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Sample records for adiabatic time-dependent hartree-fock

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

    SciTech Connect

    Kato, Tsuyoshi; Ide, Yoshihiro; Yamanouchi, Kaoru

    2015-12-31

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

  2. Time Dependent Hartree Fock Equation: Gateway to Nonequilibrium Plasmas

    SciTech Connect

    James W. Dufty

    2007-04-28

    This is the Final Technical Report for DE-FG02-2ER54677 award “Time Dependent Hartree Fock Equation - Gateway to Nonequilibrium Plasmas”. Research has focused on the nonequilibrium dynamics of electrons in the presence of ions, both via basic quantum theory and via semi-classical molecular dynamics (MD) simulation. In addition, fundamental notions of dissipative dynamics have been explored for models of grains and dust, and for scalar fields (temperature) in turbulent edge plasmas. The specific topics addressed were Quantum Kinetic Theory for Metallic Clusters, Semi-classical MD Simulation of Plasmas , and Effects of Dissipative Dynamics.

  3. Fission dynamics within time-dependent Hartree-Fock: Deformation-induced fission

    NASA Astrophysics Data System (ADS)

    Goddard, Philip; Stevenson, Paul; Rios, Arnau

    2015-11-01

    Background: Nuclear fission is a complex large-amplitude collective decay mode in heavy nuclei. Microscopic density functional studies of fission have previously concentrated on adiabatic approaches based on constrained static calculations ignoring dynamical excitations of the fissioning nucleus and the daughter products. Purpose: We explore the ability of dynamic mean-field methods to describe fast fission processes beyond the fission barrier, using the nuclide Pu240 as an example. Methods: Time-dependent Hartree-Fock calculations based on the Skyrme interaction are used to calculate nonadiabatic fission paths, beginning from static constrained Hartree-Fock calculations. The properties of the dynamic states are interpreted in terms of the nature of their collective motion. Fission product properties are compared to data. Results: Parent nuclei constrained to begin dynamic evolution with a deformation less than the fission barrier exhibit giant-resonance-type behavior. Those beginning just beyond the barrier explore large-amplitude motion but do not fission, whereas those beginning beyond the two-fragment pathway crossing fission to final states which differ according to the exact initial deformation. Conclusions: Time-dependent Hartree-Fock is able to give a good qualitative and quantitative description of fast fission, provided one begins from a sufficiently deformed state.

  4. Fission dynamics within time-dependent Hartree-Fock. II. Boost-induced fission

    NASA Astrophysics Data System (ADS)

    Goddard, Philip; Stevenson, Paul; Rios, Arnau

    2016-01-01

    Background: Nuclear fission is a complex large-amplitude collective decay mode in heavy nuclei. Microscopic density functional studies of fission have previously concentrated on adiabatic approaches based on constrained static calculations ignoring dynamical excitations of the fissioning nucleus and the daughter products. Purpose: We explore the ability of dynamic mean-field methods to describe induced fission processes, using quadrupole boosts in the nuclide 240Pu as an example. Methods: Following upon the work presented in Goddard et al. [Phys. Rev. C 92, 054610 (2015)], 10.1103/PhysRevC.92.054610, quadrupole-constrained Hartree-Fock calculations are used to create a potential energy surface. An isomeric state and a state beyond the second barrier peak are excited by means of instantaneous as well as temporally extended gauge boosts with quadrupole shapes. The subsequent deexcitation is studied in a time-dependent Hartree-Fock simulation, with emphasis on fissioned final states. The corresponding fission fragment mass numbers are studied. Results: In general, the energy deposited by the quadrupole boost is quickly absorbed by the nucleus. In instantaneous boosts, this leads to fast shape rearrangements and violent dynamics that can ultimately lead to fission. This is a qualitatively different process than the deformation-induced fission. Boosts induced within a finite time window excite the system in a relatively gentler way and do induce fission but with a smaller energy deposition. Conclusions: The fission products obtained using boost-induced fission in time-dependent Hartree-Fock are more asymmetric than the fragments obtained in deformation-induced fission or the corresponding adiabatic approaches.

  5. Time-dependent Hartree-Fock Study of Octupole Vibrations in doubly magic nuclei

    NASA Astrophysics Data System (ADS)

    Simenel, C.; Buete, J.; Vo-Phuoc, K.

    2016-09-01

    Octupole vibrations are studied in some doubly magic nuclei using the time-dependent Hartree-Fock (TDHF) theory with a Skyrme energy density functional. Through the use of the linear response theory, the energies and transition amplitudes of the low-lying vibrational modes for each of the nuclei were determined. Energies were found to be close to experimental results. However, transition amplitudes, quantified by the deformation parameter β3, are underestimated by TDHF. A comparison with single-particle excitations on the Hartree-Fock ground-state shows that the collective octupole vibrations have their energy lowered due to attractive RPA residual interaction.

  6. Landau-Zener Effect In The Time-Dependent Hartree-Fock-Bogoliubov Equations

    SciTech Connect

    Mirea, M.

    2008-01-24

    If the Hartree-Fock-Bogoliubov equations of motion are solved in the case of seniority one nuclear systems, the unpaired nucleon remains on the same orbital. The blocking effect hinders the possibility that the unpaired nucleon skips from one orbital to another. A new set of coupled channel equations based on the time dependent Hartree-Fock-Bogoliubov formalism is deduced. This system includes a mechanism similar to the Landau-Zener effect, allowing that the unpaired nucleon jumps from one level to another.

  7. Correlated multielectron systems in strong laser fields: A multiconfiguration time-dependent Hartree-Fock approach

    SciTech Connect

    Caillat, J.; Scrinzi, A.; Koch, O.; Kreuzer, W.

    2005-01-01

    The multiconfiguration time-dependent Hartree-Fock approach for the description of correlated few-electron dynamics in the presence of strong laser fields is introduced and a comprehensive description of the method is given. Total ionization and electron spectra for the ground and first excited ionic channels are calculated for one-dimensional model systems with up to six active electrons. Strong correlation effects are found in the shape of photoelectron peaks and the dependence of ionization on molecule size.

  8. Modeling the doubly excited state with time-dependent Hartree-Fock and density functional theories

    NASA Astrophysics Data System (ADS)

    Isborn, Christine M.; Li, Xiaosong

    2008-11-01

    Multielectron excited states have become a hot topic in many cutting-edge research fields, such as the photophysics of polyenes and in the possibility of multiexciton generation in quantum dots for the purpose of increasing solar cell efficiency. However, obtaining multielectron excited states has been a major obstacle as it is often done with multiconfigurational methods, which involve formidable computational cost for large systems. Although they are computationally much cheaper than multiconfigurational wave function based methods, linear response adiabatic time-dependent Hartree-Fock (TDHF) and density functional theory (TDDFT) are generally considered incapable of obtaining multielectron excited states. We have developed a real-time TDHF and adiabatic TDDFT approach that is beyond the perturbative regime. We show that TDHF/TDDFT is able to simultaneously excite two electrons from the ground state to the doubly excited state and that the real-time TDHF/TDDFT implicitly includes double excitation within a superposition state. We also present a multireference linear response theory to show that the real-time electron density response corresponds to a superposition of perturbative linear responses of the S0 and S2 states. As a result, the energy of the two-electron doubly excited state can be obtained with several different approaches. This is done within the adiabatic approximation of TDDFT, a realm in which the doubly excited state has been deemed missing. We report results on simple two-electron systems, including the energies and dipole moments for the two-electron excited states of H2 and HeH+. These results are compared to those obtained with the full configuration interaction method.

  9. Basic and heavy ion scattering in time dependent Hartree-Fock Theory

    SciTech Connect

    Weiss, M.S.

    1984-05-17

    Time Dependent Hartree-Fock theory, TDHF, is the most sophisticated, microscopic approach to nuclear dynamics yet practiced. Although it is far from a description of nature it does allow us to examine multiply interactive many-body systems semi quantum mechanically and to visualize otherwise covert processes. Some of the properties of the TDHF equations are stated leaving the interested reader to one of several excellent review articles for the derivations. Some of the applications to the collision of heavy ions are briefly described. (WHK)

  10. Two methods for restricted configuration spaces within the multiconfiguration time-dependent Hartree-Fock method

    NASA Astrophysics Data System (ADS)

    Haxton, Daniel J.; McCurdy, C. William

    2015-01-01

    The multiconfiguration time-dependent Hartree-Fock (MCTDHF) method has shown promise in calculating electronic dynamics in molecules driven by strong and high-energy lasers. It must incorporate restricted configuration spaces (meaning that a particular combination of Slater determinants is used, instead of full configuration interaction) to be applied to big systems. Two different Ansätze are used to determine the essential term in the equations. The first Ansatz is the Lagrangian variational principle. The explicit, complete MCTDHF equations of motion, satisfying that principle, for arbitrary configuration spaces, are given. The property that a restricted configuration list must satisfy in order for the Lagrangian and McLachlan variational principles to give different results is identified. The second Ansatz keeps the density matrix block diagonal among equivalent orbitals, in a generalization of the method of Worth [J. Chem. Phys. 112, 8322 (2000), 10.1063/1.481438]. The methods perform well in calculating the dynamics of Be and BC2 + subject to ultrafast, ultrastrong lasers in severely truncated Hilbert spaces, although they exhibit differing degrees of numerical stability as implemented.

  11. Calculating Auger Lifetimes Directly from Time Propagation using the Multiconfiguration Time-Dependent Hartree-Fock Method

    NASA Astrophysics Data System (ADS)

    Abeln, Brant; McCurdy, C.; Haxton, Daniel

    2013-05-01

    A recent implementation of the multiconfiguration time-dependent Hartree-Fock (MCTDHF) method using an underlying discrete variable representation for the time dependent orbitals as well exterior complex scaling of all electronic coordinates is used to calculate Auger decay rates for states of Be+. In this approach all electrons are active and the number of orbitals and thus the size of the configuration space can be increased to give improved descriptions of these metastable states. After first populating the 1 s 2s2 (2 S) , and the two 1 s 2 s 2 p (2 P) metastable states, we calculated the autocorrelation function of the initial wave function under field-free propagation. In the simplest approach, the Fourier Transform of the autocorrelation function, < Ψ (0) | Ψ (t) > , can be fit to a Breit-Wigner profile to extract the lifetime and energy of the Auger decaying states. We discuss this and other methods of using MCTDHF to compute the lifetimes of core excited states of atoms and diatomic molecules using this three-electron system as the test case. Work supported by USDOE, OBES, Office of Chemical Sciences, United States Department of Education and NSF.

  12. Time-dependent Hartree-Fock calculations for multinucleon transfer and quasifission processes in the 238U+64Ni reaction

    NASA Astrophysics Data System (ADS)

    Sekizawa, Kazuyuki; Yabana, Kazuhiro

    2016-05-01

    Background: Multinucleon transfer (MNT) and quasifission (QF) processes are dominant processes in low-energy collisions of two heavy nuclei. They are expected to be useful to produce neutron-rich unstable nuclei. Nuclear dynamics leading to these processes depends sensitively on nuclear properties such as deformation and shell structure. Purpose: We elucidate reaction mechanisms of MNT and QF processes involving heavy deformed nuclei, making detailed comparisons between microscopic time-dependent Hartree-Fock (TDHF) calculations and measurements for the 238U+64Ni reaction. Methods: Three-dimensional Skyrme-TDHF calculations are performed. Particle-number projection method is used to evaluate MNT cross sections from the TDHF wave function after collision. Results: Fragment masses, total kinetic energy (TKE), scattering angle, contact time, and MNT cross sections are investigated for the 238U+64Ni reaction. They show reasonable agreements with measurements. At small impact parameters, collision dynamics depends sensitively on the orientation of deformed 238U. In tip (side) collisions, we find a larger (smaller) TKE and a shorter (longer) contact time. In tip collisions, we find a strong influence of quantum shells around 208Pb. Conclusions: It is confirmed that the TDHF calculations reasonably describe both MNT and QF processes in the 238U64Ni reaction. Analyses of this system indicate the significance of the nuclear structure effects such as deformation and quantum shells in nuclear reaction dynamics at low energies.

  13. Characterization of multielectron dynamics in molecules: a multiconfiguration time-dependent Hartree-Fock picture.

    PubMed

    Ohmura, Shu; Kono, Hirohiko; Oyamada, Takayuki; Kato, Tsuyoshi; Nakai, Katsunori; Koseki, Shiro

    2014-09-21

    Using the framework of multiconfiguration theory, where the wavefunction Φ(t) of a many-electron system at time t is expanded as Φ(t)=Σ(I)C(I)(t)Φ(I)(t) in terms of electron configurations {Φ(I)(t)}, we divided the total electronic energy E(t) as E(t)=Σ(I)|C(I)(t)|(2)E(I)(t) . Here E(I)(t) is the instantaneous phase changes of C(I)(t) regarded as a configurational energy associated with Φ(I)(t). We then newly defined two types of time-dependent states: (i) a state at which the rates of population transfer among configurations are all zero; (ii) a state at which {E(I)(t)} associated with the quantum phases of C(I)(t) are all the same. We call the former time-dependent state a classical stationary state by analogy with the stationary (steady) states of classical reaction rate equations and the latter one a quantum stationary state. The conditions (i) and (ii) are satisfied simultaneously for the conventional stationary state in quantum mechanics. We numerically found for a LiH molecule interacting with a near-infrared (IR) field ε(t) that the condition (i) is satisfied whenever the average velocity of electrons is zero and the condition (ii) is satisfied whenever the average acceleration is zero. We also derived the chemical potentials μ(j)(t) for time-dependent natural orbitals ϕ(j)(t) of a many-electron system. The analysis of the electron dynamics of LiH indicated that the temporal change in Δμ(j)(t) ≡ μ(j)(t) + ε(t) · d(j)(t) - μ(j)(0) correlates with the motion of the dipole moment of ϕ(j)(t), d(j)(t). The values Δμ(j)(t) are much larger than the energy ζ(j)(t) directly supplied to ϕ(j)(t) by the field, suggesting that valence electrons exchange energy with inner shell electrons. For H2 in an intense near-IR field, the ionization efficiency of ϕ(j)(t) is correlated with Δμ(j)(t). Comparing Δμ(j)(t) to ζ(j)(t), we found that energy accepting orbitals of Δμ(j)(t) > ζ(j)(t) indicate high ionization efficiency. The difference between

  14. Hartree-Fock and Kohn-Sham time-dependent response theory in a second-quantization atomic-orbital formalism suitable for linear scaling.

    PubMed

    Kjaergaard, Thomas; Jørgensen, Poul; Olsen, Jeppe; Coriani, Sonia; Helgaker, Trygve

    2008-08-07

    We present a second-quantization based atomic-orbital method for the computation of time-dependent response functions within Hartree-Fock and Kohn-Sham density-functional theories. The method is suited for linear scaling. Illustrative results are presented for excitation energies, one- and two-photon transition moments, polarizabilities, and hyperpolarizabilities for hexagonal BN sheets with up to 180 atoms.

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

    PubMed

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

    2011-06-28

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

  16. Geometrical effect on the nonlinear optical properties of model rigid-rod polymers. Ab initio time-dependent coupled Hartree-Fock studies

    NASA Astrophysics Data System (ADS)

    Karna, Shashi P.; Keshari, Vijaya; Prasad, Paras N.

    1995-03-01

    The linear and nonlinear optical (NLO) properties of the cis and trans isomers of diphenylbenzobisoxazole (PBO) and diphenylbenzobisthiazole (PBT) have been calculated by ab initio time-dependent coupled perturbed Hartree-Fock method using a split-valence basis set. The second-order NLO susceptibilities of the trans isomers are calculated to be larger by a factor of 1.5 or more compared to the cis isomers over a wide range of optical frequency. Between the two homologues (PBO and PBT), the linear and the NLO susceptibilities of the thiazole systems are calculated to be slightly higher than the oxazole systems.

  17. Hartree-Fock theory in nuclear physics. Technical summary report

    SciTech Connect

    Goyny, D.; Lions, P.L.

    1986-02-01

    This document investigates the so-called Hartree-Fock theory arising in the study of the structure of nuclei. The Hartree-Fock theory is an approximation method of many-body problems modelling the interaction of nucleons (neutrons and protrons), which lead to nonlinear variational systems of elliptic equations (the Hartree-Fock equations). These equations pertain to questions related to spin dependence and spin-orbit forces, symmetries of the nucleus and symmetry breakings, and time-dependent Hartree-Fock equations. One of the main features of these problems is the translation invariance, which creates compactness difficulties that are overcome by the use of the concentration-compactness method.

  18. Multiresolution quantum chemistry in multiwavelet bases: excited states from time-dependent Hartree-Fock and density functional theory via linear response.

    PubMed

    Yanai, Takeshi; Fann, George I; Beylkin, Gregory; Harrison, Robert J

    2015-12-21

    A fully numerical method for the time-dependent Hartree-Fock and density functional theory (TD-HF/DFT) with the Tamm-Dancoff (TD) approximation is presented in a multiresolution analysis (MRA) approach. From a reformulation with effective use of the density matrix operator, we obtain a general form of the HF/DFT linear response equation in the first quantization formalism. It can be readily rewritten as an integral equation with the bound-state Helmholtz (BSH) kernel for the Green's function. The MRA implementation of the resultant equation permits excited state calculations without virtual orbitals. The integral equation is efficiently and adaptively solved using a numerical multiresolution solver with multiwavelet bases. Our implementation of the TD-HF/DFT methods is applied for calculating the excitation energies of H2, Be, N2, H2O, and C2H4 molecules. The numerical errors of the calculated excitation energies converge in proportion to the residuals of the equation in the molecular orbitals and response functions. The energies of the excited states at a variety of length scales ranging from short-range valence excitations to long-range Rydberg-type ones are consistently accurate. It is shown that the multiresolution calculations yield the correct exponential asymptotic tails for the response functions, whereas those computed with Gaussian basis functions are too diffuse or decay too rapidly. We introduce a simple asymptotic correction to the local spin-density approximation (LSDA) so that in the TDDFT calculations, the excited states are correctly bound.

  19. Fusion and quasifission dynamics in the reactions 48Ca+249Bk and 50Ti+249Bk using a time-dependent Hartree-Fock approach

    NASA Astrophysics Data System (ADS)

    Umar, A. S.; Oberacker, V. E.; Simenel, C.

    2016-08-01

    Background: Synthesis of superheavy elements (SHEs) with fusion-evaporation reactions is strongly hindered by the quasifission (QF) mechanism which prevents the formation of an equilibrated compound nucleus and which depends on the structure of the reactants. New SHEs have been recently produced with doubly-magic 48Ca beams. However, SHE synthesis experiments with single-magic 50Ti beams have so far been unsuccessful. Purpose: In connection with experimental searches for Z =117 ,119 superheavy elements, we perform a theoretical study of fusion and quasifission mechanisms in 48Ca,50Ti+249Bk reactions in order to investigate possible differences in reaction mechanisms induced by these two projectiles. Methods: The collision dynamics and the outcome of the reactions are studied using unrestricted time-dependent Hartree-Fock (TDHF) calculations as well as the density-constrained TDHF method to extract the nucleus-nucleus potentials and the excitation energy in each fragment. Results: Nucleus-nucleus potentials, nuclear contact times, masses and charges of the fragments, as well as their kinetic and excitation energies strongly depend on the orientation of the prolate 249Bk nucleus. Long contact times associated with fusion are observed in collisions of both projectiles with the side of the 249Bk nucleus, but not on collisions with its tip. The energy and impact parameter dependencies of the fragment properties, as well as their mass-angle and mass-total kinetic energy correlations are investigated. Conclusions: Entrance channel reaction dynamics are similar with both 48Ca and 50Ti projectiles. Both are expected to lead to the formation of a compound nucleus by fusion if they have enough energy to get in contact with the side of the 249Bk target.

  20. Actinide collisions for QED and superheavy elements with the time-dependent Hartree-Fock theory and the Balian-Vénéroni variational principle

    NASA Astrophysics Data System (ADS)

    Simenel, Cédric; Golabek, Cédric; Kedziora, David J.

    2011-10-01

    Collisions of actinide nuclei form, during very short times of few zs (10-21 s), the heaviest ensembles of interacting nucleons available on Earth. Such collisions are used to produce super-strong electric fields by the huge number of interacting protons to test spontaneous positron-electron pair emission (vacuum decay) predicted by the quantum electrodynamics (QED) theory. Multi-nucleon transfer in actinide collisions could also be used as an alternative way to fusion in order to produce neutron-rich heavy and superheavy elements thanks to inverse quasifission mechanisms. Actinide collisions are studied in a dynamical quantum microscopic approach. The three-dimensional time-dependent Hartree-Fock (TDHF) code tdhf3d is used with a full Skyrme energy density functional to investigate the time evolution of expectation values of one-body operators, such as fragment position and particle number. This code is also used to compute the dispersion of the particle numbers (e.g., widths of fragment mass and charge distributions) from TDHF transfer probabilities, on the one hand, and using the BalianVeneroni variational principle, on the other hand. A first application to test QED is discussed. Collision times in 238U+238U are computed to determine the optimum energy for the observation of the vacuum decay. It is shown that the initial orientation strongly affects the collision times and reaction mechanism. The highest collision times predicted by TDHF in this reaction are of the order of ~ 4 zs at a center of mass energy of 1200 MeV. According to modern calculations based on the Dirac equation, the collision times at Ecm > 1 GeV are sufficient to allow spontaneous electron-positron pair emission from QED vacuum decay, in case of bare uranium ion collision. A second application of actinide collisions to produce neutron-rich transfermiums is discussed. A new inverse quasifission mechanism associated to a specific orientation of the nuclei is proposed to produce transfermium

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

    SciTech Connect

    Rabilloud, Franck

    2014-10-14

    Absorption spectra of Ag{sub 20} and Ag{sub 55}{sup q} (q = +1, −3) nanoclusters are investigated in the framework of the time-dependent density functional theory in order to analyse the role of the d electrons in plasmon-like band of silver clusters. The description of the plasmon-like band from calculations using density functionals containing an amount of Hartree-Fock exchange at long range, namely, hybrid and range-separated hybrid (RSH) density functionals, is in good agreement with the classical interpretation of the plasmon-like structure as a collective excitation of valence s-electrons. In contrast, using local or semi-local exchange functionals (generalized gradient approximations (GGAs) or meta-GGAs) leads to a strong overestimation of the role of d electrons in the plasmon-like band. The semi-local asymptotically corrected model potentials also describe the plasmon as mainly associated to d electrons, though calculated spectra are in fairly good agreement with those calculated using the RSH scheme. Our analysis shows that a portion of non-local exchange modifies the description of the plasmon-like band.

  2. Derivative discontinuity with localized Hartree-Fock potential

    SciTech Connect

    Nazarov, V. U.; Vignale, G.

    2015-08-14

    The localized Hartree-Fock potential has proven to be a computationally efficient alternative to the optimized effective potential, preserving the numerical accuracy of the latter and respecting the exact properties of being self-interaction free and having the correct −1/r asymptotics. In this paper we extend the localized Hartree-Fock potential to fractional particle numbers and observe that it yields derivative discontinuities in the energy as required by the exact theory. The discontinuities are numerically close to those of the computationally more demanding Hartree-Fock method. Our potential enjoys a “direct-energy” property, whereby the energy of the system is given by the sum of the single-particle eigenvalues multiplied by the corresponding occupation numbers. The discontinuities c{sub ↑} and c{sub ↓} of the spin-components of the potential at integer particle numbers N{sub ↑} and N{sub ↓} satisfy the condition c{sub ↑}N{sub ↑} + c{sub ↓}N{sub ↓} = 0. Thus, joining the family of effective potentials which support a derivative discontinuity, but being considerably easier to implement, the localized Hartree-Fock potential becomes a powerful tool in the broad area of applications in which the fundamental gap is an issue.

  3. Constrained Hartree-Fock and quasi-spin projection

    NASA Astrophysics Data System (ADS)

    Cambiaggio, M. C.; Plastino, A.; Szybisz, L.

    1980-08-01

    The constrained Hartree-Fock approach of Elliott and Evans is studied in detail with reference to two quasi-spin models, and their predictions compared with those arising from a projection method. It is found that the new approach works fairly well, although limitations to its applicability are encountered.

  4. Accurate Hartree-Fock energy of extended systems using large Gaussian basis sets

    NASA Astrophysics Data System (ADS)

    Paier, Joachim; Diaconu, Cristian V.; Scuseria, Gustavo E.; Guidon, Manuel; Vandevondele, Joost; Hutter, Jürg

    2009-11-01

    Calculating highly accurate thermochemical properties of condensed matter via wave-function-based approaches (such as, e.g., Hartree-Fock or hybrid functionals) has recently attracted much interest. We here present two strategies providing accurate Hartree-Fock energies for solid LiH in a large Gaussian basis set and applying periodic boundary conditions. The total energies were obtained using two different approaches, namely, a supercell evaluation of Hartree-Fock exchange using a truncated Coulomb operator and an extrapolation toward the full-range Hartree-Fock limit of a Padé fit to a series of short-range screened Hartree-Fock calculations. These two techniques agreed to significant precision. We also present the Hartree-Fock cohesive energy of LiH (converged to within sub-millielectron volt) at the experimental equilibrium volume as well as the Hartree-Fock equilibrium lattice constant and bulk modulus.

  5. Deformed Brueckner-Hartree-Fock calculation for light nuclei

    NASA Technical Reports Server (NTRS)

    Braley, R. C.; Ford, W. F.; Becker, R. L.; Patterson, M. R.

    1971-01-01

    For the first time the Brueckner-Hartree-Fock (BHF) method was applied to nuclei whose intrinsic structure is nonspherical. One aim was to investigate whether the energy dependent reaction matrix calculated from a realistic nucleon-nucleon interaction leads to deformations similar to, or different from, those obtained from energy independent interactions in Hartree-Fock (HF) calculations. Reaction matrix elements were calculated as a function of starting energy for the Hamada-Johnston interaction, using a Pauli operator appropriate to O-16 and a shifted oscillator spectrum for virtual excited states. Binding energies, single-particle energies, radii, and shape deformations of the intrinsic state in unrenormalized as well as renormalized BHF are discussed and compared with previous HF studies. Results are presented for C-12, O-16, and Ne-20.

  6. Qualitative breakdown of the unrestricted Hartree-Fock energy

    SciTech Connect

    Mori-Sánchez, Paula; Cohen, Aron J.

    2014-10-28

    The stretching of closed-shell molecules is a qualitative problem for restricted Hartree-Fock that is usually circumvented by the use of unrestricted Hartree-Fock (UHF). UHF is well known to break the spin symmetry at the Coulson-Fischer point, leading to a discontinuous derivative in the potential energy surface and incorrect spin density. However, this is generally not considered as a major drawback. In this work, we present a set of two electron molecules which magnify the problem of symmetry breaking and lead to drastically incorrect potential energy surfaces with UHF. These molecules also fail with unrestricted density-functional calculations where a functional such as B3LYP gives both symmetry breaking and an unphysically low energy due to the delocalization error. The implications for density functional theory are also discussed.

  7. Quark matter in the Hartree-Fock approximation

    SciTech Connect

    Grassi, F.

    1987-07-01

    An equation of state is computed for quark matter interacting through a phenomenological potential in the Hartree-Fock approximation. It is shown that for color-independent confining potentials, it can be approximated by the Hartree result and leads to a first order mass phase transition. For color-dependent confining potentials, a phase transition from a Fermi sphere to a Fermi shell is possible.

  8. Implicit ladder summation in the Hartree-Fock-Bogoliubov approach

    SciTech Connect

    Pricoupenko, Ludovic

    2011-11-15

    The fully variational Hartree-Fock-Bogoliubov approach for bosons is studied in the limit of zero-range forces in two and three dimensions. The equation of state obtained in two dimensions is expressed in a parametric form. It is shown that the {Lambda} potential permits to perform an implicit summation of the ladder diagrams without leaving the variational scheme, restoring thus the consistency of this approximation.

  9. Spin contamination in unrestricted Hartree-Fock calculations.

    NASA Technical Reports Server (NTRS)

    Schug, J. C.; Phillips, D. H.

    1973-01-01

    Several pi-electron doublets are treated by both the unrestricted Hartree-Fock method and the restricted approximation of Longuet-Higgins and Pople. For two of the molecules, which contain oxygen heteroatoms, serious spin contamination occurs in the UHF wavefunctions, and this negates the usefulness of the single annihilation procedure that is often used for spin-density calculations. The restricted approximation provides a convenient alternative, especially because configuration interaction is easily taken into account.

  10. Hartree-Fock and Roothaan-Hartree-Fock energies for the ground states of He through Xe

    NASA Astrophysics Data System (ADS)

    Bunge, Carlos F.; Barrientos, José A.; Bunge, Annik Vivier; Cogordan, J. A.

    1992-10-01

    We report a compilation of Roothaan-Hartree-Fock (RHF) wave functions for the ground states of He through Xe, with atomic orbitals expressed in terms of Slater-type functions. Slight increases in the size of the basis set with respect to those used in Clementi and Roetti's tables [At. Data Nucl. Data Tables 14, 177 (1974)] turn out to yield total energies to better than eight figures, reducing between 21 and 2770 times the energy errors in the above tables, and also improving over the previous numerical HF energies computed by Froese Fischer $[-The Hartree-Fock Method for Atoms (Wiley, New York, 1977)]. We also report 10-digit numerical HF energies with different results for Cr, Cu, Nb, Mo, Ru, Rh, Pd, and Ag.

  11. Introducing constricted variational density functional theory in its relaxed self-consistent formulation (RSCF-CV-DFT) as an alternative to adiabatic time dependent density functional theory for studies of charge transfer transitions

    SciTech Connect

    Krykunov, Mykhaylo; Seth, Mike; Ziegler, Tom

    2014-05-14

    We have applied the relaxed and self-consistent extension of constricted variational density functional theory (RSCF-CV-DFT) for the calculation of the lowest charge transfer transitions in the molecular complex X-TCNE between X = benzene and TCNE = tetracyanoethylene. Use was made of functionals with a fixed fraction (α) of Hartree-Fock exchange ranging from α = 0 to α = 0.5 as well as functionals with a long range correction (LC) that introduces Hartree-Fock exchange for longer inter-electronic distances. A detailed comparison and analysis is given for each functional between the performance of RSCF-CV-DFT and adiabatic time-dependent density functional theory (TDDFT) within the Tamm-Dancoff approximation. It is shown that in this particular case, all functionals afford the same reasonable agreement with experiment for RSCF-CV-DFT whereas only the LC-functionals afford a fair agreement with experiment using TDDFT. We have in addition calculated the CT transition energy for X-TCNE with X = toluene, o-xylene, and naphthalene employing the same functionals as for X = benzene. It is shown that the calculated charge transfer excitation energies are in as good agreement with experiment as those obtained from highly optimized LC-functionals using adiabatic TDDFT. We finally discuss the relation between the optimization of length separation parameters and orbital relaxation in the RSCF-CV-DFT scheme.

  12. First Gogny-Hartree-Fock-Bogoliubov Nuclear Mass Model

    SciTech Connect

    Goriely, S.; Hilaire, S.; Girod, M.; Peru, S.

    2009-06-19

    We present the first Gogny-Hartree-Fock-Bogoliubov (HFB) model which reproduces nuclear masses with an accuracy comparable with the best mass formulas. In contrast with the Skyrme-HFB nuclear-mass models, an explicit and self-consistent account of all the quadrupole correlation energies are included within the 5D collective Hamiltonian approach. The final rms deviation with respect to the 2149 measured masses is 798 keV. In addition, the new Gogny force is shown to predict nuclear and neutron matter properties in agreement with microscopic calculations based on realistic two- and three-body forces.

  13. Density differences for near-Hartree-Fock atomic wave functions

    NASA Astrophysics Data System (ADS)

    Schmider, Hartmut; Sagar, Robin P.; Smith, Vedene H., Jr.

    1994-05-01

    The widely used near-Hartree-Fock functions of Clementi and Roetti [At. Data Nucl. Data Tables 14, 177 (1974)] are compared with the newer functions of Bunge et al. [At. Data Nucl. Tables 53, 113 (1993)] by means of different measures of functional distance on the charge density ρ for the atoms He to Xe. The results are correlated with the energy improvement, and an empriical relation between the linear deviation in the first derivative of ρ and the total energy is reported.

  14. Bimodal Fission in the Skyrme-Hartree-Fock Approach

    SciTech Connect

    Staszczak, A.; Dobaczewski, J.; Nazarewicz, Witold

    2007-01-01

    Spontaneous fission properties of 256Fm, 258Fm, and 260Fm isotopes are studied within the Skyrme-Hartree-Fock+BCS framework. In the particle-hole channel we take the Skyrme SkM* effective force, while in the particle-particle channel we employ the seniority pairing interaction. Three static fission paths for all investigated heavy fermium isotopes are found. The analysis of these fission modes allows to describe observed asymmetric fission of 256Fm, as well as bimodal fission of 258Fm and symmetric fission in 260Fm.

  15. Finite jellium models. I. Restricted Hartree-Fock calculations.

    PubMed

    Ghosh, Sankha; Gill, Peter M W

    2005-04-15

    Restricted Hartree-Fock calculations have been performed on the Fermi configurations of n electrons confined within a cube. The self-consistent-field orbitals have been expanded in a basis of N particle-in-a-box wave functions. The difficult one- and two-electron integrals have been reduced to a small set of canonical integrals that are calculated accurately using quadrature. The total energy and exchange energy per particle converge smoothly toward their limiting values as n increases; the highest occupied molecular orbital-lowest unoccupied molecular orbital gap and Dirac coefficient converge erratically. However, the convergence in all cases is slow.

  16. Using Hartree-Fock pseudopotentials in GW calculations

    NASA Astrophysics Data System (ADS)

    Hamann, D. R.; Vanderbilt, David

    2010-03-01

    The issue of including shallow ``semi-core'' states as valence has recently resurfaced in the context of self-consistent GW calculations.footnotetextF. Bruneval et al., Phys. Rev. Lett. 97, 267601 (2006). Supposing that semi-core-valence exchange is the dominant process necessitating the inclusion of semi-cores, we have investigated whether the use Hartree-Fock pseudopotentialsfootnotetextW. A. Al-Saidi, E. J. Walter, and A. M. Rappe, Phys. Rev. B 77, 075122 (2008). instead of density-functional psp's might obviate the need for semi-cores. The answers to this question appear to be ``yes'' for the case of CuCl (filled d shell), and ``semi-cores don't matter anyway'' for ScN (empty d shell). Opportunity permitting, additional examples will be discussed.

  17. Auxiliary Density Matrix Methods for Hartree-Fock Exchange Calculations.

    PubMed

    Guidon, Manuel; Hutter, Jürg; VandeVondele, Joost

    2010-08-10

    The calculation of Hartree-Fock exchange (HFX) is computationally demanding for large systems described with high-quality basis sets. In this work, we show that excellent performance and good accuracy can nevertheless be obtained if an auxiliary density matrix is employed for the HFX calculation. Several schemes to derive an auxiliary density matrix from a high-quality density matrix are discussed. Key to the accuracy of the auxiliary density matrix methods (ADMM) is the use of a correction based on standard generalized gradient approximations for HFX. ADMM integrates seamlessly in existing HFX codes and, in particular, can be employed in linear scaling implementations. Demonstrating the performance of the method, the effect of HFX on the structure of liquid water is investigated in detail using Born-Oppenheimer molecular dynamics simulations (300 ps) of a system of 64 molecules. Representative for large systems are calculations on a solvated protein (Rubredoxin), for which ADMM outperforms the corresponding standard HFX implementation by approximately a factor 20.

