well as with those calculated from the available empirical PES derived from the microwave spectra of the BKr complex. The basis proposed can be applied to larger complexes including Kr because of a reasonable computational cost and accurate results.« less

Solving the Self-Interaction Problem in Kohn-Sham Density Functional Theory. Application to Atoms

DOE PAGES

Daene, M.; Gonis, A.; Nicholson, D. M.; ...

2014-10-14

Previously, we proposed a computational methodology that addresses the elimination of the self-interaction error from the Kohn–Sham formulation of the density functional theory. We demonstrated how the exchange potential can be obtained, and presented results of calculations for atomic systems up to Kr carried out within a Cartesian coordinate system. In our paper, we provide complete details of this self-interaction free method formulated in spherical coordinates based on the explicit equidensity basis ansatz. We also prove analytically that derivatives obtained using this method satisfy the Virial theorem for spherical orbitals, where the problem can be reduced to one dimension. Wemore » present the results of calculations of ground-state energies of atomic systems throughout the periodic table carried out within the exchange-only mode.« less

Thermodynamic prediction of protein neutrality.

PubMed

Bloom, Jesse D; Silberg, Jonathan J; Wilke, Claus O; Drummond, D Allan; Adami, Christoph; Arnold, Frances H

2005-01-18

We present a simple theory that uses thermodynamic parameters to predict the probability that a protein retains the wild-type structure after one or more random amino acid substitutions. Our theory predicts that for large numbers of substitutions the probability that a protein retains its structure will decline exponentially with the number of substitutions, with the severity of this decline determined by properties of the structure. Our theory also predicts that a protein can gain extra robustness to the first few substitutions by increasing its thermodynamic stability. We validate our theory with simulations on lattice protein models and by showing that it quantitatively predicts previously published experimental measurements on subtilisin and our own measurements on variants of TEM1 beta-lactamase. Our work unifies observations about the clustering of functional proteins in sequence space, and provides a basis for interpreting the response of proteins to substitutions in protein engineering applications.

Thermodynamic prediction of protein neutrality

PubMed Central

Bloom, Jesse D.; Silberg, Jonathan J.; Wilke, Claus O.; Drummond, D. Allan; Adami, Christoph; Arnold, Frances H.

2005-01-01

We present a simple theory that uses thermodynamic parameters to predict the probability that a protein retains the wild-type structure after one or more random amino acid substitutions. Our theory predicts that for large numbers of substitutions the probability that a protein retains its structure will decline exponentially with the number of substitutions, with the severity of this decline determined by properties of the structure. Our theory also predicts that a protein can gain extra robustness to the first few substitutions by increasing its thermodynamic stability. We validate our theory with simulations on lattice protein models and by showing that it quantitatively predicts previously published experimental measurements on subtilisin and our own measurements on variants of TEM1 β-lactamase. Our work unifies observations about the clustering of functional proteins in sequence space, and provides a basis for interpreting the response of proteins to substitutions in protein engineering applications. PMID:15644440

The unification of physics: the quest for a theory of everything.

PubMed

Paulson, Steve; Gleiser, Marcelo; Freese, Katherine; Tegmark, Max

2015-12-01

The holy grail of physics has been to merge each of its fundamental branches into a unified "theory of everything" that would explain the functioning and existence of the universe. The last step toward this goal is to reconcile general relativity with the principles of quantum mechanics, a quest that has thus far eluded physicists. Will physics ever be able to develop an all-encompassing theory, or should we simply acknowledge that science will always have inherent limitations as to what can be known? Should new theories be validated solely on the basis of calculations that can never be empirically tested? Can we ever truly grasp the implications of modern physics when the basic laws of nature do not always operate according to our standard paradigms? These and other questions are discussed in this paper. © 2015 New York Academy of Sciences.

Biofuel combustion. Energetics and kinetics of hydrogen abstraction from carbon-1 in n-butanol by the hydroperoxyl radical calculated by coupled cluster and density functional theories and multistructural variational transition-state theory with multidimensional tunneling.

PubMed

Alecu, I M; Zheng, Jingjing; Papajak, Ewa; Yu, Tao; Truhlar, Donald G

2012-12-20

Multistructural canonical variational transition-state theory with small-curvature multidimensional tunneling (MS-CVT/SCT) is employed to calculate thermal rate constants for hydrogen-atom abstraction from carbon-1 of n-butanol by the hydroperoxyl radical over the temperature range 250-2000 K. The M08-SO hybrid meta-GGA density functional was validated against CCSD(T)-F12a explicitly correlated wave function calculations with the jul-cc-pVTZ basis set. It was then used to compute the properties of all stationary points and the energies and Hessians of a few nonstationary points along the reaction path, which were then used to generate a potential energy surface by the multiconfiguration Shepard interpolation (MCSI) method. The internal rotations in the transition state for this reaction (like those in the reactant alcohol) are strongly coupled to each other and generate multiple stable conformations, which make important contributions to the partition functions. It is shown that neglecting to account for the multiple-structure effects and torsional potential anharmonicity effects that arise from the torsional modes would lead to order-of-magnitude errors in the calculated rate constants at temperatures of interest in combustion.

[Pb(H2O)]2+ and [Pb(OH)]+: four-component density functional theory calculations, correlated scalar relativistic constrained-space orbital variation energy decompositions, and topological analysis.

PubMed

Gourlaouen, Christophe; Piquemal, Jean-Philip; Parisel, Olivier

2006-05-07

Within the scope of studying the molecular implications of the Pb(2+) cation in environmental and polluting processes, this paper reports Hartree-Fock and density functional theory (B3LYP) four-component relativistic calculations using an all-electron basis set applied to [Pb(H(2)O)](2+) and [Pb(OH)](+), two complexes expected to be found in the terrestrial atmosphere. It is shown that full-relativistic calculations validate the use of scalar relativistic approaches within the framework of density functional theory. [Pb(H(2)O)](2+) is found C(2v) at any level of calculations whereas [Pb(OH)](+) can be found bent or linear depending of the computational methodology used. When C(s) is found the barrier to inversion through the C(infinityv) structure is very low, and can be overcome at high enough temperature, making the molecule floppy. In order to get a better understanding of the bonding occurring between the Pb(2+) cation and the H(2)O and OH(-) ligands, natural bond orbital and atoms-in-molecule calculations have been performed. These approaches are supplemented by a topological analysis of the electron localization function. Finally, the description of these complexes is refined using constrained-space orbital variation complexation energy decompositions.

Structure and Electronic Properties of Neutral and Negatively Charged RhBn Clusters (n = 3-10): A Density Functional Theory Study.

PubMed

Li, Peifang; Mei, Tingting; Lv, Linxia; Lu, Cheng; Wang, Weihua; Bao, Gang; Gutsev, Gennady L

2017-08-31

The geometrical structure and electronic properties of the neutral RhB n and singly negatively charged RhB n - clusters are obtained in the range of 3 ≤ n ≤ 10 using the unbiased CALYPSO structure search method and density functional theory (DFT). A combination of the PBE0 functional and the def2-TZVP basis set is used for determining global minima on potential energy surfaces of the Rh-doped B n clusters. The photoelectron spectra of the anions are simulated using the time-dependent density functional theory (TD-DFT) method. Good agreement between our simulated and experimentally obtained photoelectron spectra for RhB 9 - provides support to the validity of our theoretical method. The relative stabilities of the ground-state RhB n and RhB n - clusters are estimated using the calculated binding energies, second-order total energy differences, and HOMO-LUMO gaps. It is found that RhB 7 and RhB 8 - are the most stable species in the neutral and anionic series, respectively. The chemical bonding analysis reveals that the RhB 8 - cluster possesses two sets of delocalized σ and π bonds. In both cases, the Hückel 4N + 2 rule is fulfilled and this cluster possesses both σ and π aromaticities.

Motor cognition-motor semantics: action perception theory of cognition and communication.

PubMed

Pulvermüller, Friedemann; Moseley, Rachel L; Egorova, Natalia; Shebani, Zubaida; Boulenger, Véronique

2014-03-01

A new perspective on cognition views cortical cell assemblies linking together knowledge about actions and perceptions not only as the vehicles of integrated action and perception processing but, furthermore, as a brain basis for a wide range of higher cortical functions, including attention, meaning and concepts, sequences, goals and intentions, and even communicative social interaction. This article explains mechanisms relevant to mechanistic action perception theory, points to concrete neuronal circuits in brains along with artificial neuronal network simulations, and summarizes recent brain imaging and other experimental data documenting the role of action perception circuits in cognition, language and communication. © 2013 Published by Elsevier Ltd.

RELATIVISTIC CYCLOTRON INSTABILITY IN ANISOTROPIC PLASMAS

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

López, Rodrigo A.; Moya, Pablo S.; Muñoz, Víctor

2016-11-20

A sufficiently large temperature anisotropy can sometimes drive various types of electromagnetic plasma micro-instabilities, which can play an important role in the dynamics of relativistic pair plasmas in space, astrophysics, and laboratory environments. Here, we provide a detailed description of the cyclotron instability of parallel propagating electromagnetic waves in relativistic pair plasmas on the basis of a relativistic anisotropic distribution function. Using plasma kinetic theory and particle-in-cell simulations, we study the influence of the relativistic temperature and the temperature anisotropy on the collective and noncollective modes of these plasmas. Growth rates and dispersion curves from the linear theory show amore » good agreement with simulations results.« less

Quantum cybernetics and its test in “late choice” experiments

NASA Astrophysics Data System (ADS)

Grössing, Gerhard

1986-11-01

A relativistically invariant wave equation for the propagation of wave fronts S = const ( S being the action function) is derived on the basis of a cybernetic model of quantum systems involving “hidden variables”. This equation can be considered both as an expression of Huygens' principle and as a general continuity equation providing a close link between classical and quantum mechanics. Although the theory reproduces ordinary quantum mechanics, there are particular situations providing experimental predictions differing from those existing theories. Such predictions are made for so-called “late choice” experiments, which are modified versions of the familiar “delayed choice” experiments.

Validity of virial theorem in all-electron mixed basis density functional, Hartree–Fock, and GW calculations

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

Kuwahara, Riichi; Accelrys K. K., Kasumigaseki Tokyu Building 17F, 3-7-1 Kasumigaseki, Chiyoda-ku, Tokyo 100-0013; Tadokoro, Yoichi

In this paper, we calculate kinetic and potential energy contributions to the electronic ground-state total energy of several isolated atoms (He, Be, Ne, Mg, Ar, and Ca) by using the local density approximation (LDA) in density functional theory, the Hartree–Fock approximation (HFA), and the self-consistent GW approximation (GWA). To this end, we have implemented self-consistent HFA and GWA routines in our all-electron mixed basis code, TOMBO. We confirm that virial theorem is fairly well satisfied in all of these approximations, although the resulting eigenvalue of the highest occupied molecular orbital level, i.e., the negative of the ionization potential, is inmore » excellent agreement only in the case of the GWA. We find that the wave function of the lowest unoccupied molecular orbital level of noble gas atoms is a resonating virtual bound state, and that of the GWA spreads wider than that of the LDA and thinner than that of the HFA.« less

Locally smeared operator product expansions in scalar field theory

DOE PAGES

Monahan, Christopher; Orginos, Kostas

2015-04-01

We propose a new locally smeared operator product expansion to decompose non-local operators in terms of a basis of smeared operators. The smeared operator product expansion formally connects nonperturbative matrix elements determined numerically using lattice field theory to matrix elements of non-local operators in the continuum. These nonperturbative matrix elements do not suffer from power-divergent mixing on the lattice, which significantly complicates calculations of quantities such as the moments of parton distribution functions, provided the smearing scale is kept fixed in the continuum limit. The presence of this smearing scale complicates the connection to the Wilson coefficients of the standardmore » operator product expansion and requires the construction of a suitable formalism. We demonstrate the feasibility of our approach with examples in real scalar field theory.« less

Instantaneous and scale-versatile gourdron theory: pair momentum equation, quasi-stability concept, and statistical indeterminacy revealing masses of elementary, bio-molecular, and cosmic particles

NASA Astrophysics Data System (ADS)

Naitoh, Ken

2014-04-01

Flexible particles, including hadrons, atoms, hydrated biological molecules, cells, organs containing water, liquid fuel droplets in engines, and stars commonly break up after becoming a gourd shape rather than that of a string; this leads to cyto-fluid dynamics that can explain the proliferation, differentiation, and replication of biomolecules, onto-biology that clarifies the relationship between information, structure, and function, and the gourd theory that clarifies masses, including quark-leptons and Plank energy. The masses are related to the super-magic numbers, including the asymmetric silver ratio and symmetric yamato ratio, and reveal further mechanisms underlying symmetry breaking. This paper gives further theoretical basis and evidence, because the gourd theory reported previously is a little analogical and instinctive.

Conformational analysis of cellobiose by electronic structure theories.

PubMed

French, Alfred D; Johnson, Glenn P; Cramer, Christopher J; Csonka, Gábor I

2012-03-01

Adiabatic Φ/ψ maps for cellobiose were prepared with B3LYP density functional theory. A mixed basis set was used for minimization, followed with 6-31+G(d) single-point calculations, with and without SMD continuum solvation. Different arrangements of the exocyclic groups (38 starting geometries) were considered for each Φ/ψ point. The vacuum calculations agreed with earlier computational and experimental results on the preferred gas phase conformation (anti-Φ(H), syn-ψ(H)), and the results from the solvated calculations were consistent with the (syn Φ(H)/ψ(H) conformations from condensed phases (crystals or solutions). Results from related studies were compared, and there is substantial dependence on the solvation model as well as arrangements of exocyclic groups. New stabilizing interactions were revealed by Atoms-In-Molecules theory. Published by Elsevier Ltd.

Market fallacies in health economics.

PubMed

Grant, R J

1991-12-07

Serious methodological errors that plague studies in health economics are examined with the focus on misconceptions about the nature and functions of markets. The belief that market economics do not apply to the medical marketplace involves circular reasoning that treats man-made laws and regulations as though they were unchangeable laws of nature. Arguments against the market provision of health care are questioned and the 'information gap' problem is shown to be aggravated, if not caused, by regulations that prevent normal information flows in the market. Similarly, the contention that health care insurance pushes up costs is criticised on the basis of both theory and empirical evidence. The apparent failure to contain costs may be blamed on legal restrictions, government spending and pressure from medical associations. Confusion between normative theory and positive theory is also examined.

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.

The Strange (Hi)story of Particles and Waves

NASA Astrophysics Data System (ADS)

Zeh, H. Dieter

2016-03-01

This is an attempt of a non-technical but conceptually consistent presentation of quantum theory in a historical context. While the first part is written for a general readership, Section 5 may appear a bit provocative to some quantum physicists. I argue that the single-particle wave functions of quantum mechanics have to be correctly interpreted as field modes that are "occupied once" (i.e. first excited states of the corresponding quantum oscillators in the case of boson fields). Multiple excitations lead to apparent many-particle wave functions, while the quantum states proper are defined by wave function(al)s on the "configuration" space of fundamental fields, or on another, as yet elusive, fundamental local basis.

Quantum Chemistry Study of Cycloaddition Pathways for the Reaction of o-Benzyne with Fullerenes and Carbon Nanotubes

NASA Technical Reports Server (NTRS)

Jaffe, Richard; Han, Jie; Langhoff, Stephen R. (Technical Monitor)

1997-01-01

Functionalization of fullerenes via the [2+2] cycloaddition reaction with o-benzyne has been demonstrated in the laboratory. In contrast, [2+4) cycloaddition products are formed when benzyne reacts with planar polycyclic aromatic hydrocarbons. Using density functional theory (DFT) calculations with Becke's hybrid functional and small contracted gaussian basis sets, we are able to reproduce these product preferences. The objective of this work is to explore the functionalization of carbon nanotubes. We have studied o-benzyne cycloaddition products with a [14,0] single-walled nanotube. We find both the [2+2] and [2+4] adducts to be stable, with the latter product being somewhat favored.

Thermochemistry analyses for transformation of C6 glucose compound into C9, C12 and C15 alkanes using density functional theory

NASA Astrophysics Data System (ADS)

Verma, Anand Mohan; Kishore, Nanda

2017-02-01

The hydrolysis of cellulose fraction of biomass yields C6 glucose which further can be transformed into long-chain hydrocarbons by C-C coupling. In this study, C6 glucose is transformed into three chain alkanes, namely, C9, C12 and C15 using C-C coupling reactions under the gas and aqueous phase milieus. The geometry optimisation and vibrational frequency calculations are carried out at well-known hybrid-GGA functional, B3LYP with the basis set of 6-31+g(d,p) under the density functional theory framework. The single point energetics are calculated at M05-2X/6-311+g(3df,2p) level of theory. All thermochemical properties are calculated over a wide range of temperature between 300 and 900 K at an interval of 100 K. The thermochemistry suggested that the aqueous phase behaviour is suitable for the hydrolysis of sugar into long-chain alkanes compared to gas-phase environment. The hydrodeoxygenation reactions under each reaction pathway are found as most favourable reactions in both phases; however, aqueous phase dominates over gas phase in all discussed thermodynamic parameters.