  18. Collective Inertia and Fission Barriers Within the Skyrme-Hartree-Fock Theory

    SciTech Connect

    Baran, A.; Staszczak, A.; Dobaczewski, J.; Nazarewicz, Witold

    2007-01-01

    Spontaneous fission barriers, quadrupole inertia tensor, and zero-point quadrupole correlation energy are calculated for 252,256,258Fm in the framework of the self-consistent Skyrme-Hartree-Fock+BCS theory. Two ways of computing collective inertia are employed: the Gaussian Overlap Approximation to the Generator Coordinate Method and cranking ansatz. The Skyrme results are compared with those of the Gogny-Hartree-Fock-Bogoliubov model.

  19. Shortcuts to adiabaticity in a time-dependent box

    PubMed Central

    Campo, A. del; Boshier, M. G.

    2012-01-01

    A method is proposed to drive an ultrafast non-adiabatic dynamics of an ultracold gas trapped in a time-dependent box potential. The resulting state is free from spurious excitations associated with the breakdown of adiabaticity, and preserves the quantum correlations of the initial state up to a scaling factor. The process relies on the existence of an adiabatic invariant and the inversion of the dynamical self-similar scaling law dictated by it. Its physical implementation generally requires the use of an auxiliary expulsive potential. The method is extended to a broad family of interacting many-body systems. As illustrative examples we consider the ultrafast expansion of a Tonks-Girardeau gas and of Bose-Einstein condensates in different dimensions, where the method exhibits an excellent robustness against different regimes of interactions and the features of an experimentally realizable box potential. PMID:22970340

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

    NASA Astrophysics Data System (ADS)

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

    2016-10-01

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

  1. Numerical solution of the Hartree-Fock equation in molecular geometries

    SciTech Connect

    Talman, James D.

    2010-11-15

    Solutions of the restricted Hartree-Fock equations are obtained for small molecules using a combination of variationally optimized atomic orbitals centered on the nuclei and corrections computed on a Cartesian mesh. The problem of finding the corrections is reduced to the problem of solving the Hartree-Fock equations with inhomogeneous terms. An iterative method is developed in which the equation is treated as an inhomogeneous Helmholtz equation with the potential terms transferred to the inhomogeneous term. Terms in the equation that arise from rapid variation of the orbitals in the neighborhoods of the nuclei are treated analytically. The Helmholtz equation can then be solved using a fast Fourier transform method. Results for a number of small molecules that are accurate at the millihartree level are presented. The method for solving the inhomogeneous Hartree-Fock equation should be applicable to other problems of quantum chemistry.

  2. Application of Fourth Order Vibrational Perturbation Theory with Analytic Hartree-Fock Force Fields

    NASA Astrophysics Data System (ADS)

    Gong, Justin Z.; Matthews, Devin A.; Stanton, John F.

    2014-06-01

    Fourth-Order Rayleigh-Schrodinger Perturbation Theory (VPT4) is applied to a series of small molecules. The quality of results have been shown to be heavily dependent on the quality of the quintic and sextic force constants used and that numerical sextic force constants converge poorly and are unreliable for VPT4. Using analytic Hartree-Fock force constants, it is shown that these analytic higher-order force constants are comparable to corresponding force constants from numerical calculations at a higher level of theory. Calculations show that analytic Hartree-Fock sextic force constants are reliable and can provide good results with Fourth-Order Rayleigh-Schrodinger Perturbation Theory.

  3. Fission barriers for neutron-rich nuclei by means of Skyrme-Hartree-Fock-Bogoliubov calculation

    SciTech Connect

    Hashizume, K.; Wada, T.; Ohta, M.; Samyn, M.; Goriely, S.

    2007-02-26

    The nuclear fission barrier height has been estimated by means of the constraint Skyrme Hartree-Fock-Bogoliubov method. The potential energy surfaces obtained by the method are analyzed with the flooding method to find several saddle points. The results for U, Np, Bk isotopes are compared with the barrier derived from the extended Thomas-Fermi plus Strutinsky integral method.

  4. Orbital and Total Atomic Momentum Expectation Values with Roothaan-Hartree-Fock Wave Functions

    NASA Astrophysics Data System (ADS)

    García de la Vega, J. M.; Miguel, B.

    1993-05-01

    Orbital and total momentum expectation values are computed using the Roothaan-Hartree-Fock wave functions of Clementi and Roetti. These values are calculated analytically and may be used to study the quality of basis sets. Tabulations for ground and excited states of atoms from Z = 2 to Z = 54 are presented.

  5. Roothaan-Hartree-Fock wave functions for atoms with Z<=54

    NASA Astrophysics Data System (ADS)

    Koga, Toshikatsu; Tatewaki, Hiroshi; Thakkar, Ajit J.

    1993-05-01

    The widely used Roothaan-Hartree-Fock wave functions of Clementi and Roetti [At. Data Nucl. Data Tables 14, 177 (1974)] for the atoms from He through Xe are improved by reoptimization of the exponents of the Slater-type basis functions. The largest improvement in the energy is 0.053 hartree for Cd.

  6. Robust Periodic Hartree-Fock Exchange for Large-Scale Simulations Using Gaussian Basis Sets.

    PubMed

    Guidon, Manuel; Hutter, Jürg; VandeVondele, Joost

    2009-11-10

    Hartree-Fock exchange with a truncated Coulomb operator has recently been discussed in the context of periodic plane-waves calculations [Spencer, J.; Alavi, A. Phys. Rev. B: Solid State, 2008, 77, 193110]. In this work, this approach is extended to Gaussian basis sets, leading to a stable and accurate procedure for evaluating Hartree-Fock exchange at the Γ-point. Furthermore, it has been found that standard hybrid functionals can be transformed into short-range functionals without loss of accuracy. The well-defined short-range nature of the truncated exchange operator can naturally be exploited in integral screening procedures and makes this approach interesting for both condensed phase and gas phase systems. The presented Hartree-Fock implementation is massively parallel and scales up to ten thousands of cores. This makes it feasible to perform highly accurate calculations on systems containing thousands of atoms or ten thousands of basis functions. The applicability of this scheme is demonstrated by calculating the cohesive energy of a LiH crystal close to the Hartree-Fock basis set limit and by performing an electronic structure calculation of a complete protein (rubredoxin) in solution with a large and flexible basis set.

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

    ERIC Educational Resources Information Center

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

    2014-01-01

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

  8. Communication: Projected Hartree Fock theory as a polynomial similarity transformation theory of single excitations

    NASA Astrophysics Data System (ADS)

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

    2016-09-01

    Spin-projected Hartree-Fock is written as a particle-hole excitation ansatz over a symmetry-adapted reference determinant. Remarkably, this expansion has an analytic expression that we were able to decipher. While the form of the polynomial expansion is universal, the excitation amplitudes need to be optimized. This is equivalent to the optimization of orbitals in the conventional projected Hartree-Fock framework of non-orthogonal determinants. Using the inverse of the particle-hole expansion, we similarity transform the Hamiltonian in a coupled-cluster style theory. The left eigenvector of the non-Hermitian Hamiltonian is constructed in a similar particle-hole expansion fashion, and we show that to numerically reproduce variational projected Hartree-Fock results, one needs as many pair excitations in the bra as the number of strongly correlated entangled pairs in the system. This single-excitation polynomial similarity transformation theory is an alternative to our recently presented double excitation theory, but supports projected Hartree-Fock and coupled cluster simultaneously rather than interpolating between them.

  9. FRANCHFRI: the Finite-RANge Constrained Hartree-Fock Rapid Iterator

    SciTech Connect

    Younes, W; Gogny, D

    2007-01-22

    The Hartree-Fock code FRANCHFRI, which uses a finite-range nucleon-nucleon interaction, has been written and benchmarked. This code represents a new LLNL capability for realistic calculations in both nuclear-structure and nuclear-reaction physics. The use of a finite-range interaction represents a considerable improvement over other Hartree-Fock codes currently available in the public domain, which rely on zero-range forces. The finite-range force does not simply lead to a more realistic treatment of the nuclear problem, it avoids serious mathematical pathologies inherent to zero-range interactions. This brief and non-technical report introduces the code, its design philosophy, various benchmarks used to test its accuracy, and places it within its proper physics context. The current limitations and planned extensions of the code are also discussed.

  10. Improved Roothaan-Hartree-Fock wave functions for atoms and ions with N <= 54

    NASA Astrophysics Data System (ADS)

    Koga, Toshikatsu; Watanabe, Shinya; Kanayama, Katsutoshi; Yasuda, Ryuji; Thakkar, Ajit J.

    1995-08-01

    Improved Roothaan-Hartree-Fock wave functions are reported for the ground states of all the neutral atoms from He to Xe, singly charged cations from Li+ to Cs+, and stable singly charged anions from H- to I-. Our neutral atom wave functions are an improvement over those of Clementi and Roetti [At. Data Nucl. Data Tables 14, 177 (1974)], Bunge et al. [Phys. Rev. A 46, 3691 (1992)] and Koga et al. [Phys. Rev. A 47, 4510 (1993)]. The ion wave functions are an improvement over those of Clementi and Roetti, and Koga et al. [J. Phys. B 26, 2529 (1993)]. In all cases, the current wave functions predict energies within 1.3×10-5 hartrees of the numerical Hartree-Fock limit.

  11. Accurate alkynyl radical structures from density functional calculations without Hartree-Fock exchange

    NASA Astrophysics Data System (ADS)

    Janesko, Benjamin G.; Proynov, Emil

    2017-02-01

    Density functional approximations (DFAs) often suffer from self-repulsion and delocalization errors which are reduced by exact (Hartree-Fock-like) exchange admixture. Oyeyemi and co-workers recently showed that several DFAs with little exact exchange incorrectly predict bent alkynyl radical geometries, giving errors in ab initio composite methods using density functional theory geometries [V. B. Oyeyemi et al., J. Phys. Chem. Lett. 3, 289 (2012)]. We show that the simple Hartree-Fock-Slater and Xα DFAs, which have substantial delocalization error, predict linear alkynyl radical geometries without incorporating exact exchange. Our Rung 3.5 DFAs, and rescaled generalized gradient approximations, can give either linear σ, bent σ -π , or nearly linear π radicals, all without incorporating exact exchange. This highlights the complexity of delocalization error, the utility of accurate empirical DFA geometries for ab initio composite methods, and the insights to be gained from Rung 3.5 DFAs.

  12. Hartree-Fock Theory with a Self-Generated Magnetic Field

    NASA Astrophysics Data System (ADS)

    Comelli, Silvia

    In the first part of this thesis, we give a brief introduction of the most important theories developed to describe systems of N electrons and K nuclei interacting through the Coulomb potential in the Born-Oppenheimer approximation. After that, we describe how these theories can be adapted to include the interaction of our system with magnetic fields, whether these fields are external or self-generated by the orbital motion of the electrons. Finally, we define the Hartree-Fock ground state problem for Coulomb systems in the presence of self-generated magnetic fields and when spin-field interactions are taken into account. We prove existence of minimizers for neutral or positively charged molecules. Our proof is based on variational techniques applied to the Hartree-Fock energy functional.

  13. Studies on tautomerism in tetrazole: comparison of Hartree Fock and density functional theory quantum chemical methods

    NASA Astrophysics Data System (ADS)

    Mazurek, A. P.; Sadlej-Sosnowska, N.

    2000-11-01

    A comparison of the ab initio quantum chemical methods: Hartree-Fock (HF) and hybrid density functional theory (DFT)/B3LYP for the treatment of tautomeric equilibria both in the gas phase and in the solution is made. The solvent effects were investigated in terms of the self-consistent reaction field (SCRF). Ionization potentials (IP), calculated by DFT/B3LYP, are also compared with those calculated previously within the HF frame.

  14. Comparison of quasi-Hartree-Fock wave-functions for lithium hydride

    NASA Astrophysics Data System (ADS)

    Asthalter, T.; Weyrich, W.; Harker, A. H.; Kunz, A. B.; Orlando, R.; Pisani, C.

    1992-09-01

    We compare the Hartree-Fock wave-functions for crystalline LiH obtained either with a standard Crystalline-Orbital—LCAO procedure or following the Adams-Gilbert-Kunz (AGK) prescription. Total energy, band-structure, reciprocal form factors [ B( r)] are taken as a reference, for checking the quality of the wave-function. The influence of the inclusion of high angular-quantum-number functions in the AGK basis set is explored.

  15. Fractional Electron Loss in Approximate DFT and Hartree-Fock Theory.

    PubMed

    Peach, Michael J G; Teale, Andrew M; Helgaker, Trygve; Tozer, David J

    2015-11-10

    Plots of electronic energy vs electron number, determined using approximate density functional theory (DFT) and Hartree-Fock theory, are typically piecewise convex and piecewise concave, respectively. The curves also commonly exhibit a minimum and maximum, respectively, in the neutral → anion segment, which lead to positive DFT anion HOMO energies and positive Hartree-Fock neutral LUMO energies. These minima/maxima are a consequence of using basis sets that are local to the system, preventing fractional electron loss. Ground-state curves are presented that illustrate the idealized behavior that would occur if the basis set were to be modified to enable fractional electron loss without changing the description in the vicinity of the system. The key feature is that the energy cannot increase when the electron number increases, so the slope cannot be anywhere positive, meaning frontier orbital energies cannot be positive. For the convex (DFT) case, the idealized curve is flat beyond a critical electron number such that any additional fraction of an electron added to the system is unbound. The anion HOMO energy is zero. For the concave (Hartree-Fock) case, the idealized curve is flat up to some critical electron number, beyond which it curves down to the anion energy. A minimum fraction of an electron is required before any binding occurs, but beyond that, the full fraction abruptly binds. The neutral LUMO energy is zero. Approximate DFT and Hartree-Fock results are presented for the F → F(-) segment, and results approaching the idealized behavior are recovered for highly diffuse basis sets. It is noted that if a DFT calculation using a highly diffuse basis set yields a negative LUMO energy then a fraction of an electron must bind and the electron affinity must be positive, irrespective of whether an electron binds experimentally. This is illustrated by calculations on Ne → Ne(-).

  16. Fission Half Lives of Fermium Isotopes Within Skyrme Hartree-Fock Theory

    NASA Astrophysics Data System (ADS)

    Baran, A.; Staszczak, A.; Nazarewicz, W.

    Nuclear fission barriers, mass parameters and spontaneous fission half lives of fermium isotopes calculated in a framework of the Skyrme Hartree-Fock-Bogoliubov model with the SkM* force are discussed. Zero-point energy corrections in the ground state are determined for each nucleus using the Gaussian overlap approximation of the generator coordinate method and in the cranking formalism. Results of spontaneous fission half lives are compared to experimental data.

  17. FISSION HALF LIVES OF FERMIUM ISOTOPES WITHIN SKYRME HARTREE-FOCK-BOGOLIUBOV THEORY

    SciTech Connect

    Baran, A.; Staszczak, Andrzej; Nazarewicz, A.

    2011-01-01

    Nuclear fission barriers, mass parameters and spontaneous fission half lives of fermium isotopes calculated in a framework of the Skyrme Hartree-Fock-Bogoliubov model with the SkM* force are discussed. Zero-point energy corrections in the ground state are determined for each nucleus using the Gaussian overlap approximation of the generator coordinate method and in the cranking formalism. Results of spontaneous fission half lives are compared to experimental data.

  18. On the NP-completeness of the Hartree-Fock method for translationally invariant systems

    SciTech Connect

    Whitfield, James Daniel; Zimborás, Zoltán

    2014-12-21

    The self-consistent field method utilized for solving the Hartree-Fock (HF) problem and the closely related Kohn-Sham problem is typically thought of as one of the cheapest methods available to quantum chemists. This intuition has been developed from the numerous applications of the self-consistent field method to a large variety of molecular systems. However, as characterized by its worst-case behavior, the HF problem is NP-complete. In this work, we map out boundaries of the NP-completeness by investigating restricted instances of HF. We have constructed two new NP-complete variants of the problem. The first is a set of Hamiltonians whose translationally invariant Hartree-Fock solutions are trivial, but whose broken symmetry solutions are NP-complete. Second, we demonstrate how to embed instances of spin glasses into translationally invariant Hartree-Fock instances and provide a numerical example. These findings are the first steps towards understanding in which cases the self-consistent field method is computationally feasible and when it is not.

  19. Hyper Raman spectra calculated in a time-dependent Hartree-Fock method

    NASA Astrophysics Data System (ADS)

    Mohammed, Abdelsalam; Ågren, Hans; Ringholm, Magnus; Thorvaldsen, Andreas J.; Ruud, Kenneth

    2012-10-01

    Hyper Raman scattering (HRS) of the benzonitrile (BN) and 1,3,5-trinitro-1,3,5-triazacyclohexane (RDX) molecules is studied by means of ab initio calculations. The computational procedure employs a recently developed methodology for the analytic calculations of frequency-dependent polarizability gradients of arbitrary order, including perturbation dependent basis sets. The result are compared to normal Raman scattering (NRS) and coherent anti-Stokes Raman scattering (CARS) that previously have been studied using the same technology. It is found that some suppressed or silent modes in CARS and NRS spectra are clearly seen in HRS, and that although under general excitation conditions the HRS intensities are much lower than for CARS and NRS, HRS provides complementary information useful for target identification.

  20. Semidefinite programming applications to Hartree-Fock and linear scaling electronic structure theories

    NASA Astrophysics Data System (ADS)

    Veera Raghavan, Srikant

    Semidefinite programming (SDP) is a relatively modern subfield of convex optimization which has been applied to many problems in the reduced density matrix (RDM) formulation of electronic structure. SDPs deal with minimization (or maximization) of linear objective functions of matrices, subject to linear equality and inequality constraints and positivity constraints on the eigenvalues of the matrices. Energies of chemical systems can be expressed as linear functions of RDMs, whose eigenvalues are electron occupation numbers or their products which are expected to be non-negative. Therefore, it is perhaps not surprising that SDPs fit rather naturally in the RDM framework in electronic structure. This dissertation presents SDP applications to two electronic structure theories. The first part of this dissertation (chaps. 1-3) reformulates Hartree-Fock theory in terms of SDPs in order to obtain upper and lower bounds to global Hartree-Fock energies. The upper and lower bounds on the energies are frequently equal thereby providing a first-ever certificate of global optimality for many Hartree-Fock solutions. The SDP approach provides an alternative to the conventional self-consistent field method of obtaining Hartree-Fock energies and densities with the added benefit of global optimality or a rigorous lower bound. Applications are made to the potential energy curves of (H 4)2, N2, C2, CN, Cr2 and NO2. Energies of the first-row transition elements are also calculated. In chapter 4, the effect of using the Hartree-Fock solutions that we calculate as references for coupled cluster singles doubles calculations is presented for some of the above molecules. The second part of this dissertation (chap. 5) presents a SDP approach to electronic structure methods which scale linearly with system size. Linear scaling electronic structure methods are essential in order to make calculations on large systems feasible. Among these methods the so-called density matrix based ones seek to

  1. Spectroscopic investigations of 2,5-Difluoronitrobenzene using Hartree-Fock (HF) and density functional theory (DFT) calculations

    NASA Astrophysics Data System (ADS)

    Saravanan, S. P.; Sankar, A.; Parimala, K.

    2017-01-01

    The complete structural and vibrational analysis of the 2,5-Difluoronitrobenzene (DNB) was carried out by Hartree-Fock (HF) and density functional theory (DFT) method (B3LYP) with 6-311++G (d,p) basis set. The fundamental vibrations are assigned on the basis of the potential energy distribution (PED) of the vibrational modes calculated with scaled quantum mechanics (SQM) method. Using the time-dependent density functional theory (TD-DFT) method, electronic absorption spectra of the title compound have been predicted and a good agreement with the experimental ones is determined. 13C and 1H NMR spectra were recorded and chemical shifts of the molecule were calculated using the gauge independent atomic orbital (GIAO) method. The hyperconjugative interaction energy (E(2)) and electron densities of donor (i) and acceptor (j) bonds were calculated using natural bond orbital (NBO) analysis. In addition, molecular electrostatic potential (MEP) and atomic charges were calculated using B3LYP/6-311++G (d,p) level of theory. Moreover, thermodynamic properties (heat capacities, entropy, enthalpy and Gibb's free energy) of the title compound at different temperatures were calculated.

  2. Obtaining Hartree-Fock and density functional theory doubly excited states with Car-Parrinello density matrix search

    NASA Astrophysics Data System (ADS)

    Liang, Wenkel; Isborn, Christine M.; Li, Xiaosong

    2009-11-01

    The calculation of doubly excited states is one of the major problems plaguing the modern day excited state workhorse methodology of linear response time dependent Hartree-Fock (TDHF) and density function theory (TDDFT). We have previously shown that the use of a resonantly tuned field within real-time TDHF and TDDFT is able to simultaneously excite both the α and β electrons to achieve the two-electron excited states of minimal basis H2 and HeH+ [C. M. Isborn and X. Li, J. Chem. Phys. 129, 204107 (2008)]. We now extend this method to many electron systems with the use of our Car-Parrinello density matrix search (CP-DMS) with a first-principles fictitious mass method for wave function optimization [X. Li, C. L. Moss, W. Liang, and Y. Feng, J. Chem. Phys. 130, 234115 (2009)]. Real-time TDHF/TDDFT is used during the application of the laser field perturbation, driving the electron density toward the doubly excited state. The CP-DMS method then converges the density to the nearest stationary state. We present these stationary state doubly excited state energies and properties at the HF and DFT levels for H2, HeH+, lithium hydride, ethylene, and butadiene.

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

    PubMed

    Khoromskaia, Venera; Khoromskij, Boris N

    2015-12-21

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

  4. Global solutions of restricted open-shell Hartree-Fock theory from semidefinite programming with applications to strongly correlated quantum systems.

    PubMed

    Veeraraghavan, Srikant; Mazziotti, David A

    2014-03-28

    We present a density matrix approach for computing global solutions of restricted open-shell Hartree-Fock theory, based on semidefinite programming (SDP), that gives upper and lower bounds on the Hartree-Fock energy of quantum systems. While wave function approaches to Hartree-Fock theory yield an upper bound to the Hartree-Fock energy, we derive a semidefinite relaxation of Hartree-Fock theory that yields a rigorous lower bound on the Hartree-Fock energy. We also develop an upper-bound algorithm in which Hartree-Fock theory is cast as a SDP with a nonconvex constraint on the rank of the matrix variable. Equality of the upper- and lower-bound energies guarantees that the computed solution is the globally optimal solution of Hartree-Fock theory. The work extends a previously presented method for closed-shell systems [S. Veeraraghavan and D. A. Mazziotti, Phys. Rev. A 89, 010502-R (2014)]. For strongly correlated systems the SDP approach provides an alternative to the locally optimized Hartree-Fock energies and densities with a certificate of global optimality. Applications are made to the potential energy curves of C2, CN, Cr2, and NO2.

  5. Global solutions of restricted open-shell Hartree-Fock theory from semidefinite programming with applications to strongly correlated quantum systems

    SciTech Connect

    Veeraraghavan, Srikant; Mazziotti, David A.

    2014-03-28

    We present a density matrix approach for computing global solutions of restricted open-shell Hartree-Fock theory, based on semidefinite programming (SDP), that gives upper and lower bounds on the Hartree-Fock energy of quantum systems. While wave function approaches to Hartree-Fock theory yield an upper bound to the Hartree-Fock energy, we derive a semidefinite relaxation of Hartree-Fock theory that yields a rigorous lower bound on the Hartree-Fock energy. We also develop an upper-bound algorithm in which Hartree-Fock theory is cast as a SDP with a nonconvex constraint on the rank of the matrix variable. Equality of the upper- and lower-bound energies guarantees that the computed solution is the globally optimal solution of Hartree-Fock theory. The work extends a previously presented method for closed-shell systems [S. Veeraraghavan and D. A. Mazziotti, Phys. Rev. A 89, 010502–R (2014)]. For strongly correlated systems the SDP approach provides an alternative to the locally optimized Hartree-Fock energies and densities with a certificate of global optimality. Applications are made to the potential energy curves of C{sub 2}, CN, Cr {sub 2}, and NO {sub 2}.

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

    NASA Technical Reports Server (NTRS)

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

    1994-01-01

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

  7. Semiclassical Hartree-Fock theory of a rotating Bose-Einstein condensation

    NASA Astrophysics Data System (ADS)

    Hassan, Ahmed S.; El-Badry, Azza M.; Soliman, Shemi S. M.

    2017-01-01

    In this paper, the thermodynamic behavior of a rotating Bose-Einstein condensation with non-zero interatomic interactions has been theoretically investigated. The analysis relied on a semiclassical Hartree-Fock approximation where an integral is performed over the phase space and function of the grand canonical ensemble is derived. Subsequently, this result is used to derive several thermodynamic quantities including the condensate fraction, critical temperature, entropy and heat capacity. Thereby, we investigated the effect of the rotation rate and interactions parameter on the thermodynamic behavior. The role of finite size is discussed. Our approach can be extended to consider the rotating condensate in optical potential.

  8. Efficient vibrational analysis for unrestricted Hartree-Fock based on the fragment molecular orbital method

    NASA Astrophysics Data System (ADS)

    Nakata, Hiroya; Fedorov, Dmitri G.; Yokojima, Satoshi; Kitaura, Kazuo; Nakamura, Shinichiro

    2014-05-01

    We developed the analytic second derivative of the energy for unrestricted Hartree-Fock based on the fragment molecular orbital (FMO) method. We formulated the second order derivative for the separated dimer approximation in both restricted and unrestricted methods, which accelerated the calculations by the factor of 9 for a radical system containing 704 atoms. The accuracy was evaluated for organic radicals in explicit solvent, in comparison to full ab initio results. The method was applied to study the change of IR absorption spectra in the tyrosine oxidation reaction for a polypeptide representing the active part of the photosynthetic reaction center.

  9. Rotational 2+ states of superheavy elements in the Skyrme-Hartree-Fock-Bogoliubov model

    NASA Astrophysics Data System (ADS)

    Baran, A.; Staszczak, A.

    2013-05-01

    The Skyrme-Hartree-Fock-Bogoliubov calculations of the energies of first 2+ rotational states of deformed superheavy (SH) elements in the region of 108 ⩽ Z ⩽ 126 and 148 ⩽ N ⩽ 180 are reported. The results agree well in the case of fermium isotopes after a proper scaling of the moment of inertia. The scaling factor equals 1.3. The extension of the model to the region of SH elements gives a possibility of better estimation of the Q-values of α-decay, which is a dominant decay mode of SH elements.

  10. Self-consistent Hartree-Fock approach for interacting bosons in optical lattices

    NASA Astrophysics Data System (ADS)

    Lü, Qin-Qin; Patton, Kelly R.; Sheehy, Daniel E.

    2014-12-01

    A theoretical study of interacting bosons in a periodic optical lattice is presented. Instead of the commonly used tight-binding approach (applicable near the Mott-insulating regime of the phase diagram), the present work starts from the exact single-particle states of bosons in a cubic optical lattice, satisfying the Mathieu equation, an approach that can be particularly useful at large boson fillings. The effects of short-range interactions are incorporated using a self-consistent Hartree-Fock approximation, and predictions for experimental observables such as the superfluid transition temperature, condensate fraction, and boson momentum distribution are presented.

  11. Self-consistent Pauli corrections in Brueckner-Hartree-Fock calculations

    NASA Technical Reports Server (NTRS)

    Braley, R. C.; Ford, W. F.

    1972-01-01

    A scheme is introduced which makes it feasible to make completely self-consistent Brueckner-Hartree-Fock (BHF) and renormalized BHF calculations for spherical, closed-shell and axially-symmetric deformed nuclei. The usual requirement or orbital self-consistency has been imposed, as well as self-consistency in the starting energies and occupation probabilities. Previously, only approximate forms were used for the Pauli operator. This approximation is removed and a method for making the necessary Pauli corrections to the reaction matrix during the approach to self-consistency is presented. A discussion of the symmetries which reduce the problem to one of manageable proportions is included.

  12. Search for the Skyrme-Hartree-Fock solutions for chiral rotation in N=75 isotones

    SciTech Connect

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

    2006-05-15

    A search for self-consistent solutions for the chiral rotational bands in the N=75 isotones {sup 130}Cs, {sup 132}La, {sup 134}Pr, and {sup 136}Pm is performed within the Skyrme-Hartree-Fock cranking approach using SKM* and SLy4 parametrizations. The dependence of the solutions on the time-odd contributions in the energy functional is studied. From among the four isotones considered, self-consistent chiral solutions are obtained only in {sup 132}La. The microscopic calculations are compared with the {sup 132}La experimental data and with results of a classical model that contains all the mechanisms underlying the chirality of the collective rotational motion. Strong similarities between the Hartree-Fock and classical model results are found. The suggestion formulated earlier by the authors that the chiral rotation cannot exist below a certain critical frequency is further illustrated and discussed, together with the microscopic origin of a transition from planar to chiral rotation in nuclei. We also formulate the separability rule by which the tilted-axis-cranking solutions can be inferred from three independent principal-axis-cranking solutions corresponding to three different axes of rotation.

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

    NASA Astrophysics Data System (ADS)

    Hu, Jinniu; Toki, Hiroshi; Shen, Hong

    2016-10-01

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

  14. A correction for the Hartree-Fock density of states for jellium without screening

    SciTech Connect

    Blair, Alexander I.; Kroukis, Aristeidis; Gidopoulos, Nikitas I.

    2015-02-28

    We revisit the Hartree-Fock (HF) calculation for the uniform electron gas, or jellium model, whose predictions—divergent derivative of the energy dispersion relation and vanishing density of states (DOS) at the Fermi level—are in qualitative disagreement with experimental evidence for simple metals. Currently, this qualitative failure is attributed to the lack of screening in the HF equations. Employing Slater’s hyper-Hartree-Fock (HHF) equations, derived variationally, to study the ground state and the excited states of jellium, we find that the divergent derivative of the energy dispersion relation and the zero in the DOS are still present, but shifted from the Fermi wavevector and energy of jellium to the boundary between the set of variationally optimised and unoptimised HHF orbitals. The location of this boundary is not fixed, but it can be chosen to lie at arbitrarily high values of wavevector and energy, well clear from the Fermi level of jellium. We conclude that, rather than the lack of screening in the HF equations, the well-known qualitative failure of the ground-state HF approximation is an artifact of its nonlocal exchange operator. Other similar artifacts of the HF nonlocal exchange operator, not associated with the lack of electronic correlation, are known in the literature.

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

    DOE PAGES

    Schuetrumpf, B.; Nazarewicz, W.

    2015-10-21

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

  16. Finding symmetry breaking Hartree-Fock solutions: The case of triplet instability

    NASA Astrophysics Data System (ADS)

    Tóth, Zsuzsanna; Pulay, Peter

    2016-10-01

    Determining the lowest unrestricted Hartree-Fock (UHF) solution is often difficult in even-electron systems. We have developed a deterministic method for locating approximately the UHF minimum using the restricted Hartree-Fock triplet instability matrix. The current method is truncated to fourth order. The minimum energy solution for this model can be determined by solving a small linear system of equations. This solution gives a suitable starting point to determine the exact UHF solution. This should be useful for the black-box determination of active spaces spanned by the fractionally occupied charge natural orbitals of the ground-state UHF wavefunction. The results can be generalized to higher (6th and 8th) degree expansions (odd expansion orders vanish by symmetry), and to other types of instability, including complex instability. The results are illustrated by calculations on ozone, benzene, nitrobenzene, butadiene, hexatriene, octatetraene, dichromium, and nickel porphine. Further examples are given in the supplementary material (ftp://ftp.aip.org/epaps/journ_chem_phys/E-JCPSA6-145-011640).

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

    PubMed Central

    Hu, Jinniu; Toki, Hiroshi; Shen, Hong

    2016-01-01

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

  18. Striped states in quantum Hall effect: Deriving a low-energy theory from Hartree-Fock

    NASA Astrophysics Data System (ADS)

    Lopatnikova, Anna; Simon, Steven H.; Halperin, Bertrand I.; Wen, Xiao-Gang

    2001-10-01

    There is growing experimental and theoretical evidence that very clean two-dimensional electron systems form unidirectional charge density waves (UCDW) or ``striped'' states at low temperatures and at Landau level filling fractions of the form ν=M+x with 4Hartree-Fock approach. We construct the low-energy excitations of the system by making smooth deformations of the stripe edges analogous to the construction of edge state excitations of quantum Hall droplets. These low-energy excitations are described as a coupled Luttinger liquid theory, as discussed previously by MacDonald and Fisher [Phys. Rev. B 61, 5724 (2000)]. Here, we extend that work and explicitly derive all of the parameters of this low energy theory using a Hartree-Fock approach. We also make contact with the equivalent low-energy hydrodynamic approach of Fogler and Vinokur [Phys. Rev. Lett. 84, 5828 (2000)] and similarly derive the parameters of this theory. As examples of the use of these results, we explicitly calculate the low-energy excitation spectrum and study tunneling into the striped state.

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

    SciTech Connect

    Schuetrumpf, B.; Nazarewicz, W.

    2015-10-21

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

  20. A highly optimized code for calculating atomic data at neutron star magnetic field strengths using a doubly self-consistent Hartree-Fock-Roothaan method

    NASA Astrophysics Data System (ADS)

    Schimeczek, C.; Engel, D.; Wunner, G.

    2014-05-01

    Our previously published code for calculating energies and bound-bound transitions of medium- Z elements at neutron star magnetic field strengths [D. Engel, M. Klews, G. Wunner, Comp. Phys. Comm. 180, 3-2-311 (2009)] was based on the adiabatic approximation. It assumes a complete decoupling of the (fast) gyration of the electrons under the action of the magnetic field and the (slow) bound motion along the field under the action of the Coulomb forces. For the single-particle orbitals this implied that each is a product of a Landau state and an (unknown) longitudinal wave function whose B-spline coefficients were determined self-consistently by solving the Hartree-Fock equations for the many-electron problem on a finite-element grid. In the present code we go beyond the adiabatic approximation, by allowing the transverse part of each orbital to be a superposition of Landau states, while assuming that the longitudinal part can be approximated by the same wave function in each Landau level. Inserting this ansatz into the energy variational principle leads to a system of coupled equations in which the B-spline coefficients depend on the weights of the individual Landau states, and vice versa, and which therefore has to be solved in a doubly self-consistent manner. The extended ansatz takes into account the back-reaction of the Coulomb motion of the electrons along the field direction on their motion in the plane perpendicular to the field, an effect which cannot be captured by the adiabatic approximation. The new code allows for the inclusion of up to 8 Landau levels. This reduces the relative error of energy values as compared to the adiabatic approximation results by typically a factor of three (1/3 of the original error) and yields accurate results also in regions of lower neutron star magnetic field strengths where the adiabatic approximation fails. Further improvements in the code are a more sophisticated choice of the initial wave functions, which takes into

  1. Pion tensor force and nuclear binding energy in the relativistic Hartree-Fock formalism

    NASA Astrophysics Data System (ADS)

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

    2014-03-01

    The binding energies of several isotopic families are studied within the relativistic Hartree-Fock approximation with the pseudovector coupling for the πN vertex, to find out a suitable strength for the effective pion tensor force (EPTF). An approximation for determining separately the contributions of the central and tensor forces generated by pion is considered. The results for heavy nuclei indicate that a realistic strength for the EPTF is smaller than a half of that appearing in the OPEP. This conclusion also applies to the results for the single-particle energies. Besides, it has been found that there is a genuine relativistic contribution of the EPTF in nuclear matter which is small but significant.