Plymouth Rock Landed on Us: Malcolm X's Whiteness Theory as a Basis for Alternative Literacy

ERIC Educational Resources Information Center

Miller, Keith D.

2004-01-01

Using Burkean theory, I claim that Malcolm X brilliantly exposed the rhetoric and epistemology of whiteness as he rejected the African American jeremiad--a dominant form of African American oratory for more than 150 years. Whiteness theory served as the basis for Malcolm X's alternative literacy, which raises important questions that literacy…

Vertical spatial coherence model for a transient signal forward-scattered from the sea surface

USGS Publications Warehouse

Yoerger, E.J.; McDaniel, S.T.

1996-01-01

The treatment of acoustic energy forward scattered from the sea surface, which is modeled as a random communications scatter channel, is the basis for developing an expression for the time-dependent coherence function across a vertical receiving array. The derivation of this model uses linear filter theory applied to the Fresnel-corrected Kirchhoff approximation in obtaining an equation for the covariance function for the forward-scattered problem. The resulting formulation is used to study the dependence of the covariance on experimental and environmental factors. The modeled coherence functions are then formed for various geometrical and environmental parameters and compared to experimental data.

Psychoses and creativity: is the missing link a biological mechanism related to phospholipids turnover?

PubMed Central

Folley, Bradley S.; Doop, Mikisha L.; Park, Sohee

2009-01-01

Recent evidence suggests that genetic and biochemical factors associated with psychoses may also provide an increased propensity to think creatively. The evolutionary theories linking brain growth and diet to the appearance of creative endeavors have been made recently, but they lack a direct link to research on the biological correlates of divergent and creative thought. Expanding upon Horrobin’s theory that changes in brain size and in neural microconnectivity came about as a result of changes in dietary fat and phospholipid incorporation of highly unsaturated fatty acids, we propose a theory relating phospholipase A2 (PLA2) activity to the neuromodulatory effects of the noradrenergic system. This theory offers probable links between attention, divergent thinking, and arousal through a mechanism that emphasizes optimal individual functioning of the PLA2 and NE systems as they interact with structural and biochemical states of the brain. We hope that this theory will stimulate new research in the neural basis of creativity and its connection to psychoses. PMID:14623501

On gauge independence for gauge models with soft breaking of BRST symmetry

NASA Astrophysics Data System (ADS)

Reshetnyak, Alexander

2014-12-01

A consistent quantum treatment of general gauge theories with an arbitrary gauge-fixing in the presence of soft breaking of the BRST symmetry in the field-antifield formalism is developed. It is based on a gauged (involving a field-dependent parameter) version of finite BRST transformations. The prescription allows one to restore the gauge-independence of the effective action at its extremals and therefore also that of the conventional S-matrix for a theory with BRST-breaking terms being additively introduced into a BRST-invariant action in order to achieve a consistency of the functional integral. We demonstrate the applicability of this prescription within the approach of functional renormalization group to the Yang-Mills and gravity theories. The Gribov-Zwanziger action and the refined Gribov-Zwanziger action for a many-parameter family of gauges, including the Coulomb, axial and covariant gauges, are derived perturbatively on the basis of finite gauged BRST transformations starting from Landau gauge. It is proved that gauge theories with soft breaking of BRST symmetry can be made consistent if the transformed BRST-breaking terms satisfy the same soft BRST symmetry breaking condition in the resulting gauge as the untransformed ones in the initial gauge, and also without this requirement.

Unexpected Trimerization of Pyrazine in the Coordination Sphere of Low-Valent Titanocene Fragments.

PubMed

Jung, Thomas; Beckhaus, Rüdiger; Klüner, Thorsten; Höfener, Sebastian; Klopper, Wim

2009-08-11

The titanium mediated trimerization of pyrazine leads to the formation of a tris-chelate complex employing a 4a,4b,8a,8b,12a,12b-hexahydrodiyprazino[2,3-f:2',3'-h]quinoxaline ligand (HATH6, 3). The driving force in the formation of the (Cp*2Ti)3(HATH6) complex 2 is attributed to the formation of six Ti-N bonds. We show that density functional theory (DFT) fails to predict quantitatively correct results. Therefore, post-Hartree-Fock methods, such as second-order Møller-Plesset perturbation theory (MP2), in combination with coupled-cluster (CC) methods must be used. Both MP2 and CCSD(T) levels of theory provide endothermic trimerization energies, showing that the plain pyrazine trimer is not stable with respect to decomposition into its monomers. Complete basis set (CBS) results for the MP2 level of theory were computed using explicitly correlated wave functions. With these, we estimate the CCSD(T) CBS limit of the hypothetical trimerization energy to be +0.78 eV. Thus, the trimerization is facilitated by the formation of six Ti-N bonds with a calculated formation energy of -1.32 eV per bond.

Electric transition dipole moment in pre-Born-Oppenheimer molecular structure theory.

PubMed

Simmen, Benjamin; Mátyus, Edit; Reiher, Markus

2014-10-21

This paper presents the calculation of the electric transition dipole moment in a pre-Born-Oppenheimer framework. Electrons and nuclei are treated equally in terms of the parametrization of the non-relativistic total wave function, which is written as a linear combination of basis functions constructed from explicitly correlated Gaussian functions and the global vector representation. The integrals of the electric transition dipole moment are derived corresponding to these basis functions in both the length and the velocity representation. The calculations are performed in laboratory-fixed Cartesian coordinates without relying on coordinates which separate the center of mass from the translationally invariant degrees of freedom. The effect of the overall motion is eliminated through translationally invariant integral expressions. The electric transition dipole moment is calculated between two rovibronic levels of the H2 molecule assignable to the lowest rovibrational states of the X (1)Σ(g)(+) and B (1)Σ(u)(+) electronic states in the clamped-nuclei framework. This is the first evaluation of this quantity in a full quantum mechanical treatment without relying on the Born-Oppenheimer approximation.

A rational model of function learning.

PubMed

Lucas, Christopher G; Griffiths, Thomas L; Williams, Joseph J; Kalish, Michael L

2015-10-01

Theories of how people learn relationships between continuous variables have tended to focus on two possibilities: one, that people are estimating explicit functions, or two that they are performing associative learning supported by similarity. We provide a rational analysis of function learning, drawing on work on regression in machine learning and statistics. Using the equivalence of Bayesian linear regression and Gaussian processes, which provide a probabilistic basis for similarity-based function learning, we show that learning explicit rules and using similarity can be seen as two views of one solution to this problem. We use this insight to define a rational model of human function learning that combines the strengths of both approaches and accounts for a wide variety of experimental results.

Nuclear magnetic resonance, vibrational spectroscopic studies, physico-chemical properties and computational calculations on (nitrophenyl) octahydroquinolindiones by DFT method.

PubMed

Pasha, M A; Siddekha, Aisha; Mishra, Soni; Azzam, Sadeq Hamood Saleh; Umapathy, S

2015-02-05

In the present study, 2'-nitrophenyloctahydroquinolinedione and its 3'-nitrophenyl isomer were synthesized and characterized by FT-IR, FT-Raman, (1)H NMR and (13)C NMR spectroscopy. The molecular geometry, vibrational frequencies, (1)H and (13)C NMR chemical shift values of the synthesized compounds in the ground state have been calculated by using the density functional theory (DFT) method with the 6-311++G (d,p) basis set and compared with the experimental data. The complete vibrational assignments of wave numbers were made on the basis of potential energy distribution using GAR2PED programme. Isotropic chemical shifts for (1)H and (13)C NMR were calculated using gauge-invariant atomic orbital (GIAO) method. The experimental vibrational frequencies, (1)H and (13)C NMR chemical shift values were found to be in good agreement with the theoretical values. On the basis of vibrational analysis, molecular electrostatic potential and the standard thermodynamic functions have been investigated. Copyright © 2014 Elsevier B.V. All rights reserved.

Vibrational spectra, DFT quantum chemical calculations and conformational analysis of P-iodoanisole.

PubMed

Arivazhagan, M; Anitha Rexalin, D; Geethapriya, J

2013-09-01

The solid phase FT-IR and FT-Raman spectra of P-iodoanisole (P-IA) have been recorded in the regions 400-4000 and 50-4000 cm(-1), respectively. The spectra were interpreted in terms of fundamentals modes, combination and overtone bands. The structure of the molecule was optimized and the structural characteristics were determined by ab initio (HF) and density functional theory (B3LYP) methods with LanL2DZ as basis set. The potential energy surface scan for the selected dihedral angle of P-IA has been performed to identify stable conformer. The optimized structure parameters and vibrational wavenumbers of stable conformer have been predicted by density functional B3LYP method with LanL2DZ (with effective core potential representations of electrons near the nuclei for post-third row atoms) basis set. The nucleophilic and electrophilic sites obtained from the molecular electrostatic potential (MEP) surface were calculated. The temperature dependence of thermodynamic properties has been analyzed. Several thermodynamic parameters have been calculated using B3LYP with LanL2DZ basis set. Copyright © 2013 Elsevier B.V. All rights reserved.

Adsorption of Emerging Munitions Contaminants on Cellulose Surface: A Combined Theoretical and Experimental Investigation.

PubMed

Shukla, Manoj K; Poda, Aimee

2016-06-01

This manuscript reports results of an integrated theoretical and experimental investigation of adsorption of two emerging contaminants (DNAN and FOX-7) and legacy compound TNT on cellulose surface. Cellulose was modeled as trimeric form of the linear chain of 1 → 4 linked of β-D-glucopyranos in (4)C1 chair conformation. Geometries of modeled cellulose, munitions compounds and their complexes were optimized at the M06-2X functional level of Density Functional Theory using the 6-31G(d,p) basis set in gas phase and in water solution. The effect of water solution was modeled using the CPCM approach. Nature of potential energy surfaces was ascertained through harmonic vibrational frequency analysis. Interaction energies were corrected for basis set superposition error and the 6-311G(d,p) basis set was used. Molecular electrostatic potential mapping was performed to understand the reactivity of the investigated systems. It was predicted that adsorbates will be weakly adsorbed on the cellulose surface in water solution than in the gas phase.

Optimized design for sling of stand up lift

NASA Astrophysics Data System (ADS)

Xu, Dongfang; Wang, Yue; Cui, Tengfei; Bao, Xuelian; Duan, Xingguang

2017-04-01

Stand up lift is a kind of equipment that assists those with dyskinesia of legs to stand up or move. As an important part of stand up lift, sling concerns the realization of the equipment's function and the safety of users. On the basis of ergonomics theory, this thesis will design and optimize the sling to make it safer and more comfortable and meet demands of different people.

Vibrational and electronic investigations, thermodynamic parameters, HOMO and LUMO analysis on Lornoxicam by density functional theory

NASA Astrophysics Data System (ADS)

Suhasini, M.; Sailatha, E.; Gunasekaran, S.; Ramkumaar, G. R.

2015-11-01

The Fourier transform infrared (FT-IR) and FT-Raman spectra of Lornoxicam were recorded in the region 4000-450 cm-1 and 4000-50 cm-1 respectively. Density functional theory (DFT) has been used to calculate the optimized geometrical parameters, atomic charges, and vibrational wavenumbers and intensity of the vibrational bands. The computed vibrational wave numbers were compared with the FT-IR and FT-Raman experimental data. The computational calculations at DFT/B3LYP level with 6-31G(d,p) and 6-31++G(d,p) basis sets. The complete vibrational assignments were performed on the basis of the potential energy distribution (PED) of the Vibrational modes calculated using Vibrational Energy Distribution Analysis (VEDA 4) program. The oscillator's strength calculated by TD-DFT and Lornoxicam is approach complement with the experimental findings. The NMR chemical shifts 13C and 1H were recorded and calculated using the gauge independent atomic orbital (GIAO) method. The Natural charges and intermolecular contacts have been interpreted using Natural Bond orbital (NBO) analysis and the HOMO-LUMO energy gap has been calculated. The thermodynamic properties like Entropy, Enthalpy, Specific heat capacity and zero vibrational energy have been calculated. Besides, molecular electrostatic potential (MEP) was investigated using theoretical calculations.

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.

Heats of formation of phosphorus compounds determined by current methods of computational quantum chemistry

NASA Astrophysics Data System (ADS)

Haworth, Naomi L.; Bacskay, George B.

2002-12-01

The heats of formation of a range of phosphorus containing molecules (P2, P4, PH, PH2, PH3, P2H2, P2H4, PO, PO2, PO3, P2O, P2O2, HPO, HPOH, H2POH, H3PO, HOPO, and HOPO2) have been determined by high level quantum chemical calculations. The equilibrium geometries and vibrational frequencies were computed via density functional theory, utilizing the B3LYP/6-31G(2df,p) functional and basis set. Atomization energies were obtained by the application of ab initio coupled cluster theory with single and double excitations from (spin)-restricted Hartree-Fock reference states with perturbative correction for triples [CCSD(T)], in conjunction with cc-pVnZ basis sets (n=T, Q, 5) which include an extra d function on the phosphorus atoms and diffuse functions on the oxygens, as recommended by Bauschlicher [J. Phys. Chem. A 103, 11126 (1999)]. The valence correlated atomization energies were extrapolated to the complete basis limit and corrected for core-valence (CV) correlation and scalar relativistic effects, as well as for basis set superposition errors (BSSE) in the CV terms. This methodology is effectively the same as the one adopted by Bauschlicher in his study of PO, PO2, PO3, HPO, HOPO, and HOPO2. Consequently, for these molecules the results of this work closely match Bauschlicher's computed values. The theoretical heats of formation, whose accuracy is estimated as ranging from ±1.0 to ±2.5 kcal mol-1, are consistent with the available experimental data. The current set of theoretical data represent a convenient benchmark, against which the results of other computational procedures, such as G3, G3X, and G3X2, can be compared. Despite the fact that G3X2 [which is an approximation to the quadratic CI procedure QCISD(T,Full)/G3Xlarge] is a formally higher level theory than G3X, the heats of formation obtained by these two methods are found to be of comparable accuracy. Both reproduce the benchmark heats of formation on the average to within ±2 kcal mol-1 and, for these molecules at least, they are superior to the basic G3 method. The performance of G3X2 is further improved, however, by the incorporation of BSSE corrections in the CV component of the energies. All the G3n methods have difficulties, however, with molecules which have multiple or highly strained P-P bonds, such as P2 and P4.

A general range-separated double-hybrid density-functional theory

NASA Astrophysics Data System (ADS)

Kalai, Cairedine; Toulouse, Julien

2018-04-01

A range-separated double-hybrid (RSDH) scheme which generalizes the usual range-separated hybrids and double hybrids is developed. This scheme consistently uses a two-parameter Coulomb-attenuating-method (CAM)-like decomposition of the electron-electron interaction for both exchange and correlation in order to combine Hartree-Fock exchange and second-order Møller-Plesset (MP2) correlation with a density functional. The RSDH scheme relies on an exact theory which is presented in some detail. Several semi-local approximations are developed for the short-range exchange-correlation density functional involved in this scheme. After finding optimal values for the two parameters of the CAM-like decomposition, the RSDH scheme is shown to have a relatively small basis dependence and to provide atomization energies, reaction barrier heights, and weak intermolecular interactions globally more accurate or comparable to range-separated MP2 or standard MP2. The RSDH scheme represents a new family of double hybrids with minimal empiricism which could be useful for general chemical applications.

Intrinsic point defects in β-In2S3 studied by means of hybrid density-functional theory

NASA Astrophysics Data System (ADS)

Ghorbani, Elaheh; Albe, Karsten

2018-03-01

We have employed first principles total energy calculations in the framework of density functional theory, with plane wave basis sets and screened exchange hybrid functionals to study the incorporation of intrinsic defects in bulk β-In2S3. The results are obtained for In-rich and S-rich experimental growth conditions. The charge transition level is discussed for all native defects, including VIn, VS, Ini, Si, SIn, and InS, and a comparison between the theoretically calculated charge transition levels and the available experimental findings is presented. The results imply that β-In2S3 shows n-type conductivity under both In-rich and S-rich growth conditions. The indium antiisite (InS), the indium interstitial (Ini), and the sulfur vacancy ( VS ' ) are found to be the leading sources of sample's n-type conductivity. When going from the In-rich to the S-rich condition, the conductivity of the material decreases; however, the type of conductivity remains unchanged.