  2. A comprehensive account of spectral, Hartree Fock, and Density Functional Theory studies of 2-chlorobenzothiazole

    NASA Astrophysics Data System (ADS)

    Daswani, Ujla; Sharma, Pratibha; Kumar, Ashok

    2015-01-01

    Benzothiazole moiety is found to play an important role in medicinal chemistry with a wide range of pharmacological activities. Herein, a simple, benzothiazole derivative viz., 2-chlorobenzothiazole (2CBT) has been analyzed. The spectroscopic properties of the target compound were examined by FT-IR (4400-450 cm-1), FT-Raman (4000-50 cm-1), and NMR techniques. The 1H and 13C NMR spectra were recorded in DMSO. Theoretical calculations were performed by ab initio Hartree Fock and Density Functional Theory (DFT)/B3LYP method using varied basis sets combination. The scaled B3LYP/6-311++G(d,p) results precisely complements with the experimental findings. Electronic absorption spectra along with energy and oscillator strength were obtained by TDDFT method. Atomic charges have also been reported. Total density isosurface and total density mapped with electrostatic potential surface (MESP) has been shown.

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

    NASA Astrophysics Data System (ADS)

    Praharaj, Choudhury

    2016-03-01

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

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

    NASA Technical Reports Server (NTRS)

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

    1990-01-01

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

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

    NASA Technical Reports Server (NTRS)

    Partridge, Harry

    1987-01-01

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

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

    SciTech Connect

    Galitskiy, S. A.; Artemyev, A. N.; Jänkälä, K.; Lagutin, B. M.; Demekhin, Ph. V.

    2015-01-21

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

  7. One-electron properties using a CI method based on multiple Hartree-Fock solutions

    NASA Astrophysics Data System (ADS)

    Malbouisson, L. A. C.; Martins, M. G. R.; Makiuchi, N.

    A multi-reference configuration interaction (CI) method based on multiple Hartree-Fock (HF) solutions is applied to study the permanent dipole moment of the LiH, BH, FH, and H2O systems with the minimal atomic basis. The LiH was also calculated with the double-zeta atomic basis. This method uses several HF solutions as references to expand the state functions. For each one of the systems studied, several HF solutions were obtained in the appropriate point and spin symmetry classes, i.e., 1?+ and 1A1. With each of these solutions is generated a distinct basis of the same full CI space. The set of these bases is a system of generators of the full CI space and the multi-reference HF (MRHF) bases are built mixing configuration state functions (CSFs) originated from distinct HF solutions.

  8. Spiral magnetic phases on the Kondo Lattice Model: A Hartree-Fock approach

    NASA Astrophysics Data System (ADS)

    Costa, N. C.; Lima, J. P.; dos Santos, Raimundo R.

    2017-02-01

    We study the Kondo Lattice Model (KLM) on a square lattice through a Hartree-Fock approximation in which the local spins are treated semi-classically, in the sense that their average values are modulated by a magnetic wavevector Q while they couple with the conduction electrons through fermion operators. In this way, we obtain a ground state phase diagram in which spiral magnetic phases (in which the wavevector depends on the coupling constants and on the density) interpolate between the low-density ferromagnetic phase and the antiferromagnetic phase at half filling; within small regions of the phase diagram commensurate magnetic phases can coexist with Kondo screening. We have also obtained 'Doniach-like' diagrams, showing the effect of temperature on the ground state phases, and established that for some ranges of the model parameters (the exchange coupling and conduction electron density) the magnetic wavevector changes with temperature, either continuously or abruptly (e.g., from spiral to ferromagnetic).

  9. Extension of the Coulomb-Hole-Hartree-Fock theory to molecules

    SciTech Connect

    De Windt, L.; Hofman, D.W.M.; Pisani, L.; Clementi, E. |

    1995-01-15

    The Coulomb-Hole-Hartree-Fock method introduced by E. Clementi in the early 1960s and reparametrized more recently by S. Chakraworty and E, Clementi to compute the correlated electronic energy in atomic systems, is here extended to compute molecules. The new parametrization is obtained empirically by fitting first and second atomic ionization potentials from He to Ca and a few diatomic molecules. The present formulation makes use of either one or more determinants in order to ensure proper dissociation products, following the early proposal of G.C. Lie and E.Clementi in the context of density functional computations for molecular systems. The new formulation is tested against the dissociation energies of a large number of molecules and it is found satisfactory. 22 refs., 5 figs., 7 tabs.

  10. Uncertainties of mass extrapolations in Hartree-Fock-Bogoliubov mass models

    NASA Astrophysics Data System (ADS)

    Goriely, S.; Capote, R.

    2014-05-01

    Some 27 Hartree-Fock-Bogoliubov (HFB) mass models have been developed by the Brussels-Montreal collaboration. Each of these models has been obtained with different model prescriptions or corresponds to a significantly different minimum in the parameter space. The corresponding uncertainties in the mass extrapolation are discussed. In addition, for each of these models, uncertainties associated with local variations of the model parameters exist. Those are estimated for the HFB-24 mass model using a variant of the backward-forward Monte Carlo method to propagate the uncertainties on the masses of exotic nuclei far away from the experimentally known regions. The resulting uncertainties are found to be significantly lower than those arising from the 27 HFB mass models. In addition, the derived correlations between the calculated masses and between model parameters are analyzed.

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

    PubMed

    Guidez, Emilie B; Gordon, Mark S

    2015-03-12

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

  12. Hydrogen Dissociation in Generalized Hartree-Fock Theory: Breaking the diatomic bond

    NASA Astrophysics Data System (ADS)

    Jerke, Jonathan; Masood, Samina; Tymczak, Cj

    Generalized Hartree Fock theory predicts molecular Hydrogen dissociation without correlation. A variational Gaussian-Sinc linear superposition is the basis of 50 calculations with 3-4 significant digits of quality. The spin singlet covalent bond spontaneously breaks into a pair of uncorrelated doublets at atomic separation of 1.22 Angstroms. Quantum spin numbers and energetic comparison with Configuration Interaction theory--correlation--point to a first order phase transition in the molecular Hydrogen bond without correlation. Welch Foundation (Grant J-1675), the ARO (Grant W911Nf-13-1-0162), the Texas Southern University High Performance Computing Center (http:/hpcc.tsu.edu/; Grant PHY-1126251) and NSF-CREST CRCN project (Grant HRD-1137732).

  13. A Valence-Bond/Hartree Fock method to determine the Hubbard transfer integrals in organic conductors

    NASA Astrophysics Data System (ADS)

    Castet, F.; Ducasse, L.; Fritsch, A.

    1998-06-01

    In previous reports [F. Castet, A. Fritsch, L. Ducasse, J. Phys. (Paris) I, 6 (1996) 583; L. Ducasse, A. Fritsch, F. Castet, Synth. Metals 85 (1997) 1627], we presented a new mixed Valence-Bond/Hartree-Fock (VB/HF) method to extract the Extended Hubbard Coulombic parameters in organic conductors. In our approach, calculations (restricted to all valence electrons) are performed on finite size clusters using crystal data and molecular orbitals (MOs) localised on fragments. The optimized MOs depend on the charge of the fragment. The present paper describes the calculation scheme for matrix elements between distinct Valence-Bond configurations involved in charge transfer processes, i.e. the transfer integrals. Calculations were performed for different representative salts with either quasi one-dimensional or two-dimensional character, using different semi-empirical hamiltonians.

  14. Striped states in quantum Hall effect: Deriving a low-energy theory from Hartree-Fock

    NASA Astrophysics Data System (ADS)

    Lopatnikova, Anna

    2002-03-01

    In their influential work, MacDonald and Fisher [PRB 61 5724 2000] suggested a phenomenological coupled Luttinger liquid theory to describe the low energy excitations of the striped quantum Hall state. We extend that work and explicitly derive the Luttinger liquid model using a microscopic Hartree-Fock description, in which the low energy excitations are represented by coherent states localized around the edges of the stripes. Our approach allows us to obtain analytical expressions for all of the parameters of the Luttinger liquid theory and of the equivalent hydrodynamic theory, suggested by Fogler and Vinokur [PRL 84 5828 2000]. As examples of the use of these results, we explicitly calculate the low-energy excitation spectrum and study tunneling into the striped state. Addressing a recent controversy regarding the possible instability of the striped state towards crystallization, we use our coherent-state approach to show the existence of the instability and analytically construct the stripe-crystal ground state.

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

    NASA Astrophysics Data System (ADS)

    Kobus, Jacek

    2013-03-01

    The newest version of the two-dimensional finite difference Hartree-Fock program for atoms and diatomic molecules is presented. This is an updated and extended version of the program published in this journal in 1996. It can be used to obtain reference, Hartree-Fock limit values of total energies and multipole moments for a wide range of diatomic molecules and their ions in order to calibrate existing and develop new basis sets, calculate (hyper)polarizabilities (αzz, βzzz, γzzzz, Az,zz, Bzz,zz) of atoms, homonuclear and heteronuclear diatomic molecules and their ions via the finite field method, perform DFT-type calculations using LDA or B88 exchange functionals and LYP or VWN correlations ones or the self-consistent multiplicative constant method, perform one-particle calculations with (smooth) Coulomb and Krammers-Henneberger potentials and take account of finite nucleus models. The program is easy to install and compile (tarball+configure+make) and can be used to perform calculations within double- or quadruple-precision arithmetic. Catalogue identifier: ADEB_v2_0 Program summary URL:http://cpc.cs.qub.ac.uk/summaries/ADEB_v2_0.html Program obtainable from: CPC Program Library, Queen's University, Belfast, N. Ireland Licensing provisions: GNU General Public License version 2 No. of lines in distributed program, including test data, etc.: 171196 No. of bytes in distributed program, including test data, etc.: 9481802 Distribution format: tar.gz Programming language: Fortran 77, C. Computer: any 32- or 64-bit platform. Operating system: Unix/Linux. RAM: Case dependent, from few MB to many GB Classification: 16.1. Catalogue identifier of previous version: ADEB_v1_0 Journal reference of previous version: Comput. Phys. Comm. 98(1996)346 Does the new version supersede the previous version?: Yes Nature of problem: The program finds virtually exact solutions of the Hartree-Fock and density functional theory type equations for atoms, diatomic molecules and their ions

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

    NASA Astrophysics Data System (ADS)

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

    2015-12-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2014-08-01

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

  18. Gradient of molecular Hartree-Fock-Bogoliubov energy with a linear combination of atomic orbital quasiparticle wave functions

    NASA Astrophysics Data System (ADS)

    Kobayashi, Masato

    2014-02-01

    The analytical gradient for the atomic-orbital-based Hartree-Fock-Bogoliubov (HFB) energy functional, the modified form of which was proposed by Staroverov and Scuseria to account for the static electron correlation [J. Chem. Phys. 117, 11107 (2002)], is derived. Interestingly, the Pulay force for the HFB energy is expressed with the same formula as that for the Hartree-Fock method. The efficiency of the present HFB energy gradient is demonstrated in the geometry optimizations of conjugated and biradical systems. The geometries optimized by using the HFB method with the appropriate factor ζ, which controls the degree of static correlation included, are found to show good agreement with those obtained by using a complete active-space self-consistent field method, although they are significantly dependent on ζ.

  19. Gradient of molecular Hartree-Fock-Bogoliubov energy with a linear combination of atomic orbital quasiparticle wave functions.

    PubMed

    Kobayashi, Masato

    2014-02-28

    The analytical gradient for the atomic-orbital-based Hartree-Fock-Bogoliubov (HFB) energy functional, the modified form of which was proposed by Staroverov and Scuseria to account for the static electron correlation [J. Chem. Phys. 117, 11107 (2002)], is derived. Interestingly, the Pulay force for the HFB energy is expressed with the same formula as that for the Hartree-Fock method. The efficiency of the present HFB energy gradient is demonstrated in the geometry optimizations of conjugated and biradical systems. The geometries optimized by using the HFB method with the appropriate factor ζ, which controls the degree of static correlation included, are found to show good agreement with those obtained by using a complete active-space self-consistent field method, although they are significantly dependent on ζ.

  20. Multiconfiguration Dirac-Hartree-Fock calculations of the electric dipole moment of radium induced by the nuclear Schiff moment

    SciTech Connect

    Bieron, Jacek; Gaigalas, Gediminas; Gaidamauskas, Erikas; Fritzsche, Stephan; Indelicato, Paul; Joensson, Per

    2009-07-15

    The multiconfiguration Dirac-Hartree-Fock theory has been employed to calculate the electric dipole moment of the 7s6d {sup 3}D{sub 2} state of radium induced by the nuclear Schiff moment. The results are dominated by valence and core-valence electron correlation effects. We show that the correlation effects can be evaluated in a converged series of multiconfiguration expansions.

  1. Asymptotic formula far from nucleus for exchange energy density in Hartree-Fock theory of closed-shell atoms

    NASA Astrophysics Data System (ADS)

    March, N. H.

    In Hartree-Fock theory, the exchange energy density can be expressed solely in terms of the first-order density matrix. Far from the nucleus of a closed-shell atom, idem potency of the density matrix yields the exchange energy density as the magnitude of the Coulomb energy e2/r times the electron density ρ. Thus two lengths enter the asymptotic form in contrast to ρ-1/3 alone of local-density theory.

  2. The Hartree-Fock exchange effect on the CO adsorption by the boron nitride nanocage

    NASA Astrophysics Data System (ADS)

    Vessally, E.; Soleimani-Amiri, S.; Hosseinian, A.; Edjlali, L.; Bekhradnia, A.

    2017-03-01

    We studied the effect of Hartree-Fock (HF) exchange percentage of a density functional on the adsorption properties and electronic sensitivity of the B12N12 nanocluster to CO molecule. It was found that by an increase in the %HF, the LUMO level is nearly constant while the HOMO level is strongly stabilized, expanding the HOMO-LUMO gap (Eg). Also, the volume of the all structures decreased and the sensitivity of the B12N12 is slightly increased to CO molecule. For the pristine B12N12 cluster, the B66 and B64 bonds are about 1.43 and 1.49 Å at 10% HF, and 1.23 and 1.26 Å at 100% HF, respectively. The HF exchange between 10-20% may predict an accurate Eg for the B12N12 system. We concluded that functionals with a large %HF such as M06-HF, and M06-2X may significantly overestimate the Eg, and bond strength. We obtained a parabolic relationship between the %HF and the adsorption energy of CO molecule on the B12N12 cluster. Also, an increase in the %HF predicts a larger charge transfer from the CO molecule to the cage.

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

    PubMed

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

    2015-07-05

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

  4. Hartree-Fock many-body perturbation theory for nuclear ground-states

    NASA Astrophysics Data System (ADS)

    Tichai, Alexander; Langhammer, Joachim; Binder, Sven; Roth, Robert

    2016-05-01

    We investigate the order-by-order convergence behavior of many-body perturbation theory (MBPT) as a simple and efficient tool to approximate the ground-state energy of closed-shell nuclei. To address the convergence properties directly, we explore perturbative corrections up to 30th order and highlight the role of the partitioning for convergence. The use of a simple Hartree-Fock solution for the unperturbed basis leads to a convergent MBPT series for soft interactions, in contrast to the divergent MBPT series obtained with a harmonic oscillator basis. For larger model spaces and heavier nuclei, where a direct high-order MBPT calculation is not feasible, we perform third-order calculations and compare to advanced ab initio coupled-cluster results for the same interactions and model spaces. We demonstrate that third-order MBPT provides ground-state energies for nuclei up into the tin isotopic chain in excellent agreement with the best available coupled-cluster calculations at a fraction of the computational cost.

  5. The Thermal Properties of Asymmetric Nuclear Matter within the Extended Brueckner-Hartree-Fock Approach

    NASA Astrophysics Data System (ADS)

    Hassaneen, Khaled; Mansour, Hesham

    2017-02-01

    The single-particle potentials and other properties at absolute zero temperature in isospin asymmetric nuclear matter are investigated in the frame of an extended Brueckner theory. Also thermal quantities are calculated in asymmetric nuclear matter using CD-Bonn potential and the Urbana three-body forces (3BF). Also, the effects of the hole-hole contributions are investigated within the self-consistent Greens function approach. The inclusion of 3BF or the hole-hole contributions improves the predicted saturation property of symmetric nuclear matter within the Brueckner-Hartree-Fock approach and it leads to a significant stiffening of the density dependence of symmetry energy at high densities but the exact saturation point is not reproduced. This is of great importance in astrophysical calculation. A phenomenological term simulating the three-body interaction is introduced to assure the empirical saturation property. The hot properties of asymmetric nuclear matter such as the internal energy and the pressure are analyzed using T2-approximation method at low temperatures.

  6. DBSR_HF: A B-spline Dirac-Hartree-Fock program

    NASA Astrophysics Data System (ADS)

    Zatsarinny, Oleg; Froese Fischer, Charlotte

    2016-05-01

    A B-spline version of a general Dirac-Hartree-Fock program is described. The usual differential equations are replaced by a set of generalized eigenvalue problems of the form (Ha -εa B) Pa = 0, where Ha and B are the Hamiltonian and overlap matrices, respectively, and Pa is the two-component relativistic orbit in the B-spline basis. A default universal grid allows for flexible adjustment to different nuclear models. When two orthogonal orbitals are both varied, the energy must also be stationary with respect to orthonormal transformations. At such a stationary point the off-diagonal Lagrange multipliers may be eliminated through projection operators. The self-consistent field procedure exhibits excellent convergence. Several atomic states can be considered simultaneously, including some configuration-interaction calculations. The program provides several options for the treatment of Breit interaction and QED corrections. The information about atoms up to Z = 104 is stored by the program. Along with a simple interface through command-line arguments, this information allows the user to run the program with minimal initial preparations.

  7. Basis set effects on the Hartree-Fock description of confined many-electron atoms

    NASA Astrophysics Data System (ADS)

    Garza, Jorge; Hernández-Pérez, Julio M.; Ramírez, José-Zeferino; Vargas, Rubicelia

    2012-01-01

    In this work, the basis sets designed by Clementi, Bunge and Thakkar, for atomic systems, have been used to obtain the electronic structure of confined many-electron atoms by using Roothaan's approach in the Hartree-Fock context with a new code written in C, which uses the message-passing interface library. The confinement was imposed as Ludeña suggested to simulate walls with infinity potential. For closed-shell atoms, the Thakkar basis set functions give the best total energies (TE) as a function of the confinement radius, obtaining the following ordering: TE(Thakkar) < TE(Bunge) < TE(Clementi). However, for few open-shell atoms this ordering is not preserved and a trend, for the basis sets, is not observed. Although there are differences between the TE predicted by these basis set functions, the corresponding pressures are similar to each other; it means that changes in the total energy are described almost in the same way by using any of these basis sets. By analysing the total energy as a function of the inverse of the volume we propose an equation of state; for regions of small volumes, this equation predicts that the pressure is inversely proportional to the square of the volume.

  8. Hartree-Fock-Cluster Investigation of Nuclear Quadrupole Interactions in Solid Chalcogens, Selenium and Tellurium.

    NASA Astrophysics Data System (ADS)

    Aryal, M. M.; Maharjan, N. B.; Paudyal, D. D.; Mishra, D. R.; Byahut, S. R.; Scheicher, R. H.; Badu, S. R.; Jeong, J.; Chow, Lee; Das, T. P.

    2008-03-01

    Using the first-principles Hartree-Fock Cluster Procedure, we have studied the electronic structures of pure chain like Selenium and Tellurium, pure ring structured Selenium, Tellurium impurity in chain and ring-structured Selenium and Selenium impurity in chain-structured Tellurium chain. For our investigations in all the systems we have carried out convergence studies with respect to variational basis set sizes,sizes of clusters and electron correlation effects using many-body perturbation theory. Using our calculated electronic field-gradient parameters q in the pure chain systems and employing the experimental quadrupole coupling constants (e^2qQ), the values Q(^77Se)=(0.50±0.04) 10-28 m^2 and Q(^125Te)=-(0.2±0.02) 10-28m^2. Results will also be presented for the asymmetry parameters η for the pure chain systems and the e^2qQ and η for ^77Se in selenium ring. Our calculated values for e^2qQ and η for the impurity systems will also be presented and compared with available experimental data and earlier theoretical results.

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

    SciTech Connect

    Song, Jong-Won; Hirao, Kimihiko

    2015-07-14

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

  10. Coordinate-Space Hartree-Fock-Bogoliubov Solvers for Superfluid Fermi Systems in Large Boxes

    SciTech Connect

    Pei, J. C.; Fann, George I; Harrison, Robert J; Nazarewicz, W.; Hill, Judith C; Galindo, Diego A; Jia, Jun

    2012-01-01

    The self-consistent Hartree-Fock-Bogoliubov problem in large boxes can be solved accurately in the coordinate space with the recently developed solvers HFB-AX (2D) and MADNESS-HFB (3D). This is essential for the description of superfluid Fermi systems with complicated topologies and significant spatial extend, such as fissioning nuclei, weakly-bound nuclei, nuclear matter in the neutron star rust, and ultracold Fermi atoms in elongated traps. The HFB-AX solver based on B-spline techniques uses a hybrid MPI and OpenMP programming model for parallel computation for distributed parallel computation, within a node multi-threaded LAPACK and BLAS libraries are used to further enable parallel calculations of large eigensystems. The MADNESS-HFB solver uses a novel multi-resolution analysis based adaptive pseudo-spectral techniques to enable fully parallel 3D calculations of very large systems. In this work we present benchmark results for HFB-AX and MADNESS-HFB on ultracold trapped fermions.

  11. Self-consistent theory of finite Fermi systems and Skyrme-Hartree-Fock method

    NASA Astrophysics Data System (ADS)

    Saperstein, E. E.; Tolokonnikov, S. V.

    2016-11-01

    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+ 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 surface 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.

  12. General technique for analytical derivatives of post-projected Hartree-Fock

    NASA Astrophysics Data System (ADS)

    Tsuchimochi, Takashi; Ten-no, Seiichiro

    2017-02-01

    In electronic structure theory, the availability of an analytical derivative is one of the desired features for a method to be useful in practical applications, as it allows for geometry optimization as well as computation of molecular properties. With the recent advances in the development of symmetry-projected Hartree-Fock (PHF) methods, we here aim at further extensions by devising the analytic gradients of post-PHF approaches with a special focus on spin-extended (spin-projected) configuration interaction with single and double substitutions (ECISD). Just like standard single-reference methods, the mean-field PHF part does not require the corresponding coupled-perturbed equation to be solved, while the correlation energy term needs the orbital relaxation effect to be accounted for, unless the underlying molecular orbitals are variationally optimized in the presence of the correlation energy. We present a general strategy for post-PHF analytical gradients, which closely parallels that for single-reference methods, yet addressing the major difference between them. The similarity between ECISD and multi-reference CI not only in the energy but also in the optimized geometry is clearly demonstrated by the numerical examples of ozone and cyclobutadiene.

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

    NASA Astrophysics Data System (ADS)

    Uejima, Motoyuki; Ten-no, Seiichiro

    2017-03-01

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

  14. Δ (1232 ) effects in density-dependent relativistic Hartree-Fock theory and neutron stars

    NASA Astrophysics Data System (ADS)

    Zhu, Zhen-Yu; Li, Ang; Hu, Jin-Niu; Sagawa, Hiroyuki

    2016-10-01

    The density-dependent relativistic Hartree-Fock (DDRHF) theory is extended to include Δ isobars for the study of dense nuclear matter and neutron stars. To this end, we solve the Rarita-Schwinger equation for spin-3/2 particle. Both the direct and exchange terms of the Δ isobars' self-energies are evaluated in detail. In comparison with the relativistic mean field theory (Hartree approximation), a weaker parameter dependence is found for DDRHF. An early appearance of Δ isobars is recognized at ρB˜0.28 fm-3, comparable with that of hyperons. Also, we find that the Δ isobars' softening of the equation of state is mainly due to the reduced Fock contributions from the coupling of the isoscalar mesons, while the pion contributions are negligibly small. We finally conclude that with typical parameter sets, neutron stars with Δ isobars in their interiors could be as heavy as the two massive pulsars whose masses are precisely measured, with slightly smaller radii than normal neutron stars.

  15. Ab initio nuclear many-body perturbation calculations in the Hartree-Fock basis

    NASA Astrophysics Data System (ADS)

    Hu, B. S.; Xu, F. R.; Sun, Z. H.; Vary, J. P.; Li, T.

    2016-07-01

    Starting from realistic nuclear forces, the chiral N3LO and JISP16, we have applied many-body perturbation theory (MBPT) to the structure of closed-shell nuclei, 4He and 16O. The two-body N3LO interaction is softened by a similarity renormalization group transformation while JISP16 is adopted without renormalization. The MBPT calculations are performed within the Hartree-Fock (HF) bases. The angular momentum coupled scheme is used, which can reduce the computational task. Corrections up to the third order in energy and up to the second order in radius are evaluated. Higher-order corrections in the HF basis are small relative to the leading-order perturbative result. Using the antisymmetrized Goldstone diagram expansions of the wave function, we directly correct the one-body density for the calculation of the radius, rather than calculate corrections to the occupation probabilities of single-particle orbits as found in other treatments. We compare our results with other methods where available and find good agreement. This supports the conclusion that our methods produce reasonably converged results with these interactions. We also compare our results with experimental data.

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

    SciTech Connect

    Sirjoosingh, Andrew; Pak, Michael V.; Brorsen, Kurt R.; Hammes-Schiffer, Sharon

    2015-06-07

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

  17. Hartree Fock and DFT Study of Models for Amorphous Chalcogenide Alloys

    NASA Astrophysics Data System (ADS)

    Edwards, Arthur; Shedd, Walter; Pugh, Robert

    2001-03-01

    Recently, it has been shown that certain chalcogenide alloys can be switched electrically between polycrystalline and amorphous phases for up to 10^14 cycles and that there is an accompanying large change in conductivity. The most prevalent alloy is a pseudo-binary (GeTe)_2(Sb_2Te_3). While there is some X-Ray data and one band structure calculation on the crystalline phase, there is to date neither theory nor spectroscopy on the amorphous phase. We present a series of Hartree-Fock and DFT molecular orbital studies on models for the amorphous state of the constituent materials and of the alloy. The amorphous models are built on the assumption that normal valence is preserved and that the solid should, in principle, be constructed from repeating the chosen bonding unit. For the pseudo-binary we assume single bonds between Ge and Sb. The surfaces of the clusters are terminated with hydrogen atoms to preserve the normal valence. We have calculated equilibrium geometries using a variety of bases and thes

  18. Many-body computations by stochastic sampling in Hartree-Fock-Bogoliubov space

    NASA Astrophysics Data System (ADS)

    Shi, Hao; Zhang, Shiwei

    2017-01-01

    We describe the computational ingredients for an approach to treat interacting fermion systems with pairing fields, based on path integrals in the space of Hartree-Fock-Bogoliubov (HFB) wave functions. The path integrals can be evaluated by Monte Carlo, via random walks of HFB wave functions whose orbitals evolve stochastically. The approach combines the advantage of HFB theory in paired fermion systems and many-body quantum Monte Carlo techniques. The properties of HFB states, written in the form of either product states or Thouless states, are discussed. The states preserve forms when propagated by generalized one-body operators. They can be stabilized for numerical iteration. Overlaps and one-body Green's functions between two such states can be computed. A constrained-path or phaseless approximation can be applied to the random walks of the HFB states if a sign problem or phase problem is present. The method is illustrated with an exact numerical projection in the Kitaev model, and in the Hubbard model with attractive interaction under an external pairing field.

  19. A simple and efficient dispersion correction to the Hartree-Fock theory.

    PubMed

    Yoshida, Tatsusada; Mashima, Akira; Sasahara, Katsunori; Chuman, Hiroshi

    2014-02-15

    One of the most challenging problems in computational chemistry and in drug discovery is the accurate prediction of the binding energy between a ligand and a protein receptor. It is well known that the binding energy calculated with the Hartree-Fock molecular orbital theory (HF) lacks the dispersion interaction energy that significantly affects the accuracy of the total binding energy of a large molecular system. We propose a simple and efficient dispersion energy correction to the HF theory (HF-Dtq). The performance of HF-Dtq was compared with those of several recently proposed dispersion corrected density functional theory methods (DFT-Ds) as to the binding energies of 68 small non-covalent complexes. The overall performance of HF-Dtq was found to be nearly equivalent to that of more sophisticated B3LYP-D3. HF-Dtq will thus be a useful and powerful method for accurately predicting the binding energy between a ligand and a protein, albeit it is a simple correction procedure based on HF.

  20. Parallel and Low-Order Scaling Implementation of Hartree-Fock Exchange Using Local Density Fitting.

    PubMed

    Köppl, Christoph; Werner, Hans-Joachim

    2016-07-12

    Calculations using modern linear-scaling electron-correlation methods are often much faster than the necessary reference Hartree-Fock (HF) calculations. We report a newly implemented HF program that speeds up the most time-consuming step, namely, the evaluation of the exchange contributions to the Fock matrix. Using localized orbitals and their sparsity, local density fitting (LDF), and atomic orbital domains, we demonstrate that the calculation of the exchange matrix scales asymptotically linearly with molecular size. The remaining parts of the HF calculation scale cubically but become dominant only for very large molecular sizes or with many processing cores. The method is well parallelized, and the speedup scales well with up to about 100 CPU cores on multiple compute nodes. The effect of the local approximations on the accuracy of computed HF and local second-order Møller-Plesset perturbation theory energies is systematically investigated, and default values are established for the parameters that determine the domain sizes. Using these values, calculations for molecules with hundreds of atoms in combination with triple-ζ basis sets can be carried out in less than 1 h, with just a few compute nodes. The method can also be used to speed up density functional theory calculations with hybrid functionals that contain HF exchange.

  1. Hartree-Fock Cluster Study of Electronic Structures and Nuclear Quadrupole Interactions in Solid Nucleobases.

    NASA Astrophysics Data System (ADS)

    Scheicher, R. H.; Dubey, Archana; Badu, S. R.; Saha, H. P.; Pink, R. H.; Nagamine, K.; Torikai, E.; Chow, Lee; Das, T. P.

    2008-03-01

    In recent work [1] we have studied nucleobases attached to a CH3 group to simulate the influence of their binding to the sugar rings and the phosphate groups in DNA and RNA and the effect of this binding on the nuclear quadrupole interactions of ^14N, ^17O and ^2H nuclei. Our results from this work have indicated that for ^17O, the binding to the CH3 group moves our results from the free nucleobases closer to the experimentally observed data [2] in the solid nucleobases. We are now investigating the solid nucleobases by the first --principles Hartree-Fock cluster procedure that we have employed earlier for the halogen molecular solids [3]. Our results for the binding energy of an imidazole molecule in the molecular solid system and the ^14N, ^17O and ^2H nuclear quadrupole interaction parameters will be presented. [1] T.P. Das et al (at this APS meeting), [2] Gang Wu et al, J. Am.Chem. Soc. 124, 1768(2002). [3] M.M. Aryal et al Hyperfine Interactions (to be published).

  2. Generalized Hartree-Fock-Bogoliubov description of the Fröhlich polaron

    NASA Astrophysics Data System (ADS)

    Kain, Ben; Ling, Hong Y.

    2016-07-01

    We adapt the generalized Hartree-Fock-Bogoliubov (HFB) method to an interacting many-phonon system free of impurities. The many-phonon system is obtained from applying the Lee-Low-Pine (LLP) transformation to the Fröhlich model which describes a mobile impurity coupled to noninteracting phonons. We specialize our general HFB description of the Fröhlich polaron to Bose polarons in quasi-one-dimensional cold-atom mixtures. The LLP-transformed many-phonon system distinguishes itself with an artificial phonon-phonon interaction which is very different from the usual two-body interaction. We use the quasi-one-dimensional model, which is free of an ultraviolet divergence that exists in higher dimensions, to better understand how this unique interaction affects polaron states and how the density and pair correlations inherent to the HFB method conspire to create a polaron ground state with an energy in good agreement with and far closer to the prediction from Feynman's variational path integral approach than mean-field theory where HFB correlations are absent.

  3. Transient energy excitation in shortcuts to adiabaticity for the time-dependent harmonic oscillator

    SciTech Connect

    Chen Xi; Muga, J. G.

    2010-11-15

    We study for the time-dependent harmonic oscillator the transient energy excitation in speed-up processes ('shortcuts to adiabaticity') designed to reproduce the initial populations at some predetermined final frequency and time. We provide lower bounds and examples. Implications for the limits imposed to the process times and for the principle of unattainability of the absolute zero, in a single expansion or in quantum refrigerator cycles, are drawn.

  4. Hartree-Fock-Bogoliubov calculation of ground state properties of even-even and odd Mo and Ru isotopes

    NASA Astrophysics Data System (ADS)

    El Bassem, Y.; Oulne, M.

    2017-01-01

    In a previous work (El Bassem and Oulne (2015) [20]), hereafter referred to as paper I, we have investigated the ground-state properties of Nd, Ce and Sm isotopes within Hartree-Fock-Bogoliubov method with SLy5 Skyrme force in which the pairing strength has been generalized with a new proposed formula. However, that formula is more appropriate for the region of Nd. In this work, we have studied the ground-state properties of both even-even and odd Mo and Ru isotopes. For this, we have used Hartree-Fock-Bogoliubov method with SLy4 Skyrme force, and a new formula of the pairing strength which is more accurate for this region of nuclei. The results have been compared with available experimental data, the results of Hartree-Fock-Bogoliubov calculations based on the D1S Gogny effective nucleon-nucleon interaction and predictions of some nuclear models such as Finite Range Droplet Model (FRDM) and Relativistic Mean Field (RMF) theory.

  5. Adiabatic Green's function technique and transient behavior in time-dependent fermion-boson coupled models

    NASA Astrophysics Data System (ADS)

    Oh, Yun-Tak; Higashi, Yoichi; Chan, Ching-Kit; Han, Jung Hoon

    2016-08-01

    The Lang-Firsov Hamiltonian, a well-known solvable model of interacting fermion-boson system with sideband features in the fermion spectral weight, is generalized to have the time-dependent fermion-boson coupling constant. We show how to derive the two-time Green's function for the time-dependent problem in the adiabatic limit, defined as the slow temporal variation of the coupling over the characteristic oscillator period. The idea we use in deriving the Green's function is akin to the use of instantaneous basis states in solving the adiabatic evolution problem in quantum mechanics. With such "adiabatic Green's function" at hand we analyze the transient behavior of the spectral weight as the coupling is gradually tuned to zero. Time-dependent generalization of a related model, the spin-boson Hamiltonian, is analyzed in the same way. In both cases the sidebands arising from the fermion-boson coupling can be seen to gradually lose their spectral weights over time. Connections of our solution to the two-dimensional Dirac electrons coupled to quantized photons are discussed.

  6. Constrained adiabatic trajectory method: a global integrator for explicitly time-dependent Hamiltonians.

    PubMed

    Leclerc, A; Jolicard, G; Viennot, D; Killingbeck, J P

    2012-01-07

    The constrained adiabatic trajectory method (CATM) is reexamined as an integrator for the Schrödinger equation. An initial discussion places the CATM in the context of the different integrators used in the literature for time-independent or explicitly time-dependent Hamiltonians. The emphasis is put on adiabatic processes and within this adiabatic framework the interdependence between the CATM, the wave operator, the Floquet, and the (t, t') theories is presented in detail. Two points are then more particularly analyzed and illustrated by a numerical calculation describing the H(2)(+) ion submitted to a laser pulse. The first point is the ability of the CATM to dilate the Hamiltonian spectrum and thus to make the perturbative treatment of the equations defining the wave function possible, possibly by using a Krylov subspace approach as a complement. The second point is the ability of the CATM to handle extremely complex time-dependencies, such as those which appear when interaction representations are used to integrate the system.

  7. 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.

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

    SciTech Connect

    Cinal, M.; Holas, A.

    2011-06-15

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

  9. Charge transfer excitations from excited state Hartree-Fock subsequent minimization scheme

    SciTech Connect

    Theophilou, Iris; Tassi, M.; Thanos, S.

    2014-04-28

    Photoinduced charge-transfer processes play a key role for novel photovoltaic phenomena and devices. Thus, the development of ab initio methods that allow for an accurate and computationally inexpensive treatment of charge-transfer excitations is a topic that nowadays attracts a lot of scientific attention. In this paper we extend an approach recently introduced for the description of single and double excitations [M. Tassi, I. Theophilou, and S. Thanos, Int. J. Quantum Chem. 113, 690 (2013); M. Tassi, I. Theophilou, and S. Thanos, J. Chem. Phys. 138, 124107 (2013)] to allow for the description of intermolecular charge-transfer excitations. We describe an excitation where an electron is transferred from a donor system to an acceptor one, keeping the excited state orthogonal to the ground state and avoiding variational collapse. These conditions are achieved by decomposing the space spanned by the Hartree-Fock (HF) ground state orbitals into four subspaces: The subspace spanned by the occupied orbitals that are localized in the region of the donor molecule, the corresponding for the acceptor ones and two more subspaces containing the virtual orbitals that are localized in the neighborhood of the donor and the acceptor, respectively. Next, we create a Slater determinant with a hole in the subspace of occupied orbitals of the donor and a particle in the virtual subspace of the acceptor. Subsequently we optimize both the hole and the particle by minimizing the HF energy functional in the corresponding subspaces. Finally, we test our approach by calculating the lowest charge-transfer excitation energies for a set of tetracyanoethylene-hydrocarbon complexes that have been used earlier as a test set for such kind of excitations.

  10. Molecular structure and vibrational assignment of 1-[N-(2-pyridyl) aminomethylidene}-2(1H)-Naphtalenone by density functional theory (DFT) and ab initio Hartree-Fock (HF) calculations

    NASA Astrophysics Data System (ADS)

    Tanak, Hasan; Toy, Mehmet

    2016-01-01

    The molecular geometry and vibrational frequencies of 1-[N-(2-pyridyl)aminomethylidene}-2(1H)-Naphtalenone in the ground state have been calculated by using the Hartree-Fock (HF) and density functional method (B3LYP) with 6-311++G(d,p) basis set. The results of the optimized molecular structure are presented and compared with the experimental X-ray diffraction. The computed vibrational frequencies were used to determine the types of molecular motions associated with each of the experimental bands observed. In addition, calculated results are related to the linear correlation plot of computed data versus experimental geometric parameters and IR data. From the results it was concluded that the B3LYP method is superior to the HF method for the vibrational frequencies. Using the time-dependent density functional theory (TD-DFT) and Hartree-Fock (TD-HF) methods, electronic absorption spectra of the title compound have been predicted and a good agreement with the TD-DFT method and experimental ones is determined.

  11. Molecular structure and vibrational assignment of 1-[N-(2-pyridyl) aminomethylidene}-2(1H)-Naphtalenone by density functional theory (DFT) and ab initio Hartree-Fock (HF) calculations.

    PubMed

    Tanak, Hasan; Toy, Mehmet

    2016-01-05

    The molecular geometry and vibrational frequencies of 1-[N-(2-pyridyl)aminomethylidene}-2(1H)-Naphtalenone in the ground state have been calculated by using the Hartree-Fock (HF) and density functional method (B3LYP) with 6-311++G(d,p) basis set. The results of the optimized molecular structure are presented and compared with the experimental X-ray diffraction. The computed vibrational frequencies were used to determine the types of molecular motions associated with each of the experimental bands observed. In addition, calculated results are related to the linear correlation plot of computed data versus experimental geometric parameters and IR data. From the results it was concluded that the B3LYP method is superior to the HF method for the vibrational frequencies. Using the time-dependent density functional theory (TD-DFT) and Hartree-Fock (TD-HF) methods, electronic absorption spectra of the title compound have been predicted and a good agreement with the TD-DFT method and experimental ones is determined.

  12. Natural orbitals for electrons and nuclei within the diatomic multiconfiguration time-dependent Hartree-Fock (MCTDHF) method

    NASA Astrophysics Data System (ADS)

    Haxton, Daniel; Lawler, Keith; McCurdy, C. William

    2011-05-01

    We discuss natural orbitals in the context of the MCTDHF method for ultrafast dynamics of diatomic molecules with nuclear motion. We show that the natural orbitals for electrons and nuclei, as well as the eigenfunctions other reduced density operators which could be called natural wavefunctions, are a useful tool for visualization, similar in some respects to a diabatic basis. Furthermore through the Schmidt decomposition, these objects provide the most compact representation of a wavefunction with interacting degrees of freedom. The natural wavefunction electronic state basis is an alternative to the (dressed) Born-Oppenheimer representation and we show the Schmidt decompositions of various diatomic MCTDHF wavefunctions in short laser pulses. We compare the Schmidt decomposition of H2+in prolate spheroidal coordinates (which are parametric) against that in nonparametric coordinates (e.g. cartesian or cylindrical) and discuss the implications for the multielectron problem. These bases may provide an advantageous numerical framework and we outline implementations of various schemes for propagating natural orbitals within our diatomic MCTDHF code.

  13. Near Hartree-Fock quality Gaussian type orbital basis sets for the first- and third-row atoms

    NASA Technical Reports Server (NTRS)

    Partridge, Harry

    1989-01-01

    Energy-optimized, near Hartree-Fock (NHF) quality Gaussian type orbital (GTO) basis sets are reported for the second-row (Li to Ne) and fourth-row (K to Kr) atoms. The most accurate basis sets reported for the second row are (18s 13p) sets which are with 4 micro E(H) of the numerical Hartree-Fock (NHF) results. For B to Ne basis sets with more than 15s functions are quadruple zeta in the valence space. For the second-row transition metal atoms the (20s 12p 9d) basis sets are triple zeta in the valence space and are approximately equivalent to Clementi and Roetti's accurate Slater type orbital sets. Supplementing the (20s 12p 9d) basis sets optimized for the lowest state with the 4s(2)3d(n) occupation with a diffuse d function gives self-consistent-field energy separations to the 4s(1)3d(n+1) and 3d(n+2) states which are within 100 micro E(H) of the NHF results. The most accurate basis sets for the transition metal atoms are with 30 micro E(H) of the NHF results. In addition, energy optimized sets are reported for He(3P), Li(2P) and Be(3P).

  14. Restricted Hartree Fock using complex-valued orbitals: A long-known but neglected tool in electronic structure theory

    SciTech Connect

    Small, David W.; Sundstrom, Eric J.; Head-Gordon, Martin

    2015-01-14

    Restricted Hartree Fock using complex-valued orbitals (cRHF) is studied. We introduce an orbital pairing theorem, with which we obtain a concise connection between cRHF and real-valued RHF, and use it to uncover the close relationship between cRHF, unrestricted Hartree Fock, and generalized valence bond perfect pairing. This enables an intuition for cRHF, contrasting with the generally unintuitive nature of complex orbitals. We also describe an efficient computer implementation of cRHF and its corresponding stability analysis. By applying cRHF to the Be + H{sub 2} insertion reaction, a Woodward-Hoffmann violating reaction, and a symmetry-driven conical intersection, we demonstrate in genuine molecular systems that cRHF is capable of removing certain potential energy surface singularities that plague real-valued RHF and related methods. This complements earlier work that showed this capability in a model system. We also describe how cRHF is the preferred RHF method for certain radicaloid systems like singlet oxygen and antiaromatic molecules. For singlet O{sub 2}, we show that standard methods fail even at the equilibrium geometry. An implication of this work is that, regardless of their individual efficacies, cRHF solutions to the HF equations are fairly commonplace.

  15. A New Approach to the Modeling of Local Defects in Crystals: The Reduced Hartree-Fock Case

    NASA Astrophysics Data System (ADS)

    Cancès, Éric; Deleurence, Amélie; Lewin, Mathieu

    2008-07-01

    This article is concerned with the derivation and the mathematical study of a new mean-field model for the description of interacting electrons in crystals with local defects. We work with a reduced Hartree-Fock model, obtained from the usual Hartree-Fock model by neglecting the exchange term. First, we recall the definition of the self-consistent Fermi sea of the perfect crystal, which is obtained as a minimizer of some periodic problem, as was shown by Catto, Le Bris and Lions. We also prove some of its properties which were not mentioned before. Then, we define and study in detail a nonlinear model for the electrons of the crystal in the presence of a defect. We use formal analogies between the Fermi sea of a perturbed crystal and the Dirac sea in Quantum Electrodynamics in the presence of an external electrostatic field. The latter was recently studied by Hainzl, Lewin, Séré and Solovej, based on ideas from Chaix and Iracane. This enables us to define the ground state of the self-consistent Fermi sea in the presence of a defect. We end the paper by proving that our model is in fact the thermodynamic limit of the so-called supercell model, widely used in numerical simulations.

  16. Development of a general time-dependent absorbing potential for the constrained adiabatic trajectory method.

    PubMed

    Leclerc, Arnaud; Jolicard, Georges; Killingbeck, John P

    2011-05-21

    The constrained adiabatic trajectory method (CATM) allows us to compute solutions of the time-dependent Schrödinger equation using the Floquet formalism and Fourier decomposition, using matrix manipulation within a non-orthogonal basis set, provided that suitable constraints can be applied to the initial conditions for the Floquet eigenstate. A general form is derived for the inherent absorbing potential, which can reproduce any dispersed boundary conditions. This new artificial potential acting over an additional time interval transforms any wavefunction into a desired state, with an error involving exponentially decreasing factors. Thus, a CATM propagation can be separated into several steps to limit the size of the required Fourier basis. This approach is illustrated by some calculations for the H(2)(+) molecular ion illuminated by a laser pulse.

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

    NASA Technical Reports Server (NTRS)

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

    1987-01-01

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

  18. Electronic responses of long chains to electrostatic fields: Hartree-Fock vs. density-functional theory: A model study

    SciTech Connect

    Vargas, Jorge; Springborg, Michael; Kirtman, Bernard

    2014-02-07

    The response to an electrostatic field is determined through simple model calculations, within both the restricted Hartree-Fock and density functional theory methods, for long, finite as well as infinite, periodic chains. The permanent dipole moment, μ{sub 0}, the polarizability, α, and the hyperpolarizabilities β and γ, calculated using a finite-field approach, are extensively analyzed. Our simple model allows for treatment of large systems and for separation of the properties into atomic and unit-cell contributions. That part of the response properties attributable to the terminations of the finite system change into delocalized current contributions in the corresponding infinite periodic system. Special emphasis is placed on analyzing the reasons behind the dramatic overestimation of the response properties found with density functional theory methods presently in common use.

  19. 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.

  20. Electronic correlation without double counting via a combination of spin projected Hartree-Fock and density functional theories

    SciTech Connect

    Garza, Alejandro J.; Jiménez-Hoyos, Carlos A.; Scuseria, Gustavo E.

    2014-06-28

    Several schemes to avoid the double counting of correlations in methods that merge multireference wavefunctions with density functional theory (DFT) are studied and here adapted to a combination of spin-projected Hartree-Fock (SUHF) and DFT. The advantages and limitations of the new method, denoted SUHF+f{sub c}DFT, are explored through calculations on benchmark sets in which the accounting of correlations is challenging for pure SUHF or DFT. It is shown that SUHF+f{sub c}DFT can greatly improve the description of certain molecular properties (e.g., singlet-triplet energy gaps) which are not improved by simple addition of DFT dynamical correlation to SUHF. However, SUHF+f{sub c}DFT is also shown to have difficulties dissociating certain types of bonds and describing highly charged ions with static correlation. Possible improvements to the current SUHF+f{sub c}DFT scheme are discussed in light of these results.

  1. Ab initio projected-unrestricted Hartree-Fock calculation of some potential energy curves for carbonyl fluoride

    NASA Technical Reports Server (NTRS)

    Brewer, D. A.; Schug, J. C.; Phillips, D. H.

    1980-01-01

    Some potential energy curves for CF2O were calculated using projected-unrestricted Hartree-Fock (PUHF) theory. The calculations employed a contracted (4s 3p) Gaussian-type atomic orbital basis set. Bound states were found for the X-tilde 1A1 and 1,3A2 states while the 1,3B1 and 1,3B2 states were repulsive in the valence representation. The merits of the PUHF treatment for excited states are discussed. The results are discussed in terms of available experimental information and previous calculations with particular emphasis on the question of the photolysis channels open in the solar spectral region.

  2. Linear-scaling calculation of Hartree-Fock exchange energy with non-orthogonal generalised Wannier functions

    NASA Astrophysics Data System (ADS)

    Dziedzic, J.; Hill, Q.; Skylaris, C.-K.

    2013-12-01

    We present a method for the calculation of four-centre two-electron repulsion integrals in terms of localised non-orthogonal generalised Wannier functions (NGWFs). Our method has been implemented in the ONETEP program and is used to compute the Hartree-Fock exchange energy component of Hartree-Fock and Density Functional Theory (DFT) calculations with hybrid exchange-correlation functionals. As the NGWFs are optimised in situ in terms of a systematically improvable basis set which is equivalent to plane waves, it is possible to achieve large basis set accuracy in routine calculations. The spatial localisation of the NGWFs allows us to exploit the exponential decay of the density matrix in systems with a band gap in order to compute the exchange energy with a computational effort that increases linearly with the number of atoms. We describe the implementation of this approach in the ONETEP program for linear-scaling first principles quantum mechanical calculations. We present extensive numerical validation of all the steps in our method. Furthermore, we find excellent agreement in energies and structures for a wide variety of molecules when comparing with other codes. We use our method to perform calculations with the B3LYP exchange-correlation functional for models of myoglobin systems bound with O2 and CO ligands and confirm that the same qualitative behaviour is obtained as when the same myoglobin models are studied with the DFT+U approach which is also available in ONETEP. Finally, we confirm the linear-scaling capability of our method by performing calculations on polyethylene and polyacetylene chains of increasing length.

  3. Prediction of electron paramagnetic resonance g values using coupled perturbed Hartree-Fock and Kohn-Sham theory

    NASA Astrophysics Data System (ADS)

    Neese, Frank

    2001-12-01

    A method for calculating the EPR g-tensor based on coupled perturbed Hartree-Fock (HF) and density functional theory (DFT) is presented. The one-electron molecular orbitals of a spin- unrestricted Slater determinant are calculated up to first order in the applied magnetic field. The g-tensor is evaluated as a mixed second derivative property with respect to the applied field and the electron magnetic moment. Thus, spin-polarization and spin-orbit coupling are simultaneously included in the calculation. The treatment focuses on orbitally nondegenerate molecules but is valid for a general ground state spin S and, for the first time, it is possible to include hybrid density functionals in the treatment. The relativistic mass and diamagnetic gauge corrections are also considered. An implementation of the theory is described. Extensive numerical calculations for a series of small molecules are reported with the Hartree-Fock (HF) method, the local density approximation (LSD), the generalized gradient approximation (GGA) and hybrid density functionals such as B3LYP and PBE0 and large Gaussian basis sets. Detailed comparison with available ab initio and DFT calculations are made. The results indicate that the hybrid functionals offer little or no improvement over the GGA functionals for small radicals made of light atoms. For transition metal complexes the situation is different. The hybrid functionals give, on average, better results than the GGA functionals but significant disagreement between theoretical and experimental g-shifts still remain. Overall, the results indicate that the present method is among the most accurate so far developed models for the prediction of g values.

  4. A highly optimized code for calculating atomic data at neutron star magnetic field strengths using a doubly self-consistent Hartree-Fock-Roothaan method

    NASA Astrophysics Data System (ADS)

    Schimeczek, C.; Engel, D.; Wunner, G.

    2012-07-01

    Our previously published code for calculating energies and bound-bound transitions of medium-Z elements at neutron star magnetic field strengths [D. Engel, M. Klews, G. Wunner, Comput. Phys. Comm. 180 (2009) 302-311] was based on the adiabatic approximation. It assumes a complete decoupling of the (fast) gyration of the electrons under the action of the magnetic field and the (slow) bound motion along the field under the action of the Coulomb forces. For the single-particle orbitals this implied that each is a product of a Landau state and an (unknown) longitudinal wave function whose B-spline coefficients were determined self-consistently by solving the Hartree-Fock equations for the many-electron problem on a finite-element grid. In the present code we go beyond the adiabatic approximation, by allowing the transverse part of each orbital to be a superposition of Landau states, while assuming that the longitudinal part can be approximated by the same wave function in each Landau level. Inserting this ansatz into the energy variational principle leads to a system of coupled equations in which the B-spline coefficients depend on the weights of the individual Landau states, and vice versa, and which therefore has to be solved in a doubly self-consistent manner. The extended ansatz takes into account the back-reaction of the Coulomb motion of the electrons along the field direction on their motion in the plane perpendicular to the field, an effect which cannot be captured by the adiabatic approximation. The new code allows for the inclusion of up to 8 Landau levels. This reduces the relative error of energy values as compared to the adiabatic approximation results by typically a factor of three (1/3 of the original error), and yields accurate results also in regions of lower neutron star magnetic field strengths where the adiabatic approximation fails. Further improvements in the code are a more sophisticated choice of the initial wave functions, which takes into

  5. Global analysis of isospin dependent microscopic nucleon-nucleus optical potentials in a Dirac-Brueckner-Hartree-Fock approach

    NASA Astrophysics Data System (ADS)

    Xu, Ruirui; Ma, Zhongyu; Zhang, Yue; Tian, Yuan; van Dalen, E. N. E.; Müther, H.

    2016-09-01

    Background: For the study of exotic nuclei it is important to have an optical model potential that is reliable not only for stable nuclei but can also be extrapolated to nuclear systems with exotic numbers of protons and neutrons. An efficient way to obtain such a potential is to develop a microscopic optical potential (MOP) based on a fundamental theory with a minimal number of free parameters, which are adjusted to describe stable nuclei all over the nuclide chart. Purpose: The choice adopted in the present work is to develop the MOP within a relativistic scheme which provides a natural and consistent relation between the spin-orbit part and the central part of the potential. The Dirac-Brueckner-Hartree-Fock (DBHF) approach provides such a microscopic relativistic scheme, which is based on a realistic nucleon-nucleon interaction and reproduces the saturation properties of symmetric nuclear matter without any adjustable parameter. Its solution using the projection technique within the subtracted T -matrix representation provides a reliable extension to asymmetric nuclear matter, which is important to describe the features of isospin asymmetric nuclei. The present work performs a global analysis of the isospin dependent nucleon-nucleus MOP based on the DBHF calculation in symmetric and asymmetric nuclear matter. Methods: The DBHF approach is used to evaluate the relativistic structure of the nucleon self-energies in nuclear matter at various densities and asymmetries. The Schrödinger equivalent potentials of finite nuclei are derived from these Dirac components by a local density approximation (LDA). The density distributions of finite nuclei are taken from the Hartree-Fock-Bogoliubov approach with Gogny D1S force. An improved LDA approach (ILDA) is employed to get a better prediction of the scattering observables. A χ2 assessment system based on the global simulated annealing algorithm is developed to optimize the very few free components in this study. Results

  6. A simple way to test for collinearity in spin symmetry broken wave functions: General theory and application to generalized Hartree Fock

    SciTech Connect

    Small, David W.; Sundstrom, Eric J.; Head-Gordon, Martin

    2015-03-07

    We introduce a necessary and sufficient condition for an arbitrary wavefunction to be collinear, i.e., its spin is quantized along some axis. It may be used to obtain a cheap and simple computational procedure to test for collinearity in electronic structure theory calculations. We adapt the procedure for Generalized Hartree Fock (GHF), and use it to study two dissociation pathways in CO{sub 2}. For these dissociation processes, the GHF wave functions transform from low-spin Unrestricted Hartree Fock (UHF) type states to noncollinear GHF states and on to high-spin UHF type states, phenomena that are succinctly illustrated by the constituents of the collinearity test. This complements earlier GHF work on this molecule.

  7. Hartree-Fock-Roothaan energies and expectation values for the neutral atoms He to Uuo: The B-spline expansion method

    SciTech Connect

    Saito, Shiro L.

    2009-11-15

    The ground state energies and expectation values of atoms are given by Hartree-Fock-Roothaan calculations with one B-spline set. For the neutral atoms He to Uuo, the total energies, kinetic energies, potential energies, and virial ratios are tabulated. Our total energies are in excellent agreement with the highly accurate 10-digit numerical Hartree-Fock energies given by Koga and Thakkar [T. Koga, A.J. Thakkar, J. Phys. B 29 (1996) 2973]. The virial ratios are in complete agreement to within 12-digits of the exact value -2. Orbital energies, electron densities at the nucleus, electron-nucleus cusp ratios, and radial expectation values (n = 2, 1, -1, -2, -3) are also given.

  8. Modeling CO and N2 adsorption at Cr surface species of Phillips catalyst by hybrid density functionals: effect of Hartree-Fock exchange percentage.

    PubMed

    Damin, Alessandro; Vitillo, Jenny G; Ricchiardi, Gabriele; Bordiga, Silvia; Lamberti, Carlo; Groppo, Elena; Zecchina, Adriano

    2009-12-31

    In this article, we present a computational study of the structure and vibrational properties of the species formed by the interaction between Cr sites of Phillips catalyst and probe molecules (CO, N(2)). The vibrational properties of these surface species, intensively investigated in the past, form a very rich and ideal set of experimental data to test computational approaches. By adopting the X(4)Si(2)O(3)Cr (X = H, OH, F) cluster as a simplified model of the ([triple bond]SiO)(2)Cr(II) species present at the surface of the real catalyst, we found that the B3LYP hybrid functional (containing 20% of Hartree-Fock exchange), when applied to this model, is unable to reproduce with reasonable accuracy the currently available experimental data (principally coming from IR spectroscopy). Better agreement is obtained when the percentage of Hartree-Fock exchange is increased (up to 35-40%).

  9. Modeling CO and N2 Adsorption at Cr Surface Species of Phillips Catalyst by Hybrid Density Functionals: Effect of Hartree-Fock Exchange Percentage

    NASA Astrophysics Data System (ADS)

    Damin, Alessandro; Vitillo, Jenny G.; Ricchiardi, Gabriele; Bordiga, Silvia; Lamberti, Carlo; Groppo, Elena; Zecchina, Adriano

    2009-07-01

    In this article, we present a computational study of the structure and vibrational properties of the species formed by the interaction between Cr sites of Phillips catalyst and probe molecules (CO, N2). The vibrational properties of these surface species, intensively investigated in the past, form a very rich and ideal set of experimental data to test computational approaches. By adopting the X4Si2O3Cr (X = H, OH, F) cluster as a simplified model of the (≡SiO)2Cr(II) species present at the surface of the real catalyst, we found that the B3LYP hybrid functional (containing 20% of Hartree-Fock exchange), when applied to this model, is unable to reproduce with reasonable accuracy the currently available experimental data (principally coming from IR spectroscopy). Better agreement is obtained when the percentage of Hartree-Fock exchange is increased (up to 35-40%).

  10. Multiferroic nature of intrinsic point defects in BiFeO3: A hybrid Hartree-Fock density functional study

    NASA Astrophysics Data System (ADS)

    Shimada, Takahiro; Matsui, Takahiro; Xu, Tao; Arisue, Kou; Zhang, Yajun; Wang, Jie; Kitamura, Takayuki

    2016-05-01

    To achieve a fundamental understanding of the multiferroic behavior and electronic properties of intrinsic vacancies in BiFe O3 , here we performed first-principles calculations based on hybrid Hartree-Fock density functional theories, which can accurately describe defect electronic structures. Oxygen vacancies, which behave as deep donors with high concentrations under oxygen-poor conditions, reduce the magnetic moments at neighboring Fe ions in the neutral state, while charged oxygen vacancies induce additional ferroelectric polarizations. Cation vacancies, on the other hand, are likely to form under oxygen-rich conditions and result in multiferroic properties distinct from those induced by oxygen vacancies. Bi vacancies act as triple-shallow acceptors and strongly suppress spontaneous polarization regardless of charge states, while Fe vacancies locally interfere with both electric and spin polarization and are thus regarded as multiferroic singular points in BiFe O3 . A rich variety of the multiferroic behavior of vacancies can be systematically understood from the localized/delocalized features of defect states, and the different formation conditions for vacancies provide a strategy to tailor the multiferroic properties of BiFe O3 through control of the concentration and charge states of vacancies.

  11. A comparison of Hartree-Fock and exact diagonalization solutions for a model two-electron system.

    PubMed

    Thompson, David C; Alavi, Ali

    2005-03-22

    We compare the restricted (RHF) and unrestricted (UHF) Hartree-Fock solutions with the exact configuration interaction (CI) solutions for the model problem of two interacting electrons confined within an infinite spherical potential of radius R. An investigation of the ground state energy, electron density, and a population analysis of the wave functions reveals that the UHF solution compares favorably with the CI one in both the small and large R limits. The Coulson-Fischer transition (the point at which the RHF and UHF solutions are no longer degenerate) occurs at an r(s) identical with R/2(1/3) approximately 6 a.u., close to the crossover r(s) where the exact CI density acquires a minimum at the sphere center; this behavior captures the onset of Wigner molecule formation. In this regime, however, the HF densities and energies are not quantitatively accurate when compared to the CI ones. This failure is further quantified by computing Ec/E to determine the ability of each method at capturing the exact correlation energy; we conclude that the UHF solutions can be reasonably accurate at both high and low densities, but not at intermediate r(s).

  12. Configuration interaction singles based on the real-space numerical grid method: Kohn-Sham versus Hartree-Fock orbitals.

    PubMed

    Kim, Jaewook; Hong, Kwangwoo; Choi, Sunghwan; Hwang, Sang-Yeon; Youn Kim, Woo

    2015-12-21

    We developed a program code of configuration interaction singles (CIS) based on a numerical grid method. We used Kohn-Sham (KS) as well as Hartree-Fock (HF) orbitals as a reference configuration and Lagrange-sinc functions as a basis set. Our calculations show that KS-CIS is more cost-effective and more accurate than HF-CIS. The former is due to the fact that the non-local HF exchange potential greatly reduces the sparsity of the Hamiltonian matrix in grid-based methods. The latter is because the energy gaps between KS occupied and virtual orbitals are already closer to vertical excitation energies and thus KS-CIS needs small corrections, whereas HF results in much larger energy gaps and more diffuse virtual orbitals. KS-CIS using the Lagrange-sinc basis set also shows a better or a similar accuracy to smaller orbital space compared to the standard HF-CIS using Gaussian basis sets. In particular, KS orbitals from an exact exchange potential by the Krieger-Li-Iafrate approximation lead to more accurate excitation energies than those from conventional (semi-) local exchange-correlation potentials.

  13. Approaching the Hartree-Fock Limit through the Complementary Auxiliary Basis Set Singles Correction and Auxiliary Basis Sets.

    PubMed

    Shaw, Robert A; Hill, J Grant

    2017-03-08

    Auxiliary basis sets for use in the resolution of the identity (RI) approximation in explicitly correlated methods are presented for the elements H-Ar. These extend the cc-pVnZ-F12/OptRI (n = D-Q) auxiliary basis sets of Peterson and co-workers by the addition of a small number of s- and p-functions, optimized so as to yield the greatest complementary auxiliary basis set (CABS) singles correction to the Hartree-Fock energy. The new sets, denoted OptRI+, also lead to a reduction in errors due to the RI approximation and hence an improvement in correlation energies. The atomization energies and heats of formation for a test set of small molecules, and spectroscopic constants for 27 diatomics, calculated at the CCSD(T)-F12b level, are shown to have improved error distributions for the new auxiliary basis sets with negligible additional effort. The OptRI+ sets retain all of the desirable properties of the original OptRI, including the production of smooth potential energy surfaces, while maintaining a compact nature.

  14. Noncovalent attachment of psoralen derivatives with DNA: Hartree-Fock and density functional studies on the probes

    NASA Astrophysics Data System (ADS)

    El-Gogary, Tarek M.; El-Gendy, Eman M.

    2003-09-01

    Two psoralen derivatives (probes) were prepared. Their geometries were optimized at the Hartree-Fock (HF) and Density Functional (B3LYP) levels employing 6-31G** and cc-pVDZ basis sets. Their interaction with DNA was investigated using spectrophotometric and computational techniques. Both of them have shown strong binding to calf thymus DNA. The red-shift and hypochromism that detected in the spectrum were taken as an evidence for the strong interaction between these probes and DNA. The spectrophotometric DNA titration data were treated by two different methodologies to calculate the intercalation affinity. Half-reciprocal plots gave binding constants of 5.5065×10 4 and 6.4727×10 4 for 8-butoxypsoralen (8-BOP) and 8-hexoxypsoralen (8-HOP), respectively. Schatchard plots gave a comparable intercalation binding constants and also the surface binding constants along with the number of intercalated probe molecules per base pair. The interaction between these probes and DNA were studied theoretically. The energy of interaction was computed using molecular mechanics method. Strength of interaction of these probes with different types of DNA was computed and compared. Calculated energies of interaction were compared with the observed intercalation affinities. HOMO and LUMO energies were computed and used to account for the strength of interaction.

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

    SciTech Connect

    Yost, Shane R.; Kowalczyk, Tim; Van Voorhis, Troy

    2013-11-07

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

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

    NASA Astrophysics Data System (ADS)

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

    2015-11-01

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

  17. Multiconfigurational Hartree-Fock close-coupling ansatz: Application to the argon photoionization cross section and delays

    NASA Astrophysics Data System (ADS)

    Carette, T.; Dahlström, J. M.; Argenti, L.; Lindroth, E.

    2013-02-01

    We present a robust, ab initio method for addressing atom-light interactions and apply it to photoionization of argon. We use a close-coupling ansatz constructed on a multiconfigurational Hartree-Fock description of localized states and B-spline expansions of the electron radial wave functions. In this implementation, the general many-electron problem can be tackled thanks to the use of the atsp2k libraries [C. Froese Fischer , Comput. Phys. Commun.CPHCBZ0010-465510.1016/j.cpc.2007.01.006 176, 559 (2007)]. In the present contribution, we combine this method with exterior complex scaling, thereby allowing for the computation of the complex partial amplitudes that encode the whole dynamics of the photoionization process. The method is validated on the 3s3p6np series of resonances converging to the 3s extraction. Then, it is used for computing the energy dependent differential atomic delay between 3p and 3s photoemission, and agreement is found with the measurements of Guénot [Phys. Rev. APLRAAN1050-294710.1103/PhysRevA.85.053424 85, 053424 (2012)]. The effect of the presence of resonances in the one-photon spectrum on photoionization delay measurements is studied.

  18. Nuclear-electronic orbital reduced explicitly correlated Hartree-Fock approach: Restricted basis sets and open-shell systems

    SciTech Connect

    Brorsen, Kurt R.; Sirjoosingh, Andrew; Pak, Michael V.; Hammes-Schiffer, Sharon

    2015-06-07

    The nuclear electronic orbital (NEO) reduced explicitly correlated Hartree-Fock (RXCHF) approach couples select electronic orbitals to the nuclear orbital via Gaussian-type geminal functions. This approach is extended to enable the use of a restricted basis set for the explicitly correlated electronic orbitals and an open-shell treatment for the other electronic orbitals. The working equations are derived and the implementation is discussed for both extensions. The RXCHF method with a restricted basis set is applied to HCN and FHF{sup −} and is shown to agree quantitatively with results from RXCHF calculations with a full basis set. The number of many-particle integrals that must be calculated for these two molecules is reduced by over an order of magnitude with essentially no loss in accuracy, and the reduction factor will increase substantially for larger systems. Typically, the computational cost of RXCHF calculations with restricted basis sets will scale in terms of the number of basis functions centered on the quantum nucleus and the covalently bonded neighbor(s). In addition, the RXCHF method with an odd number of electrons that are not explicitly correlated to the nuclear orbital is implemented using a restricted open-shell formalism for these electrons. This method is applied to HCN{sup +}, and the nuclear densities are in qualitative agreement with grid-based calculations. Future work will focus on the significance of nonadiabatic effects in molecular systems and the further enhancement of the NEO-RXCHF approach to accurately describe such effects.

  19. Nuclear-electronic orbital reduced explicitly correlated Hartree-Fock approach: Restricted basis sets and open-shell systems

    NASA Astrophysics Data System (ADS)

    Brorsen, Kurt R.; Sirjoosingh, Andrew; Pak, Michael V.; Hammes-Schiffer, Sharon

    2015-06-01

    The nuclear electronic orbital (NEO) reduced explicitly correlated Hartree-Fock (RXCHF) approach couples select electronic orbitals to the nuclear orbital via Gaussian-type geminal functions. This approach is extended to enable the use of a restricted basis set for the explicitly correlated electronic orbitals and an open-shell treatment for the other electronic orbitals. The working equations are derived and the implementation is discussed for both extensions. The RXCHF method with a restricted basis set is applied to HCN and FHF- and is shown to agree quantitatively with results from RXCHF calculations with a full basis set. The number of many-particle integrals that must be calculated for these two molecules is reduced by over an order of magnitude with essentially no loss in accuracy, and the reduction factor will increase substantially for larger systems. Typically, the computational cost of RXCHF calculations with restricted basis sets will scale in terms of the number of basis functions centered on the quantum nucleus and the covalently bonded neighbor(s). In addition, the RXCHF method with an odd number of electrons that are not explicitly correlated to the nuclear orbital is implemented using a restricted open-shell formalism for these electrons. This method is applied to HCN+, and the nuclear densities are in qualitative agreement with grid-based calculations. Future work will focus on the significance of nonadiabatic effects in molecular systems and the further enhancement of the NEO-RXCHF approach to accurately describe such effects.

  20. Comparison of density functional approximations and the finite-temperature Hartree-Fock approximation in warm dense lithium.

    PubMed

    Karasiev, Valentin V; Sjostrom, Travis; Trickey, S B

    2012-11-01

    We compare the behavior of the finite-temperature Hartree-Fock model with that of thermal density functional theory using both ground-state and temperature-dependent approximate exchange functionals. The test system is bcc Li in the temperature-density regime of warm dense matter (WDM). In this exchange-only case, there are significant qualitative differences in results from the three approaches. Those differences may be important for Born-Oppenheimer molecular dynamics studies of WDM with ground-state approximate density functionals and thermal occupancies. Such calculations require reliable regularized potentials over a demanding range of temperatures and densities. By comparison of pseudopotential and all-electron results at T=0 K for small Li clusters of local bcc symmetry and bond lengths equivalent to high density bulk Li, we determine the density ranges for which standard projector augmented wave (PAW) and norm-conserving pseudopotentials are reliable. Then, we construct and use all-electron PAW data sets with a small cutoff radius that are valid for lithium densities up to at least 80 g/cm{3}.