Properties of electronically excited states of four squaraine dyes and their complexes with fullerene C70: A theoretical investigation

NASA Astrophysics Data System (ADS)

Zhang, Jian; Li, Tingyu

2017-09-01

Solar cells sensitized by polypyridyl Ru(II) complexes exhibit relatively high efficiency, however those photo-sensitizers did not absorb the photons in the far-red and near-infrared region. At present, squaraine dyes have received considerable attention as their attractively intrinsic red light absorption and unusual high molar extinction coefficient. Here we applied density functional theory and time dependent density functional theory to investigate the properties of electronically excited states of four squaraine dyes and their complexes with fullerene C70. The influences of different functionals, basis sets and solvent effects are evaluated. To understand the photophysical properties, the investigations are basing on a classification method which splits the squaraine dyes and their complexes with fullerene C70 into two units to characterize the intramolecular density distribution. We present the signatures of their electronically excited states which are characterized as local excitation or charge-transfer excitation. The relationship between open-circuit voltage and the number of intramolecular hydrogen bonds in squaraine dyes are discussed.

Global and critical test of the perturbation density-functional theory based on extensive simulation of Lennard-Jones fluid near an interface and in confined systems.

PubMed

Zhou, Shiqi; Jamnik, Andrej

2005-09-22

The structure of a Lennard-Jones (LJ) fluid subjected to diverse external fields maintaining the equilibrium with the bulk LJ fluid is studied on the basis of the third-order+second-order perturbation density-functional approximation (DFA). The chosen density and potential parameters for the bulk fluid correspond to the conditions situated at "dangerous" regions of the phase diagram, i.e., near the critical temperature or close to the gas-liquid coexistence curve. The accuracy of DFA predictions is tested against the results of a grand canonical ensemble Monte Carlo simulation. It is found that the DFA theory presented in this work performs successfully for the nonuniform LJ fluid only on the condition of high accuracy of the required bulk second-order direct correlation function. The present report further indicates that the proposed perturbation DFA is efficient and suitable for both supercritical and subcritical temperatures.

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

Maiolo, M., E-mail: massimo.maiolo@zhaw.ch; ZHAW, Institut für Angewandte Simulation, Grüental, CH-8820 Wädenswil; Vancheri, A., E-mail: alberto.vancheri@supsi.ch

In this paper, we apply Multiresolution Analysis (MRA) to develop sparse but accurate representations for the Multiscale Coarse-Graining (MSCG) approximation to the many-body potential of mean force. We rigorously framed the MSCG method into MRA so that all the instruments of this theory become available together with a multitude of new basis functions, namely the wavelets. The coarse-grained (CG) force field is hierarchically decomposed at different resolution levels enabling to choose the most appropriate wavelet family for each physical interaction without requiring an a priori knowledge of the details localization. The representation of the CG potential in this new efficientmore » orthonormal basis leads to a compression of the signal information in few large expansion coefficients. The multiresolution property of the wavelet transform allows to isolate and remove the noise from the CG force-field reconstruction by thresholding the basis function coefficients from each frequency band independently. We discuss the implementation of our wavelet-based MSCG approach and demonstrate its accuracy using two different condensed-phase systems, i.e. liquid water and methanol. Simulations of liquid argon have also been performed using a one-to-one mapping between atomistic and CG sites. The latter model allows to verify the accuracy of the method and to test different choices of wavelet families. Furthermore, the results of the computer simulations show that the efficiency and sparsity of the representation of the CG force field can be traced back to the mathematical properties of the chosen family of wavelets. This result is in agreement with what is known from the theory of multiresolution analysis of signals.« less

Numerical Optimization of Density Functional Tight Binding Models: Application to Molecules Containing Carbon, Hydrogen, Nitrogen, and Oxygen

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

Krishnapriyan, A.; Yang, P.; Niklasson, A. M. N.

New parametrizations for semiempirical density functional tight binding (DFTB) theory have been developed by the numerical optimization of adjustable parameters to minimize errors in the atomization energy and interatomic forces with respect to ab initio calculated data. Initial guesses for the radial dependences of the Slater- Koster bond integrals and overlap integrals were obtained from minimum basis density functional theory calculations. The radial dependences of the pair potentials and the bond and overlap integrals were represented by simple analytic functions. The adjustable parameters in these functions were optimized by simulated annealing and steepest descent algorithms to minimize the value ofmore » an objective function that quantifies the error between the DFTB model and ab initio calculated data. The accuracy and transferability of the resulting DFTB models for the C, H, N, and O system were assessed by comparing the predicted atomization energies and equilibrium molecular geometries of small molecules that were not included in the training data from DFTB to ab initio data. The DFTB models provide accurate predictions of the properties of hydrocarbons and more complex molecules containing C, H, N, and O.« less

Numerical Optimization of Density Functional Tight Binding Models: Application to Molecules Containing Carbon, Hydrogen, Nitrogen, and Oxygen

DOE PAGES

Krishnapriyan, A.; Yang, P.; Niklasson, A. M. N.; ...

2017-10-17

New parametrizations for semiempirical density functional tight binding (DFTB) theory have been developed by the numerical optimization of adjustable parameters to minimize errors in the atomization energy and interatomic forces with respect to ab initio calculated data. Initial guesses for the radial dependences of the Slater- Koster bond integrals and overlap integrals were obtained from minimum basis density functional theory calculations. The radial dependences of the pair potentials and the bond and overlap integrals were represented by simple analytic functions. The adjustable parameters in these functions were optimized by simulated annealing and steepest descent algorithms to minimize the value ofmore » an objective function that quantifies the error between the DFTB model and ab initio calculated data. The accuracy and transferability of the resulting DFTB models for the C, H, N, and O system were assessed by comparing the predicted atomization energies and equilibrium molecular geometries of small molecules that were not included in the training data from DFTB to ab initio data. The DFTB models provide accurate predictions of the properties of hydrocarbons and more complex molecules containing C, H, N, and O.« less

Electronic states of aryl radical functionalized graphenes: Density functional theory study

NASA Astrophysics Data System (ADS)

Tachikawa, Hiroto; Kawabata, Hiroshi

2016-06-01

Functionalized graphenes are known as a high-performance molecular device. In the present study, the structures and electronic states of the aryl radical functionalized graphene have been investigated by the density functional theory (DFT) method to elucidate the effects of functionalization on the electronic states of graphene (GR). Also, the mechanism of aryl radical reaction with GR was investigated. The benzene, biphenyl, p-terphenyl, and p-quaterphenyl radicals [denoted by (Bz) n (n = 1-4), where n means numbers of benzene rings in aryl radical] were examined as aryl radicals. The DFT calculation of GR-(Bz) n (n = 1-4) showed that the aryl radical binds to the carbon atom of GR, and a C-C single bond was formed. The binding energies of aryl radicals to GR were calculated to be ca. 6.0 kcal mol-1 at the CAM-B3LYP/6-311G(d,p) level. It was found that the activation barrier exists in the aryl radical addition: the barrier heights were calculated to be 10.0 kcal mol-1. The electronic states of GR-(Bz) n were examined on the basis of theoretical results.

Full Waveform Modeling of Transient Electromagnetic Response Based on Temporal Interpolation and Convolution Method

NASA Astrophysics Data System (ADS)

Qi, Youzheng; Huang, Ling; Wu, Xin; Zhu, Wanhua; Fang, Guangyou; Yu, Gang

2017-07-01

Quantitative modeling of the transient electromagnetic (TEM) response requires consideration of the full transmitter waveform, i.e., not only the specific current waveform in a half cycle but also the bipolar repetition. In this paper, we present a novel temporal interpolation and convolution (TIC) method to facilitate the accurate TEM modeling. We first calculate the temporal basis response on a logarithmic scale using the fast digital-filter-based methods. Then, we introduce a function named hamlogsinc in the framework of discrete signal processing theory to reconstruct the basis function and to make the convolution with the positive half of the waveform. Finally, a superposition procedure is used to take account of the effect of previous bipolar waveforms. Comparisons with the established fast Fourier transform method demonstrate that our TIC method can get the same accuracy with a shorter computing time.

QUADRATIC SERENDIPITY FINITE ELEMENTS ON POLYGONS USING GENERALIZED BARYCENTRIC COORDINATES.

PubMed

Rand, Alexander; Gillette, Andrew; Bajaj, Chandrajit

2014-01-01

We introduce a finite element construction for use on the class of convex, planar polygons and show it obtains a quadratic error convergence estimate. On a convex n -gon, our construction produces 2 n basis functions, associated in a Lagrange-like fashion to each vertex and each edge midpoint, by transforming and combining a set of n ( n + 1)/2 basis functions known to obtain quadratic convergence. The technique broadens the scope of the so-called 'serendipity' elements, previously studied only for quadrilateral and regular hexahedral meshes, by employing the theory of generalized barycentric coordinates. Uniform a priori error estimates are established over the class of convex quadrilaterals with bounded aspect ratio as well as over the class of convex planar polygons satisfying additional shape regularity conditions to exclude large interior angles and short edges. Numerical evidence is provided on a trapezoidal quadrilateral mesh, previously not amenable to serendipity constructions, and applications to adaptive meshing are discussed.

Experimental and theoretical study on DPPH radical scavenging mechanism of some chalcone quinoline derivatives

NASA Astrophysics Data System (ADS)

Hamlaoui, Ikram; Bencheraiet, Reguia; Bensegueni, Rafik; Bencharif, Mustapha

2018-03-01

In this study, the antioxidant capacity of three chalcone derivatives was evaluated by DPPH free radical scavenging. Experimental data showed low antioxidant activity (IC50±SD) of these molecules in comparison with BHT. The mechanism of DPPH radical scavenging elucidated by means of density functional theory (DFT) calculations. The tested compounds and their corresponding radicals and anions were optimized using B3LYP functional with 6-31G (d,p) basis set in the gas phase. The C-PCM model was used to perform solvent medium calculations. On the basis of theoretical calculations, it was shown that HAT mechanism was predominant in the gas phase, whereas SET-PT and SPLET mechanisms were favored in the presence of the solvent. Moreover, the HOMO orbitals and spin density distribution was evaluated to predict the probable sites for free radical attack.

Fault detection for hydraulic pump based on chaotic parallel RBF network

NASA Astrophysics Data System (ADS)

Lu, Chen; Ma, Ning; Wang, Zhipeng

2011-12-01

In this article, a parallel radial basis function network in conjunction with chaos theory (CPRBF network) is presented, and applied to practical fault detection for hydraulic pump, which is a critical component in aircraft. The CPRBF network consists of a number of radial basis function (RBF) subnets connected in parallel. The number of input nodes for each RBF subnet is determined by different embedding dimension based on chaotic phase-space reconstruction. The output of CPRBF is a weighted sum of all RBF subnets. It was first trained using the dataset from normal state without fault, and then a residual error generator was designed to detect failures based on the trained CPRBF network. Then, failure detection can be achieved by the analysis of the residual error. Finally, two case studies are introduced to compare the proposed CPRBF network with traditional RBF networks, in terms of prediction and detection accuracy.

Computational study of the reactions of methanol with the hydroperoxyl and methyl radicals. 1. Accurate thermochemistry and barrier heights.

PubMed

Alecu, I M; Truhlar, Donald G

2011-04-07

The reactions of CH(3)OH with the HO(2) and CH(3) radicals are important in the combustion of methanol and are prototypes for reactions of heavier alcohols in biofuels. The reaction energies and barrier heights for these reaction systems are computed with CCSD(T) theory extrapolated to the complete basis set limit using correlation-consistent basis sets, both augmented and unaugmented, and further refined by including a fully coupled treatment of the connected triple excitations, a second-order perturbative treatment of quadruple excitations (by CCSDT(2)(Q)), core-valence corrections, and scalar relativistic effects. It is shown that the M08-HX and M08-SO hybrid meta-GGA density functionals can achieve sub-kcal mol(-1) agreement with the high-level ab initio results, identifying these functionals as important potential candidates for direct dynamics studies on the rates of these and homologous reaction systems.

A theoretical study of potentially observable chirality-sensitive NMR effects in molecules.

PubMed

Garbacz, Piotr; Cukras, Janusz; Jaszuński, Michał

2015-09-21

Two recently predicted nuclear magnetic resonance effects, the chirality-induced rotating electric polarization and the oscillating magnetization, are examined for several experimentally available chiral molecules. We discuss in detail the requirements for experimental detection of chirality-sensitive NMR effects of the studied molecules. These requirements are related to two parameters: the shielding polarizability and the antisymmetric part of the nuclear magnetic shielding tensor. The dominant second contribution has been computed for small molecules at the coupled cluster and density functional theory levels. It was found that DFT calculations using the KT2 functional and the aug-cc-pCVTZ basis set adequately reproduce the CCSD(T) values obtained with the same basis set. The largest values of parameters, thus most promising from the experimental point of view, were obtained for the fluorine nuclei in 1,3-difluorocyclopropene and 1,3-diphenyl-2-fluoro-3-trifluoromethylcyclopropene.

An adaptive trajectory tracking control of four rotor hover vehicle using extended normalized radial basis function network

NASA Astrophysics Data System (ADS)

ul Amin, Rooh; Aijun, Li; Khan, Muhammad Umer; Shamshirband, Shahaboddin; Kamsin, Amirrudin

2017-01-01

In this paper, an adaptive trajectory tracking controller based on extended normalized radial basis function network (ENRBFN) is proposed for 3-degree-of-freedom four rotor hover vehicle subjected to external disturbance i.e. wind turbulence. Mathematical model of four rotor hover system is developed using equations of motions and a new computational intelligence based technique ENRBFN is introduced to approximate the unmodeled dynamics of the hover vehicle. The adaptive controller based on the Lyapunov stability approach is designed to achieve tracking of the desired attitude angles of four rotor hover vehicle in the presence of wind turbulence. The adaptive weight update based on the Levenberg-Marquardt algorithm is used to avoid weight drift in case the system is exposed to external disturbances. The closed-loop system stability is also analyzed using Lyapunov stability theory. Simulations and experimental results are included to validate the effectiveness of the proposed control scheme.

TGA, Hirshfeld, Raman spectroscopy and computational studies of diethylammonium hexachloroplumbate [(C2H5)2NH2]2PbCl6

NASA Astrophysics Data System (ADS)

Ouasri, A.; El-Adel, L.; Zouihri, H.; Rhandour, A.; Jalbout, A. F.

2018-04-01

Diethylammonium hexachloroplumbate [(C2H5)2NH2]2PbCl6 was found to be monoclinic with P21/n (Z = 2) as space group at room temperature. The TGA analysis shows that this compound is slightly hygroscopic and presents moisture in itself. The Raman spectrum (50-4000 cm-1) of this compound recorded at room temperature was discussed on the basis of the factor group analysis using the structural data obtained recently [5]. The experimental frequencies are compared to those obtained by Density Functional Theory (DFT) by using the B3LYP functional and the 6-31G(d) (SDD) basis set. The thermodynamic properties and geometries of this compound have been determinated and characterized. The significant intermolecular interactions in the crystal structure are identified and analyzed using the Hirshfeld surface and fingerprint plots computational methods.

Estimation of Δ R/ R values by benchmark study of the Mössbauer Isomer shifts for Ru, Os complexes using relativistic DFT calculations

NASA Astrophysics Data System (ADS)

Kaneko, Masashi; Yasuhara, Hiroki; Miyashita, Sunao; Nakashima, Satoru

2017-11-01

The present study applies all-electron relativistic DFT calculation with Douglas-Kroll-Hess (DKH) Hamiltonian to each ten sets of Ru and Os compounds. We perform the benchmark investigation of three density functionals (BP86, B3LYP and B2PLYP) using segmented all-electron relativistically contracted (SARC) basis set with the experimental Mössbauer isomer shifts for 99Ru and 189Os nuclides. Geometry optimizations at BP86 theory of level locate the structure in a local minimum. We calculate the contact density to the wavefunction obtained by a single point calculation. All functionals show the good linear correlation with experimental isomer shifts for both 99Ru and 189Os. Especially, B3LYP functional gives a stronger correlation compared to BP86 and B2PLYP functionals. The comparison of contact density between SARC and well-tempered basis set (WTBS) indicated that the numerical convergence of contact density cannot be obtained, but the reproducibility is less sensitive to the choice of basis set. We also estimate the values of Δ R/ R, which is an important nuclear constant, for 99Ru and 189Os nuclides by using the benchmark results. The sign of the calculated Δ R/ R values is consistent with the predicted data for 99Ru and 189Os. We obtain computationally the Δ R/ R values of 99Ru and 189Os (36.2 keV) as 2.35×10-4 and -0.20×10-4, respectively, at B3LYP level for SARC basis set.

Efficient and Flexible Computation of Many-Electron Wave Function Overlaps.

PubMed

Plasser, Felix; Ruckenbauer, Matthias; Mai, Sebastian; Oppel, Markus; Marquetand, Philipp; González, Leticia

2016-03-08

A new algorithm for the computation of the overlap between many-electron wave functions is described. This algorithm allows for the extensive use of recurring intermediates and thus provides high computational efficiency. Because of the general formalism employed, overlaps can be computed for varying wave function types, molecular orbitals, basis sets, and molecular geometries. This paves the way for efficiently computing nonadiabatic interaction terms for dynamics simulations. In addition, other application areas can be envisaged, such as the comparison of wave functions constructed at different levels of theory. Aside from explaining the algorithm and evaluating the performance, a detailed analysis of the numerical stability of wave function overlaps is carried out, and strategies for overcoming potential severe pitfalls due to displaced atoms and truncated wave functions are presented.

Prediction of Iron K-Edge Absorption Spectra Using Time-Dependent Density Functional Theory

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

George, S.DeBeer; Petrenko, T.; Neese, F.

2009-05-14

Iron K-edge X-ray absorption pre-edge features have been calculated using a time-dependent density functional approach. The influence of functional, solvation, and relativistic effects on the calculated energies and intensities has been examined by correlation of the calculated parameters to experimental data on a series of 10 iron model complexes, which span a range of high-spin and low-spin ferrous and ferric complexes in O{sub h} to T{sub d} geometries. Both quadrupole and dipole contributions to the spectra have been calculated. We find that good agreement between theory and experiment is obtained by using the BP86 functional with the CP(PPP) basis setmore » on the Fe and TZVP one of the remaining atoms. Inclusion of solvation yields a small improvement in the calculated energies. However, the inclusion of scalar relativistic effects did not yield any improved correlation with experiment. The use of these methods to uniquely assign individual spectral transitions and to examine experimental contributions to backbonding is discussed.« less

Vibrational spectroscopy and DFT calculations of flavonoid derriobtusone A

NASA Astrophysics Data System (ADS)

Marques, A. N. L.; Mendes Filho, J.; Freire, P. T. C.; Santos, H. S.; Albuquerque, M. R. J. R.; Bandeira, P. N.; Leite, R. V.; Braz-Filho, R.; Gusmão, G. O. M.; Nogueira, C. E. S.; Teixeira, A. M. R.

2017-02-01

Flavonoids are secondary metabolites of plants which perform various functions. One subclass of flavonoid is auronol that can present immunostimulating activity. In this work Fourier-Transform Infrared with Attenuated Total Reflectance (FTIR-ATR) and Fourier-Transform Raman (FT-Raman) spectra of an auronol, derriobtusone A (C18H12O4), were obtained at room temperature. Theoretical calculations using Density Functional Theory (DFT) were performed in order to assign the normal modes and to interpret the spectra of the derriobtusone A molecule. The FTIR-ATR and FT-Raman spectra of the crystal, were recorded at room temperature in the regions 600 cm-1 to 4000 cm-1 and 40 cm-1 to 4000 cm-1, respectively. The normal modes of vibrations were obtained using Density Functional Theory with B3LYP functional and 6-31G+ (d,p) basis set. The calculated frequencies are in good agreement with those obtained experimentally. Detailed assignments of the normal modes present in both the Fourier-Transform infrared and the Fourier-Transform Raman spectra of the crystal are given.

Coupled-cluster and density functional theory studies of the electronic 0-0 transitions of the DNA bases.

PubMed

Ovchinnikov, Vasily A; Sundholm, Dage

2014-04-21

The 0-0 transitions of the electronic excitation spectra of the lowest tautomers of the four nucleotide (DNA) bases have been studied using linear-response approximate coupled-cluster singles and doubles (CC2) calculations. Excitation energies have also been calculated at the linear-response time-dependent density functional theory (TDDFT) level using the B3LYP functional. Large basis sets have been employed for ensuring that the obtained excitation energies are close to the basis-set limit. Zero-point vibrational energy corrections have been calculated at the B3LYP and CC2 levels for the ground and excited states rendering direct comparisons with high-precision spectroscopy measurements feasible. The obtained excitation energies for the 0-0 transitions of the first excited states of guanine tautomers are in good agreement with experimental values confirming the experimental assignment of the energetic order of the tautomers of the DNA bases. For the experimentally detected guanine tautomers, the first excited state corresponds to a π→π* transition, whereas for the tautomers of adenine, thymine, and the lowest tautomer of cytosine the transition to the first excited state has n →π* character. The calculations suggest that the 0-0 transitions of adenine, thymine, and cytosine are not observed in the absorption spectrum due to the weak oscillator strength of the formally symmetry-forbidden transitions, while 0-0 transitions of thymine have been detected in fluorescence excitation spectra.

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

Frusciante, Noemi; Papadomanolakis, Georgios; Silvestri, Alessandra, E-mail: fruscian@iap.fr, E-mail: papadomanolakis@lorentz.leidenuniv.nl, E-mail: silvestri@lorentz.leidenuniv.nl

We present a generalization of the effective field theory (EFT) formalism for dark energy and modified gravity models to include operators with higher order spatial derivatives. This allows the extension of the EFT framework to a wider class of gravity theories such as Hořava gravity. We present the corresponding extended action, both in the EFT and the Arnowitt-Deser-Misner (ADM) formalism, and proceed to work out a convenient mapping between the two, providing a self contained and general procedure to translate a given model of gravity into the EFT language at the basis of the Einstein-Boltzmann solver EFTCAMB. Putting this mappingmore » at work, we illustrate, for several interesting models of dark energy and modified gravity, how to express them in the ADM notation and then map them into the EFT formalism. We also provide for the first time, the full mapping of GLPV models into the EFT framework. We next perform a thorough analysis of the physical stability of the generalized EFT action, in absence of matter components. We work out viability conditions that correspond to the absence of ghosts and modes that propagate with a negative speed of sound in the scalar and tensor sector, as well as the absence of tachyonic modes in the scalar sector. Finally, we extend and generalize the phenomenological basis in terms of α-functions introduced to parametrize Horndeski models, to cover all theories with higher order spatial derivatives included in our extended action. We elaborate on the impact of the additional functions on physical quantities, such as the kinetic term and the speeds of propagation for scalar and tensor modes.« less

Limitations of the clump-correlation theories of shear-induced turbulence suppression

NASA Astrophysics Data System (ADS)

Zhang, Y. Z.; Mahajan, S. M.

2017-05-01

The clump theory, primarily constructed by Dupree [Phys. Fluids 15, 334 (1972)] based on the moment approach and then generalized to the correlation theory [Y. Z. Zhang and S. M. Mahajan, Phys. Fluids B 5, 2000 (1993)], has long served as a basis for constructing theories of turbulence suppression by shear flow. In order to reveal the "intrinsic approximation" invoked in the clump-correlation theory, we examine a model based on two dimensional magnetized drift waves. After a rigorous derivation of the exact response function—a key to average the Green function of the system—we show that the Dupree, Zhang-Mahajan approach is recovered as the lowest order approximation in a small dimensionless parameter ϒ which is a triple product of the correlation time, wave number, and fluctuating drift velocity. The clump-correlation theory, thus, constitutes the Gaussian and lowest order non-Markovian process for a homogeneous stationary turbulence. We also provide, especially for the tokamak community, a readily usable formula to evaluate the effectiveness of shear-flow suppression; this formula pertains regardless of the specific model of correlation time.

Quantum chemical calculations of glycine glutaric acid

NASA Astrophysics Data System (ADS)

Arioǧlu, ćaǧla; Tamer, Ömer; Avci, Davut; Atalay, Yusuf

2017-02-01

Density functional theory (DFT) calculations of glycine glutaric acid were performed by using B3LYP levels with 6-311++G(d,p) basis set. The theoretical structural parameters such as bond lengths and bond angles are in a good agreement with the experimental values of the title compound. HOMO and LUMO energies were calculated, and the obtained energy gap shows that charge transfer occurs in the title compound. Vibrational frequencies were calculated and compare with experimental ones. 3D molecular surfaces of the title compound were simulated using the same level and basis set. Finally, the 13C and 1H NMR chemical shift values were calculated by the application of the gauge independent atomic orbital (GIAO) method.

On the performance of infrared sensors in earth observations

NASA Technical Reports Server (NTRS)

Johnson, L. F.

1972-01-01

The performance of infrared sensing systems is dependent upon the radiative properties of targets in addition to constraints imposed by system components. The unclassified state-of-the-art of infrared system performance figures is reviewed to indicate the relevance to system performance of target radiative properties. A theory of rough surface scattering is developed which allows the formulation of the reflective characteristics of extended targets. The thermal radiation emission from extended targets is formulated on the basis of internal radiation characteristics of natural materials and the transmissive scattering effects at the surface. Finally, the total radiative characteristics may be expressed as functions of material properties and incident and received directions, although the expressions are extremely complex functions and do not account for the effects of shadowing or multiple scattering. It is believed that the theory may be extended to include these effects and to incorporate the local radii of curvature of the surface.

Lattice dynamics of Ru2FeX (X = Si, Ge) Full Heusler alloys

NASA Astrophysics Data System (ADS)

Rizwan, M.; Afaq, A.; Aneeza, A.

2018-05-01

In present work, the lattice dynamics of Ru2FeX (X = Si, Ge) full Heusler alloys are investigated using density functional theory (DFT) within generalized gradient approximation (GGA) in a plane wave basis, with norm-conserving pseudopotentials. Phonon dispersion curves and phonon density of states are obtained using first-principles linear response approach of density functional perturbation theory (DFPT) as implemented in Quantum ESPRESSO code. Phonon dispersion curves indicates for both Heusler alloys that there is no imaginary phonon in whole Brillouin zone, confirming dynamical stability of these alloys in L21 type structure. There is a considerable overlapping between acoustic and optical phonon modes predicting no phonon band gap exists in dispersion curves of alloys. The same result is shown by phonon density of states curves for both Heusler alloys. Reststrahlen band for Ru2FeSi is found smaller than Ru2FeGe.

A Variational Reduction and the Existence of a Fully Localised Solitary Wave for the Three-Dimensional Water-Wave Problem with Weak Surface Tension

NASA Astrophysics Data System (ADS)

Buffoni, Boris; Groves, Mark D.; Wahlén, Erik

2017-12-01

Fully localised solitary waves are travelling-wave solutions of the three- dimensional gravity-capillary water wave problem which decay to zero in every horizontal spatial direction. Their existence has been predicted on the basis of numerical simulations and model equations (in which context they are usually referred to as `lumps'), and a mathematically rigorous existence theory for strong surface tension (Bond number {β} greater than {1/3} ) has recently been given. In this article we present an existence theory for the physically more realistic case {0 < β < 1/3} . A classical variational principle for fully localised solitary waves is reduced to a locally equivalent variational principle featuring a perturbation of the functional associated with the Davey-Stewartson equation. A nontrivial critical point of the reduced functional is found by minimising it over its natural constraint set.

A Variational Reduction and the Existence of a Fully Localised Solitary Wave for the Three-Dimensional Water-Wave Problem with Weak Surface Tension

NASA Astrophysics Data System (ADS)

Buffoni, Boris; Groves, Mark D.; Wahlén, Erik

2018-06-01

Fully localised solitary waves are travelling-wave solutions of the three- dimensional gravity-capillary water wave problem which decay to zero in every horizontal spatial direction. Their existence has been predicted on the basis of numerical simulations and model equations (in which context they are usually referred to as `lumps'), and a mathematically rigorous existence theory for strong surface tension (Bond number {β} greater than {1/3}) has recently been given. In this article we present an existence theory for the physically more realistic case {0 < β < 1/3}. A classical variational principle for fully localised solitary waves is reduced to a locally equivalent variational principle featuring a perturbation of the functional associated with the Davey-Stewartson equation. A nontrivial critical point of the reduced functional is found by minimising it over its natural constraint set.

Ab Initio Study of Polarizabilities of Oligothiophene, Oligocyclopentadiene and Oligofulvene and their Cyano Substituted Oligomers

NASA Astrophysics Data System (ADS)

Lagowski, Jolanta; Ferdous, Sultana

2005-03-01

Ab Initio polarizabilities of thiophene, fulvene and cyclopentadiene based conducting oligomers and polymers and their cyano derivatives have been calculated using the Hartree-Fock (HF), configuration interaction (singles) (CIS ) and density functional (DF) theories with 3-21G* basis using Gaussian software. The main motivation of this investigation is to determine the correlation between the excitation energies and polarizabilities for the conjugated systems studied. It has been found that HF and DF approaches give similar magnitudes for polarizabilities whereas CIS theory provides results that are considerably different. All three methods predict similar trends in polarizabilities as a function of oligomer length and bond alternation along the backbone of the oligomers. It has also been observed that the end groups and the number of `double' bonds have a significant effect on the magnitude of polarizability per C-C bond. Comparison with experimental results will be made where possible.

Experimental and density functional theory studies on benzalkonium ibuprofenate, a double active pharmaceutical ingredient.

PubMed

Safna Hussan, K P; Thayyil, M Shahin; Rajan, Vijisha K; Muraleedharan, K

2018-02-01

Molecular aspects of a double active pharmaceutical ingredient in ionic liquid form, benzalkonium ibuprofenate (BaIb), were studied using density functional theory (DFT/B3LYP/6-31+G (d, p)). A detailed discussion on optimized geometry, energy, heat and the enthalpy of BaIb was carried out. The computed vibrational results agree well with the experimental results. The stability and biological activity were compared to the parent drugs on the basis of global descriptive parameters. The electrophilic and nucleophilic sites were pointed out in the MESP structures well evidently. NBO analysis was also done to predict the relative aromaticity, delocalization effects and the contribution towards stabilization energy of the title compound. The information about non-covalent, non-ionic weak interaction between the cation and anion was obtained from the list of Mulliken charges and NBO analysis. Copyright © 2017 Elsevier Ltd. All rights reserved.

Regulation of metabolism and body fat mass by leptin.

PubMed

Baile, C A; Della-Fera, M A; Martin, R J

2000-01-01

The relative stability of body weight over the long term and under a variety of environmental conditions that alter short-term energy intake and expenditure provides strong evidence for the regulation of body energy content. The lipostatic theory of energy balance regulation proposed 40 years ago that circulating factors, generated in proportion to body fat stores, acted as signals to the brain, eliciting changes in energy intake and expenditure. The discovery of leptin and its receptors has now provided a molecular basis for this theory. Leptin functions as much more than an adipocyte-derived signal of lipid stores, however. Although suppression of food intake is an important centrally mediated effect of leptin, considerable evidence indicates that leptin also functions both directly and indirectly, via the brain, to orchestrate complex metabolic changes in a number of organs and tissues, altering nutrient flux to favor energy expenditure over energy storage.

Natural bond orbital analysis, electronic structure, non-linear properties and vibrational spectral analysis of L-histidinium bromide monohydrate: a density functional theory.

PubMed

Sajan, D; Joseph, Lynnette; Vijayan, N; Karabacak, M

2011-10-15

The spectroscopic properties of the crystallized nonlinear optical molecule L-histidinium bromide monohydrate (abbreviated as L-HBr-mh) have been recorded and analyzed by FT-IR, FT-Raman and UV techniques. The equilibrium geometry, vibrational wavenumbers and the first order hyperpolarizability of the crystal were calculated with the help of density functional theory computations. The optimized geometric bond lengths and bond angles obtained by using DFT (B3LYP/6-311++G(d,p)) show good agreement with the experimental data. The complete assignments of fundamental vibrations were performed on the basis of the total energy distribution (TED) of the vibrational modes, calculated with scaled quantum mechanics (SQM) method. The natural bond orbital (NBO) analysis confirms the occurrence of strong intra and intermolecular N-H⋯O hydrogen bonding. Copyright © 2011 Elsevier B.V. All rights reserved.

An ab initio molecular dynamics and density functional theory study of the formation of phosphate chains from metathiophosphates.

PubMed

Mosey, Nicholas J; Woo, Tom K

2006-09-04

The reactions that occur between metathiophosphate (MTP) molecules are identified and examined through ab initio molecular dynamics simulations and static quantum chemical calculations at the density functional level of theory. The simulations show that certain types of MTPs can react to yield phosphate chains, while others only dimerize. These differences are rationalized in terms of reaction energies and the electronic structures of these molecules. In the reaction leading to the formation of phosphate chains, the reactive center, a tri-coordinate phosphorus atom, is continually regenerated. A polymerization mechanism linking MTPs to phosphate chains is developed on the basis of these results. This information sheds light on the underlying processes that may be responsible for the formation of phosphates under high-temperature conditions and may prove useful in the development of protocols for the rational synthesis of complex phosphate structures.