  1. Path integral density matrix dynamics: A method for calculating time-dependent properties in thermal adiabatic and non-adiabatic systems

    NASA Astrophysics Data System (ADS)

    Habershon, Scott

    2013-09-01

    We introduce a new approach for calculating quantum time-correlation functions and time-dependent expectation values in many-body thermal systems; both electronically adiabatic and non-adiabatic cases can be treated. Our approach uses a path integral simulation to sample an initial thermal density matrix; subsequent evolution of this density matrix is equivalent to solution of the time-dependent Schrödinger equation, which we perform using a linear expansion of Gaussian wavepacket basis functions which evolve according to simple classical-like trajectories. Overall, this methodology represents a formally exact approach for calculating time-dependent quantum properties; by introducing approximations into both the imaginary-time and real-time propagations, this approach can be adapted for complex many-particle systems interacting through arbitrary potentials. We demonstrate this method for the spin Boson model, where we find good agreement with numerically exact calculations. We also discuss future directions of improvement for our approach with a view to improving accuracy and efficiency.

  2. Calculation of the zero-field splitting tensor on the basis of hybrid density functional and Hartree-Fock theory.

    PubMed

    Neese, Frank

    2007-10-28

    The zero-field splitting (ZFS) (expressed in terms of the D tensor) is the leading spin-Hamiltonian parameter for systems with a ground state spin S>12. To first order in perturbation theory, the ZFS arises from the direct spin-spin dipole-dipole interaction. To second order, contributions arise from spin-orbit coupling (SOC). The latter contributions are difficult to treat since the SOC mixes states of different multiplicities. This is an aspect of dominant importance for the correct prediction of the D tensor. In this work, the theory of the D tensor is discussed from the point of view of analytic derivative theory. Starting from a general earlier perturbation treatment [F. Neese and E. I. Soloman, Inorg. Chem. 37, 6568 (1998)], straightforward response equations are derived that are readily transferred to the self-consistent field (SCF) Hartree-Fock (HF) or density functional theory (DFT) framework. The main additional effort in such calculations arises from the solution of nine sets of nonstandard coupled-perturbed SCF equations. These equations have been implemented together with the spin-orbit mean-field representation of the SOC operator and a mean-field treatment of the direct spin-spin interaction into the ORCA electronic structure program. A series of test calculations on diatomic molecules with accurately known zero-field splittings shows that the new approach corrects most of the shortcomings of previous DFT based methods and, on average, leads to predictions within 10% of the experimental values. The slope of the correlation line is essentially unity for the B3LYP and BLYP functionals compared to approximately 0.5 in previous treatments.

  3. Reduced explicitly correlated Hartree-Fock approach within the nuclear-electronic orbital framework: applications to positronic molecular systems.

    PubMed

    Sirjoosingh, Andrew; Pak, Michael V; Swalina, Chet; Hammes-Schiffer, Sharon

    2013-07-21

    In the application of the nuclear-electronic orbital (NEO) method to positronic systems, all electrons and the positron are treated quantum mechanically on the same level. Explicit electron-positron correlation can be included using Gaussian-type geminal functions within the variational self-consistent-field procedure. In this paper, we apply the recently developed reduced explicitly correlated Hartree-Fock (RXCHF) approach to positronic molecular systems. In the application of RXCHF to positronic systems, only a single electronic orbital is explicitly correlated to the positronic orbital. We apply NEO-RXCHF to three systems: positron-lithium, lithium positride, and positron-lithium hydride. For all three of these systems, the RXCHF approach provides accurate two-photon annihilation rates, average contact densities, electronic and positronic single-particle densities, and electron-positron contact densities. Moreover, the RXCHF approach is significantly more accurate than the original XCHF approach, in which all electronic orbitals are explicitly correlated to the positronic orbital in the same manner, because the RXCHF wavefunction is optimized to produce a highly accurate description of the short-ranged electron-positron interaction that dictates the annihilation rates and other local properties. Furthermore, RXCHF methods that neglect or approximate the electronic exchange interactions between the geminal-coupled electronic orbital and the regular electronic orbitals lead to virtually identical annihilation rates and densities as the fully antisymmetric RXCHF method but offer substantial advantages in computational tractability. Thus, NEO-RXCHF is a promising, computationally practical approach for studying larger positron-containing systems.

  4. Further explorations of Skyrme-Hartree-Fock-Bogoliubov mass formulas. XIII. The 2012 atomic mass evaluation and the symmetry coefficient

    NASA Astrophysics Data System (ADS)

    Goriely, S.; Chamel, N.; Pearson, J. M.

    2013-08-01

    Our family of three Hartree-Fock-Bogoliubov (HFB) mass models, labeled BSk19, BSk20, and BSk21, is here extended by (a) refitting to the 2012 Atomic Mass Evaluation (AME), and (b) varying the symmetry coefficient J. Five new models, labeled BSk22 to BSk26, along with their mass tables, HFB-22 to HFB-26, respectively, are presented. These models are characterized by unconventional Skyrme forces containing t4 and t5 terms, i.e., density-dependent generalizations of the usual t1 and t2 terms, respectively. Highly realistic contact pairing forces are used. The Skyrme forces are constrained to fit realistic equations of state of neutron matter stiff enough to support the massive neutron stars PSR J1614-2230 and PSR J0348+0432. Unphysical spin and spin-isospin instabilities of homogeneous nuclear matter, including the transition to a polarized state in neutron-star matter, are eliminated with the new forces. The best fits to the new database of 2353 nuclei are found for models BSk24 (J=30 MeV) and BSk25 (J=29 MeV), for which the root-mean square (rms) deviations are 0.55 and 0.54 MeV, respectively. Despite the larger database this is even better than the rms deviation of 0.58 MeV that we found with our fits to the 2003 AME. With J=32 MeV the rms deviation rises to 0.63 MeV. The neutron-skin thicknesses derived from antiproton scattering are shown to be consistent with the conclusions that we have drawn from masses.

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

    NASA Astrophysics Data System (ADS)

    Gavrielides, A.; Duguet, T.; Esvan, J.; Lacaze-Dufaure, C.; Bagus, P. S.

    2016-08-01

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

  6. Excited-state nuclear forces on adiabatic potential-energy surfaces by time-dependent density-functional theory

    NASA Astrophysics Data System (ADS)

    Haruyama, Jun; Suzuki, Takahiro; Hu, Chunping; Watanabe, Kazuyuki

    2012-01-01

    We present a simple and computationally efficient method to calculate excited-state nuclear forces on adiabatic potential-energy surfaces (APES) from linear-response time-dependent density-functional theory within a real-space framework. The Casida ansatz, which has been validated for computing first-order nonadiabatic couplings in previous studies, was applied to the calculation of the excited-state forces. Our method is validated by the consistency of results in the lower excited states, which reproduce well those obtained by the numerical derivative of each APES. We emphasize the usefulness of this technique by demonstrating the excited-state molecular-dynamics simulation.

  7. Adiabatic approximation in time-dependent reduced-density-matrix functional theory

    SciTech Connect

    Requist, Ryan; Pankratov, Oleg

    2010-04-15

    With the aim of describing real-time electron dynamics, we introduce an adiabatic approximation for the equation of motion of the one-body reduced density matrix (one-matrix). The eigenvalues of the one-matrix, which represent the occupation numbers of single-particle orbitals, are obtained from the constrained minimization of the instantaneous ground-state energy functional rather than from their dynamical equations. The performance of the approximation vis-a-vis nonadiabatic effects is assessed in real-time simulations of a two-site Hubbard model. Due to Landau-Zener-type transitions, the system evolves into a nonstationary state with persistent oscillations in the observables. The amplitude of the oscillations displays a strongly nonmonotonic dependence on the strength of the electron-electron interaction and the rate of variation of the external potential. We interpret an associated resonance behavior in the phase of the oscillations in terms of 'scattering' with spectator energy levels. To clarify the motivation for the minimization condition, we derive a sequence of energy functionals E{sub v}{sup (n)}, for which the corresponding sequence of minimizing one-matrices is asymptotic to the exact one-matrix in the adiabatic limit.

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

    PubMed

    Kussmann, Jörg; Ochsenfeld, Christian

    2007-11-28

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

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

    PubMed

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

    2015-02-05

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

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

    NASA Astrophysics Data System (ADS)

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

    2015-02-01

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

  11. Negative-energy states in the Dirac-Hartree-Fock problem - The effect of omission of two-electron integrals involving the small component

    NASA Technical Reports Server (NTRS)

    Dyall, Kenneth G.

    1992-01-01

    The effect of omission of two-electron integrals involving basis functions for the small component of the wavefunction on the eigenvalue spectrum in the Dirac-Hartree-Fock problem is studied. From an analysis of the Fock matrix it is shown that omission of these integrals moves the negative-energy states down, not up. Their complete omission does not give rise to intruder states. The appearance of intruder states occurs when only some of the core integrals are omitted, due to the nature of particular contraction schemes used for the core basis functions. Use of radially localized functions rather than atomic functions alleviates the intruder state problem.

  12. Roothaan-Hartree-Fock Ground-State Atomic Wave Functions: Slater-Type Orbital Expansions and Expectation Values for Z = 2-54

    NASA Astrophysics Data System (ADS)

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

    1993-01-01

    Roothaan-Hartree-Fock orbitals expressed in a Slater-type basis are reported for the ground states of He through Xe. Energy accuracy ranges between 8 and 10 significant figures, reducing by between 21 and 2770 times the energy errors of the previous such compilation (E. Clementi and C. Roetti, Atomic Data and Nuclear Data Tables 14, 177, 1974). For each atom, the total energy, kinetic energy, potential energy, virial ratio, electron density at the nucleus, and the Kato cusp are given together with radial expectation values with n from -3 to 2 for each orbital, orbital energies, and orbital expansion coefficients.

  13. Analysis of the spin Hall effect in CuIr alloys: Combined approach of density functional theory and Hartree-Fock approximation

    SciTech Connect

    Xu, Zhuo Gu, Bo; Mori, Michiyasu; Maekawa, Sadamichi; Ziman, Timothy

    2015-05-07

    We analyze the spin Hall effect in CuIr alloys in theory by the combined approach of the density functional theory (DFT) and Hartree-Fock (HF) approximation. The spin Hall angle (SHA) is obtained to be negative without the local correlation effects. After including the local correlation effects of the 5d orbitals of Ir impurities, the SHA becomes positive with realistic correlation parameters and consistent with experiment [Niimi et al., Phys. Rev. Lett. 106, 126601 (2011)]. Moreover, our analysis shows that the DFT + HF approach is a convenient and general method to study the influence of local correlation effects on the spin Hall effect.

  14. Ab initio analytical Raman intensities for periodic systems through a coupled perturbed Hartree-Fock/Kohn-Sham method in an atomic orbital basis. I. Theory.

    PubMed

    Maschio, Lorenzo; Kirtman, Bernard; Rérat, Michel; Orlando, Roberto; Dovesi, Roberto

    2013-10-28

    We present a fully analytical formulation for calculating Raman intensities of crystalline periodic systems using a local basis set. Numerical differentiation with respect to atomic coordinates and with respect to wavevectors is entirely avoided as is the determination of crystal orbital coefficient derivatives with respect to nuclear displacements. Instead, our method utilizes the orbital energy-weighted density matrix and is based on the self-consistent solution of first- and second-order Coupled Perturbed Hartree-Fock/Kohn-Sham equations for the electronic response to external electric fields at the equilibrium geometry. This method has also been implemented in the Crystal program, which uses a Gaussian type basis set.

  15. Symbolic computation of the Hartree-Fock energy from a chiral EFT three-nucleon interaction at N 2LO

    NASA Astrophysics Data System (ADS)

    Gebremariam, B.; Bogner, S. K.; Duguet, T.

    2010-06-01

    We present the first of a two-part Mathematica notebook collection that implements a symbolic approach for the application of the density matrix expansion (DME) to the Hartree-Fock (HF) energy from a chiral effective field theory (EFT) three-nucleon interaction at N 2LO. The final output from the notebooks is a Skyrme-like energy density functional that provides a quasi-local approximation to the non-local HF energy. In this paper, we discuss the derivation of the HF energy and its simplification in terms of the scalar/vector-isoscalar/isovector parts of the one-body density matrix. Furthermore, a set of steps is described and illustrated on how to extend the approach to other three-nucleon interactions. Program summaryProgram title: SymbHFNNN Catalogue identifier: AEGC_v1_0 Program summary URL:http://cpc.cs.qub.ac.uk/summaries/AEGC_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.: 96 666 No. of bytes in distributed program, including test data, etc.: 378 083 Distribution format: tar.gz Programming language: Mathematica 7.1 Computer: Any computer running Mathematica 6.0 and later versions Operating system: Windows Xp, Linux/Unix RAM: 256 Mb Classification: 5, 17.16, 17.22 Nature of problem: The calculation of the HF energy from the chiral EFT three-nucleon interaction at N 2LO involves tremendous spin-isospin algebra. The problem is compounded by the need to eventually obtain a quasi-local approximation to the HF energy, which requires the HF energy to be expressed in terms of scalar/vector-isoscalar/isovector parts of the one-body density matrix. The Mathematica notebooks discussed in this paper solve the latter issue. Solution method: The HF energy from the chiral EFT three-nucleon interaction at N 2LO is cast into a form suitable for an automatic simplification of

  16. A new relativistic Hartree-Fock calculation scheme and its application to the evaluation of fine-structure intervals for nd (n = 3-40) series of sodium

    NASA Astrophysics Data System (ADS)

    He, Liming; Zhu, Yunxia; Zhang, Meng; Tu, Yaoquan

    2011-11-01

    We present a new second-order representation of the relativistic Hartree-Fock equation, which can be solved by the standard Hartree-Fock technique. An alternative reduction for the magnetic part of the Breit interaction is presented in an explicit expression. A corresponding program has been developed, which improves significantly the scaled linear mesh introduced by Herman and Skillman. The structures for a number of atoms and ions are calculated and the agreement of our results with those published is excellent. We evaluate the fine-structure intervals of nd(n = 3-40) Rydberg series for sodium. The inverted fine-structure splitting values are obtained directly as the differences of eigenvalues obtained from a self-consistent field procedure. Taking into account the Gaunt effect enables the accuracy of the calculation to be substantially improved. The complete treatments reproduce very well the inverted fine structures along the Rydberg series and the relative difference between the present results and the experiments does not exceed 4.4%.

  17. An improved generator coordinate Hartree-Fock method applied to the choice of contracted Gaussian basis sets for first-row diatomic molecules

    SciTech Connect

    Pinheiro, J.C.; Jorge, F.E.; Castro, E.V.R. de

    2000-05-15

    Accurate Gaussian basis sets (18s for Li and Be and 20s11p for the atoms from B to Ne) for the first-row atoms, generated with an improved generator coordinate Hartree-Fock method, were contracted and enriched with polarization functions. These basis sets were tested for B{sub 2}, C{sub 2}, BeO, Cn{sup {minus}}, LiF, N{sub 2}, CO, BF, NO{sup +}, O{sub 2}, and F{sub 2}. At the Hartree-Fock (HP), second-order Moeller-Plesset (MP2), fourth-order Moeller-Plesset (MP4), and density functional theory (DFT) levels, the dipole moments, bond lengths, and harmonic vibrational frequencies were studied, and at the MP2, MP4, and DFT levels, the dissociation energies were evaluated and compared with the corresponding experimental values and with values obtained using other contracted Gaussian basis sets and numerical HF calculations. For all diatomic molecules studied, the differences between the total energies, obtained with the largest contracted basis set [6s5p3d1f], and those calculated with the numerical HF methods were always less than 3.2 mhartree.

  18. Multi-reference Hartree-Fock configuration interaction calculations of LiH and Be using a new double-zeta atomic base.

    PubMed

    de Cerqueira Sobrinho, Antonio Moreira; de Andrade, Micael Dias; Nascimento, Marco Antônio Chaer; Malbouisson, Luiz Augusto Carvalho

    2014-08-01

    In this work, we propose new double-zeta atomic bases for the Li and Be atoms. These were obtained by applying the Hartree-Fock-Gauss generalized simulated annealing (GSA) method-a modified form of the GSA algorithm. The new bases were generated through optimization of the atomic electronic energy functional with regards to the linear combination of atomic orbitals-molecular orbital (LCAO-MO) coefficients, and exponent and contraction coefficients of the primitive Gaussian functions, simultaneously. These new bases were tested by performing calculations of the ground state energy of the Be atom, and the ground state energy and permanent electrical dipole moment of the LiH molecule, using the multi-reference Hartree-Fock (HF) configuration interaction method-a multi-reference method based on multiple HF solutions. In addition, multi-reference HF configuration interaction calculations were performed for the Be atom using the standard double-zeta, triple-zeta and polarized double-zeta bases. With the new double-zeta bases and with reduced multi-reference HF bases, it was possible to obtain lower energies than those obtained with the full configuration interaction calculations using the standard double-zeta bases and dipole moment values in close agreement with experimental values.

  19. Exact-exchange time-dependent density-functional theory for static and dynamic polarizabilities

    SciTech Connect

    Hirata, So; Ivanov, Stanislav; Bartlett, Rodney J.; Grabowski, Ireneusz

    2005-03-01

    Time-dependent density-functional theory (TDDFT) employing the exact-exchange functional has been formulated on the basis of the optimized-effective-potential (OEP) method of Talman and Shadwick for second-order molecular properties and implemented into a Gaussian-basis-set, trial-vector algorithm. The only approximation involved, apart from the lack of correlation effects and the use of Gaussian-type basis functions, was the consistent use of the adiabatic approximation in the exchange kernel and in the linear response function. The static and dynamic polarizabilities and their anisotropy predicted by the TDDFT with exact exchange (TDOEP) agree accurately with the corresponding values from time-dependent Hartree-Fock theory, the exact-exchange counterpart in the wave function theory. The TDOEP is free from the nonphysical asymptotic decay of the exchange potential of most conventional density functionals or from any other manifestations of the incomplete cancellation of the self-interaction energy. The systematic overestimation of the absolute values and dispersion of polarizabilities that plagues most conventional TDDFT cannot be seen in the TDOEP.

  20. Coordinate-space solution of the Skyrme-Hartree-Fock- Bogolyubov equations within spherical symmetry. The program HFBRAD (v1.00)

    NASA Astrophysics Data System (ADS)

    Bennaceur, K.; Dobaczewski, J.

    2005-06-01

    We describe the first version (v1.00) of the code HFBRAD which solves the Skyrme-Hartree-Fock or Skyrme-Hartree-Fock-Bogolyubov equations in the coordinate representation with spherical symmetry. A realistic representation of the quasiparticle wave functions on the space lattice allows calculations to be performed up to the particle drip lines. Zero-range density-dependent interactions are used in the pairing channel. The pairing energy is calculated by either using a cut-off energy in the quasiparticle spectrum or the regularization scheme proposed by A. Bulgac and Y. Yu. Program summaryTitle of the program:HFBRAD (v1.00) Catalogue indentifier:ADVM Program summary URL:http://cpc.cs.qub.ac.uk/summaries/ADVM Program obtainable from: CPC Program Library, Queen's University of Belfast, N. Ireland Licensing provisions: none Computers on which the program has been tested: Pentium-III, Pentium-IV Operating systems: LINUX, Windows Programming language used:FORTRAN-95 Memory required to execute with typical data: 30 MBytes No. of bits in a word: The code is written with a type real and uses the intrinsic function selected_real_kind at the beginning of the code to ask for at least 12 significant digits. This can be easily modified by asking for more significant digits if the architecture of the computer can handle it. No. of processors used:1 Has the code been vectorized?:No No. of bytes in distributed program, including test data, etc.: 40 308 No. of lines in distributed program, including test data, etc.: 5370 Distribution format:tar.gz Nature of physical problem: For a self-consistent description of nuclear pair correlations, both the particle-hole (field) and particle-particle (pairing) channels of the nuclear mean field must be treated within a common approach, which is the Hartree-Fock-Bogolyubov theory. By expressing these fields in spatial coordinates one can obtain the best possible solutions of the problem; however, without assuming specific symmetries the

  1. Time-dependent pairing equations for seniority-one nuclear systems

    SciTech Connect

    Mirea, M.

    2008-10-15

    When the time-dependent Hartree-Fock-Bogoliubov intrinsic equations of motion are solved in the case of seniority-one nuclear systems, the unpaired nucleon remains on the same orbital. The blocking effect hinders the possibility to skip from one orbital to another. This unpleasant feature is by-passed with a new set of pairing time-dependent equations that allows the possibility that the unpaired nucleon changes its single-particle level. These equations generalize the time-dependent Hartree-Fock-Bogoliubov equations of motion by including the Landau-Zener effect. The derivation of these new equations is presented in detail. These equations are applied to the case of a superasymmetric fission process, that is, to explain the fine structure the {sup 14}C emission from {sup 233}Ra. In this context, a new version of the Woods-Saxon model extended for two-center potentials is used.

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

    SciTech Connect

    Nascimento, Daniel R.; DePrince, A. Eugene

    2015-12-07

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

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

    NASA Technical Reports Server (NTRS)

    Dyall, Kenneth G.

    1993-01-01

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

  4. Ab initio study of MF2 (M=Mn, Fe, Co, Ni) rutile-type compounds using the periodic unrestricted Hartree-Fock approach

    NASA Astrophysics Data System (ADS)

    de P. R. Moreira, Ibério; Dovesi, Roberto; Roetti, Carla; Saunders, Victor R.; Orlando, Roberto

    2000-09-01

    The ab initio periodic unrestricted Hartree-Fock method has been applied in the investigation of the ground-state structural, electronic, and magnetic properties of the rutile-type compounds MF2 (M=Mn, Fe, Co, and Ni). All electron Gaussian basis sets have been used. The systems turn out to be large band-gap antiferromagnetic insulators; the optimized geometrical parameters are in good agreement with experiment. The calculated most stable electronic state shows an antiferromagnetic order in agreement with that resulting from neutron scattering experiments. The magnetic coupling constants between nearest-neighbor magnetic ions along the [001], [111], and [100] (or [010]) directions have been calculated using several supercells. The resulting ab initio magnetic coupling constants are reasonably satisfactory when compared with available experimental data. The importance of the Jahn-Teller effect in FeF2 and CoF2 is also discussed.

  5. Unrestricted Hartree-Fock Investigation of the Electron Distribution on the Heme System in Azidohemoglobin-^57mFe and ^14N Hyperfine Interactions.

    NASA Astrophysics Data System (ADS)

    Dubey, Archana; Saha, H. P.; Chow, Lee; Scheicher, R. H.; Sahoo, N.; Pink, R. H.; Mahato, Dip N.; Huang, M. B.; Das, T. P.

    2006-03-01

    We have a program of investigations in progress on the electronic structure of azidohemoglobin by the first-principles Unrestricted Hartree-Fock procedure to understand the substantial amount of magnetic (g-tensor), magnetic hyperfine, and nuclear quadrupole interaction, data available [1] from electron paramagnetic resonance, Mosbauer and electron-nuclear double resonance measurements. Earlier semi-empirical Self-Consistent Charge Extended Huckel investigations have provided semiquantitative results [2] with different degrees of agreement for the available properties and suggested the need for more accurate and quantitative investigations. Results of our investigations will be presented for the ^57mFe and ^14N nuclear quadrupole and magnetic hyperfine interaction properties and compared with experimental data. *Also UCF Orlando [1] See Refs. 2-4 listed in Ref.[2]. [2] Santosh K. Mishra, J.N. Roy, K.C. Mishra and T.P. Das, Theo. Chim. Acta 75, 195(1989).

  6. Comparison between the performances of the spin-projected Hartree-Fock, generalized valence-bond, and spin-coupled approaches

    NASA Astrophysics Data System (ADS)

    Karadakov, Peter B.; Cooper, David L.

    The total energies from spin-projected Hartree-Fock (spin-PHF), generalized valence-bond with perfect-pairing and strong orthogonality restrictions (GVB-PP-SO), and fully-variational spin-coupled (SC) calculations are compared for a series of unsaturated alternant hydrocarbons, ranging from trans buta-1,3-diene to naphthalene. The extent to which the spin-PHF and GVB-PP-SO wavefunctions for these molecules can approximate the more general SC wavefunction can be understood by analyzing the weights of the different modes of spin coupling in the full SC treatment. The spin-PHF wavefunction is found to display a surprising ability to capture more of the π-space correlation effects in aromatic and antiaromatic systems than its GVB-PP-SO counterpart, even in the case of naphthalene, a molecule with 10 π electrons.

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

    NASA Astrophysics Data System (ADS)

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

    2011-01-01

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

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

    NASA Technical Reports Server (NTRS)

    Dyall, Kenneth G.

    1991-01-01

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

  9. Molecular structure, vibrational spectra and HOMO, LUMO analysis of yohimbine hydrochloride by density functional theory and ab initio Hartree-Fock calculations

    NASA Astrophysics Data System (ADS)

    Joshi, Bhawani Datt; Srivastava, Anubha; Tandon, Poonam; Jain, Sudha

    2011-11-01

    Yohimbine hydrochloride (YHCl) is an aphrodisiac and promoted for erectile dysfunction, weight loss and depression. The optimized geometry, total energy, potential energy surface and vibrational wavenumbers of yohimbine hydrochloride have been determined using ab initio, Hartree-Fock (HF) and density functional theory (DFT/B3LYP) method with 6-311++G(d,p) basis set. A complete vibrational assignment is provided for the observed Raman and IR spectra of YHCl. The UV absorption spectrum was examined in ethanol solvent and compared with the calculated one in gas phase as well as in solvent environment (polarizable continuum model, PCM) using TD-DFT/6-31G basis set. These methods are proposed as a tool to be applied in the structural characterization of YHCl. The calculated highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) with frontier orbital gap are presented.

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

    NASA Technical Reports Server (NTRS)

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

    1976-01-01

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

  11. Magnetic state of K0.8Fe1.6Se2 from a five-orbital Hubbard model in the Hartree-Fock approximation

    SciTech Connect

    Luo, Qinlong; Nicholson, Andrew D; Riera, J. A.; Yao, Dao-Xin; Moreo, Adriana; Dagotto, Elbio R

    2011-01-01

    Motivated by the recent discovery of Fe-based superconductors close to an antiferromagnetic insulator in the experimental phase diagram, here the five-orbital Hubbard model (without lattice distortions) is studied using the real-space Hartree-Fock approximation, employing a 10 10 Fe cluster with Fe vacancies in a5 5 pattern. Varying the Hubbard and Hund couplings, and at electronic density n = 6.0, the phase diagram contains an insulating state with the same spin pattern as observed experimentally, involving 2 2 ferromagnetic plaquettes coupled with one another antiferromagnetically. The presence of local ferromagnetic tendencies is in qualitative agreement with Lanczos results for the three-orbital model also reported here. The magnetic moment 3 B /Fe is in good agreement with experiments. Several other phases are also stabilized in the phase diagram, in agreement with recent calculations using phenomenological models.

  12. A simple and efficient dispersion correction to the Hartree-Fock theory (2): Incorporation of a geometrical correction for the basis set superposition error.

    PubMed

    Yoshida, Tatsusada; Hayashi, Takahisa; Mashima, Akira; Chuman, Hiroshi

    2015-10-01

    One of the most challenging problems in computer-aided drug discovery is the accurate prediction of the binding energy between a ligand and a protein. For accurate estimation of net binding energy ΔEbind in the framework of the Hartree-Fock (HF) theory, it is necessary to estimate two additional energy terms; the dispersion interaction energy (Edisp) and the basis set superposition error (BSSE). We previously reported a simple and efficient dispersion correction, Edisp, to the Hartree-Fock theory (HF-Dtq). In the present study, an approximation procedure for estimating BSSE proposed by Kruse and Grimme, a geometrical counterpoise correction (gCP), was incorporated into HF-Dtq (HF-Dtq-gCP). The relative weights of the Edisp (Dtq) and BSSE (gCP) terms were determined to reproduce ΔEbind calculated with CCSD(T)/CBS or /aug-cc-pVTZ (HF-Dtq-gCP (scaled)). The performance of HF-Dtq-gCP (scaled) was compared with that of B3LYP-D3(BJ)-bCP (dispersion corrected B3LYP with the Boys and Bernadi counterpoise correction (bCP)), by taking ΔEbind (CCSD(T)-bCP) of small non-covalent complexes as 'a golden standard'. As a critical test, HF-Dtq-gCP (scaled)/6-31G(d) and B3LYP-D3(BJ)-bCP/6-31G(d) were applied to the complex model for HIV-1 protease and its potent inhibitor, KNI-10033. The present results demonstrate that HF-Dtq-gCP (scaled) is a useful and powerful remedy for accurately and promptly predicting ΔEbind between a ligand and a protein, albeit it is a simple correction procedure.

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

    PubMed

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

    2015-07-21

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

  14. Basis sets for ab initio periodic Hartree-Fock studies of zeolite/adsorbate interactions: He, Ne, and Ar in silica sodalite

    SciTech Connect

    Nada, R.; Nicholas, J.B.; McCarthy, M.I.; Hess, A.C.

    1996-11-15

    Silica sodalite is an ideal model system to establish base-line computer requirements of ab initio periodic Hartree-Fock (PHF) calculations of zeolites. In this article, the authors investigate the effect of various basis sets on the structural and electronic properties of bulk silica sodalite. They also study the interaction of He, Ne, and Ar with the sodalite cage. This work shows that basis-set superposition errors (BSSE) in calculations using STO-3G and 6-21G(*) basis sets are as large as the interaction energies, leading to poor confidence in the results. To cure this problem, the authors present high-quality basis sets for si, O, He, Ne, and Ar, optimized for use with PHF methods, and demonstrate that the new basis set greatly reduces BSSE. The theoretical barriers for transfer of the rare gases between sodalite cages are 5.6, 13.2, and 62.1 kcal/mol for He, Ne, and Ar. 27 refs., 6 figs., 8 tabs.

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

    SciTech Connect

    Lara-Castells, María Pilar de; Mitrushchenkov, Alexander O.; Stoll, Hermann

    2015-09-14

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

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

    PubMed

    Kussmann, Jörg; Ochsenfeld, Christian

    2007-08-07

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

  17. Magnetic phase diagram of a five-orbital Hubbard model in the real-space Hartree-Fock approximation varying the electronic density

    NASA Astrophysics Data System (ADS)

    Luo, Qinlong; Dagotto, Elbio

    2014-01-01

    Using the real-space Hartree-Fock approximation, the magnetic phase diagram of a five-orbital Hubbard model for the iron-based superconductors is studied varying the electronic density n in the range from five to seven electrons per transition metal atom. The Hubbard interaction U is also varied, at a fixed Hund coupling J /U=0.25. Several qualitative trends and a variety of competing magnetic states are observed. At n =5, a robust G-type antiferromagnetic insulator is found, in agreement with experimental results for BaMn2As2. As n increases away from 5, magnetic states with an increasing number of nearest-neighbors ferromagnetic links become energetically stable. This includes the well-known C-type antiferromagnetic state at n =6, the E-phase known to exist in FeTe, and also a variety of novel states not found yet experimentally, some of them involving blocks of ferromagnetically oriented spins. Regions of phase separation, as in Mn oxides, have also been detected. Comparison to previous theoretical investigations indicate that these qualitative trends may be generic characteristics of phase diagrams of multi-orbital Hubbard models.

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

    SciTech Connect

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

    2015-07-21

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

  19. Recommending Hartree-Fock theory with London-dispersion and basis-set-superposition corrections for the optimization or quantum refinement of protein structures.

    PubMed

    Goerigk, Lars; Collyer, Charles A; Reimers, Jeffrey R

    2014-12-18

    We demonstrate the importance of properly accounting for London dispersion and basis-set-superposition error (BSSE) in quantum-chemical optimizations of protein structures, factors that are often still neglected in contemporary applications. We optimize a portion of an ensemble of conformationally flexible lysozyme structures obtained from highly accurate X-ray crystallography data that serve as a reliable benchmark. We not only analyze root-mean-square deviations from the experimental Cartesian coordinates, but also, for the first time, demonstrate how London dispersion and BSSE influence crystallographic R factors. Our conclusions parallel recent recommendations for the optimization of small gas-phase peptide structures made by some of the present authors: Hartree-Fock theory extended with Grimme's recent dispersion and BSSE corrections (HF-D3-gCP) is superior to popular density functional theory (DFT) approaches. Not only are statistical errors on average lower with HF-D3-gCP, but also the convergence behavior is much better. In particular, we show that the BP86/6-31G* approach should not be relied upon as a black-box method, despite its widespread use, as its success is based on an unpredictable cancellation of errors. Using HF-D3-gCP is technically straightforward, and we therefore encourage users of quantum-chemical methods to adopt this approach in future applications.

  20. Spin-free Dirac-Coulomb calculations augmented with a perturbative treatment of spin-orbit effects at the Hartree-Fock level

    SciTech Connect

    Cheng, Lan; Stopkowicz, Stella; Gauss, Jürgen

    2013-12-07

    A perturbative approach to compute second-order spin-orbit (SO) corrections to a spin-free Dirac-Coulomb Hartree-Fock (SFDC-HF) calculation is suggested. The proposed scheme treats the difference between the DC and SFDC Hamiltonian as perturbation and exploits analytic second-derivative techniques. In addition, a cost-effective scheme for incorporating relativistic effects in high-accuracy calculations is suggested consisting of a SFDC coupled-cluster treatment augmented by perturbative SO corrections obtained at the HF level. Benchmark calculations for the hydrogen halides HX, X = F-At as well as the coinage-metal fluorides CuF, AgF, and AuF demonstrate the accuracy of the proposed perturbative treatment of SO effects on energies and electrical properties in comparison with the more rigorous full DC treatment. Furthermore, we present, as an application of our scheme, results for the electrical properties of AuF and XeAuF.

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

    SciTech Connect

    Song, Jong-Won; Hirao, Kimihiko

    2015-10-14

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

  2. Linear-response time-dependent density-functional theory with pairing fields.

    PubMed

    Peng, Degao; van Aggelen, Helen; Yang, Yang; Yang, Weitao

    2014-05-14

    Recent development in particle-particle random phase approximation (pp-RPA) broadens the perspective on ground state correlation energies [H. van Aggelen, Y. Yang, and W. Yang, Phys. Rev. A 88, 030501 (2013), Y. Yang, H. van Aggelen, S. N. Steinmann, D. Peng, and W. Yang, J. Chem. Phys. 139, 174110 (2013); D. Peng, S. N. Steinmann, H. van Aggelen, and W. Yang, J. Chem. Phys. 139, 104112 (2013)] and N ± 2 excitation energies [Y. Yang, H. van Aggelen, and W. Yang, J. Chem. Phys. 139, 224105 (2013)]. So far Hartree-Fock and approximated density-functional orbitals have been utilized to evaluate the pp-RPA equation. In this paper, to further explore the fundamentals and the potential use of pairing matrix dependent functionals, we present the linear-response time-dependent density-functional theory with pairing fields with both adiabatic and frequency-dependent kernels. This theory is related to the density-functional theory and time-dependent density-functional theory for superconductors, but is applied to normal non-superconducting systems for our purpose. Due to the lack of the proof of the one-to-one mapping between the pairing matrix and the pairing field for time-dependent systems, the linear-response theory is established based on the representability assumption of the pairing matrix. The linear response theory justifies the use of approximated density-functionals in the pp-RPA equation. This work sets the fundamentals for future density-functional development to enhance the description of ground state correlation energies and N ± 2 excitation energies.