Molecular structure, vibrational spectra and DFT molecular orbital calculations (TD-DFT and NMR) of the antiproliferative drug Methotrexate

NASA Astrophysics Data System (ADS)

Ayyappan, S.; Sundaraganesan, N.; Aroulmoji, V.; Murano, E.; Sebastian, S.

2010-09-01

The FT-IR and FT-Raman spectral studies of the Methotrexate (MTX) were carried out. The equilibrium geometry, various bonding features and harmonic vibrational frequencies of MTX have been investigated with the help of B3LYP density functional theory (DFT) using 6-31G(d) as basis set. Detailed analysis of the vibrational spectra has been made with the aid of theoretically predicted vibrational frequencies. The vibrational analysis confirms the differently acting ring modes, steric repulsion, conjugation and back-donation. The energy and oscillator strength calculated by Time-Dependent Density Functional Theory (TD-DFT) results complement with the experimental findings. The calculated HOMO and LUMO energies show that charge transfer occur within the molecule. Good correlations between the experimental 1H and 13C NMR chemical shifts in DMSO solution and calculated GIAO shielding tensors were found.

INFRARED SPECTRUM OF POTASSIUM-CATIONIZED TRIETHYLPHOSPHATE GENERATED USING TANDEM MASS SPECTROMETRY AND INFRARED MULTIPLE PHOTON DISSOCIATION

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

Gary S. Groenewold; Christopher M. Leavitt; Ryan P. Dain

2009-09-01

Tandem mass spectrometry and wavelength selective infrared photodissociation was used to generate an infrared spectrum of gas-phase triethylphosphate cationized by attachment of K+. Prominent absorptions were observed in the region of 900 to 1300 cm-1 that are characteristic of phosphate P=O and P-O-R stretches. The relative positions and intensities of the IR absorptions were reproduced well by density functional theory (DFT) calculations performed using the B3LYP functional and the 6-31+g(d), 6-311+g(d,p) and 6-311++G(3df,2pd) basis sets. Because of good correspondence between experiment and theory for the cation, DFT was then used to generate a theoretical spectrum for neutral triethylphosphate, which inmore » turn accurately reproduces the IR spectrum of the neat liquid when solvent effects are included in the calculations.« less

Long-term strength and damage accumulation in laminates

NASA Astrophysics Data System (ADS)

Dzenis, Yuris A.; Joshi, Shiv P.

1993-04-01

A modified version of the probabilistic model developed by authors for damage evolution analysis of laminates subjected to random loading is utilized to predict long-term strength of laminates. The model assumes that each ply in a laminate consists of a large number of mesovolumes. Probabilistic variation functions for mesovolumes stiffnesses as well as strengths are used in the analysis. Stochastic strains are calculated using the lamination theory and random function theory. Deterioration of ply stiffnesses is calculated on the basis of the probabilities of mesovolumes failures using the theory of excursions of random process beyond the limits. Long-term strength and damage accumulation in a Kevlar/epoxy laminate under tension and complex in-plane loading are investigated. Effects of the mean level and stochastic deviation of loading on damage evolution and time-to-failure of laminate are discussed. Long-term cumulative damage at the time of the final failure at low loading levels is more than at high loading levels. The effect of the deviation in loading is more pronounced at lower mean loading levels.

Spin-Orbit Effect on the Molecular Properties of TeXn (X = F, Cl, Br, and I; n = 1, 2, and 4): A Density Functional Theory and Ab Initio Study.

PubMed

Moon, Jiwon; Kim, Joonghan

2016-09-29

Density functional theory (DFT) and ab initio calculations, including spin-orbit coupling (SOC), were performed to investigate the spin-orbit (SO) effect on the molecular properties of tellurium halides, TeXn (X = F, Cl, Br, and I; n = 1, 2, and 4). SOC elongates the Te-X bond and slightly reduces the vibrational frequencies. Consideration of SOC leads to better agreement with experimental values. Møller-Plesset second-order perturbation theory (MP2) seriously underestimates the Te-X bond lengths. In contrast, B3LYP significantly overestimates them. SO-PBE0 and multireference configuration interactions with the Davidson correction (MRCI+Q), which include SOC via a state-interaction approach, give the Te-I bond length of TeI2 that matches the experimental value. On the basis of the calculated thermochemical energy and optimized molecular structure, TeI4 is unlikely to be stable. The use of PBE0 including SOC is strongly recommended for predicting the molecular properties of Te-containing compounds.

Quartic scaling MP2 for solids: A highly parallelized algorithm in the plane wave basis

NASA Astrophysics Data System (ADS)

Schäfer, Tobias; Ramberger, Benjamin; Kresse, Georg

2017-03-01

We present a low-complexity algorithm to calculate the correlation energy of periodic systems in second-order Møller-Plesset (MP2) perturbation theory. In contrast to previous approximation-free MP2 codes, our implementation possesses a quartic scaling, O ( N 4 ) , with respect to the system size N and offers an almost ideal parallelization efficiency. The general issue that the correlation energy converges slowly with the number of basis functions is eased by an internal basis set extrapolation. The key concept to reduce the scaling is to eliminate all summations over virtual orbitals which can be elegantly achieved in the Laplace transformed MP2 formulation using plane wave basis sets and fast Fourier transforms. Analogously, this approach could allow us to calculate second order screened exchange as well as particle-hole ladder diagrams with a similar low complexity. Hence, the presented method can be considered as a step towards systematically improved correlation energies.

A projection-free method for representing plane-wave DFT results in an atom-centered basis

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

Dunnington, Benjamin D.; Schmidt, J. R., E-mail: schmidt@chem.wisc.edu

2015-09-14

Plane wave density functional theory (DFT) is a powerful tool for gaining accurate, atomic level insight into bulk and surface structures. Yet, the delocalized nature of the plane wave basis set hinders the application of many powerful post-computation analysis approaches, many of which rely on localized atom-centered basis sets. Traditionally, this gap has been bridged via projection-based techniques from a plane wave to atom-centered basis. We instead propose an alternative projection-free approach utilizing direct calculation of matrix elements of the converged plane wave DFT Hamiltonian in an atom-centered basis. This projection-free approach yields a number of compelling advantages, including strictmore » orthonormality of the resulting bands without artificial band mixing and access to the Hamiltonian matrix elements, while faithfully preserving the underlying DFT band structure. The resulting atomic orbital representation of the Kohn-Sham wavefunction and Hamiltonian provides a gateway to a wide variety of analysis approaches. We demonstrate the utility of the approach for a diverse set of chemical systems and example analysis approaches.« less

Density functional Gaussian-type-orbital approach to theoretical study of nitric oxide dimers

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

Jursic, B.S.; Zdravkovski, Z.

Structure and total energies of the cis NO dimer, the trans NO dimer, and the NO monomer were calculated by ab initio methods (UHF, UMP2, and MP3) and density functional theory methods (LSDA and BLYP) with different basis sets [from 3-21G* to 6-311++(3df,3pd)]. The system is especially hard to model because two NO molecules are weakly associated in a dimer that has very long N-N bond. The results obtained by different methods are compared and the necessity of correlational methods for studying these systems is discussed.

SCF and CI calculations of the dipole moment function of ozone. [Self-Consistent Field and Configuration-Interaction

NASA Technical Reports Server (NTRS)

Curtiss, L. A.; Langhoff, S. R.; Carney, G. D.

1979-01-01

The constant and linear terms in a Taylor series expansion of the dipole moment function of the ground state of ozone are calculated with Cartesian Gaussian basis sets ranging in quality from minimal to double zeta plus polarization. Results are presented at both the self-consistent field and configuration-interaction levels. Although the algebraic signs of the linear dipole moment derivatives are all established to be positive, the absolute magnitudes of these quantities, as well as the infrared intensities calculated from them, vary considerably with the level of theory.

A phase space approach to imaging from limited data

NASA Astrophysics Data System (ADS)

Testorf, Markus E.

2015-09-01

The optical instrument function is used as the basis to develop optical system theory for imaging applications. The detection of optical signals is conveniently described as the overlap integral of the Wigner distribution functions of instrument and optical signal. Based on this framework various optical imaging systems, including plenoptic cameras, phase-retrieval algorithms, and Shack-Hartman sensors are shown to acquire information about a domain in phase-space, with finite extension and finite resolution. It is demonstrated how phase space optics can be used both to analyze imaging systems, as well as for designing methods for image reconstruction.

Cerebral localization in the nineteenth century--the birth of a science and its modern consequences.

PubMed

Steinberg, David A

2009-07-01

Although many individuals contributed to the development of the science of cerebral localization, its conceptual framework is the work of a single man--John Hughlings Jackson (1835-1911), a Victorian physician practicing in London. Hughlings Jackson's formulation of a neurological science consisted of an axiomatic basis, an experimental methodology, and a clinical neurophysiology. His axiom--that the brain is an exclusively sensorimotor machine--separated neurology from psychiatry and established a rigorous and sophisticated structure for the brain and mind. Hughlings Jackson's experimental method utilized the focal lesion as a probe of brain function and created an evolutionary structure of somatotopic representation to explain clinical neurophysiology. His scientific theory of cerebral localization can be described as a weighted ordinal representation. Hughlings Jackson's theory of weighted ordinal representation forms the scientific basis for modern neurology. Though this science is utilized daily by every neurologist and forms the basis of neuroscience, the consequences of Hughlings Jackson's ideas are still not generally appreciated. For example, they imply the intrinsic inconsistency of some modern fields of neuroscience and neurology. Thus, "cognitive imaging" and the "neurology of art"--two topics of modern interest--are fundamentally oxymoronic according to the science of cerebral localization. Neuroscientists, therefore, still have much to learn from John Hughlings Jackson.

A new way of visualising quantum fields

NASA Astrophysics Data System (ADS)

Linde, Helmut

2018-05-01

Quantum field theory (QFT) is the basis of some of the most fundamental theories in modern physics, but it is not an easy subject to learn. In the present article we intend to pave the way from quantum mechanics to QFT for students at early graduate or advanced undergraduate level. More specifically, we propose a new way of visualising the wave function Ψ of a linear chain of interacting quantum harmonic oscillators, which can be seen as a model for a simple one-dimensional bosonic quantum field. The main idea is to draw randomly chosen classical states of the chain superimposed upon each other and use a grey scale to represent the value of Ψ at the corresponding coordinates of the quantised system. Our goal is to establish a better intuitive understanding of the mathematical objects underlying quantum field theories and solid state physics.

On vector-valued Poincaré series of weight 2

NASA Astrophysics Data System (ADS)

Meneses, Claudio

2017-10-01

Given a pair (Γ , ρ) of a Fuchsian group of the first kind, and a unitary representation ρ of Γ of arbitrary rank, the problem of construction of vector-valued Poincaré series of weight 2 is considered. Implications in the theory of parabolic bundles are discussed. When the genus of the group is zero, it is shown how an explicit basis for the space of these functions can be constructed.

Electronic Structure Methods Based on Density Functional Theory

DTIC Science & Technology

2010-01-01

0188 The public reporting burden for this collection of information is estimated to average 1 hour per response, including the time for reviewing...chapter in the ASM Handbook , Volume 22A: Fundamentals of Modeling for Metals Processing, 2010. PAO Case Number: 88ABW-2009-3258; Clearance Date: 16 Jul...are represented using a linear combination, or basis, of plane waves. Over time several methods were developed to avoid the large number of planewaves

The evolutionary origin and diversification of feathers.

PubMed

Prum, Richard O; Brush, Alan H

2002-09-01

Progress on the evolutionary origin and diversification of feathers has been hampered by conceptual problems and by the lack of plesiomorphic feather fossils. Recently, both of these limitations have been overcome by the proposal of the developmental theory of the origin of feathers, and the discovery of primitive feather fossils on nonavian theropod dinosaurs. The conceptual problems of previous theories of the origin of feathers are reviewed, and the alternative developmental theory is presented and discussed. The developmental theory proposes that feathers evolved through a series of evolutionary novelties in developmental mechanisms of the follicle and feather germ. The discovery of primitive and derived fossil feathers on a diversity of coelurosaurian theropod dinosaurs documents that feathers evolved and diversified in nonavian theropods before the origin of birds and before the origin of flight. The morphologies of these primitive feathers are congruent with the predictions of the developmental theory. Alternatives to the theropod origin of feathers are critique and rejected. Hypotheses for the initial function of feathers are reviewed. The aerodynamic theory of feather origins is falsified, but many other functions remain developmentally and phylogenetically plausible. Whatever their function, feathers evolved by selection for a follicle that would grow an emergent tubular appendage. Feathers are inherently tubular structures. The homology of feathers and scales is weakly supported. Feathers are composed of a suite of evolutionary novelties that evolved by the duplication, hierarchical organization, interaction, dissociation, and differentiation of morphological modules. The unique capacity for modular subdivision of the tubular feather follicle and germ has fostered the evolution of numerous innovations that characterize feathers. The evolution of feather keratin and the molecular basis of feather development are also discussed.

Computing sextic centrifugal distortion constants by DFT: A benchmark analysis on halogenated compounds

NASA Astrophysics Data System (ADS)

Pietropolli Charmet, Andrea; Stoppa, Paolo; Tasinato, Nicola; Giorgianni, Santi

2017-05-01

This work presents a benchmark study on the calculation of the sextic centrifugal distortion constants employing cubic force fields computed by means of density functional theory (DFT). For a set of semi-rigid halogenated organic compounds several functionals (B2PLYP, B3LYP, B3PW91, M06, M06-2X, O3LYP, X3LYP, ωB97XD, CAM-B3LYP, LC-ωPBE, PBE0, B97-1 and B97-D) were used for computing the sextic centrifugal distortion constants. The effects related to the size of basis sets and the performances of hybrid approaches, where the harmonic data obtained at higher level of electronic correlation are coupled with cubic force constants yielded by DFT functionals, are presented and discussed. The predicted values were compared to both the available data published in the literature and those obtained by calculations carried out at increasing level of electronic correlation: Hartree-Fock Self Consistent Field (HF-SCF), second order Møller-Plesset perturbation theory (MP2), and coupled-cluster single and double (CCSD) level of theory. Different hybrid approaches, having the cubic force field computed at DFT level of theory coupled to harmonic data computed at increasing level of electronic correlation (up to CCSD level of theory augmented by a perturbational estimate of the effects of connected triple excitations, CCSD(T)) were considered. The obtained results demonstrate that they can represent reliable and computationally affordable methods to predict sextic centrifugal terms with an accuracy almost comparable to that yielded by the more expensive anharmonic force fields fully computed at MP2 and CCSD levels of theory. In view of their reduced computational cost, these hybrid approaches pave the route to the study of more complex systems.

A cumulant functional for static and dynamic correlation

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

Hollett, Joshua W., E-mail: j.hollett@uwinnipeg.ca; Department of Chemistry, University of Manitoba, Winnipeg, Manitoba R3T 2N2; Hosseini, Hessam

A functional for the cumulant energy is introduced. The functional is composed of a pair-correction and static and dynamic correlation energy components. The pair-correction and static correlation energies are functionals of the natural orbitals and the occupancy transferred between near-degenerate orbital pairs, rather than the orbital occupancies themselves. The dynamic correlation energy is a functional of the statically correlated on-top two-electron density. The on-top density functional used in this study is the well-known Colle-Salvetti functional. Using the cc-pVTZ basis set, the functional effectively models the bond dissociation of H{sub 2}, LiH, and N{sub 2} with equilibrium bond lengths and dissociationmore » energies comparable to those provided by multireference second-order perturbation theory. The performance of the cumulant functional is less impressive for HF and F{sub 2}, mainly due to an underestimation of the dynamic correlation energy by the Colle-Salvetti functional.« less

[Brain imaging in autism spectrum disorders. A review].

PubMed

Dziobek, I; Köhne, S

2011-05-01

In the past two decades, an increasing number of functional and structural brain imaging studies has provided insights into the neurobiological basis of autism spectrum disorders (ASD). This article summarizes pertinent functional brain imaging studies addressing the neuronal underpinnings of ASD symptomatology (impairments in social interaction and communication, repetitive and restrictive behavior) and associated neuropsychological deficits (theory of mind, executive functions, central coherence), complemented by relevant structural imaging findings. The results of these studies show that although cognitive functions in ASD are generally mediated by the same brain regions as in typically developed individuals, the degree and especially the patterns of brain activation often differ. Therefore, a hypothesis of aberrant network connectivity has increasingly been favored over one of focal brain dysfunction.

Smartphone-Based, Self-Administered Intervention System for Alcohol Use Disorders: Theory and Empirical Evidence Basis

PubMed Central

Dulin, Patrick L.; Gonzalez, Vivian M.; King, Diane K.; Giroux, Danielle; Bacon, Samantha

2013-01-01

Advances in mobile technology provide an opportunity to deliver in-the-moment interventions to individuals with alcohol use disorders, yet availability of effective “apps” that deliver evidence-based interventions is scarce. We developed an immediately available, portable, smartphone-based intervention system whose purpose is to provide stand-alone, self-administered assessment and intervention. In this paper, we describe how theory and empirical evidence, combined with smartphone functionality contributed to the construction of a user-friendly, engaging alcohol intervention. With translation in mind, we discuss how we selected appropriate intervention components including assessments, feedback and tools, that work together to produce the hypothesized outcomes. PMID:24347811

Collective phase description of oscillatory convection

NASA Astrophysics Data System (ADS)

Kawamura, Yoji; Nakao, Hiroya

2013-12-01

We formulate a theory for the collective phase description of oscillatory convection in Hele-Shaw cells. It enables us to describe the dynamics of the oscillatory convection by a single degree of freedom which we call the collective phase. The theory can be considered as a phase reduction method for limit-cycle solutions in infinite-dimensional dynamical systems, namely, stable time-periodic solutions to partial differential equations, representing the oscillatory convection. We derive the phase sensitivity function, which quantifies the phase response of the oscillatory convection to weak perturbations applied at each spatial point, and analyze the phase synchronization between two weakly coupled Hele-Shaw cells exhibiting oscillatory convection on the basis of the derived phase equations.

Premelting phenomena in pseudo-binary ionic crystals

NASA Astrophysics Data System (ADS)

Matsunaga, Shigeki

2010-04-01

The theory of the premelting phenomena in ionic crystals on the basis of the concept of the heterophase fluctuation has been applied to the pseudo-binary ionic crystals, KCl-NaCl, AgBr-AgCl and AgBr-CuBr systems. Molecular dynamics simulations (MD) have been performed to examine the ionic configurations in their premelting region in the vicinity of their melting points. Liquid-like clusters have been observed in the results of MD utilizing the Lindemann instability condition. The sizes of liquid-like clusters have been estimated by theory and MD. The characteristics of the dynamical behavior of ions in the premelting region have been examined by the mean square displacement and the velocity correlation functions.

Capillary-tube-based extension of thermoacoustic theory for a random medium

NASA Astrophysics Data System (ADS)

Roh, Heui-Seol; Raspet, Richard; Bass, Henry E.

2005-09-01

Thermoacoustic theory for a single capillary tube is extended to random bulk medium on the basis of capillary tubes. The characteristics of the porous stack inside the resonator such as the tortuosity, dynamic shape factor, and porosity are introduced for the extension of wave equation by following Attenborough's approach. Separation of the dynamic shape factor for the viscous and thermal effect is adopted and scaling using the dynamic shape factor and tortuosity factor is demonstrated. The theoretical and experimental comparison of thermoviscous functions in reticulated vitreous carbon (RVC) and aluminum foam shows reasonable agreement. The extension is useful for investigations of the properties of a stack with arbitrary shapes of non-parallel pores.

An electron momentum spectroscopy and density functional theory study of the outer valence electronic structure of stella-2,6-dione

NASA Astrophysics Data System (ADS)

Nixon, K. L.; Wang, F.; Campbell, L.; Maddern, T.; Winkler, D.; Gleiter, R.; Loeb, P.; Weigold, E.; Brunger, M. J.

2003-07-01

We report on the first electron momentum spectroscopy (EMS) study into the outer valence electronic structure of the ground electronic state for the organic molecule stella-2,6-dione (C8H8O2). Experimentally measured binding-energy spectra are compared against a He(Ialpha) photoelectron spectroscopy result, while our derived momentum distributions (MDs) are compared against corresponding results from the plane wave impulse approximation (PWIA) level calculations. These computations employed density functional theory (DFT) basis states at the triple zeta valence polarization (TZVP) level, with a range of exchange-correlation (XC) functionals. A detailed comparison between the experimental and PWIA DFT-XC/TZVP calculated MDs enabled us to evaluate the accuracy of the various functionals, the Becke-Perdew (BP) XC functional being found to provide the most accurate description here. The importance of the through-bond interaction to the molecular orbitals (MOs) of stella-2,6-dione is demonstrated using the orbital imaging capability of EMS. Finally we show that the molecular geometry of this molecule, as derived from BP/TZVP, is in quite good agreement with corresponding independent experimental data.

Computational Investigation of the Geometrical and Electronic Structures of VGen-/0 (n = 1-4) Clusters by Density Functional Theory and Multiconfigurational CASSCF/CASPT2 Method.

PubMed

Tran, Van Tan; Nguyen, Minh Thao; Tran, Quoc Tri

2017-10-12

Density functional theory and the multiconfigurational CASSCF/CASPT2 method have been employed to study the low-lying states of VGe n -/0 (n = 1-4) clusters. For VGe -/0 and VGe 2 -/0 clusters, the relative energies and geometrical structures of the low-lying states are reported at the CASSCF/CASPT2 level. For the VGe 3 -/0 and VGe 4 -/0 clusters, the computational results show that due to the large contribution of the Hartree-Fock exact exchange, the hybrid B3LYP, B3PW91, and PBE0 functionals overestimate the energies of the high-spin states as compared to the pure GGA BP86 and PBE functionals and the CASPT2 method. On the basis of the pure GGA BP86 and PBE functionals and the CASSCF/CASPT2 results, the ground states of anionic and neutral clusters are defined, the relative energies of the excited states are computed, and the electron detachment energies of the anionic clusters are evaluated. The computational results are employed to give new assignments for all features in the photoelectron spectra of VGe 3 - and VGe 4 - clusters.

A geometrical correction for the inter- and intra-molecular basis set superposition error in Hartree-Fock and density functional theory calculations for large systems

NASA Astrophysics Data System (ADS)

Kruse, Holger; Grimme, Stefan

2012-04-01

A semi-empirical counterpoise-type correction for basis set superposition error (BSSE) in molecular systems is presented. An atom pair-wise potential corrects for the inter- and intra-molecular BSSE in supermolecular Hartree-Fock (HF) or density functional theory (DFT) calculations. This geometrical counterpoise (gCP) denoted scheme depends only on the molecular geometry, i.e., no input from the electronic wave-function is required and hence is applicable to molecules with ten thousands of atoms. The four necessary parameters have been determined by a fit to standard Boys and Bernadi counterpoise corrections for Hobza's S66×8 set of non-covalently bound complexes (528 data points). The method's target are small basis sets (e.g., minimal, split-valence, 6-31G*), but reliable results are also obtained for larger triple-ζ sets. The intermolecular BSSE is calculated by gCP within a typical error of 10%-30% that proves sufficient in many practical applications. The approach is suggested as a quantitative correction in production work and can also be routinely applied to estimate the magnitude of the BSSE beforehand. The applicability for biomolecules as the primary target is tested for the crambin protein, where gCP removes intramolecular BSSE effectively and yields conformational energies comparable to def2-TZVP basis results. Good mutual agreement is also found with Jensen's ACP(4) scheme, estimating the intramolecular BSSE in the phenylalanine-glycine-phenylalanine tripeptide, for which also a relaxed rotational energy profile is presented. A variety of minimal and double-ζ basis sets combined with gCP and the dispersion corrections DFT-D3 and DFT-NL are successfully benchmarked on the S22 and S66 sets of non-covalent interactions. Outstanding performance with a mean absolute deviation (MAD) of 0.51 kcal/mol (0.38 kcal/mol after D3-refit) is obtained at the gCP-corrected HF-D3/(minimal basis) level for the S66 benchmark. The gCP-corrected B3LYP-D3/6-31G* model chemistry yields MAD=0.68 kcal/mol, which represents a huge improvement over plain B3LYP/6-31G* (MAD=2.3 kcal/mol). Application of gCP-corrected B97-D3 and HF-D3 on a set of large protein-ligand complexes prove the robustness of the method. Analytical gCP gradients make optimizations of large systems feasible with small basis sets, as demonstrated for the inter-ring distances of 9-helicene and most of the complexes in Hobza's S22 test set. The method is implemented in a freely available FORTRAN program obtainable from the author's website.

Why Darwin would have loved evolutionary game theory

PubMed Central

2016-01-01

Humans have marvelled at the fit of form and function, the way organisms' traits seem remarkably suited to their lifestyles and ecologies. While natural selection provides the scientific basis for the fit of form and function, Darwin found certain adaptations vexing or particularly intriguing: sex ratios, sexual selection and altruism. The logic behind these adaptations resides in frequency-dependent selection where the value of a given heritable phenotype (i.e. strategy) to an individual depends upon the strategies of others. Game theory is a branch of mathematics that is uniquely suited to solving such puzzles. While game theoretic thinking enters into Darwin's arguments and those of evolutionists through much of the twentieth century, the tools of evolutionary game theory were not available to Darwin or most evolutionists until the 1970s, and its full scope has only unfolded in the last three decades. As a consequence, game theory is applied and appreciated rather spottily. Game theory not only applies to matrix games and social games, it also applies to speciation, macroevolution and perhaps even to cancer. I assert that life and natural selection are a game, and that game theory is the appropriate logic for framing and understanding adaptations. Its scope can include behaviours within species, state-dependent strategies (such as male, female and so much more), speciation and coevolution, and expands beyond microevolution to macroevolution. Game theory clarifies aspects of ecological and evolutionary stability in ways useful to understanding eco-evolutionary dynamics, niche construction and ecosystem engineering. In short, I would like to think that Darwin would have found game theory uniquely useful for his theory of natural selection. Let us see why this is so. PMID:27605503

Why Darwin would have loved evolutionary game theory.

PubMed

Brown, Joel S

2016-09-14

Humans have marvelled at the fit of form and function, the way organisms' traits seem remarkably suited to their lifestyles and ecologies. While natural selection provides the scientific basis for the fit of form and function, Darwin found certain adaptations vexing or particularly intriguing: sex ratios, sexual selection and altruism. The logic behind these adaptations resides in frequency-dependent selection where the value of a given heritable phenotype (i.e. strategy) to an individual depends upon the strategies of others. Game theory is a branch of mathematics that is uniquely suited to solving such puzzles. While game theoretic thinking enters into Darwin's arguments and those of evolutionists through much of the twentieth century, the tools of evolutionary game theory were not available to Darwin or most evolutionists until the 1970s, and its full scope has only unfolded in the last three decades. As a consequence, game theory is applied and appreciated rather spottily. Game theory not only applies to matrix games and social games, it also applies to speciation, macroevolution and perhaps even to cancer. I assert that life and natural selection are a game, and that game theory is the appropriate logic for framing and understanding adaptations. Its scope can include behaviours within species, state-dependent strategies (such as male, female and so much more), speciation and coevolution, and expands beyond microevolution to macroevolution. Game theory clarifies aspects of ecological and evolutionary stability in ways useful to understanding eco-evolutionary dynamics, niche construction and ecosystem engineering. In short, I would like to think that Darwin would have found game theory uniquely useful for his theory of natural selection. Let us see why this is so. © 2016 The Author(s).

Overcomplete compact representation of two-particle Green's functions

NASA Astrophysics Data System (ADS)

Shinaoka, Hiroshi; Otsuki, Junya; Haule, Kristjan; Wallerberger, Markus; Gull, Emanuel; Yoshimi, Kazuyoshi; Ohzeki, Masayuki

2018-05-01

Two-particle Green's functions and the vertex functions play a critical role in theoretical frameworks for describing strongly correlated electron systems. However, numerical calculations at the two-particle level often suffer from large computation time and massive memory consumption. We derive a general expansion formula for the two-particle Green's functions in terms of an overcomplete representation based on the recently proposed "intermediate representation" basis. The expansion formula is obtained by decomposing the spectral representation of the two-particle Green's function. We demonstrate that the expansion coefficients decay exponentially, while all high-frequency and long-tail structures in the Matsubara-frequency domain are retained. This representation therefore enables efficient treatment of two-particle quantities and opens a route to the application of modern many-body theories to realistic strongly correlated electron systems.

Basis set and electron correlation effects on the polarizability and second hyperpolarizability of model open-shell π-conjugated systems

NASA Astrophysics Data System (ADS)

Champagne, Benoı̂t; Botek, Edith; Nakano, Masayoshi; Nitta, Tomoshige; Yamaguchi, Kizashi

2005-03-01

The basis set and electron correlation effects on the static polarizability (α) and second hyperpolarizability (γ) are investigated ab initio for two model open-shell π-conjugated systems, the C5H7 radical and the C6H8 radical cation in their doublet state. Basis set investigations evidence that the linear and nonlinear responses of the radical cation necessitate the use of a less extended basis set than its neutral analog. Indeed, double-zeta-type basis sets supplemented by a set of d polarization functions but no diffuse functions already provide accurate (hyper)polarizabilities for C6H8 whereas diffuse functions are compulsory for C5H7, in particular, p diffuse functions. In addition to the 6-31G*+pd basis set, basis sets resulting from removing not necessary diffuse functions from the augmented correlation consistent polarized valence double zeta basis set have been shown to provide (hyper)polarizability values of similar quality as more extended basis sets such as augmented correlation consistent polarized valence triple zeta and doubly augmented correlation consistent polarized valence double zeta. Using the selected atomic basis sets, the (hyper)polarizabilities of these two model compounds are calculated at different levels of approximation in order to assess the impact of including electron correlation. As a function of the method of calculation antiparallel and parallel variations have been demonstrated for α and γ of the two model compounds, respectively. For the polarizability, the unrestricted Hartree-Fock and unrestricted second-order Møller-Plesset methods bracket the reference value obtained at the unrestricted coupled cluster singles and doubles with a perturbative inclusion of the triples level whereas the projected unrestricted second-order Møller-Plesset results are in much closer agreement with the unrestricted coupled cluster singles and doubles with a perturbative inclusion of the triples values than the projected unrestricted Hartree-Fock results. Moreover, the differences between the restricted open-shell Hartree-Fock and restricted open-shell second-order Møller-Plesset methods are small. In what concerns the second hyperpolarizability, the unrestricted Hartree-Fock and unrestricted second-order Møller-Plesset values remain of similar quality while using spin-projected schemes fails for the charged system but performs nicely for the neutral one. The restricted open-shell schemes, and especially the restricted open-shell second-order Møller-Plesset method, provide for both compounds γ values close to the results obtained at the unrestricted coupled cluster level including singles and doubles with a perturbative inclusion of the triples. Thus, to obtain well-converged α and γ values at low-order electron correlation levels, the removal of spin contamination is a necessary but not a sufficient condition. Density-functional theory calculations of α and γ have also been carried out using several exchange-correlation functionals. Those employing hybrid exchange-correlation functionals have been shown to reproduce fairly well the reference coupled cluster polarizability and second hyperpolarizability values. In addition, inclusion of Hartree-Fock exchange is of major importance for determining accurate polarizability whereas for the second hyperpolarizability the gradient corrections are large.

One-point functions in defect CFT and integrability

NASA Astrophysics Data System (ADS)

de Leeuw, Marius; Kristjansen, Charlotte; Zarembo, Konstantin

2015-08-01

We calculate planar tree level one-point functions of non-protected operators in the defect conformal field theory dual to the D3-D5 brane system with k units of the world volume flux. Working in the operator basis of Bethe eigenstates of the Heisenberg XXX 1/2 spin chain we express the one-point functions as overlaps of these eigenstates with a matrix product state. For k = 2 we obtain a closed expression of determinant form for any number of excitations, and in the case of half-filling we find a relation with the Néel state. In addition, we present a number of results for the limiting case k → ∞.

Modern money theory and ecological tax reform: A functional finance approach to energy conservation

NASA Astrophysics Data System (ADS)

McConnell, Scott L. B.