  3. Investigation of the ionization of neon by an attosecond XUV pulse with the time-dependent Schrödinger equation

    NASA Astrophysics Data System (ADS)

    Carette, T.; Argenti, L.; Lindroth, E.

    2012-11-01

    We investigate theoretically the single ionization of neon by an attosecond XUV pulse, aiming at a better understanding of the outgoing electron wave-packet in the early stages of its detachment. To do so, we integrate the one-electron time-dependent Schrödinger equation numerically. The non-local interaction with the spectator electrons in the time-dependent hamiltonian is accounted for with a configuration-averaged effective Hartree-Fock potential.

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

    NASA Astrophysics Data System (ADS)

    Dobaczewski, J.; Olbratowski, P.

    2005-05-01

    We describe the new version (v2.08k) of the code HFODD which solves the nuclear Skyrme-Hartree-Fock or Skyrme-Hartree-Fock-Bogolyubov problem by using the Cartesian deformed harmonic-oscillator basis. Similarly as in the previous version (v2.08i), all symmetries can be broken, which allows for calculations with angular frequency and angular momentum tilted with respect to the mass distribution. In the new version, three minor errors have been corrected. New Version Program SummaryTitle of program: HFODD; version: 2.08k Catalogue number: ADVA Catalogue number of previous version: ADTO (Comput. Phys. Comm. 158 (2004) 158) Program summary URL:http://cpc.cs.qub.ac.uk/summaries/ADVA Program obtainable from: CPC Program Library, Queen's University of Belfast, N. Ireland Does the new version supersede the previous one: yes Computers on which this or another recent version has been tested: SG Power Challenge L, Pentium-II, Pentium-III, AMD-Athlon Operating systems under which the program has been tested: UNIX, LINUX, Windows-2000 Programming language used: Fortran Memory required to execute with typical data: 10M words No. of bits in a word: 64 No. of lines in distributed program, including test data, etc.: 52 631 No. of bytes in distributed program, including test data, etc.: 266 885 Distribution format:tar.gz Nature of physical problem: The nuclear mean-field and an analysis of its symmetries in realistic cases are the main ingredients of a description of nuclear states. Within the Local Density Approximation, or for a zero-range velocity-dependent Skyrme interaction, the nuclear mean-field is local and velocity dependent. The locality allows for an effective and fast solution of the self-consistent Hartree-Fock equations, even for heavy nuclei, and for various nucleonic ( n-particle n-hole) configurations, deformations, excitation energies, or angular momenta. Similar Local Density Approximation in the particle-particle channel, which is equivalent to using a zero

  5. Spectroscopic constants of diatomic molecules computed correcting Hartree-Fock or general-valence-bond potential-energy curves with correlation-energy functionals

    NASA Astrophysics Data System (ADS)

    Pérez-Jordá, José M.; San-Fabián, Emilio; Moscardó, Federico

    1992-04-01

    The Kohn-Sham energy with exact exchange [using the exact Hartree-Fock (HF) exchange but an approximate correlation-energy functional] may be computed very accurately by adding the correlation obtained from the HF density to the total HF energy. Three density functionals are used: local spin density (LSD), LSD with self-interaction correction, and LSD with generalized gradient correction. This scheme has been extended (Lie-Clementi, Colle-Salvetti, and Moscardo-San-Fabian) to be used with general-valence-bond (GVB) energies and wave functions, so that the extra correlation included in the GVB energy is not counted again. The effect of all these approximate correlations on HF or GVB spectroscopic constants (Re,ωe, and De) is studied. Approximate relations showing how correlation affects them are derived, and may be summarized as follows: (1) the effect on Re and ωe depends only on the correlation derivative at Re, and (2) the effect on De depends mainly on the correlation difference between quasidissociated and equilibrium geometries. A consequence is that all the correlation corrections tested here give larger ωe and De and shorter Re than the uncorrected HF or GVB values. This trend is correct for De for both HF and GVB. For Re and ωe, it is correct in most cases for GVB, but it often fails for the HF cases. A comparison is made with Kohn-Sham calculations with both exchange and correlation approximated. As a final conclusion, it is found that, within the present scheme, a qualitatively correct HF or GVB potential-energy curve, together with a correlation-energy approximation with correct dissociation behavior, is crucial for obtaining good estimates of spectroscopic constants.

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

    NASA Astrophysics Data System (ADS)

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

    2009-04-01

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

  7. Finite-element multiconfiguration Hartree-Fock calculations of the atomic quadrupole moments of excited states of Be, Al, In, Ne, Ar, Kr, and Xe

    NASA Astrophysics Data System (ADS)

    Sundholm, Dage; Olsen, Jeppe

    1993-04-01

    The atomic quadrupole moments Qzz of Be(2s2p;3P2), Al(3p;2P3/2), In(5p;2P3/2), Ne(2p53s3P2), Ar(3p54s;3P2), Kr(4p55s;3P2), and Xe(5p56s;3P2) have been calculated using a finite-element multiconfiguration Hartree-Fock method. The obtained Qzz(Be) of 2.265 a.u. agrees with previously calculated values. The calculated Qzz(Al) and Qzz(In) of 2.579 and 3.165 a.u. are in good agreement with the experimental values of 2.53(15) a.u. and 2.94(10) a.u. A large s-d polarization contribution to the Qzz of the rare gases is found in the present calculations. The correlation contributions from double (D), triple (T), and quadruple (Q) excitations to the Qzz of the rare gases alternate; the total DTQ correlation contribution is negligibly small for Ne, Ar, and Kr, while the DTQ correlation contribution to the Qzz(Xe) is 25% of the final Qzz. The final values are Qzz(Ne)=-0.0506 a.u., Qzz(Ar)=-0.0553 a.u., Qzz(Kr)=+0.0601 a.u., and Qzz(Xe)=+0.4505 a.u., as compared to the experimental values of -0.048(5) a.u., -0.042(4) a.u., +0.046(5) a.u., and +0.30(3) a.u. for Ne, Ar, Kr, and Xe, respectively.

  8. A simple and efficient dispersion correction to the Hartree-Fock theory (3): A comprehensive performance comparison of HF-Dtq with MP2 and DFT-Ds.

    PubMed

    Yoshida, Tatsusada; Hayashi, Takahisa; Mashima, Akira; Sasahara, Katsunori; Chuman, Hiroshi

    2016-01-15

    Accurate prediction of the intermolecular interaction energy (ΔEbind) has been a challenging and serious problem. Current in silico drug screening demands efficient and accurate evaluation of ΔEbind for ligands and their target proteins. It is desirable that ΔEbind including the dispersion interaction energy (Edisp) is calculated using a post-Hartree-Fock (HF) theory, such as the high-order coupled-cluster one, with a larger basis set. However, it remains computationally too expensive to apply such a one to large molecular systems. As another problem, it is necessary to consider the contribution of the basis set superposition error (BSSE) in calculation of ΔEbind. In Bioorg. Med. Chem. Lett. 2014 and 2015, we proposed simple and efficient corrections of dispersion and BSSE for the HF theory, which is not able to express the dispersion interaction energy correctly. The current Letter, as the final one in the series, aims to verify the HF theory enhanced by the dispersion correction (HF-Dtq) in the light of reproducibility of 'accurate' intermolecular ligand-protein interaction energy values, with comprehensive comparison with the MP2 and recently proposed various DFT-D theories. Taking ΔEbind calculated with the coupled-cluster theory coupled with a complete basis set as a reference, ΔEbind of over a hundred small sized noncovalent complexes as well as real ligand-protein complexes models was systematically examined in terms of accuracy and computational cost. The comprehensive comparison in the current work showed that HF-Dtq is a practical and reliable approach for in silico drug screening and quantitative structure-activity relationships.

  9. The role of range-separated Hartree-Fock exchange in the calculation of magnetic exchange couplings in transition metal complexes.

    PubMed

    Phillips, Jordan J; Peralta, Juan E

    2011-01-21

    We assess the dependence of magnetic exchange couplings on the variation of Hartree-Fock exchange (HFX) admixture in global hybrid functionals and the range-separation parameter ω in range-separated hybrid functionals in a set of 12 spin-1/2 binuclear transition metal complexes. The global hybrid PBEh (hybrid Perdew-Burke-Ernzerhof) and range-separated hybrids HSE (Heyd-Scuseria-Ernzerhof) and LC-ωPBE (long-range corrected hybrid PBE) are employed for this assessment, and exchange couplings are calculated from energy differences within the framework of the spin-projected approach. It is found that these functionals perform optimally for magnetic exchange couplings with 35% HFX admixture for PBEh, ω = 0.50 a.u.(-1) for LC-ωPBE, and ω at or near 0.0 a.u.(-1) for HSE (which corresponds to PBEh). We find that in their standard respective forms, LC-ωPBE slightly outperforms PBEh, while PBEh with 35% HFX yields exchange couplings closer to experiment than those of LC-ωPBE with ω = 0.50 a.u.(-1). Additionally, we show that the profile of exchange couplings with respect to ω in HSE is appreciably flat from 0 to 0.2 a.u.(-1). This combined with the fact that HSE is computationally more tractable than global hybrids makes HSE an attractive alternative for the evaluation of exchange couplings in extended systems. These results are rationalized with respect to how varying the parameters within these functionals affects the delocalization of the magnetic orbitals, and conclusions are made regarding the relative importance of range separation versus global mixing of HFX for the calculation of exchange couplings.

  10. Multi-electron systems in strong magnetic fields II: A fixed-phase diffusion quantum Monte Carlo application based on trial functions from a Hartree-Fock-Roothaan method

    NASA Astrophysics Data System (ADS)

    Boblest, S.; Meyer, D.; Wunner, G.

    2014-11-01

    We present a quantum Monte Carlo application for the computation of energy eigenvalues for atoms and ions in strong magnetic fields. The required guiding wave functions are obtained with the Hartree-Fock-Roothaan code described in the accompanying publication (Schimeczek and Wunner, 2014). Our method yields highly accurate results for the binding energies of symmetry subspace ground states and at the same time provides a means for quantifying the quality of the results obtained with the above-mentioned Hartree-Fock-Roothaan method. Catalogue identifier: AETV_v1_0 Program summary URL:http://cpc.cs.qub.ac.uk/summaries/AETV_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.: 72 284 No. of bytes in distributed program, including test data, etc.: 604 948 Distribution format: tar.gz Programming language: C++. Computer: Cluster of 1-˜500 HP Compaq dc5750. Operating system: Linux. Has the code been vectorized or parallelized?: Yes. Code includes MPI directives. RAM: 500 MB per node Classification: 2.1. External routines: Boost::Serialization, Boost::MPI, LAPACK BLAS Nature of problem: Quantitative modelings of features observed in the X-ray spectra of isolated neutron stars are hampered by the lack of sufficiently large and accurate databases for atoms and ions up to the last fusion product iron, at high magnetic field strengths. The predominant amount of line data in the literature has been calculated with Hartree-Fock methods, which are intrinsically restricted in precision. Our code is intended to provide a powerful tool for calculating very accurate energy values from, and thereby improving the quality of, existing Hartree-Fock results. Solution method: The Fixed-phase quantum Monte Carlo method is used in combination with guiding functions obtained in Hartree-Fock

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

    NASA Technical Reports Server (NTRS)

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

    1991-01-01

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

  12. All-electron molecular Dirac-Hartree-Fock calculations - Properties of the XH4 and XH2 molecules and the reaction energy XH4 yields XH2 + H2, X = Si, Ge, Sn, Pb

    NASA Technical Reports Server (NTRS)

    Dyall, Kenneth G.

    1992-01-01

    Relativistic corrections to a number of properties of the Group IV hydrides are calculated using the Dirac-Hartree-Fock method. The use of first-order perturbation theory is sufficient to obtain relativistic corrections for Ge, but the effects of spin-orbit interaction and other higher-order effects begin to show for Sn and become important for Pb. The energy of the reaction XH4 yields XH2 + H2 (X = Si, Ge, Sn, and Pb) is also calculated. The results are compared with relativistic effective core potential calculations, first-order perturbation theory calculations, and limited experimental data.

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

    NASA Technical Reports Server (NTRS)

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

    1990-01-01

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

  14. Transferability and accuracy by combining dispersionless density functional and incremental post-Hartree-Fock theories: Noble gases adsorption on coronene/graphene/graphite surfaces

    SciTech Connect

    Lara-Castells, María Pilar de Bartolomei, Massimiliano; Mitrushchenkov, Alexander O.; Stoll, Hermann

    2015-11-21

    The accuracy and transferability of the electronic structure approach combining dispersionless density functional theory (DFT) [K. Pernal et al., Phys. Rev. Lett. 103, 263201 (2009)] with the method of increments [H. Stoll, J. Chem. Phys. 97, 8449 (1992)], are validated for the interaction between the noble-gas Ne, Ar, Kr, and Xe atoms and coronene/graphene/graphite surfaces. This approach uses the method of increments for surface cluster models to extract intermonomer dispersion-like (2- and 3-body) correlation terms at coupled cluster singles and doubles and perturbative triples level, while periodic dispersionless density functionals calculations are performed to estimate the sum of Hartree-Fock and intramonomer correlation contributions. Dispersion energy contributions are also obtained using DFT-based symmetry-adapted perturbation theory [SAPT(DFT)]. An analysis of the structure of the X/surface (X = Ne, Ar, Kr, and Xe) interaction energies shows the excellent transferability properties of the leading intermonomer correlation contributions across the sequence of noble-gas atoms, which are also discussed using the Drude oscillator model. We further compare these results with van der Waals-(vdW)-corrected DFT-based approaches. As a test of accuracy, the energies of the low-lying nuclear bound states supported by the laterally averaged X/graphite potentials (X = {sup 3}He, {sup 4}He, Ne, Ar, Kr, and Xe) are calculated and compared with the best estimations from experimental measurements and an atom-bond potential model using the ab initio-assisted fine-tuning of semiempirical parameters. The bound-state energies determined differ by less than 6–7 meV (6%) from the atom-bond potential model. The crucial importance of including incremental 3-body dispersion-type terms is clearly demonstrated, showing that the SAPT(DFT) approach effectively account for these terms. With the deviations from the best experimental-based estimations smaller than 2.3 meV (1.9%), the

  15. Accurate prediction of higher-level electronic structure energies for large databases using neural networks, Hartree-Fock energies, and small subsets of the database.

    PubMed

    Malshe, M; Pukrittayakamee, A; Raff, L M; Hagan, M; Bukkapatnam, S; Komanduri, R

    2009-09-28

    A novel method is presented that significantly reduces the computational bottleneck of executing high-level, electronic structure calculations of the energies and their gradients for a large database that adequately samples the configuration space of importance for systems containing more than four atoms that are undergoing multiple, simultaneous reactions in several energetically open channels. The basis of the method is the high-degree of correlation that generally exists between the Hartree-Fock (HF) and higher-level electronic structure energies. It is shown that if the input vector to a neural network (NN) includes both the configuration coordinates and the HF energies of a small subset of the database, MP4(SDQ) energies with the same basis set can be predicted for the entire database using only the HF and MP4(SDQ) energies for the small subset and the HF energies for the remainder of the database. The predictive error is shown to be less than or equal to the NN fitting error if a NN is fitted to the entire database of higher-level electronic structure energies. The general method is applied to the computation of MP4(SDQ) energies of 68,308 configurations that comprise the database for the simultaneous, unimolecular decomposition of vinyl bromide into six different reaction channels. The predictive accuracy of the method is investigated by employing successively smaller subsets of the database to train the NN to predict the MP4(SDQ) energies of the remaining configurations of the database. The results indicate that for this system, the subset can be as small as 8% of the total number of configurations in the database without loss of accuracy beyond that expected if a NN is employed to fit the higher-level energies for the entire database. The utilization of this procedure is shown to save about 78% of the total computational time required for the execution of the MP4(SDQ) calculations. The sampling error involved with selection of the subset is shown to be

  16. Transferability and accuracy by combining dispersionless density functional and incremental post-Hartree-Fock theories: Noble gases adsorption on coronene/graphene/graphite surfaces

    NASA Astrophysics Data System (ADS)

    de Lara-Castells, María Pilar; Bartolomei, Massimiliano; Mitrushchenkov, Alexander O.; Stoll, Hermann

    2015-11-01

    The accuracy and transferability of the electronic structure approach combining dispersionless density functional theory (DFT) [K. Pernal et al., Phys. Rev. Lett. 103, 263201 (2009)] with the method of increments [H. Stoll, J. Chem. Phys. 97, 8449 (1992)], are validated for the interaction between the noble-gas Ne, Ar, Kr, and Xe atoms and coronene/graphene/graphite surfaces. This approach uses the method of increments for surface cluster models to extract intermonomer dispersion-like (2- and 3-body) correlation terms at coupled cluster singles and doubles and perturbative triples level, while periodic dispersionless density functionals calculations are performed to estimate the sum of Hartree-Fock and intramonomer correlation contributions. Dispersion energy contributions are also obtained using DFT-based symmetry-adapted perturbation theory [SAPT(DFT)]. An analysis of the structure of the X/surface (X = Ne, Ar, Kr, and Xe) interaction energies shows the excellent transferability properties of the leading intermonomer correlation contributions across the sequence of noble-gas atoms, which are also discussed using the Drude oscillator model. We further compare these results with van der Waals-(vdW)-corrected DFT-based approaches. As a test of accuracy, the energies of the low-lying nuclear bound states supported by the laterally averaged X/graphite potentials (X = 3He, 4He, Ne, Ar, Kr, and Xe) are calculated and compared with the best estimations from experimental measurements and an atom-bond potential model using the ab initio-assisted fine-tuning of semiempirical parameters. The bound-state energies determined differ by less than 6-7 meV (6%) from the atom-bond potential model. The crucial importance of including incremental 3-body dispersion-type terms is clearly demonstrated, showing that the SAPT(DFT) approach effectively account for these terms. With the deviations from the best experimental-based estimations smaller than 2.3 meV (1.9%), the accuracy of the

  17. Transferability and accuracy by combining dispersionless density functional and incremental post-Hartree-Fock theories: Noble gases adsorption on coronene/graphene/graphite surfaces.

    PubMed

    de Lara-Castells, María Pilar; Bartolomei, Massimiliano; Mitrushchenkov, Alexander O; Stoll, Hermann

    2015-11-21

    The accuracy and transferability of the electronic structure approach combining dispersionless density functional theory (DFT) [K. Pernal et al., Phys. Rev. Lett. 103, 263201 (2009)] with the method of increments [H. Stoll, J. Chem. Phys. 97, 8449 (1992)], are validated for the interaction between the noble-gas Ne, Ar, Kr, and Xe atoms and coronene/graphene/graphite surfaces. This approach uses the method of increments for surface cluster models to extract intermonomer dispersion-like (2- and 3-body) correlation terms at coupled cluster singles and doubles and perturbative triples level, while periodic dispersionless density functionals calculations are performed to estimate the sum of Hartree-Fock and intramonomer correlation contributions. Dispersion energy contributions are also obtained using DFT-based symmetry-adapted perturbation theory [SAPT(DFT)]. An analysis of the structure of the X/surface (X = Ne, Ar, Kr, and Xe) interaction energies shows the excellent transferability properties of the leading intermonomer correlation contributions across the sequence of noble-gas atoms, which are also discussed using the Drude oscillator model. We further compare these results with van der Waals-(vdW)-corrected DFT-based approaches. As a test of accuracy, the energies of the low-lying nuclear bound states supported by the laterally averaged X/graphite potentials (X = (3)He, (4)He, Ne, Ar, Kr, and Xe) are calculated and compared with the best estimations from experimental measurements and an atom-bond potential model using the ab initio-assisted fine-tuning of semiempirical parameters. The bound-state energies determined differ by less than 6-7 meV (6%) from the atom-bond potential model. The crucial importance of including incremental 3-body dispersion-type terms is clearly demonstrated, showing that the SAPT(DFT) approach effectively account for these terms. With the deviations from the best experimental-based estimations smaller than 2.3 meV (1.9%), the accuracy of

  18. Accurate prediction of higher-level electronic structure energies for large databases using neural networks, Hartree-Fock energies, and small subsets of the database

    NASA Astrophysics Data System (ADS)

    Malshe, M.; Pukrittayakamee, A.; Raff, L. M.; Hagan, M.; Bukkapatnam, S.; Komanduri, R.

    2009-09-01

    A novel method is presented that significantly reduces the computational bottleneck of executing high-level, electronic structure calculations of the energies and their gradients for a large database that adequately samples the configuration space of importance for systems containing more than four atoms that are undergoing multiple, simultaneous reactions in several energetically open channels. The basis of the method is the high-degree of correlation that generally exists between the Hartree-Fock (HF) and higher-level electronic structure energies. It is shown that if the input vector to a neural network (NN) includes both the configuration coordinates and the HF energies of a small subset of the database, MP4(SDQ) energies with the same basis set can be predicted for the entire database using only the HF and MP4(SDQ) energies for the small subset and the HF energies for the remainder of the database. The predictive error is shown to be less than or equal to the NN fitting error if a NN is fitted to the entire database of higher-level electronic structure energies. The general method is applied to the computation of MP4(SDQ) energies of 68 308 configurations that comprise the database for the simultaneous, unimolecular decomposition of vinyl bromide into six different reaction channels. The predictive accuracy of the method is investigated by employing successively smaller subsets of the database to train the NN to predict the MP4(SDQ) energies of the remaining configurations of the database. The results indicate that for this system, the subset can be as small as 8% of the total number of configurations in the database without loss of accuracy beyond that expected if a NN is employed to fit the higher-level energies for the entire database. The utilization of this procedure is shown to save about 78% of the total computational time required for the execution of the MP4(SDQ) calculations. The sampling error involved with selection of the subset is shown to be

  19. How dependent are molecular and atomic properties on the electronic structure method? Comparison of Hartree-Fock, DFT, and MP2 on a biologically relevant set of molecules.

    PubMed

    Matta, Chérif F

    2010-04-30

    This article compares molecular properties and atomic properties defined by the quantum theory of atoms in molecules (QTAIM) obtained from three underlying levels of theory: MP2(full), density functional theory (DFT) (B3LYP), and Hartree-Fock (H-F). The same basis set (6-311++G(d,p)) has been used throughout the study. The calculations and comparisons were applied to a set of 30 small molecules representing common fragments of biological molecules. The molecular properties investigated are the energies and the electrostatic moments (up to and including the quadrupoles), and the atomic properties include electron populations (and atomic charge), atomic dipolar and quadrupolar polarizations, atomic volumes, and corrected and raw atomic energies. The Cartesian distance between dipole vectors and the Frobenius distance between the quadrupole tensors calculated at the three levels of theory provide a measure of their correlation (or lack thereof). With the exception of energies (atomic and molecular), it is found that both DFT and H-F are in excellent agreement with MP2, especially with regards to the electrostatic mutipoles up to the quadrupoles, but DFT and MP2 agree better in almost all studied properties (with the exception of molecular geometries). QTAIM properties whether obtained from H-F, DFT(B3LYP), or MP2 calculations when used in the construction of empirical correlations with experiment such as quantitative structure-activity-(or property)-relationships (QSAR/QSPR) are equivalent (because the properties calculated at the three levels are very highly correlated among themselves with r(2) typically >0.95, and therefore preserving trends). These results suggest that the massive volume of results that were published in the older literature at the H-F level is valid especially when used to study trends or in QSAR or QSPR studies, and, as long as our test set of molecules is representative, there is no pressing need to re-evaluate them at other levels of theory

  20. Calculation of Positron Binding Energies and Electron-Positron Annihilation Rates for Atomic Systems with the Reduced Explicitly Correlated Hartree-Fock Method in the Nuclear-Electronic Orbital Framework.

    PubMed

    Brorsen, Kurt R; Pak, Michael V; Hammes-Schiffer, Sharon

    2017-01-19

    Although the binding of a positron to a neutral atom has not been directly observed experimentally, high-level theoretical methods have predicted that a positron will bind to a neutral atom. In the present study, the binding energies of a positron to lithium, sodium, beryllium, and magnesium, as well as the electron-positron annihilation rates for these systems, are calculated using the reduced explicitly correlated Hartree-Fock (RXCHF) method within the nuclear-electronic orbital (NEO) framework. Due to the lack of explicit electron-positron correlation, NEO Hartree-Fock and full configuration interaction calculations with reasonable electronic and positronic basis sets do not predict positron binding to any of these atoms. In contrast, the RXCHF calculations predict positron binding energies and electron-positron annihilation rates in qualitative agreement with previous highly accurate but computationally expensive stochastic variational method calculations. These results illustrate that the RXCHF method can successfully describe the binding of a positron to a neutral species with no dipole moment. Moreover, the RXCHF method will be computationally tractable for calculating positron binding to molecular systems. The RXCHF approach offers a balance of accuracy and computational tractability for studying these types of positronic systems.

  1. Solution of the Skyrme-Hartree-Fock-Bogolyubov equations in the Cartesian deformed harmonic-oscillator basis. (VII) HFODD (v2.49t): A new version of the program

    SciTech Connect

    Schunck, Nicolas F; McDonnell, J.; Sheikh, J. A.; Staszczak, A.; Stoitsov, Mario; Dobaczewski, J.; Toivanen, P.

    2012-01-01

    We describe the new version (v2.49t) of the code HFODD which solves the nuclear Skyrme Hartree-Fock (HF) or Skyrme Hartree-Fock-Bogolyubov (HFB) problem by using the Cartesian deformed harmonic-oscillator basis. In the new version, we have implemented the following physics features: (i) the isospin mixing and projection, (ii) the finite temperature formalism for the HFB and HF+BCS methods, (iii) the Lipkin translational energy correction method, (iv) the calculation of the shell correction. A number of specific numerical methods have also been implemented in order to deal with large-scale multi-constraint calculations and hardware limitations: (i) the two-basis method for the HFB method, (ii) the Augmented Lagrangian Method (ALM) for multi-constraint calculations, (iii) the linear constraint method based on the approximation of the RPA matrix for multi-constraint calculations, (iv) an interface with the axial and parity-conserving Skyrme-HFB code HFBTHO, (v) the mixing of the HF or HFB matrix elements instead of the HF fields. Special care has been paid to using the code on massively parallel leadership class computers. For this purpose, the following features are now available with this version: (i) the Message Passing Interface (MPI) framework, (ii) scalable input data routines, (iii) multi-threading via OpenMP pragmas, (iv) parallel diagonalization of the HFB matrix in the simplex breaking case using the ScaLAPACK library. Finally, several little significant errors of the previous published version were corrected.

  2. 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

  3. Systematic study of low-lying E1 strength using the time-dependent mean field theory

    SciTech Connect

    Ebata, S.; Nakatsukasa, T.; Inakura, T.

    2012-11-12

    We carry out systematic investigation of electric dipole (E1) mode from light to heavy nuclei, using a new time-dependent mean field theory: the Canonical-basis Time-Dependent Hartree-Fock-Bogoliubov (Cb-TDHFB) theory. The Cb-TDHFB in the three-dimensional coordinate space representation can deal with pairing correlation and any kind of deformation in the timedependent framework. We report the neutron-number dependence of the low-energy E1 mode for light (A > 40) and heavy isotopes (A < 100) around N= 82.

  4. Coupled 3D time-dependent wave-packet approach in hyperspherical coordinates: application to the adiabatic singlet-state(1(1)A') D(+) + H2 reaction.

    PubMed

    Sahoo, Tapas; Ghosh, Sandip; Adhikari, Satrajit; Sharma, Rahul; Varandas, António J C

    2014-07-03

    We explore a coupled three-dimensional (3D) time-dependent wave packet formalism in hyperspherical coordinates for a 4D reactive scattering problem on the lowest adiabatic singlet surface (1(1)A') of the D(+) + H2 reaction. The coupling among the wavepackets arises through quantization of the rotation matrix, which represents the orientation of the three particles in space. The required transformation from Jacobi to hyperspherical coordinates and vice versa during initialization and projection of the wave packet on the asymptotic state(s), and the coupled equations of motion, are briefly discussed. With the long-range potential known to contribute significantly on the D(+) + H2 system, we demonstrate the workability of our approach, where the convergence profiles of the reaction probability for the reactive noncharge transfer (RNCT) process [D(+) + H2(v=0, j=0,1) → HD(v',j') + H(+)] are shown for three different collisional energies (1.7, 2.1, and 2.5 eV) with respect to the helicity (K) and total angular momentum (J) quantum numbers. The calculated reactive cross-section is presented as a function of the collision energy for two different initial states of the diatom (v = 0, j = 0, 1).

  5. Valence excitation energies of alkenes, carbonyl compounds, and azabenzenes by time-dependent density functional theory: linear response of the ground state compared to collinear and noncollinear spin-flip TDDFT with the Tamm-Dancoff approximation.

    PubMed

    Isegawa, Miho; Truhlar, Donald G

    2013-04-07

    Time-dependent density functional theory (TDDFT) holds great promise for studying photochemistry because of its affordable cost for large systems and for repeated calculations as required for direct dynamics. The chief obstacle is uncertain accuracy. There have been many validation studies, but there are also many formulations, and there have been few studies where several formulations were applied systematically to the same problems. Another issue, when TDDFT is applied with only a single exchange-correlation functional, is that errors in the functional may mask successes or failures of the formulation. Here, to try to sort out some of the issues, we apply eight formulations of adiabatic TDDFT to the first valence excitations of ten molecules with 18 density functionals of diverse types. The formulations examined are linear response from the ground state (LR-TDDFT), linear response from the ground state with the Tamm-Dancoff approximation (TDDFT-TDA), the original collinear spin-flip approximation with the Tamm-Dancoff (TD) approximation (SF1-TDDFT-TDA), the original noncollinear spin-flip approximation with the TDA approximation (SF1-NC-TDDFT-TDA), combined self-consistent-field (SCF) and collinear spin-flip calculations in the original spin-projected form (SF2-TDDFT-TDA) or non-spin-projected (NSF2-TDDFT-TDA), and combined SCF and noncollinear spin-flip calculations (SF2-NC-TDDFT-TDA and NSF2-NC-TDDFT-TDA). Comparing LR-TDDFT to TDDFT-TDA, we observed that the excitation energy is raised by the TDA; this brings the excitation energies underestimated by full linear response closer to experiment, but sometimes it makes the results worse. For ethylene and butadiene, the excitation energies are underestimated by LR-TDDFT, and the error becomes smaller making the TDA. Neither SF1-TDDFT-TDA nor SF2-TDDFT-TDA provides a lower mean unsigned error than LR-TDDFT or TDDFT-TDA. The comparison between collinear and noncollinear kernels shows that the noncollinear kernel

  6. Valence excitation energies of alkenes, carbonyl compounds, and azabenzenes by time-dependent density functional theory: Linear response of the ground state compared to collinear and noncollinear spin-flip TDDFT with the Tamm-Dancoff approximation

    NASA Astrophysics Data System (ADS)

    Isegawa, Miho; Truhlar, Donald G.

    2013-04-01

    Time-dependent density functional theory (TDDFT) holds great promise for studying photochemistry because of its affordable cost for large systems and for repeated calculations as required for direct dynamics. The chief obstacle is uncertain accuracy. There have been many validation studies, but there are also many formulations, and there have been few studies where several formulations were applied systematically to the same problems. Another issue, when TDDFT is applied with only a single exchange-correlation functional, is that errors in the functional may mask successes or failures of the formulation. Here, to try to sort out some of the issues, we apply eight formulations of adiabatic TDDFT to the first valence excitations of ten molecules with 18 density functionals of diverse types. The formulations examined are linear response from the ground state (LR-TDDFT), linear response from the ground state with the Tamm-Dancoff approximation (TDDFT-TDA), the original collinear spin-flip approximation with the Tamm-Dancoff (TD) approximation (SF1-TDDFT-TDA), the original noncollinear spin-flip approximation with the TDA approximation (SF1-NC-TDDFT-TDA), combined self-consistent-field (SCF) and collinear spin-flip calculations in the original spin-projected form (SF2-TDDFT-TDA) or non-spin-projected (NSF2-TDDFT-TDA), and combined SCF and noncollinear spin-flip calculations (SF2-NC-TDDFT-TDA and NSF2-NC-TDDFT-TDA). Comparing LR-TDDFT to TDDFT-TDA, we observed that the excitation energy is raised by the TDA; this brings the excitation energies underestimated by full linear response closer to experiment, but sometimes it makes the results worse. For ethylene and butadiene, the excitation energies are underestimated by LR-TDDFT, and the error becomes smaller making the TDA. Neither SF1-TDDFT-TDA nor SF2-TDDFT-TDA provides a lower mean unsigned error than LR-TDDFT or TDDFT-TDA. The comparison between collinear and noncollinear kernels shows that the noncollinear kernel

  7. Solution of the Self-consistent Skyrme Hartree-Fock-Bogoliubov Equations in the Cartesian Deformed Harmonic Oscillator Bssis (VII_HFODD (v.2.73y): a new version of the jprogram

    SciTech Connect

    Schunck, N.; Dobaczewski, J.; Satula, W.; Baczyk, P.; Dudek, J.; Gao, Y.; Konieczka, M.; Sato, K.; Shi, Y.; Wang, X. B.; Werner, T. R.

    2016-10-05

    HFODD is a physics computer code that is used to model the structure of the nucleus. It is an implimentation of the nuclear energy Density Functional Theory (DFT), where the energy of the nucleus is obtained by intergration over space of some phenomenological energy density, which is itself a functional of the neutron and proton densities. In HFODD, the energy density derives from either the Skyre or the Gogny effective two-body interaction between nucleons. Nuclear super-fluidity is treated a the Hartree-Fock-Boboliubov (HFB) approximation. This version is the 8th release of the code; the 7 previous versions have been published in Computer Physics Communications (see references). Version 2.49p was partly developed at LLNL and was released under a GPL License and IM number LLNL-CODE-470611. The currect version 2.73y is the second version that has been partly developed a LLNL.

  8. Implementation of Analytical Energy Gradient of Spin-Dependent General Hartree-Fock Method Based on the Infinite-Order Douglas-Kroll-Hess Relativistic Hamiltonian with Local Unitary Transformation.

    PubMed

    Nakajima, Yuya; Seino, Junji; Nakai, Hiromi

    2016-05-10

    An analytical energy gradient for the spin-dependent general Hartree-Fock method based on the infinite-order Douglas-Kroll-Hess (IODKH) method was developed. To treat realistic systems, the local unitary transformation (LUT) scheme was employed both in energy and energy gradient calculations. The present energy gradient method was numerically assessed to investigate the accuracy in several diatomic molecules containing fifth- and sixth-period elements and to examine the efficiency in one-, two-, and three-dimensional silver clusters. To arrive at a practical calculation, we also determined the geometrical parameters of fac-tris(2-phenylpyridine)iridium and investigated the efficiency. The numerical results confirmed that the present method describes a highly accurate relativistic effect with high efficiency. The present method can be a powerful scheme for determining geometries of large molecules, including heavy-element atoms.

  9. Finite-field Calculations of Molecular Polarizabilities Using Field-Induced Polarization Functions: Second- and Third-order Perturbation Correlation Corrections to the Coupled Hartree-Fock Polarizability of H2O

    NASA Technical Reports Server (NTRS)

    Langhoff, S. R.; Scott, W. R.; Suzuki, N.; Chong, D. P.