This dissertation contributes to heterodox economics by developing a theoretical and policy-relevant link that will promote the conservation of energy while driving the value of the domestic currency. The analysis relies upon the theoretical foundation of modern money theory and functional finance, which states that "taxes-drive-money" where the value of a sovereign nation's currency is imputed through the acceptance by the sovereign nation of the currency in payment of taxation. This theoretical perspective lends itself to various public policy prescriptions, such as government employment policies or the employer of last resort (ELR), which has been discussed at length elsewhere (Wray 1998; Tcherneva 2007, Forstater 2003). This research contributes to this overall program by arguing that the basis for taxation under modern money theory allows public policy makers various alternatives regarding the make-up of the tax system in place. In particular, following functional finance, taxes do not have the sole purpose of paying for government spending, but rather drive the value of the currency and may be designed to perform other functions as well, such as penalizing socially undesirable behavior. The focus in this dissertation is on the amelioration of pollution and increasing energy conservation. The research question for this dissertation is this: what federally implemented tax would best serve the multiple criteria of 1) driving the value of the currency, 2) promoting energy conservation and 3) ameliorating income and wealth disparities inherent in a monetary production economy? This dissertation provides a suggestion for such a tax that would be part of a much larger overall policy program based upon the tenets of modern money theory and functional finance. Additionally, this research seeks to provide an important theoretical contribution to the emerging Post Keynesian and ecological economics dialog.

On the relationship between matched filter theory as applied to gust loads and phased design loads analysis

NASA Technical Reports Server (NTRS)

Zeiler, Thomas A.; Pototzky, Anthony S.

1989-01-01

A theoretical basis and example calculations are given that demonstrate the relationship between the Matched Filter Theory approach to the calculation of time-correlated gust loads and Phased Design Load Analysis in common use in the aerospace industry. The relationship depends upon the duality between Matched Filter Theory and Random Process Theory and upon the fact that Random Process Theory is used in Phased Design Loads Analysis in determining an equiprobable loads design ellipse. Extensive background information describing the relevant points of Phased Design Loads Analysis, calculating time-correlated gust loads with Matched Filter Theory, and the duality between Matched Filter Theory and Random Process Theory is given. It is then shown that the time histories of two time-correlated gust load responses, determined using the Matched Filter Theory approach, can be plotted as parametric functions of time and that the resulting plot, when superposed upon the design ellipse corresponding to the two loads, is tangent to the ellipse. The question is raised of whether or not it is possible for a parametric load plot to extend outside the associated design ellipse. If it is possible, then the use of the equiprobable loads design ellipse will not be a conservative design practice in some circumstances.

Structure, stability, thermodynamic properties, and infrared spectra of the protonated water octamer H(+)(H2O)8.

PubMed

Karthikeyan, S; Park, Mina; Shin, Ilgyou; Kim, Kwang S

2008-10-16

We investigated various two-dimensional (2D) and three-dimensional (3D) structures of H (+)(H 2O) 8, using density functional theory (DFT), Moller-Plesset second-order perturbation theory (MP2), and coupled cluster theory with single, double, and perturbative triple excitations (CCSD(T)). The 3D structure is more stable than the 2D structure at all levels of theory on the Born-Oppenheimer surface. With the zero-point energy (ZPE) correction, the predicted structure varies depending on the level of theory. The DFT employing Becke's three parameters with Lee-Yang-Parr functionals (B3LYP) favors the 2D structure. At the complete basis set (CBS) limit, the MP2 calculation favors the 3D structure by 0.29 kcal/mol, and the CCSD(T) calculation favors the 3D structure by 0.27 kcal/mol. It is thus expected that both 2D and 3D structures are nearly isoenergetic near 0 K. At 100 K, all the calculations show that the 2D structure is much more stable in free binding energy than the 3D structure. The DFT and MP2 vibrational spectra of the 2D structure are consistent with the experimental spectra. First-principles Car-Parrinello molecular dynamics (CPMD) simulations show that the 2D Zundel-type vibrational spectra are in good agreement with the experiment.

Analysis of Pull-In Instability of Geometrically Nonlinear Microbeam Using Radial Basis Artificial Neural Network Based on Couple Stress Theory

PubMed Central

Heidari, Mohammad; Heidari, Ali; Homaei, Hadi

2014-01-01

The static pull-in instability of beam-type microelectromechanical systems (MEMS) is theoretically investigated. Two engineering cases including cantilever and double cantilever microbeam are considered. Considering the midplane stretching as the source of the nonlinearity in the beam behavior, a nonlinear size-dependent Euler-Bernoulli beam model is used based on a modified couple stress theory, capable of capturing the size effect. By selecting a range of geometric parameters such as beam lengths, width, thickness, gaps, and size effect, we identify the static pull-in instability voltage. A MAPLE package is employed to solve the nonlinear differential governing equations to obtain the static pull-in instability voltage of microbeams. Radial basis function artificial neural network with two functions has been used for modeling the static pull-in instability of microcantilever beam. The network has four inputs of length, width, gap, and the ratio of height to scale parameter of beam as the independent process variables, and the output is static pull-in voltage of microbeam. Numerical data, employed for training the network, and capabilities of the model have been verified in predicting the pull-in instability behavior. The output obtained from neural network model is compared with numerical results, and the amount of relative error has been calculated. Based on this verification error, it is shown that the radial basis function of neural network has the average error of 4.55% in predicting pull-in voltage of cantilever microbeam. Further analysis of pull-in instability of beam under different input conditions has been investigated and comparison results of modeling with numerical considerations shows a good agreement, which also proves the feasibility and effectiveness of the adopted approach. The results reveal significant influences of size effect and geometric parameters on the static pull-in instability voltage of MEMS. PMID:24860602

A promising tool to achieve chemical accuracy for density functional theory calculations on Y-NO homolysis bond dissociation energies.

PubMed

Li, Hong Zhi; Hu, Li Hong; Tao, Wei; Gao, Ting; Li, Hui; Lu, Ying Hua; Su, Zhong Min

2012-01-01

A DFT-SOFM-RBFNN method is proposed to improve the accuracy of DFT calculations on Y-NO (Y = C, N, O, S) homolysis bond dissociation energies (BDE) by combining density functional theory (DFT) and artificial intelligence/machine learning methods, which consist of self-organizing feature mapping neural networks (SOFMNN) and radial basis function neural networks (RBFNN). A descriptor refinement step including SOFMNN clustering analysis and correlation analysis is implemented. The SOFMNN clustering analysis is applied to classify descriptors, and the representative descriptors in the groups are selected as neural network inputs according to their closeness to the experimental values through correlation analysis. Redundant descriptors and intuitively biased choices of descriptors can be avoided by this newly introduced step. Using RBFNN calculation with the selected descriptors, chemical accuracy (≤1 kcal·mol(-1)) is achieved for all 92 calculated organic Y-NO homolysis BDE calculated by DFT-B3LYP, and the mean absolute deviations (MADs) of the B3LYP/6-31G(d) and B3LYP/STO-3G methods are reduced from 4.45 and 10.53 kcal·mol(-1) to 0.15 and 0.18 kcal·mol(-1), respectively. The improved results for the minimal basis set STO-3G reach the same accuracy as those of 6-31G(d), and thus B3LYP calculation with the minimal basis set is recommended to be used for minimizing the computational cost and to expand the applications to large molecular systems. Further extrapolation tests are performed with six molecules (two containing Si-NO bonds and two containing fluorine), and the accuracy of the tests was within 1 kcal·mol(-1). This study shows that DFT-SOFM-RBFNN is an efficient and highly accurate method for Y-NO homolysis BDE. The method may be used as a tool to design new NO carrier molecules.

A Promising Tool to Achieve Chemical Accuracy for Density Functional Theory Calculations on Y-NO Homolysis Bond Dissociation Energies

PubMed Central

Li, Hong Zhi; Hu, Li Hong; Tao, Wei; Gao, Ting; Li, Hui; Lu, Ying Hua; Su, Zhong Min

2012-01-01

A DFT-SOFM-RBFNN method is proposed to improve the accuracy of DFT calculations on Y-NO (Y = C, N, O, S) homolysis bond dissociation energies (BDE) by combining density functional theory (DFT) and artificial intelligence/machine learning methods, which consist of self-organizing feature mapping neural networks (SOFMNN) and radial basis function neural networks (RBFNN). A descriptor refinement step including SOFMNN clustering analysis and correlation analysis is implemented. The SOFMNN clustering analysis is applied to classify descriptors, and the representative descriptors in the groups are selected as neural network inputs according to their closeness to the experimental values through correlation analysis. Redundant descriptors and intuitively biased choices of descriptors can be avoided by this newly introduced step. Using RBFNN calculation with the selected descriptors, chemical accuracy (≤1 kcal·mol−1) is achieved for all 92 calculated organic Y-NO homolysis BDE calculated by DFT-B3LYP, and the mean absolute deviations (MADs) of the B3LYP/6-31G(d) and B3LYP/STO-3G methods are reduced from 4.45 and 10.53 kcal·mol−1 to 0.15 and 0.18 kcal·mol−1, respectively. The improved results for the minimal basis set STO-3G reach the same accuracy as those of 6-31G(d), and thus B3LYP calculation with the minimal basis set is recommended to be used for minimizing the computational cost and to expand the applications to large molecular systems. Further extrapolation tests are performed with six molecules (two containing Si-NO bonds and two containing fluorine), and the accuracy of the tests was within 1 kcal·mol−1. This study shows that DFT-SOFM-RBFNN is an efficient and highly accurate method for Y-NO homolysis BDE. The method may be used as a tool to design new NO carrier molecules. PMID:22942689

Efficient time-dependent density functional theory approximations for hybrid density functionals: analytical gradients and parallelization.

PubMed

Petrenko, Taras; Kossmann, Simone; Neese, Frank

2011-02-07

In this paper, we present the implementation of efficient approximations to time-dependent density functional theory (TDDFT) within the Tamm-Dancoff approximation (TDA) for hybrid density functionals. For the calculation of the TDDFT/TDA excitation energies and analytical gradients, we combine the resolution of identity (RI-J) algorithm for the computation of the Coulomb terms and the recently introduced "chain of spheres exchange" (COSX) algorithm for the calculation of the exchange terms. It is shown that for extended basis sets, the RIJCOSX approximation leads to speedups of up to 2 orders of magnitude compared to traditional methods, as demonstrated for hydrocarbon chains. The accuracy of the adiabatic transition energies, excited state structures, and vibrational frequencies is assessed on a set of 27 excited states for 25 molecules with the configuration interaction singles and hybrid TDDFT/TDA methods using various basis sets. Compared to the canonical values, the typical error in transition energies is of the order of 0.01 eV. Similar to the ground-state results, excited state equilibrium geometries differ by less than 0.3 pm in the bond distances and 0.5° in the bond angles from the canonical values. The typical error in the calculated excited state normal coordinate displacements is of the order of 0.01, and relative error in the calculated excited state vibrational frequencies is less than 1%. The errors introduced by the RIJCOSX approximation are, thus, insignificant compared to the errors related to the approximate nature of the TDDFT methods and basis set truncation. For TDDFT/TDA energy and gradient calculations on Ag-TB2-helicate (156 atoms, 2732 basis functions), it is demonstrated that the COSX algorithm parallelizes almost perfectly (speedup ~26-29 for 30 processors). The exchange-correlation terms also parallelize well (speedup ~27-29 for 30 processors). The solution of the Z-vector equations shows a speedup of ~24 on 30 processors. The parallelization efficiency for the Coulomb terms can be somewhat smaller (speedup ~15-25 for 30 processors), but their contribution to the total calculation time is small. Thus, the parallel program completes a Becke3-Lee-Yang-Parr energy and gradient calculation on the Ag-TB2-helicate in less than 4 h on 30 processors. We also present the necessary extension of the Lagrangian formalism, which enables the calculation of the TDDFT excited state properties in the frozen-core approximation. The algorithms described in this work are implemented into the ORCA electronic structure system.

Toward a more embedded/extended perspective on the cognitive function of gestures

PubMed Central

Pouw, Wim T. J. L.; de Nooijer, Jacqueline A.; van Gog, Tamara; Zwaan, Rolf A.; Paas, Fred

2014-01-01

Gestures are often considered to be demonstrative of the embodied nature of the mind (Hostetter and Alibali, 2008). In this article, we review current theories and research targeted at the intra-cognitive role of gestures. We ask the question how can gestures support internal cognitive processes of the gesturer? We suggest that extant theories are in a sense disembodied, because they focus solely on embodiment in terms of the sensorimotor neural precursors of gestures. As a result, current theories on the intra-cognitive role of gestures are lacking in explanatory scope to address how gestures-as-bodily-acts fulfill a cognitive function. On the basis of recent theoretical appeals that focus on the possibly embedded/extended cognitive role of gestures (Clark, 2013), we suggest that gestures are external physical tools of the cognitive system that replace and support otherwise solely internal cognitive processes. That is gestures provide the cognitive system with a stable external physical and visual presence that can provide means to think with. We show that there is a considerable amount of overlap between the way the human cognitive system has been found to use its environment, and how gestures are used during cognitive processes. Lastly, we provide several suggestions of how to investigate the embedded/extended perspective of the cognitive function of gestures. PMID:24795687

Adaptation, acclimation, and assembly: How optimality principles govern the scaling of form, function, and diversity of ecosystem function in the light of climate change.

NASA Astrophysics Data System (ADS)

Enquist, B. J.

2016-12-01

The link between variation in species-specific traits - due to acclimation, adaptation, and how ecological communities assemble in time and space - and larger scale ecosystem processes is an important focus for global change research. Understanding such linkages requires synthesis of evolutionary, biogeograpahic, and biogeochemical approaches. Recent observations reveal several paradoxical patterns across ecosystems. Optimality principles provide a novel framework for generating numerous predictions for how ecosystems have and will reorganize and respond to climate change. Tropical elevation gradients are natural laboratories to assess how changing climate can ramify to influence tropical forest diversity and ecosystem functioning. We tested several new predictions from trait- and metabolic scaling theories by assessing the covariation between climate, traits, biomass and gross and net primary productivity (GPP and NPP) across tropical forest plots spanning elevation gradients. We measured multiple leaf physiological, morphological, and stoichiometric traits linked to variation in tree growth. Consistent with theory, observed decreases in NPP and GPP with temperature were best predicted by forest biomass, and scaled allometrically as predicted by theory but the effect of temperature was much less, characterized by a kinetic response much lower ( 0.1eV) than predicted ( 0.65eV). This is likely due to an observed exponential increase in the mean community leaf P:N ratio and photosynthetic nutrient use efficiency with decreases in temperature. Our results are consistent with predictions from Trait Driver Theory, where adaptive/acclamatory shifts in plant traits compensate for the kinetic effects of temperature on tree growth. Further, most of the traits measured showed significantly skewed trait distributions consistent with recent observations that observed shifts in species composition. The development of trait-based scaling theory provides a robust basis to predict how shifts in climate have and will influence functional composition and ecosystem functioning. Together, these results highlight the potential critical importance optimality principles for understanding the role of the biosphere within the integrated earth system.

A new class of weight and WA systems of the Kravchenko-Kaiser functions

NASA Astrophysics Data System (ADS)

Kravchenko, V. F.; Pustovoit, V. I.; Churikov, D. V.

2014-05-01

A new class of weight and WA-systems of the Kravchenko-Kaiser functions which showed its efficiency in various physical applications is proposed and substantiated. This publication consists of three parts. In the first the Kravchenko-Kaiser weight functions are constructed on basis of the theory of atomic functions (AFs) and the Kaiser windows for the first time. In the second part new constructions of analytic WA-systems of the Kravchenko-Kaiser functions are costructed. In the third part their applications to problems of weight averaging of the difference frequency signals are considered. The numerical experiment and the physical analysis of the results for concrete physical models confirmed their efficiency. This class of functions can find wide physical applications in problems of digital signal processing, restoration of images, radar, radiometry, radio astronomy, remote sensing, etc.

Effective charges of ionic liquid determined self-consistently through combination of molecular dynamics simulation and density-functional theory.

PubMed

Ishizuka, Ryosuke; Matubayasi, Nobuyuki

2017-11-15

A self-consistent scheme combining the molecular dynamics (MD) simulation and density functional theory (DFT) was recently proposed to incorporate the effects of the charge transfer and polarization of ions into non-poralizable force fields of ionic liquids for improved description of energetics and dynamics. The purpose of the present work is to analyze the detailed setups of the MD/DFT scheme by focusing on how the basis set, exchange-correlation (XC) functional, charge-fitting method or force field for the intramolecular and Lennard-Jones interactions affects the MD/DFT results of 1,3-dimethylimidazolium bis(trifluoromethylsulfonyl) imide ( [C1mim][NTf2]) and 1-ethyl-3-methylimidazolium glycinate ( [C2mim][Gly]). It was found that the double-zeta valence polarized or larger size of basis set is required for the convergence of the effective charge of the ion. The choice of the XC functional was further not influential as far as the generalized gradient approximation is used. The charge-fitting method and force field govern the accuracy of the MD/DFT scheme, on the other hand. We examined the charge-fitting methods of Blöchl, the iterative Hirshfeld (Hirshfeld-I), and REPEAT in combination with Lopes et al.'s force field and general AMBER force field. There is no single combination of charge fitting and force field that provides good agreements with the experiments, while the MD/DFT scheme reduces the effective charges of the ions and leads to better description of energetics and dynamics compared to the original force field with unit charges. © 2017 Wiley Periodicals, Inc. © 2017 Wiley Periodicals, Inc.

Electronic and optical properties of hexathiapentacene in the gas and crystal phases

NASA Astrophysics Data System (ADS)

Cardia, R.; Malloci, G.; Rignanese, G.-M.; Blase, X.; Molteni, E.; Cappellini, G.

2016-06-01

Using density functional theory (DFT) and its time-dependent (TD) extension, the electronic and optical properties of the hexathiapentacene (HTP) molecule, a derivative of pentacene (PNT) obtained by symmetric substitution of the six central H atoms with S atoms, are investigated for its gas and solid phases. For the molecular structure, all-electron calculations are performed using a Gaussian localized orbital basis set in conjunction with the Becke three-parameter Lee-Yang-Parr (B3LYP) hybrid exchange-correlation functional. Electron affinities, ionization energies, quasiparticle energy gaps, optical absorption spectra, and exciton binding energies are calculated and compared with the corresponding results for PNT, as well as with the available experimental data. The DFT and TDDFT results are also validated by performing many-body perturbation theory calculations within the G W and Bethe-Salpeter equation formalisms. The functionalization with S atoms induces an increase of both ionization energies and electron affinities, a sizable reduction of the fundamental electronic gap, and a redshift of the optical absorption onset. Notably, the intensity of the first absorption peak of HTP falling in the visible region is found to be nearly tripled with respect to the pure PNT molecule. For the crystal structures, pseudopotential calculations are adopted using a plane-wave basis set together with the Perdew-Burke-Ernzerhof exchange-correlation functional empirically corrected in order to take dispersive interactions into account. The electronic excitations are also obtained within a perturbative B3LYP scheme. A comparative analysis is carried out between the ground-state and excited-state properties of crystalline HTP and PNT linking to the findings obtained for the isolated molecules.

Covalency in Metal-Oxygen Multiple Bonds Evaluated Using Oxygen K-edge Spectroscopy and Electronic Structure Theory

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

Minasian, Stefan G.; Keith, Jason M.; Batista, Enrique R.

Advancing theories of how metal oxygen bonding influences metal oxo properties can expose new avenues for innovation in materials science, catalysis, and biochemistry. Historically, spectroscopic analyses of the transition metal peroxyanions, MO4x-, have formed the basis for new M O bonding theories. Herein, relative changes in M O orbital mixing in MO42- (M = Cr, Mo, W) and MO41- (M = Mn, Tc, Re) are evaluated for the first time by non-resonant inelastic X-ray scattering, X-ray absorption spectroscopy using fluorescence and transmission (via a scanning transmission X-ray microscope), and linear-response density functional theory. The results suggest that moving from Groupmore » 6 to Group 7 or down the triads increases M O e () mixing. Meanwhile, t2 mixing ( + ) remains relatively constant within the same Group. These unexpected changes in frontier orbital energy and composition are evaluated in terms of periodic trends in d orbital energy and radial extension.« less

Dual chain perturbation theory: A new equation of state for polyatomic molecules

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

Marshall, Bennett D., E-mail: bennett.d.marshall@exxonmobil.com

In the development of equations of state for polyatomic molecules, thermodynamic perturbation theory (TPT) is widely used to calculate the change in free energy due to chain formation. TPT is a simplification of a more general and exact multi-density cluster expansion for associating fluids. In TPT, all contributions to the cluster expansion which contain chain–chain interactions are neglected. That is, all inter-chain interactions are treated at the reference fluid level. This allows for the summation of the cluster theory in terms of reference system correlation functions only. The resulting theory has been shown to be accurate and has been widelymore » employed as the basis of many engineering equations of state. While highly successful, TPT has many handicaps which result from the neglect of chain–chain contributions. The subject of this document is to move beyond the limitations of TPT and include chain–chain contributions to the equation of state.« less

The trispectrum in the Effective Field Theory of Large Scale Structure

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

Bertolini, Daniele; Schutz, Katelin; Solon, Mikhail P.

2016-06-01

We compute the connected four point correlation function (the trispectrum in Fourier space) of cosmological density perturbations at one-loop order in Standard Perturbation Theory (SPT) and the Effective Field Theory of Large Scale Structure (EFT of LSS). This paper is a companion to our earlier work on the non-Gaussian covariance of the matter power spectrum, which corresponds to a particular wavenumber configuration of the trispectrum. In the present calculation, we highlight and clarify some of the subtle aspects of the EFT framework that arise at third order in perturbation theory for general wavenumber configurations of the trispectrum. We consistently incorporatemore » vorticity and non-locality in time into the EFT counterterms and lay out a complete basis of building blocks for the stress tensor. We show predictions for the one-loop SPT trispectrum and the EFT contributions, focusing on configurations which have particular relevance for using LSS to constrain primordial non-Gaussianity.« less

Derivation of the cut-off length from the quantum quadratic enhancement of a mass in vacuum energy constant Lambda

NASA Astrophysics Data System (ADS)

Fukushima, Kimichika; Sato, Hikaru

2018-04-01

Ultraviolet self-interaction energies in field theory sometimes contain meaningful physical quantities. The self-energies in such as classical electrodynamics are usually subtracted from the rest mass. For the consistent treatment of energies as sources of curvature in the Einstein field equations, this study includes these subtracted self-energies into vacuum energy expressed by the constant Lambda (used in such as Lambda-CDM). In this study, the self-energies in electrodynamics and macroscopic classical Einstein field equations are examined, using the formalisms with the ultraviolet cut-off scheme. One of the cut-off formalisms is the field theory in terms of the step-function-type basis functions, developed by the present authors. The other is a continuum theory of a fundamental particle with the same cut-off length. Based on the effectiveness of the continuum theory with the cut-off length shown in the examination, the dominant self-energy is the quadratic term of the Higgs field at a quantum level (classical self-energies are reduced to logarithmic forms by quantum corrections). The cut-off length is then determined to reproduce today's tiny value of Lambda for vacuum energy. Additionally, a field with nonperiodic vanishing boundary conditions is treated, showing that the field has no zero-point energy.

Reevaluation of the Amsterdam Inventory for Auditory Disability and Handicap Using Item Response Theory.

PubMed

Boeschen Hospers, J Mirjam; Smits, Niels; Smits, Cas; Stam, Mariska; Terwee, Caroline B; Kramer, Sophia E

2016-04-01

We reevaluated the psychometric properties of the Amsterdam Inventory for Auditory Disability and Handicap (AIADH; Kramer, Kapteyn, Festen, & Tobi, 1995) using item response theory. Item response theory describes item functioning along an ability continuum. Cross-sectional data from 2,352 adults with and without hearing impairment, ages 18-70 years, were analyzed. They completed the AIADH in the web-based prospective cohort study "Netherlands Longitudinal Study on Hearing." A graded response model was fitted to the AIADH data. Category response curves, item information curves, and the standard error as a function of self-reported hearing ability were plotted. The graded response model showed a good fit. Item information curves were most reliable for adults who reported having hearing disability and less reliable for adults with normal hearing. The standard error plot showed that self-reported hearing ability is most reliably measured for adults reporting mild up to moderate hearing disability. This is one of the few item response theory studies on audiological self-reports. All AIADH items could be hierarchically placed on the self-reported hearing ability continuum, meaning they measure the same construct. This provides a promising basis for developing a clinically useful computerized adaptive test, where item selection adapts to the hearing ability of individuals, resulting in efficient assessment of hearing disability.

A high level computational study of the CH4/CF4 dimer: how does it compare with the CH4/CH4 and CF4/CF4 dimers?

NASA Astrophysics Data System (ADS)

Biller, Matthew J.; Mecozzi, Sandro

2012-04-01

The interaction within the methane-methane (CH4/CH4), perfluoromethane-perfluoromethane (CF4/CF4) methane-perfluoromethane dimers (CH4/CF4) was calculated using the Hartree-Fock (HF) method, multiple orders of Møller-Plesset perturbation theory [MP2, MP3, MP4(DQ), MP4(SDQ), MP4(SDTQ)], and coupled cluster theory [CCSD, CCSD(T)], as well as the PW91, B97D, and M06-2X density functional theory (DFT) functionals. The basis sets of Dunning and coworkers (aug-cc-pVxZ, x = D, T, Q), Krishnan and coworkers [6-311++G(d,p), 6-311++G(2d,2p)], and Tsuzuki and coworkers [aug(df, pd)-6-311G(d,p)] were used. Basis set superposition error (BSSE) was corrected via the counterpoise method in all cases. Interaction energies obtained with the MP2 method do not fit with the experimental finding that the methane-perfluoromethane system phase separates at 94.5 K. It was not until the CCSD(T) method was considered that the interaction energy of the methane-perfluoromethane dimer (-0.69 kcal mol-1) was found to be intermediate between the methane (-0.51 kcal mol-1) and perfluoromethane (-0.78 kcal mol-1) dimers. This suggests that a perfluoromethane molecule interacts preferentially with another perfluoromethane (by about 0.09 kcal mol-1) than with a methane molecule. At temperatures much lower than the CH4/CF4 critical solution temperature of 94.5 K, this energy difference becomes significant and leads perfluoromethane molecules to associate with themselves, forming a phase separation. The DFT functionals yielded erratic results for the three dimers. Further development of DFT is needed in order to model dispersion interactions in hydrocarbon/perfluorocarbon systems.

Fractional spectral and pseudo-spectral methods in unbounded domains: Theory and applications

NASA Astrophysics Data System (ADS)

Khosravian-Arab, Hassan; Dehghan, Mehdi; Eslahchi, M. R.

2017-06-01

This paper is intended to provide exponentially accurate Galerkin, Petrov-Galerkin and pseudo-spectral methods for fractional differential equations on a semi-infinite interval. We start our discussion by introducing two new non-classical Lagrange basis functions: NLBFs-1 and NLBFs-2 which are based on the two new families of the associated Laguerre polynomials: GALFs-1 and GALFs-2 obtained recently by the authors in [28]. With respect to the NLBFs-1 and NLBFs-2, two new non-classical interpolants based on the associated- Laguerre-Gauss and Laguerre-Gauss-Radau points are introduced and then fractional (pseudo-spectral) differentiation (and integration) matrices are derived. Convergence and stability of the new interpolants are proved in detail. Several numerical examples are considered to demonstrate the validity and applicability of the basis functions to approximate fractional derivatives (and integrals) of some functions. Moreover, the pseudo-spectral, Galerkin and Petrov-Galerkin methods are successfully applied to solve some physical ordinary differential equations of either fractional orders or integer ones. Some useful comments from the numerical point of view on Galerkin and Petrov-Galerkin methods are listed at the end.

Experimental and DFT studies on the vibrational spectra of 1H-indene-2-boronic acid

NASA Astrophysics Data System (ADS)

Alver, Özgur; Kaya, Mehmet Fatih

2014-11-01

Stable conformers and geometrical molecular structures of 1H-indene-2-boronic acid (I-2B(OH)2) were studied experimentally and theoretically using FT-IR and FT-Raman spectroscopic methods. FT-IR and FT-Raman spectra were recorded in the region of 4000-400 cm-1, and 3700-400 cm-1, respectively. The optimized geometric structures were searched by Becke-3-Lee-Yang-Parr (B3LYP) hybrid density functional theory method with 6-31++G(d,p) basis set. Vibrational wavenumbers of I-2B(OH)2 were calculated using B3LYP density functional methods including 6-31++G(d,p) basis set. Experimental and theoretical results show that density functional B3LYP method gives satisfactory results for predicting vibrational wavenumbers except OH stretching modes which is probably due to increasing unharmonicity in the high wave number region and possible intra and inter molecular interaction at OH edges. To support the assigned vibrational wavenumbers, the potential energy distribution (PED) values were also calculated using VEDA 4 (Vibrational Energy Distribution Analysis) program.

Molecular structure and spectroscopic characterization of Carbamazepine with experimental techniques and DFT quantum chemical calculations

NASA Astrophysics Data System (ADS)

Suhasini, M.; Sailatha, E.; Gunasekaran, S.; Ramkumaar, G. R.

2015-04-01

A systematic vibrational spectroscopic assignment and analysis of Carbamazepine has been carried out by using FT-IR, FT-Raman and UV spectral data. The vibrational analysis were aided by electronic structure calculations - ab initio (RHF) and hybrid density functional methods (B3LYP) performed with standard basis set 6-31G(d,p). Molecular equilibrium geometries, electronic energies, natural bond order analysis, harmonic vibrational frequencies and IR intensities have been computed. A detailed interpretation of the vibrational spectra of the molecule has been made on the basis of the calculated Potential Energy Distribution (PED) by VEDA program. UV-visible spectrum of the compound was also recorded and the electronic properties, such as HOMO and LUMO energies and λmax were determined by HF/6-311++G(d,p) Time-Dependent method. The thermodynamic functions of the title molecule were also performed using the RHF and DFT methods. The restricted Hartree-Fock and density functional theory-based nuclear magnetic resonance (NMR) calculation procedure was also performed, and it was used for assigning the 13C and 1H NMR chemical shifts of Carbamazepine.

The 3d Rydberg (3A2) electronic state observed by Herzberg and Shoosmith for methylene

NASA Astrophysics Data System (ADS)

Yamaguchi, Yukio; Schaefer, Henry F., III

1997-06-01

In 1959 and 1961 Herzberg and Shoosmith reported the vacuum ultraviolet spectrum of the triplet state of CH2. The present study focuses on a characterization of the upper state, the 3d Rydberg (3A2) state, observed at 1415 Å. The theoretical interpretation of these experiments is greatly complicated by the presence of a lower-lying 3A2 valence state with a very small equilibrium bond angle. Ab initio electronic structure methods involving self-consistent-field (SCF), configuration interaction with single and double excitations (CISD), complete active space (CAS) SCF, state-averaged (SA) CASSCF, coupled cluster with single and double excitations (CCSD), CCSD with perturbative triple excitations [CCSD(T)], CASSCF second-order (SO) CI, and SACASSCF-SOCI have been employed with six distinct basis sets. With the largest basis set, triple zeta plus triple polarization with two sets of higher angular momentum functions and three sets of diffuse functions TZ3P(2 f,2d)+3diff, the CISD level of theory predicts the equilibrium geometry of the 3d Rydberg (3A2) state to be re=1.093 Å and θe=141.3 deg. With the same basis set the energy (Te value) of the 3d Rydberg state relative to the ground (X˜ 3B1) state has been determined to be 201.6 kcal mol-1 (70 500 cm-1) at the CCSD (T) level, 200.92kcal mol-1 (70 270 cm-1) at the CASSCF-SOCI level, and 200.89kcal mol-1 (70 260 cm-1) at the SACASSCF-SOCI level of theory. These predictions are in excellent agreement with the experimental T0 value of 201.95 kcalmol-1 (70 634 cm-1) reported by Herzberg.

Dynamical properties of liquid water from ab initio molecular dynamics performed in the complete basis set limit

NASA Astrophysics Data System (ADS)

Lee, Hee-Seung; Tuckerman, Mark E.

2007-04-01

Dynamical properties of liquid water were studied using Car-Parrinello [Phys. Rev. Lett. 55, 2471 (1985)] ab initio molecular dynamics (AIMD) simulations within the Kohn-Sham (KS) density functional theory employing the Becke-Lee-Yang-Parr exchange-correlation functional for the electronic structure. The KS orbitals were expanded in a discrete variable representation basis set, wherein the complete basis set limit can be easily reached and which, therefore, provides complete convergence of ionic forces. In order to minimize possible nonergodic behavior of the simulated water system in a constant energy (NVE) ensemble, a long equilibration run (30ps) preceded a 60ps long production run. The temperature drift during the entire 60ps trajectory was found to be minimal. The diffusion coefficient [0.055Å2/ps] obtained from the present work for 32 D2O molecules is a factor of 4 smaller than the most up to date experimental value, but significantly larger than those of other recent AIMD studies. Adjusting the experimental result so as to match the finite-sized system used in the present study brings the comparison between theory and experiment to within a factor of 3. More importantly, the system is not observed to become "glassy" as has been reported in previous AIMD studies. The computed infrared spectrum is in good agreement with experimental data, especially in the low frequency regime where the translational and librational motions of water are manifested. The long simulation length also made it possible to perform detailed studies of hydrogen bond dynamics. The relaxation dynamics of hydrogen bonds observed in the present AIMD simulation is slower than those of popular force fields, such as the TIP4P potential, but comparable to that of the TIP5P potential.