    1979-01-01

    Ordinary Rayleigh-Schroudinger perturbation theory with Moller-Plesset (RSMP) partitioning is used to calculate second- and third-order correlation corrections to the CHF polarizability and dipole moment of the water molecule by a finite-field procedure. Pade approximants are found to be useful in accelerating the convergence of the property perturbation expansions. Field-induced polarization functions suitable for polarizability calculations are determined. The average polarizability calculated, neglecting vibrational averaging, with Dunning's (9s5p/4s-4s2p/2s) contracted GTO basis set augmented by field-induced lslp2d/lp polarization functions is within 3 per cent of the experimental result. Correlation corrections to the dipole moment and polarizability of the water molecule calculated by the finite-field RSMP and single + double excitation CI(SDCI) methods for the same basis set are found to be in close agreement. The RSMP approach has the advantages of being size-consistent and of being capable of greater efficiency than the SCDI method. Comparative calculations carried out using Epstein-Nesbet partitioning show that through third order RSEN correlation perturbation expansions for the dipole moment and polarizability are less rapidly convergent than RSMP expansions. However, reasonable accord with RSMP results can be achieved by using Pade approximants to accelerate the convergence of RSEN energy perturbation expansions. The convergence of RSMP property correlation expansions based on the zeroth-order uncoupled-Hartree-Fock (UCHF) and coupled-Hartree-Fock (CHF) approximations are compared through third order. Whereas the CHF + RSMP expansions are for practical purposes fully converged, the UCHF + RSMP expansions are not adequately converged.

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

    NASA Astrophysics Data System (ADS)

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

    2009-11-01

    We describe the new version (v2.40h) of the code HFODD which solves the nuclear Skyrme-Hartree-Fock or Skyrme-Hartree-Fock-Bogolyubov problem by using the Cartesian deformed harmonic-oscillator basis. In the new version, we have implemented: (i) projection on good angular momentum (for the Hartree-Fock states), (ii) calculation of the GCM kernels, (iii) calculation of matrix elements of the Yukawa interaction, (iv) the BCS solutions for state-dependent pairing gaps, (v) the HFB solutions for broken simplex symmetry, (vi) calculation of Bohr deformation parameters, (vii) constraints on the Schiff moments and scalar multipole moments, (viii) the DT2h transformations and rotations of wave functions, (ix) quasiparticle blocking for the HFB solutions in odd and odd-odd nuclei, (x) the Broyden method to accelerate the convergence, (xi) the Lipkin-Nogami method to treat pairing correlations, (xii) the exact Coulomb exchange term, (xiii) several utility options, and we have corrected three insignificant errors. New version program summaryProgram title: HFODD (v2.40h) Catalogue identifier: ADFL_v2_2 Program summary URL:http://cpc.cs.qub.ac.uk/summaries/ADFL_v2_2.html Program obtainable from: CPC Program Library, Queen's University, Belfast, N. Ireland Licensing provisions: Standard CPC licence, http://cpc.cs.qub.ac.uk/licence/licence.html No. of lines in distributed program, including test data, etc.: 79 618 No. of bytes in distributed program, including test data, etc.: 372 548 Distribution format: tar.gz Programming language: FORTRAN-77 and Fortran-90 Computer: Pentium-III, AMD-Athlon, AMD-Opteron Operating system: UNIX, LINUX, Windows XP Has the code been

  11. Exploring water radiolysis in proton cancer therapy: Time-dependent, non-adiabatic simulations of H+ + (H2O)1-6.

    PubMed

    Privett, Austin J; Teixeira, Erico S; Stopera, Christopher; Morales, Jorge A

    2017-01-01

    To elucidate microscopic details of proton cancer therapy (PCT), we apply the simplest-level electron nuclear dynamics (SLEND) method to H+ + (H2O)1-6 at ELab = 100 keV. These systems are computationally tractable prototypes to simulate water radiolysis reactions-i.e. the PCT processes that generate the DNA-damaging species against cancerous cells. To capture incipient bulk-water effects, ten (H2O)1-6 isomers are considered, ranging from quasi-planar/multiplanar (H2O)1-6 to "smallest-drop" prism and cage (H2O)6 structures. SLEND is a time-dependent, variational, non-adiabatic and direct method that adopts a nuclear classical-mechanics description and an electronic single-determinantal wavefunction in the Thouless representation. Short-time SLEND/6-31G* (n = 1-6) and /6-31G** (n = 1-5) simulations render cluster-to-projectile 1-electron-transfer (1-ET) total integral cross sections (ICSs) and 1-ET probabilities. In absolute quantitative terms, SLEND/6-31G* 1-ET ICS compares satisfactorily with alternative experimental and theoretical results only available for n = 1 and exhibits almost the same accuracy of the best alternative theoretical result. SLEND/6-31G** overestimates 1-ET ICS for n = 1, but a comparable overestimation is also observed with another theoretical method. An investigation on H+ + H indicates that electron direct ionization (DI) becomes significant with the large virtual-space quasi-continuum in large basis sets; thus, SLEND/6-31G** 1-ET ICS is overestimated by DI contributions. The solution to this problem is discussed. In relative quantitative terms, both SLEND/6-31* and /6-31G** 1-ET ICSs precisely fit into physically justified scaling formulae as a function of the cluster size; this indicates SLEND's suitability for predicting properties of water clusters with varying size. Long-time SLEND/6-31G* (n = 1-4) simulations predict the formation of the DNA-damaging radicals H, OH, O and H3O. While "smallest-drop" isomers are included, no early

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

    NASA Astrophysics Data System (ADS)

    Dobaczewski, J.; Olbratowski, P.

    2004-04-01

    We describe the new version (v2.08i) of the code HFODD which solves the nuclear Skyrme-Hartree-Fock or Skyrme-Hartree-Fock-Bogolyubov problem by using the Cartesian deformed harmonic-oscillator basis. In the new version, all symmetries can be broken, which allows for calculations with angular frequency and angular momentum tilted with respect to the mass distribution. The new version contains an interface to the LAPACK subroutine ZHPEVX. Program summaryTitle of the program:HFODD (v2.08i) Catalogue number: ADTO Program obtainable from: CPC Program Library, Queen's University of Belfast, N. Ireland Program summary URL:http://cpc.cs.qub.ac.uk/summaries/ADTO Reference in CPC for earlier version of program: J. Dobaczewski and J. Dudek, Comput. Phys. Commun. 131 (2000) 164 (v1.75r) Catalogue number of previous version: ADML Licensing provisions: none Does the new version supersede the previous one: yes Computers on which the program has been tested: SG Power Challenge L, Pentium-II, Pentium-III, AMD-Athlon Operating systems: UNIX, LINUX, Windows-2000 Programming language used: FORTRAN-77 and FORTRAN-90 Memory required to execute with typical data: 10 Mwords No. of bits in a word: The code is written in single-precision for the use on a 64-bit processor. The compiler option -r8 or +autodblpad (or equivalent) has to be used to promote all real and complex single-precision floating-point items to double precision when the code is used on a 32-bit machine. Has the code been vectorised?: Yes No. of bytes in distributed program, including test data, etc.: 265352 No. of lines in distributed program: 52656 Distribution format: tar gzip file Nature of physical problem: The nuclear mean-field and an analysis of its symmetries in realistic cases are the main ingredients of a description of nuclear states. Within the Local Density Approximation, or for a zero-range velocity-dependent Skyrme interaction, the nuclear mean-field is local and velocity dependent. The locality allows for

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

    PubMed

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

    2012-03-21

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

  14. Time-dependent stochastic Bethe-Salpeter approach

    NASA Astrophysics Data System (ADS)

    Rabani, Eran; Baer, Roi; Neuhauser, Daniel

    2015-06-01

    A time-dependent formulation for electron-hole excitations in extended finite systems, based on the Bethe-Salpeter equation (BSE), is developed using a stochastic wave function approach. The time-dependent formulation builds on the connection between time-dependent Hartree-Fock (TDHF) theory and the configuration-interaction with single substitution (CIS) method. This results in a time-dependent Schrödinger-like equation for the quasiparticle orbital dynamics based on an effective Hamiltonian containing direct Hartree and screened exchange terms, where screening is described within the random-phase approximation (RPA). To solve for the optical-absorption spectrum, we develop a stochastic formulation in which the quasiparticle orbitals are replaced by stochastic orbitals to evaluate the direct and exchange terms in the Hamiltonian as well as the RPA screening. This leads to an overall quadratic scaling, a significant improvement over the equivalent symplectic eigenvalue representation of the BSE. Application of the time-dependent stochastic BSE (TDsBSE) approach to silicon and CdSe nanocrystals up to size of ≈3000 electrons is presented and discussed.

  15. Finite-temperature second-order many-body perturbation and Hartree-Fock theories for one-dimensional solids: an application to Peierls and charge-density-wave transitions in conjugated polymers.

    PubMed

    He, Xiao; Ryu, Shinsei; Hirata, So

    2014-01-14

    Finite-temperature extensions of ab initio Gaussian-basis-set spin-restricted Hartree-Fock (HF) and second-order many-body perturbation (MP2) theories are implemented for infinitely extended, periodic, one-dimensional solids and applied to the Peierls and charge-density-wave (CDW) transitions in polyyne and all-trans polyacetylene. The HF theory predicts insulating CDW ground states for both systems in their equidistant structures at low temperatures. In the same structures, they turn metallic at high temperatures. Starting from the "dimerized" low-temperature equilibrium structures, the systems need even higher temperatures to undergo a Peierls transition, which is accompanied by geometric as well as electronic distortions from dimerized to non-dimerized forms. The conventional finite-temperature MP2 theory shows a sign of divergence in any phase at any nonzero temperature and is useless. The renormalized finite-temperature MP2 (MP2R) theory is divergent only near metallic electronic structures, but is well behaved elsewhere. MP2R also predicts CDW and Peierls transitions occurring at two different temperatures. The effect of electron correlation is primarily to lower the Peierls transition temperature.

  16. Core-level electronic structure of solid-phase glycine, glycyl-glycine, diglycyl-glycine, and polyglycine: X-ray photoemission analysis and Hartree-Fock calculations of their zwitterions.

    PubMed

    Chatterjee, Avisek; Zhao, Liyan; Zhang, Lei; Pradhan, Debabrata; Zhou, Xiaojing; Leung, K T

    2008-09-14

    X-ray photoelectron spectroscopy (XPS) has been used to investigate the core-level electronic structures of glycine (G) and its peptides, including glycyl-glycine (GG), diglycyl-glycine (GGG), and polyglycine (poly-G), in their powder forms. Increasing the number of G units in the peptides does not change the locations of the respective C 1s, N 1s, and O 1s features corresponding to different functional groups: -COO(-), -NH(3)(+), >CH(2), and -CONH-. The electronic structures of the zwitterions of these molecules have been calculated as isolated molecules and as molecules in an aqueous environment under the periodic boundary conditions by quantum-mechanical and molecular mechanics methods. In the case of glycine zwitterion, the binding energies of the C 1s, N 1s, and O 1s XPS features are found to be in reasonable accord with the respective orbital energies obtained by Hartree-Fock self-consistent-field calculations, within the context of Koopmans' approximation. However, considerably worse agreement in the binding energies is found for the larger zwitterions (with the specific conformations considered in this work), indicating the need for higher-level calculations. The present work shows that optimizing the zwitterion in an aqueous environment under the periodic boundary conditions by molecular mechanics could be a very cost-effective approach for calculating the electronic structures of large, complex biomolecular systems.

  17. Multiconfiguration Dirac-Hartree-Fock Adjusted Energy-Consistent Pseudopotential for Uranium: Spin-Orbit Configuration Interaction and Fock-Space Coupled-Cluster Study of U4+ and U5+

    NASA Astrophysics Data System (ADS)

    Weigand, Anna; Cao, Xiaoyan; Vallet, Valérie; Flament, Jean-Pierre; Dolg, Michael

    2009-07-01

    In order to assess the accuracy of a recently adjusted relativistic energy-consistent small-core pseudopotential for uranium, the U5+ (5f1 subconfiguration) spin-orbit splitting as well as the fine structure of the U4+ (5f2 subconfiguration) spectrum have been calculated. The pseudopotential has been adjusted to four-component all-electron data, i.e., at the multiconfiguration Dirac-Hartree-Fock level using the Dirac-Coulomb Hamiltonian with a Fermi nucleus charge distribution and perturbatively including the Breit interaction. Its performance in a dressed effective Hamiltonian spin-orbit configuration interaction framework is compared to that of an older scalar-relativistic Wood-Boring adjusted pseudopotential, supplemented by a valence spin-orbit term, as well as to all-electron calculations using the Douglas-Kroll-Hess Hamiltonian. Electron correlation is accounted for by the multireference configuration interaction method with and without the Davidson correction and with different frozen-orbital spaces. Our best calculations show satisfactory agreement with experimental data; i.e., the mean absolute (relative) deviations amount to 183 (2.4%) and 948 cm-1 (5.1%) for the U5+ and the U4+ fine-structure energy levels, respectively. Even better agreement, comparable to the one for rigorous highly correlated four-component all-electron data, is obtained in intermediate Hamiltonian Fock-space coupled-cluster calculations applying the new pseudopotential.

  18. The study of the action of self-friction field on the atom and molecular structures by using combined Hartree-Fock-Roothaan theory for closed and open shells of any symmetry

    NASA Astrophysics Data System (ADS)

    Mamedov, B. A.; Çopuroğlu, E.

    2016-06-01

    In this work, we study the effects of self-friction field on the states of a single configuration of closed and open shells by using the Combined Hartree-Fock-Roothaan equations for atomic-molecular and nuclear systems. Here, we present a program that implements the evaluation of the various properties of atoms and molecular systems with respect to the various values of self-friction quantum numbers. An especially fast and accurate algorithm for the calculation of the self-friction multicenter molecular integrals is obtained by using one-range addition theorems. To demonstrate the action of self-friction field on the atomic and molecular systems we have performed the calculations of H2O, CH3, CH2 and NH3 molecules. For the derivations of the orbital, kinetic and total energies and linear combination coefficients, the results are given for various values of self-friction quantum numbers. For various values of self-friction quantum numbers the obtained results of the orbital, kinetic and total energies and linear combination coefficients have been analyzed.

  19. Representation independent algorithms for molecular response calculations in time-dependent self-consistent field theories

    SciTech Connect

    Tretiak, Sergei

    2008-01-01

    Four different numerical algorithms suitable for a linear scaling implementation of time-dependent Hartree-Fock and Kohn-Sham self-consistent field theories are examined. We compare the performance of modified Lanczos, Arooldi, Davidson, and Rayleigh quotient iterative procedures to solve the random-phase approximation (RPA) (non-Hermitian) and Tamm-Dancoff approximation (TDA) (Hermitian) eigenvalue equations in the molecular orbital-free framework. Semiempirical Hamiltonian models are used to numerically benchmark algorithms for the computation of excited states of realistic molecular systems (conjugated polymers and carbon nanotubes). Convergence behavior and stability are tested with respect to a numerical noise imposed to simulate linear scaling conditions. The results single out the most suitable procedures for linear scaling large-scale time-dependent perturbation theory calculations of electronic excitations.

  20. Representation independent algorithms for molecular response calculations in time-dependent self-consistent field theories

    NASA Astrophysics Data System (ADS)

    Tretiak, Sergei; Isborn, Christine M.; Niklasson, Anders M. N.; Challacombe, Matt

    2009-02-01

    Four different numerical algorithms suitable for a linear scaling implementation of time-dependent Hartree-Fock and Kohn-Sham self-consistent field theories are examined. We compare the performance of modified Lanczos, Arooldi, Davidson, and Rayleigh quotient iterative procedures to solve the random-phase approximation (RPA) (non-Hermitian) and Tamm-Dancoff approximation (TDA) (Hermitian) eigenvalue equations in the molecular orbital-free framework. Semiempirical Hamiltonian models are used to numerically benchmark algorithms for the computation of excited states of realistic molecular systems (conjugated polymers and carbon nanotubes). Convergence behavior and stability are tested with respect to a numerical noise imposed to simulate linear scaling conditions. The results single out the most suitable procedures for linear scaling large-scale time-dependent perturbation theory calculations of electronic excitations.

  1. High-harmonic spectra from time-dependent two-particle reduced-density-matrix theory

    NASA Astrophysics Data System (ADS)

    Lackner, Fabian; Březinová, Iva; Sato, Takeshi; Ishikawa, Kenichi L.; Burgdörfer, Joachim

    2017-03-01

    The ab initio description of the nonlinear response of many-electron systems to strong-laser fields remains a major challenge. In order to address larger systems, alternative methods need to be developed that bypass the exponential scaling with particle number inherent to conventional wave-function-based approaches. In this paper we present a fully three-dimensional implementation of the time-dependent two-particle reduced-density-matrix (TD-2RDM) method for many-electron atoms. We benchmark this approach by a comparison with multiconfigurational time-dependent Hartree-Fock results for the harmonic spectra of beryllium and neon. We show that the TD-2RDM is very well suited to describe the nonlinear atomic response and to reveal the influence of electron-correlation effects.

  2. A new approach to time-dependent transport through an interacting quantum dot within the Keldysh formalism.

    PubMed

    Vovchenko, V; Anchishkin, D; Azema, J; Lombardo, P; Hayn, R; Daré, A-M

    2014-01-08

    The time-dependent transport through a nanoscale device consisting of a single spin-degenerate orbital with on-site Coulomb interaction, coupled to two leads, is investigated. Various gate and bias voltage time dependences are considered. The key and new point lies in the proposed way to avoid the difficulties of the usual heavy computation when dealing with two-time Green's functions within the Keldysh formalism. The time-dependent retarded dot Green's functions are evaluated, in an efficient manner within a non-canonical Hubbard I approximation. Calculations of the time-dependent current are then presented in the wide-band limit for different parameter sets. A comparison between the method and the Hartree-Fock approximation is performed as well. It is shown that the latter cannot account reliably for dynamical aspects of transport phenomena.

  3. Description of molecular dynamics in intense laser fields by the time-dependent adiabatic state approach: application to simultaneous two-bond dissociation of CO2 and its control.

    PubMed

    Sato, Yukio; Kono, Hirohiko; Koseki, Shiro; Fujimura, Yuichi

    2003-07-02

    We theoretically investigated the dynamics of structural deformations of CO(2) and its cations in near-infrared intense laser fields (approximately 10(15) W cm(-2)) by using the time-dependent adiabatic state approach. To obtain "field-following" adiabatic potentials for nuclear dynamics, the electronic Hamiltonian including the interaction with the instantaneous laser electric field is diagonalized by the multiconfiguration self-consistent-field molecular orbital method. In the CO(2) and CO(2+) stages, ionization occurs before the field intensity becomes high enough to deform the molecule. In the CO(2)(2+) stage, simultaneous symmetric two-bond stretching occurs as well as one-bond stretching. Two-bond stretching is induced by an intense field in the lowest time-dependent adiabatic state |1> of CO(2)(2+), and this two-bond stretching is followed by the occurrence of a large-amplitude bending motion mainly in the second-lowest adiabatic state |2> nonadiabatically created at large internuclear distances by the field from |1>. It is concluded that the experimentally observed stretched and bent structure of CO(2)(3+) just before Coulomb explosions originates from the structural deformation of CO(2)(2+). We also show in this report that the concept of "optical-cycle-averaged potential" is useful for designing schemes to control molecular (reaction) dynamics, such as dissociation dynamics of CO(2), in intense fields. The present approach is simple but has wide applicability for analysis and prediction of electronic and nuclear dynamics of polyatomic molecules in intense laser fields.

  4. Solution of the Skyrme-Hartree-Fock-Bogolyubov equations in the Cartesian deformed harmonic-oscillator basis.. (VII) HFODD (v2.49t): A new version of the program

    NASA Astrophysics Data System (ADS)

    Schunck, N.; Dobaczewski, J.; McDonnell, J.; Satuła, W.; Sheikh, J. A.; Staszczak, A.; Stoitsov, M.; Toivanen, P.

    2012-01-01

    We describe the new version (v2.49t) of the code HFODD which solves the nuclear Skyrme-Hartree-Fock (HF) or Skyrme-Hartree-Fock-Bogolyubov (HFB) problem by using the Cartesian deformed harmonic-oscillator basis. In the new version, we have implemented the following physics features: (i) the isospin mixing and projection, (ii) the finite-temperature formalism for the HFB and HF + BCS methods, (iii) the Lipkin translational energy correction method, (iv) the calculation of the shell correction. A number of specific numerical methods have also been implemented in order to deal with large-scale multi-constraint calculations and hardware limitations: (i) the two-basis method for the HFB method, (ii) the Augmented Lagrangian Method (ALM) for multi-constraint calculations, (iii) the linear constraint method based on the approximation of the RPA matrix for multi-constraint calculations, (iv) an interface with the axial and parity-conserving Skyrme-HFB code HFBTHO, (v) the mixing of the HF or HFB matrix elements instead of the HF fields. Special care has been paid to using the code on massively parallel leadership class computers. For this purpose, the following features are now available with this version: (i) the Message Passing Interface (MPI) framework, (ii) scalable input data routines, (iii) multi-threading via OpenMP pragmas, (iv) parallel diagonalization of the HFB matrix in the simplex-breaking case using the ScaLAPACK library. Finally, several little significant errors of the previous published version were corrected. New version program summaryProgram title:HFODD (v2.49t) Catalogue identifier: ADFL_v3_0 Program summary URL:http://cpc.cs.qub.ac.uk/summaries/ADFL_v3_0.html Program obtainable from: CPC Program Library, Queen's University, Belfast, N. Ireland Licensing provisions: GNU General Public Licence v3 No. of lines in distributed program, including test data, etc.: 190 614 No. of bytes in distributed program, including test data, etc.: 985 898 Distribution

  5. Homogeneous Ni Catalysts for H2 Oxidation and Production: An Assessment of Theoretical Methods, from Density Functional Theory to Post Hartree-Fock Correlated Wave-Function Theory

    SciTech Connect

    Chen, Shentan; Raugei, Simone; Rousseau, Roger; Dupuis, Michel; Bullock, R. Morris

    2010-12-09

    A systematic assessment of theoretical methods applicable to the accurate characterization of catalytic cycles of homogeneous catalysts for H2 oxidation and evolution is reported. The key elementary steps involve heterolytic cleavage of the H-H bond and formation/cleavage of Ni-H and N-H bonds. In the context of density functional theory (DFT), we investigated the use of functionals in the generalized gradient approximation (GGA) as well as hybrid functionals. We compared the results with wave-function theories based on perturbation theory (MP2 and MP4) and on coupled-cluster expansions [CCD, CCSD, and CCSD(T)]. Our findings indicate that DFT results based on Perdew correlation functionals are in semiquantitative agreement with the CCSD(T) results, with deviations of only a few kilocalories/mole. On the other hand, the B3LYP functional is not even in qualitative agreement with CCSD(T). Surprisingly, the MP2 results are found to be extremely poor, in particular for the diproton Ni(0) and dihydride Ni(IV) species on the reaction potential energy surface. The Hartree-Fock reference wave function in MP2 theory gives a poor reference state description for these states that are electron rich on Ni, giving rise to erroneous MP2 energies. Finally, we present a detailed potential-energy diagram for the oxidation of H2 by these catalysts after accounting for the effects of solvation, as modeled by a polarizable continuum, and of free energy estimated at the harmonic level of theory.

  6. Axially deformed solution of the Skyrme-Hartree-Fock-Bogoliubov equations using the transformed harmonic oscillator basis (II) HFBTHO v2.00d: A new version of the program

    NASA Astrophysics Data System (ADS)

    Stoitsov, M. V.; Schunck, N.; Kortelainen, M.; Michel, N.; Nam, H.; Olsen, E.; Sarich, J.; Wild, S.

    2013-06-01

    We describe the new version 2.00d of the code HFBTHO that solves the nuclear Skyrme-Hartree-Fock (HF) or Skyrme-Hartree-Fock-Bogoliubov (HFB) problem by using the cylindrical transformed deformed harmonic oscillator basis. In the new version, we have implemented the following features: (i) the modified Broyden method for non-linear problems, (ii) optional breaking of reflection symmetry, (iii) calculation of axial multipole moments, (iv) finite temperature formalism for the HFB method, (v) linear constraint method based on the approximation of the Random Phase Approximation (RPA) matrix for multi-constraint calculations, (vi) blocking of quasi-particles in the Equal Filling Approximation (EFA), (vii) framework for generalized energy density with arbitrary density-dependences, and (viii) shared memory parallelism via OpenMP pragmas. Program summaryProgram title: HFBTHO v2.00d Catalog identifier: ADUI_v2_0 Program summary URL:http://cpc.cs.qub.ac.uk/summaries/ADUI_v2_0.html Program obtainable from: CPC Program Library, Queen's University, Belfast, N. Ireland Licensing provisions: GNU General Public License version 3 No. of lines in distributed program, including test data, etc.: 167228 No. of bytes in distributed program, including test data, etc.: 2672156 Distribution format: tar.gz Programming language: FORTRAN-95. Computer: Intel Pentium-III, Intel Xeon, AMD-Athlon, AMD-Opteron, Cray XT5, Cray XE6. Operating system: UNIX, LINUX, WindowsXP. RAM: 200 Mwords Word size: 8 bits Classification: 17.22. Does the new version supercede the previous version?: Yes Catalog identifier of previous version: ADUI_v1_0 Journal reference of previous version: Comput. Phys. Comm. 167 (2005) 43 Nature of problem: The solution of self-consistent mean-field equations for weakly-bound paired nuclei requires a correct description of the asymptotic properties of nuclear quasi-particle wave functions. In the present implementation, this is achieved by using the single-particle wave functions

  7. Bimolecular recombination reactions: K-adiabatic and K-active forms of RRKM theory, nonstatistical aspects, low-pressure rates, and time-dependent survival probabilities with application to ozone. 2.

    PubMed

    Ghaderi, Nima; Marcus, R A

    2014-11-06

    We consider for bimolecular recombination reactions the K-adiabatic versus the K-active forms of RRKM theory, where K is the component of the total angular momentum along the axis of least moment of inertia of the recombination product. When that product is approximately a prolate symmetric top, with two moments of inertia of the product substantially larger than the third, K becomes a dynamically slowly varying quantity and the K-adiabatic form of RRKM theory is the appropriate version to use. Using classical trajectory results for the rate constant for ozone formation in the low-pressure region as an example, excellent agreement for the recombination rate constant k(rec) with the K-adiabatic RRKM theory is observed. Use of a two transition state (inner, outer TS) formalism also obviates any need for assessing recrossings in the exit channel. In contrast, the K-active form of RRKM theory for this system disagrees with the trajectory results by a factor of about 2.5. In this study we also consider the distribution of the (E, J) resolved time-dependent survival probabilities P(E, J, t) of the intermediate O3* formed from O + O2. It is calculated using classical trajectories. The initial conditions for classical trajectories were selected using action-angle variables and a total J representation for (E, J) resolved systems, as described in Part I.1 The difference between K-active and K-adiabatic treatments is reflected also in a difference of the K-active RRKM survival probability P(E, J, t) from its trajectory-based value and from its often non-single-exponential decay. It is shown analytically that krec (K-active) ≥ k(rec) (K-adiabatic), independent of the details of the TS (e.g., variational or fixed RRKM theory, 1-TS or 2-TS). Nonstatistical effects for O3* formation include a small initial recrossing of the transition state, a slow (several picoseconds) equipartitioning of energy among the two O-O bonds of the newly formed O3*, and a small nondissociation (a

  8. Two-component hybrid time-dependent density functional theory within the Tamm-Dancoff approximation

    SciTech Connect

    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){sub 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.

  9. Two-component hybrid time-dependent density functional theory within the Tamm-Dancoff approximation

    NASA Astrophysics Data System (ADS)

    Kühn, Michael; Weigend, Florian

    2015-01-01

    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.

  10. 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.

  11. Photoassociation of cold atoms with chirped laser pulses: Time-dependent calculations and analysis of the adiabatic transfer within a two-state model

    SciTech Connect

    Luc-Koenig, E.; Masnou-Seeuws, F.; Kosloff, R.; Vatasescu, M.

    2004-09-01

    This theoretical paper presents numerical calculations for the photoassociation of ultracold cesium atoms with a chirped laser pulse and a detailed analysis of the results. In contrast with earlier work, the initial state is represented by a stationary continuum wave function. In the chosen example, it is shown that an important population transfer is achieved to {approx_equal}15 vibrational levels in the vicinity of the v=98 bound level in the external well of the 0{sub g}{sup -}(6s+6p{sub 3/2}) potential. Such levels lie in the energy range swept by the instantaneous frequency of the pulse, thus defining a 'photoassociation window'. Levels outside this window may be significantly excited during the pulse, but no population remains there after the pulse. Finally, the population transfer to the last vibrational levels of the ground a {sup 3}{sigma}{sub u}{sup +}(6s+6s) state is significant, making stable molecules. The results are interpreted in the framework of a two-state model as an adiabatic inversion mechanism, efficient only within the photoassociation window. The large value found for the photoassociation rate suggests promising applications. The present chirp has been designed in view of creating in the excited state a vibrational wave packet that is focusing at the barrier of the double-well potential.

  12. A fast parallel code for calculating energies and oscillator strengths of many-electron atoms at neutron star magnetic field strengths in adiabatic approximation

    NASA Astrophysics Data System (ADS)

    Engel, D.; Klews, M.; Wunner, G.

    2009-02-01

    We have developed a new method for the fast computation of wavelengths and oscillator strengths for medium-Z atoms and ions, up to iron, at neutron star magnetic field strengths. The method is a parallelized Hartree-Fock approach in adiabatic approximation based on finite-element and B-spline techniques. It turns out that typically 15-20 finite elements are sufficient to calculate energies to within a relative accuracy of 10-5 in 4 or 5 iteration steps using B-splines of 6th order, with parallelization speed-ups of 20 on a 26-processor machine. Results have been obtained for the energies of the ground states and excited levels and for the transition strengths of astrophysically relevant atoms and ions in the range Z=2…26 in different ionization stages. Catalogue identifier: AECC_v1_0 Program summary URL:http://cpc.cs.qub.ac.uk/summaries/AECC_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.: 3845 No. of bytes in distributed program, including test data, etc.: 27 989 Distribution format: tar.gz Programming language: MPI/Fortran 95 and Python Computer: Cluster of 1-26 HP Compaq dc5750 Operating system: Fedora 7 Has the code been vectorised or parallelized?: Yes RAM: 1 GByte Classification: 2.1 External routines: MPI/GFortran, LAPACK, PyLab/Matplotlib Nature of problem: Calculations of synthetic spectra [1] of strongly magnetized neutron stars are bedevilled by the lack of data for atoms in intense magnetic fields. While the behaviour of hydrogen and helium has been investigated in detail (see, e.g., [2]), complete and reliable data for heavier elements, in particular iron, are still missing. Since neutron stars are formed by the collapse of the iron cores of massive stars, it may be assumed that their atmospheres contain an iron plasma. Our objective is to fill the gap

  13. Time-dependent variational approach in terms of squeezed coherent states: Implication to semi-classical approximation

    NASA Technical Reports Server (NTRS)

    Tsue, Yasuhiko

    1994-01-01

    A general framework for time-dependent variational approach in terms of squeezed coherent states is constructed with the aim of describing quantal systems by means of classical mechanics including higher order quantal effects with the aid of canonicity conditions developed in the time-dependent Hartree-Fock theory. The Maslov phase occurring in a semi-classical quantization rule is investigated in this framework. In the limit of a semi-classical approximation in this approach, it is definitely shown that the Maslov phase has a geometric nature analogous to the Berry phase. It is also indicated that this squeezed coherent state approach is a possible way to go beyond the usual WKB approximation.

  14. State-resolved time-dependent wave packet and quasiclassical trajectory studies of the adiabatic reaction S(3P) + HD on the (1(3)A″) state.

    PubMed

    Cheng, Dahai; Yuan, Jiuchuang; Chen, Maodu

    2014-01-09

    Time-dependent wave packet (TDWP) and quasiclassical trajectory (QCT) calculations have been carried out for the reaction S(3P) + HD(X1Σg+) at the lowest 13A″ state with both rotational and vibrational excitations of reactant HD. The calculated integral cross sections from QCT agree fairly well with the TDWP calculations. The reaction probability results from TDWP show that the reaction displays a strong tendency to the SD channel. When the reactant HD is vibrationally excited, both channels are promoted apparently. The vibration of the HD bond tends to reduce the difference of reactivity between the two channels. The detailed state-to-state differential cross sections (DCSs) are calculated. These distributions show some significant characters of the barrier-type reactions. At the same time, the scattering width of product SD has a certain relationship with its rotation excitation. For the vector properties, P(θr), P(r), and P(θr,r) distributions are calculated by QCT, and the increased collision energy weakens the rotational polarization of the SD molecule.

  15. Many-Body Perturbation Theory (MBPT) and Time-Dependent Density-Functional Theory (TD-DFT): MBPT Insights About What Is Missing In, and Corrections To, the TD-DFT Adiabatic Approximation.

    PubMed

    Casida, Mark E; Huix-Rotllant, Miquel

    2016-01-01

    In their famous paper, Kohn and Sham formulated a formally exact density-functional theory (DFT) for the ground-state energy and density of a system of N interacting electrons, albeit limited at the time by certain troubling representability questions. As no practical exact form of the exchange-correlation (xc) energy functional was known, the xc-functional had to be approximated, ideally by a local or semilocal functional. Nowadays, however, the realization that Nature is not always so nearsighted has driven us up Perdew's Jacob's ladder to find increasingly nonlocal density/wavefunction hybrid functionals. Time-dependent (TD-) DFT is a younger development which allows DFT concepts to be used to describe the temporal evolution of the density in the presence of a perturbing field. Linear response (LR) theory then allows spectra and other information about excited states to be extracted from TD-DFT. Once again the exact TD-DFT xc-functional must be approximated in practical calculations and this has historically been done using the TD-DFT adiabatic approximation (AA) which is to TD-DFT very similar to what the local density approximation (LDA) is to conventional ground-state DFT. Although some of the recent advances in TD-DFT focus on what can be done within the AA, others explore ways around the AA. After giving an overview of DFT, TD-DFT, and LR-TD-DFT, this chapter focuses on many-body corrections to LR-TD-DFT as one way to build hybrid density-functional/wavefunction methodology for incorporating aspects of nonlocality in time not present in the AA.

  16. Time-dependent non-equilibrium dielectric response in QM/continuum approaches

    SciTech Connect

    Ding, Feizhi; Lingerfelt, David B.; Li, Xiaosong E-mail: li@chem.washington.edu; Mennucci, Benedetta E-mail: li@chem.washington.edu

    2015-01-21

    The Polarizable Continuum Models (PCMs) are some of the most inexpensive yet successful methods for including the effects of solvation in quantum-mechanical calculations of molecular systems. However, when applied to the electronic excitation process, these methods are restricted to dichotomously assuming either that the solvent has completely equilibrated with the excited solute charge density (infinite-time limit), or that it retains the configuration that was in equilibrium with the solute prior to excitation (zero-time limit). This renders the traditional PCMs inappropriate for resolving time-dependent solvent effects on non-equilibrium solute electron dynamics like those implicated in the instants following photoexcitation of a solvated molecular species. To extend the existing methods to this non-equilibrium regime, we herein derive and apply a new formalism for a general time-dependent continuum embedding method designed to be propagated alongside the solute’s electronic degrees of freedom in the time domain. Given the frequency-dependent dielectric constant of the solvent, an equation of motion for the dielectric polarization is derived within the PCM framework and numerically integrated simultaneously with the time-dependent Hartree fock/density functional theory equations. Results for small molecular systems show the anticipated dipole quenching and electronic state dephasing/relaxation resulting from out-of-phase charge fluctuations in the dielectric and embedded quantum system.

  17. Time dependent holography

    NASA Astrophysics Data System (ADS)

    Das, Diptarka

    One of the most important results emerging from string theory is the gauge gravity duality (AdS/CFT correspondence) which tells us that certain problems in particular gravitational backgrounds can be exactly mapped to a particular dual gauge theory a quantum theory very similar to the one explaining the interactions between fundamental subatomic particles. The chief merit of the duality is that a difficult problem in one theory can be mapped to a simpler and solvable problem in the other theory. The duality can be used both ways. Most of the current theoretical framework is suited to study equilibrium systems, or systems where time dependence is at most adiabatic. However in the real world, systems are almost always out of equilibrium. Generically these scenarios are described by quenches, where a parameter of the theory is made time dependent. In this dissertation I describe some of the work done in the context of studying quantum quench using the AdS/CFT correspondence. We recover certain universal scaling type of behavior as the quenching is done through a quantum critical point. Another question that has been explored in the dissertation is time dependence of the gravity theory. Present cosmological observations indicate that our universe is accelerating and is described by a spacetime called de-Sitter(dS). In 2011 there had been a speculation over a possible duality between de-Sitter gravity and a particular field theory (Euclidean SP(N) CFT). However a concrete realization of this proposition was still lacking. Here we explicitly derive the dS/CFT duality using well known methods in field theory. We discovered that the time dimension emerges naturally in the derivation. We also describe further applications and extensions of dS/CFT. KEYWORDS: Holography, AdS/CFT correspondence, Quantum Quench, dS/CFT correspondence, Chaos.

  18. Predictions of Optical Excitations in Transition-Metal Complexes with Time Dependent-Density Functional Theory:  Influence of Basis Sets.

    PubMed

    Petit, Laurence; Maldivi, Pascale; Adamo, Carlo

    2005-09-01

    The calculation of the absorption spectra of four families of transition-metal complexes (Ni(CO)4, MnO4(-), MF6 (M = Cr, Mo, W) and CpM(CO)2 (M = Rh, Ir)) has been undertaken to unravel the influence of basis sets onto excitation energies, oscillator strengths, and assignments. Three among the most common pseudopotentials, with the corresponding valence basis sets, and two all-electron basis sets have been used for the metal center description in the framework of the time dependent Density Functional Theory (TD-DFT). Our results show that this approach does not particularly depend on the basis set used on the metal atoms. Furthermore, the chosen functional PBE0 provides transitions in good agreement with experiments, and it provides an accuracy of about 0.3 eV, comparable to that of refined post-Hartree-Fock methods.

  19. On the multi-layer multi-configurational time-dependent Hartree approach for bosons and fermions

    NASA Astrophysics Data System (ADS)

    Manthe, Uwe; Weike, Thomas

    2017-02-01

    A multi-layer multi-configurational time-dependent Hartree (MCTDH) approach using a second quantization representation (SQR) based on optimized time-dependent orbitals is introduced. The approach combines elements of the multi-layer MCTDH-SQR approach of Wang and Thoss, which employs a preselected time-independent orbital basis, and the MCTDH for bosons and multi-configuration time-dependent Hartree-Fock approaches, which do not use multi-layering but employ time-dependent orbital bases. In contrast to existing MCTDH-type approaches, the results of the present approach for a given number of configurations are not invariant with respect to unitary transformations of the time-dependent orbital basis. Thus a natural orbital representation is chosen to achieve fast convergence with respect to the number of configurations employed. Equations of motion for the present ansatz, called (multi-layer) MCTDH in optimized second quantization representation, are derived. Furthermore, a scheme for the calculation of optimized unoccupied single-particle functions is given which can be used to avoid singularities in the equations of motion.

  20. Self-consistent collective coordinate for reaction path and inertial mass

    NASA Astrophysics Data System (ADS)

    Wen, Kai; Nakatsukasa, Takashi

    2016-11-01

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

  1. Mean-field dynamics of a Bose-Einstein condensate in a time-dependent triple-well trap: Nonlinear eigenstates, Landau-Zener models, and stimulated Raman adiabatic passage

    SciTech Connect

    Graefe, E. M.; Korsch, H. J.; Witthaut, D.

    2006-01-15

    We investigate the dynamics of a Bose-Einstein condensate in a triple-well trap in a three-level approximation. The interatomic interactions are taken into account in a mean-field approximation (Gross-Pitaevskii equation), leading to a nonlinear three-level model. Additional eigenstates emerge due to the nonlinearity, depending on the system parameters. Adiabaticity breaks down if such a nonlinear eigenstate disappears when the parameters are varied. The dynamical implications of this loss of adiabaticity are analyzed for two important special cases: A three-level Landau-Zener model and the stimulated Raman adiabatic passage (STIRAP) scheme. We discuss the emergence of looped levels for an equal-slope Landau-Zener model. The Zener tunneling probability does not tend to zero in the adiabatic limit and shows pronounced oscillations as a function of the velocity of the parameter variation. Furthermore we generalize the STIRAP scheme for adiabatic coherent population transfer between atomic states to the nonlinear case. It is shown that STIRAP breaks down if the nonlinearity exceeds the detuning.

  2. Time-dependent theoretical treatments of the dynamics of electrons and nuclei in molecular systems

    NASA Astrophysics Data System (ADS)

    Deumens, E.; Diz, A.; Longo, R.; Öhrn, Y.

    1994-07-01

    An overview is presented of methods for time-dependent treatments of molecules as systems of electrons and nuclei. The theoretical details of these methods are reviewed and contrasted in the light of a recently developed time-dependent method called electron-nuclear dynamics. Electron-nuclear dynamics (END) is a formulation of the complete dynamics of electrons and nuclei of a molecular system that eliminates the necessity of constructing potential-energy surfaces. Because of its general formulation, it encompasses many aspects found in other formulations and can serve as a didactic device for clarifying many of the principles and approximations relevant in time-dependent treatments of molecular systems. The END equations are derived from the time-dependent variational principle applied to a chosen family of efficiently parametrized approximate state vectors. A detailed analysis of the END equations is given for the case of a single-determinantal state for the electrons and a classical treatment of the nuclei. The approach leads to a simple formulation of the fully nonlinear time-dependent Hartree-Fock theory including nuclear dynamics. The nonlinear END equations with the ab initio Coulomb Hamiltonian have been implemented at this level of theory in a computer program, ENDyne, and have been shown feasible for the study of small molecular systems. Implementation of the Austin Model 1 semiempirical Hamiltonian is discussed as a route to large molecular systems. The linearized END equations at this level of theory are shown to lead to the random-phase approximation for the coupled system of electrons and nuclei. The qualitative features of the general nonlinear solution are analyzed using the results of the linearized equations as a first approximation. Some specific applications of END are presented, and the comparison with experiment and other theoretical approaches is discussed.

  3. Towards Efficient and Accurate Description of Many-Electron Problems: Developments of Static and Time-Dependent Electronic Structure Methods

    NASA Astrophysics Data System (ADS)

    Ding, Feizhi

    Understanding electronic behavior in molecular and nano-scale systems is fundamental to the development and design of novel technologies and materials for application in a variety of scientific contexts from fundamental research to energy conversion. This dissertation aims to provide insights into this goal by developing novel methods and applications of first-principle electronic structure theory. Specifically, we will present new methods and applications of excited state multi-electron dynamics based on the real-time (RT) time-dependent Hartree-Fock (TDHF) and time-dependent density functional theory (TDDFT) formalism, and new development of the multi-configuration self-consist field theory (MCSCF) for modeling ground-state electronic structure. The RT-TDHF/TDDFT based developments and applications can be categorized into three broad and coherently integrated research areas: (1) modeling of the interaction between moleculars and external electromagnetic perturbations. In this part we will first prove both analytically and numerically the gauge invariance of the TDHF/TDDFT formalisms, then we will present a novel, efficient method for calculating molecular nonlinear optical properties, and last we will study quantum coherent plasmon in metal namowires using RT-TDDFT; (2) modeling of excited-state charge transfer in molecules. In this part, we will investigate the mechanisms of bridge-mediated electron transfer, and then we will introduce a newly developed non-equilibrium quantum/continuum embedding method for studying charge transfer dynamics in solution; (3) developments of first-principles spin-dependent many-electron dynamics. In this part, we will present an ab initio non-relativistic spin dynamics method based on the two-component generalized Hartree-Fock approach, and then we will generalized it to the two-component TDDFT framework and combine it with the Ehrenfest molecular dynamics approach for modeling the interaction between electron spins and nuclear

  4. Eigenfunction expansions for time dependent hamiltonians

    NASA Astrophysics Data System (ADS)

    Jauslin, H. R.; Guerin, S.; Deroussiaux, A.

    We describe a generalization of Floquet theory for non periodic time dependent Hamiltonians. It allows to express the time evolution in terms of an expansion in eigenfunctions of a generalized quasienergy operator. We discuss a conjecture on the extension of the adiabatic theorem to this type of systems, which gives a procedure for the physical preparation of Floquet states. *** DIRECT SUPPORT *** A3418380 00004

  5. Multi-configuration Dirac-Hartree-Fock calculations of the transition rates of 2s22p2 - 2s2p3 and 2s2p3 - 2s22pnl (n ≥ 3) E1 transitions of N+

    NASA Astrophysics Data System (ADS)

    Shen, Xiaozhi; Liu, Juan; Zhou, Fuyang

    2016-10-01

    Wavefunctions were determined using the multi-configuration Dirac-Hartree-Fock method. The core-core, core-valence, valence correlation, Breit interaction and quantum electrodynamics effects, as well as some higher-order correlation effects, were considered to obtain accurate wavelengths (λ), oscillator strengths (gf) and transition rates (A) of 2s22p2 - 2s2p3, 2s2p3 - 2s22pnl (n ≥ 3) and 2s2p3 - 2s2p23s E1 transitions. The branching ratio of 2s2p3 5S^o_2 (namely Aλ2143.45/Aλ2139.68) based on the latest calculation of 2.462 ± 0.119 is recommended for the determination of a nebula's electron temperature and electron density. The largest calculated gf value of 2s2p3 - 2s22p4p is λ630.65, differing from that of λ1060.2 (i.e. 2s2p3 3P^o_2 - 2s22p4p 3S1) that was observed with the largest intensities in the Orion Nebula spectrum. In addition, the energy levels and the splittings of 2s2p3, the extremely difficult calculations of the rates of two-electron one-photon transitions as well as those of the very small intercombination A of 2s2p3 5S^o_2 were studied in detail. Because of the weak spin-orbit interaction, accurately calculating the levels 3P^o_{1,2,0} (or 3D^o_{3,2,1}) and their transition matrix elements is very sensitive to relativistic and electron correlation effects. A special case for this is when the transition operators synchronously applied to wavefunctions with regard to 2s2p3 3Po and 2s22pnl (n = 4) become extremely sensitive to some higher-order correlation effects.

  6. Integral processing in beyond-Hartree-Fock calculations

    NASA Technical Reports Server (NTRS)

    Taylor, P. R.

    1986-01-01

    The increasing rate at which improvements in processing capacity outstrip improvements in input/output performance of large computers has led to recent attempts to bypass generation of a disk-based integral file. The direct self-consistent field (SCF) method of Almlof and co-workers represents a very successful implementation of this approach. This paper is concerned with the extension of this general approach to configuration interaction (CI) and multiconfiguration-self-consistent field (MCSCF) calculations. After a discussion of the particular types of molecular orbital (MO) integrals for which -- at least for most current generation machines -- disk-based storage seems unavoidable, it is shown how all the necessary integrals can be obtained as matrix elements of Coulomb and exchange operators that can be calculated using a direct approach. Computational implementations of such a scheme are discussed.

  7. Metropolis Evaluation of the Hartree-Fock Exchange Energy.

    PubMed

    Cytter, Yael; Neuhauser, Daniel; Baer, Roi

    2014-10-14

    We examine the possibility of using a Metropolis algorithm for computing the exchange energy in a large molecular system. Following ideas set forth in a recent publication (Baer, Neuhauser, and Rabani, Phys. Rev. Lett. 111, 106402 (2013)) we focus on obtaining the exchange energy per particle (ExPE, as opposed to the total exchange energy) to a predefined statistical error and on determining the numerical scaling of the calculation achieving this. For this we assume that the occupied molecular orbitals (MOs) are known and given in terms of a standard Gaussian atomic basis set. The Metropolis random walk produces a sequence of pairs of three-dimensional points (x,x'), which are distributed in proportion to ρ(x,x')(2), where ρ(x,x') is the density matrix. The exchange energy per particle is then simply the average of the Coulomb repulsion energy υC(|x-x'|) over these pairs. To reduce the statistical error we separate the exchange energy into a short-range term that can be calculated deterministically in a linear scaling fashion and a long-range term that is treated by the Metropolis method. We demonstrate the method on water clusters and silicon nanocrystals showing the magnitude of the ExPE standard deviation is independent of system size. In the water clusters a longer random walk was necessary to obtain full ergodicity as Metropolis walkers tended to get stuck for a while in localized regions. We developed a diagnostic tool that can alert a user when such a situation occurs. The calculation effort scales linearly with system size if one uses an atom screening procedure that can be made numerically exact. In systems where the MOs can be localized efficiently the ExPE can even be computed with "sublinear scaling" as the MOs themselves can be screened.

  8. Time-dependent restricted-active-space self-consistent-field theory with space partition

    NASA Astrophysics Data System (ADS)

    Miyagi, Haruhide; Madsen, Lars Bojer

    2017-02-01

    Aiming at efficient numerical analysis of time-dependent (TD) many-electron dynamics of atoms involving multielectron continua, the TD restricted-active-space self-consistent-field theory with space partition (TD-RASSCF-SP) is presented. The TD-RASSCF-SP wave function is expanded in terms of TD configuration-interaction coefficients with Slater determinants composed of two kinds of TD orbitals: M ̂ orbitals are defined to be nonvanishing in the inner region (V ̂), a small volume around the atomic nucleus, and M ˇ orbitals are nonvanishing in the large outer region (V ˇ). For detailed discussion of the SP strategy, the equations of motion are derived by two different formalisms for comparison. To ensure continuous differentiability of the wave function across the two regions, one of the formalisms makes use of the property of the finite-element discrete-variable-representation (FEDVR) functions and introduces additional time-independent orbitals. The other formalism is more general and is based on the Bloch operator as in the R -matrix theory, but turns out to be less practical for numerical applications. Hence, using the FEDVR-based formalism, the numerical performance is tested by computing double-ionization dynamics of atomic beryllium in intense light fields. To achieve high accuracy, M ̂ should be set large to take into account the strong many-electron correlation around the nucleus. On the other hand, M ˇ can be set much smaller than M ̂ for capturing the weaker correlation between the two outgoing photoelectrons. As a result, compared with more accurate multiconfigurational TD Hartree-Fock (MCTDHF) method, the TD-RASSCF-SP method may achieve comparable accuracy in the description of the double-ionization dynamics. There are, however, difficulties related to the stiffness of the equations of motion of the TD-RASSCF-SP method, which makes the required time step for this method smaller than the one needed for the MCTDHF approach.

  9. Time Dependent Fluids

    ERIC Educational Resources Information Center

    Collyer, A. A.

    1974-01-01

    Discusses the flow characteristics of thixotropic and negative thixotropic fluids; various theories underlying the thixotropic behavior; and thixotropic phenomena exhibited in drilling muds, commercial paints, pastes, and greases. Inconsistencies in the terminology used to label time dependent effects are revealed. (CC)

  10. Vibrational frequencies and structure of 2-thiouracil by Hartree-Fock, post-Hartree-Fock and density functional methods.

    PubMed

    Palafox, M Alcolea; Rastogi, V K; Tanwar, R P; Mittal, Lalit

    2003-09-01

    Vibrational study of the biomolecule 2-thiouracil was carried out. Ab initio and density functional calculations were performed to assign the experimental spectra. A comparison with the uracil molecule was made, and specific scale factors were deduced and employed in the predicted frequencies of 2-thiouracil. Several scaling procedures were used. The geometry structure of the molecule was determined. The effect of sulfur substitution at C2 position in the uracil molecule, on the N1-H and N3-H frequencies and intensities reflects changes in proton donor abilities of these groups. Calculations with the 6-31 G** basis set with HF and DFT methods appear in general to be useful for interpretation of the general features of the IR and Raman spectra of the molecule. Using specific scale factors a very small error was obtained. The use of these specific scale factors resolve and correct some of the controversial assignments in the literature.

  11. Static correlation beyond the random phase approximation: dissociating H2 with the Bethe-Salpeter equation and time-dependent GW.

    PubMed

    Olsen, Thomas; Thygesen, Kristian S

    2014-04-28

    We investigate various approximations to the correlation energy of a H2 molecule in the dissociation limit, where the ground state is poorly described by a single Slater determinant. The correlation energies are derived from the density response function and it is shown that response functions derived from Hedin's equations (Random Phase Approximation (RPA), Time-dependent Hartree-Fock (TDHF), Bethe-Salpeter equation (BSE), and Time-Dependent GW) all reproduce the correct dissociation limit. We also show that the BSE improves the correlation energies obtained within RPA and TDHF significantly for intermediate binding distances. A Hubbard model for the dimer allows us to obtain exact analytical results for the various approximations, which is readily compared with the exact diagonalization of the model. Moreover, the model is shown to reproduce all the qualitative results from the ab initio calculations and confirms that BSE greatly improves the RPA and TDHF results despite the fact that the BSE excitation spectrum breaks down in the dissociation limit. In contrast, second order screened exchange gives a poor description of the dissociation limit, which can be attributed to the fact that it cannot be derived from an irreducible response function.

  12. Time Dependent Nuclear Scattering Calculations

    NASA Astrophysics Data System (ADS)

    Weeks, David

    2005-04-01

    A new time dependent method for calculating scattering matrix elements of two and three body nuclear collisions below 50 Mev is being developed. The procedure closely follows the channel packet method (CPM) used to compute scattering matrix elements for non-adiabatic molecular reactions.ootnotetextT.A.Niday and D.E.Weeks, Chem. Phys. Letters 308 (1999) 106 Currently, one degree of freedom calculations using a simple square well have been completed and a two body scattering calculation using the Yukawa potential is anticipated. To perform nuclear scattering calculations with the CPM that will incorporate the nucleon-nucleon tensor force, we plan to position initial reactant and product channel packets in the asymptotic limit on single coupled potential energy surfaces labeled by the spin, isospin, and total angular momentum of the reactant nucleons. The wave packets will propagated numerically using the split operator method augmented by a coordinate dependant unitary transformation used to diagonalize the potential. Scattering matrix elements will be determined by the Fourier transform of the correlation function between the evolving reactant and product wave packets. A brief outline of the Argonne v18 nucleon-nucleon potentialootnotetextR.B.Wiringa, V.G.J.Stoks, and R.Schiavilla, Physical Review C 51(1995) 38 and the proposed wave packet calculations will be presented.

  13. Quantum anholonomies in time-dependent Aharonov-Bohm rings

    SciTech Connect

    Tanaka, Atushi; Cheon, Taksu

    2010-08-15

    Anholonomies in eigenstates are studied through time-dependent variations of a magnetic flux in an Aharonov-Bohm ring. The anholonomies in the eigenenergy and the expectation values of eigenstates are shown to persist beyond the adiabatic regime. The choice of the gauge of the magnetic flux is shown to be crucial to clarify the relationship of these anholonomies to the eigenspace anholonomy, which is described by a non-Abelian connection in the adiabatic limit.

  14. Time-dependent freezing rate parcel model

    NASA Astrophysics Data System (ADS)

    Vali, G.; Snider, J. R.

    2015-02-01

    The time-dependent freezing rate (TDFR) model here described represents the formation of ice particles by immersion freezing within an air parcel. The air parcel trajectory follows an adiabatic ascent and includes a period in time when the parcel remains stationary at the top of its ascent. The description of the ice nucleating particles (INPs) in the air parcel is taken from laboratory experiments with cloud and precipitation samples and is assumed to represent the INP content of the cloud droplets in the parcel. Time dependence is included to account for variations in updraft velocity and for the continued formation of ice particles under isothermal conditions. The magnitudes of these factors are assessed on the basis of laboratory measurements. Results show that both factors give rise to three-fold variations in ice concentration for a realistic range of the input parameters. Refinements of the parameters specifying time dependence and INP concentrations are needed to make the results more specific to different atmospheric aerosol types. The simple model framework described in this paper can be adapted to more elaborate cloud models. The results here presented can help guide decisions on whether to include a time-dependent ice nucleation scheme or a simpler singular description in models.

  15. Time-dependent freezing rate parcel model

    NASA Astrophysics Data System (ADS)

    Vali, G.; Snider, J. R.

    2014-11-01

    The Time-Dependent Freezing Rate (TDFR) model here described represents the formation of ice particles by immersion freezing within an air parcel. The air parcel trajectory follows an adiabatic ascent and includes a period at time with the parcel remaining stationary at the top of its ascent. The description of the ice nucleating particles (INPs) in the air parcel is taken from laboratory experiments with cloud and precipitation samples and is assumed to represent the INP content of the cloud droplets in the parcel. Time-dependence is included to account for variations in updraft velocity and for the continued formation of ice particles at isothermal conditions. The magnitudes of these factors are assessed on the basis of laboratory measurements. Results show that both factors give rise to factors of about 3 variations in ice concentration for a realistic range of the input parameters. Refinements of the parameters specifying time-dependence and INP concentrations are needed to make the results more specific to different atmospheric aerosol types. The simple model framework described in this paper can be adapted to more elaborate cloud models. The results here presented can help guide decisions on whether to include a time-dependent ice nucleation scheme or a simpler singular description in models.

  16. Transitionless driving on adiabatic search algorithm

    SciTech Connect

    Oh, Sangchul; Kais, Sabre

    2014-12-14

    We study quantum dynamics of the adiabatic search algorithm with the equivalent two-level system. Its adiabatic and non-adiabatic evolution is studied and visualized as trajectories of Bloch vectors on a Bloch sphere. We find the change in the non-adiabatic transition probability from exponential decay for the short running time to inverse-square decay in asymptotic running time. The scaling of the critical running time is expressed in terms of the Lambert W function. We derive the transitionless driving Hamiltonian for the adiabatic search algorithm, which makes a quantum state follow the adiabatic path. We demonstrate that a uniform transitionless driving Hamiltonian, approximate to the exact time-dependent driving Hamiltonian, can alter the non-adiabatic transition probability from the inverse square decay to the inverse fourth power decay with the running time. This may open up a new but simple way of speeding up adiabatic quantum dynamics.

  17. Transitionless driving on adiabatic search algorithm

    NASA Astrophysics Data System (ADS)

    Oh, Sangchul; Kais, Sabre

    2014-12-01

    We study quantum dynamics of the adiabatic search algorithm with the equivalent two-level system. Its adiabatic and non-adiabatic evolution is studied and visualized as trajectories of Bloch vectors on a Bloch sphere. We find the change in the non-adiabatic transition probability from exponential decay for the short running time to inverse-square decay in asymptotic running time. The scaling of the critical running time is expressed in terms of the Lambert W function. We derive the transitionless driving Hamiltonian for the adiabatic search algorithm, which makes a quantum state follow the adiabatic path. We demonstrate that a uniform transitionless driving Hamiltonian, approximate to the exact time-dependent driving Hamiltonian, can alter the non-adiabatic transition probability from the inverse square decay to the inverse fourth power decay with the running time. This may open up a new but simple way of speeding up adiabatic quantum dynamics.

  18. Transitionless driving on adiabatic search algorithm.

    PubMed

    Oh, Sangchul; Kais, Sabre

    2014-12-14

    We study quantum dynamics of the adiabatic search algorithm with the equivalent two-level system. Its adiabatic and non-adiabatic evolution is studied and visualized as trajectories of Bloch vectors on a Bloch sphere. We find the change in the non-adiabatic transition probability from exponential decay for the short running time to inverse-square decay in asymptotic running time. The scaling of the critical running time is expressed in terms of the Lambert W function. We derive the transitionless driving Hamiltonian for the adiabatic search algorithm, which makes a quantum state follow the adiabatic path. We demonstrate that a uniform transitionless driving Hamiltonian, approximate to the exact time-dependent driving Hamiltonian, can alter the non-adiabatic transition probability from the inverse square decay to the inverse fourth power decay with the running time. This may open up a new but simple way of speeding up adiabatic quantum dynamics.

  19. Time-dependent Dyson orbital theory.

    PubMed

    Gritsenko, O V; Baerends, E J

    2016-08-21

    Although time-dependent density functional theory (TDDFT) has become the tool of choice for real-time propagation of the electron density ρ(N)(t) of N-electron systems, it also encounters problems in this application. The first problem is the neglect of memory effects stemming from the, in TDDFT virtually unavoidable, adiabatic approximation, the second problem is the reliable evaluation of the probabilities P(n)(t) of multiple photoinduced ionization, while the third problem (which TDDFT shares with other approaches) is the reliable description of continuum states of the electrons ejected in the process of ionization. In this paper time-dependent Dyson orbital theory (TDDOT) is proposed. Exact TDDOT equations of motion (EOMs) for time-dependent Dyson orbitals are derived, which are linear differential equations with just static, feasible potentials of the electron-electron interaction. No adiabatic approximation is used, which formally resolves the first TDDFT problem. TDDOT offers formally exact expressions for the complete evolution in time of the wavefunction of the outgoing electron. This leads to the correlated probability of single ionization P(1)(t) as well as the probabilities of no ionization (P(0)(t)) and multiple ionization of n electrons, P(n)(t), which formally solves the second problem of TDDFT. For two-electron systems a proper description of the required continuum states appears to be rather straightforward, and both P(1)(t) and P(2)(t) can be calculated. Because of the exact formulation, TDDOT is expected to reproduce a notorious memory effect, the "knee structure" of the non-sequential double ionization of the He atom.

  20. On Adiabatic Pair Creation

    NASA Astrophysics Data System (ADS)

    Pickl, Peter; Dürr, Detlef

    2008-08-01

    We give here a rigorous proof of the well known prediction of pair creation as it arises from the Dirac equation with an external time dependent potential. Pair creation happens with probability one if the potential changes adiabatically in time and becomes overcritical, which means that an eigenvalue curve (as a function of time) bridges the gap between the negative and positive spectral continuum. The potential can be thought of as being zero at large negative and large positive times. The rigorous treatment of this effect has been lacking since the pioneering work of Beck, Steinwedel and Süßmann [1] in 1963 and Gershtein and Zeldovich [8] in 1970.

  1. Time-dependent drift Hamiltonian

    SciTech Connect

    Boozer, A.H.

    1983-03-01

    The lowest-order drift equations are given in a canonical magnetic coordinate form for time-dependent magnetic and electric fields. The advantages of the canonical Hamiltonian form are also discussed.

  2. Regarding the use and misuse of retinal protonated Schiff base photochemistry as a test case for time-dependent density-functional theory

    SciTech Connect

    Valsson, Omar; Filippi, Claudia; Casida, Mark E.

    2015-04-14

    The excited-state relaxation of retinal protonated Schiff bases (PSBs) is an important test case for biological applications of time-dependent (TD) density-functional theory (DFT). While well-known shortcomings of approximate TD-DFT might seem discouraging for application to PSB relaxation, progress continues to be made in the development of new functionals and of criteria allowing problematic excitations to be identified within the framework of TD-DFT itself. Furthermore, experimental and theoretical ab initio advances have recently lead to a revised understanding of retinal PSB photochemistry, calling for a reappraisal of the performance of TD-DFT in describing this prototypical photoactive system. Here, we re-investigate the performance of functionals in (TD-)DFT calculations in light of these new benchmark results, which we extend to larger PSB models. We focus on the ability of the functionals to describe primarily the early skeletal relaxation of the chromophore and investigate how far along the out-of-plane pathways these functionals are able to describe the subsequent rotation around formal single and double bonds. Conventional global hybrid and range-separated hybrid functionals are investigated as the presence of Hartree-Fock exchange reduces problems with charge-transfer excitations as determined by the Peach-Benfield-Helgaker-Tozer Λ criterion and by comparison with multi-reference perturbation theory results. While we confirm that most functionals cannot render the complex photobehavior of the retinal PSB, do we also observe that LC-BLYP gives the best description of the initial part of the photoreaction.

  3. Regarding the use and misuse of retinal protonated Schiff base photochemistry as a test case for time-dependent density-functional theory.

    PubMed

    Valsson, Omar; Filippi, Claudia; Casida, Mark E

    2015-04-14

    The excited-state relaxation of retinal protonated Schiff bases (PSBs) is an important test case for biological applications of time-dependent (TD) density-functional theory (DFT). While well-known shortcomings of approximate TD-DFT might seem discouraging for application to PSB relaxation, progress continues to be made in the development of new functionals and of criteria allowing problematic excitations to be identified within the framework of TD-DFT itself. Furthermore, experimental and theoretical ab initio advances have recently lead to a revised understanding of retinal PSB photochemistry, calling for a reappraisal of the performance of TD-DFT in describing this prototypical photoactive system. Here, we re-investigate the performance of functionals in (TD-)DFT calculations in light of these new benchmark results, which we extend to larger PSB models. We focus on the ability of the functionals to describe primarily the early skeletal relaxation of the chromophore and investigate how far along the out-of-plane pathways these functionals are able to describe the subsequent rotation around formal single and double bonds. Conventional global hybrid and range-separated hybrid functionals are investigated as the presence of Hartree-Fock exchange reduces problems with charge-transfer excitations as determined by the Peach-Benfield-Helgaker-Tozer Λ criterion and by comparison with multi-reference perturbation theory results. While we confirm that most functionals cannot render the complex photobehavior of the retinal PSB, do we also observe that LC-BLYP gives the best description of the initial part of the photoreaction.

  4. Regarding the use and misuse of retinal protonated Schiff base photochemistry as a test case for time-dependent density-functional theory

    NASA Astrophysics Data System (ADS)

    Valsson, Omar; Filippi, Claudia; Casida, Mark E.

    2015-04-01

    The excited-state relaxation of retinal protonated Schiff bases (PSBs) is an important test case for biological applications of time-dependent (TD) density-functional theory (DFT). While well-known shortcomings of approximate TD-DFT might seem discouraging for application to PSB relaxation, progress continues to be made in the development of new functionals and of criteria allowing problematic excitations to be identified within the framework of TD-DFT itself. Furthermore, experimental and theoretical ab initio advances have recently lead to a revised understanding of retinal PSB photochemistry, calling for a reappraisal of the performance of TD-DFT in describing this prototypical photoactive system. Here, we re-investigate the performance of functionals in (TD-)DFT calculations in light of these new benchmark results, which we extend to larger PSB models. We focus on the ability of the functionals to describe primarily the early skeletal relaxation of the chromophore and investigate how far along the out-of-plane pathways these functionals are able to describe the subsequent rotation around formal single and double bonds. Conventional global hybrid and range-separated hybrid functionals are investigated as the presence of Hartree-Fock exchange reduces problems with charge-transfer excitations as determined by the Peach-Benfield-Helgaker-Tozer Λ criterion and by comparison with multi-reference perturbation theory results. While we confirm that most functionals cannot render the complex photobehavior of the retinal PSB, do we also observe that LC-BLYP gives the best description of the initial part of the photoreaction.

  5. Time dependent view factor methods

    SciTech Connect

    Kirkpatrick, R.C.

    1998-03-01

    View factors have been used for treating radiation transport between opaque surfaces bounding a transparent medium for several decades. However, in recent years they have been applied to problems involving intense bursts of radiation in enclosed volumes such as in the laser fusion hohlraums. In these problems, several aspects require treatment of time dependence.

  6. Time-dependent potential-functional embedding theory

    SciTech Connect

    Huang, Chen; Libisch, Florian; Carter, Emily A.

    2014-03-28

    We introduce a time-dependent potential-functional embedding theory (TD-PFET), in which atoms are grouped into subsystems. In TD-PFET, subsystems can be propagated by different suitable time-dependent quantum mechanical methods and their interactions can be treated in a seamless, first-principles manner. TD-PFET is formulated based on the time-dependent quantum mechanics variational principle. The action of the total quantum system is written as a functional of the time-dependent embedding potential, i.e., a potential-functional formulation. By exploiting the Runge-Gross theorem, we prove the uniqueness of the time-dependent embedding potential under the constraint that all subsystems share a common embedding potential. We derive the integral equation that such an embedding potential needs to satisfy. As proof-of-principle, we demonstrate TD-PFET for a Na{sub 4} cluster, in which each Na atom is treated as one subsystem and propagated by time-dependent Kohn-Sham density functional theory (TDDFT) using the adiabatic local density approximation (ALDA). Our results agree well with a direct TDDFT calculation on the whole Na{sub 4} cluster using ALDA. We envision that TD-PFET will ultimately be useful for studying ultrafast quantum dynamics in condensed matter, where key regions are solved by highly accurate time-dependent quantum mechanics methods, and unimportant regions are solved by faster, less accurate methods.

  7. Time-dependent potential-functional embedding theory.

    PubMed

    Huang, Chen; Libisch, Florian; Peng, Qing; Carter, Emily A

    2014-03-28

    We introduce a time-dependent potential-functional embedding theory (TD-PFET), in which atoms are grouped into subsystems. In TD-PFET, subsystems can be propagated by different suitable time-dependent quantum mechanical methods and their interactions can be treated in a seamless, first-principles manner. TD-PFET is formulated based on the time-dependent quantum mechanics variational principle. The action of the total quantum system is written as a functional of the time-dependent embedding potential, i.e., a potential-functional formulation. By exploiting the Runge-Gross theorem, we prove the uniqueness of the time-dependent embedding potential under the constraint that all subsystems share a common embedding potential. We derive the integral equation that such an embedding potential needs to satisfy. As proof-of-principle, we demonstrate TD-PFET for a Na4 cluster, in which each Na atom is treated as one subsystem and propagated by time-dependent Kohn-Sham density functional theory (TDDFT) using the adiabatic local density approximation (ALDA). Our results agree well with a direct TDDFT calculation on the whole Na4 cluster using ALDA. We envision that TD-PFET will ultimately be useful for studying ultrafast quantum dynamics in condensed matter, where key regions are solved by highly accurate time-dependent quantum mechanics methods, and unimportant regions are solved by faster, less accurate methods.

  8. Time-dependent density functional theory for quantum transport.

    PubMed

    Zheng, Xiao; Chen, GuanHua; Mo, Yan; Koo, SiuKong; Tian, Heng; Yam, ChiYung; Yan, YiJing

    2010-09-21

    Based on our earlier works [X. Zheng et al., Phys. Rev. B 75, 195127 (2007); J. S. Jin et al., J. Chem. Phys. 128, 234703 (2008)], we propose a rigorous and numerically convenient approach to simulate time-dependent quantum transport from first-principles. The proposed approach combines time-dependent density functional theory with quantum dissipation theory, and results in a useful tool for studying transient dynamics of electronic systems. Within the proposed exact theoretical framework, we construct a number of practical schemes for simulating realistic systems such as nanoscopic electronic devices. Computational cost of each scheme is analyzed, with the expected level of accuracy discussed. As a demonstration, a simulation based on the adiabatic wide-band limit approximation scheme is carried out to characterize the transient current response of a carbon nanotube based electronic device under time-dependent external voltages.

  9. Full-counting statistics of time-dependent conductors

    NASA Astrophysics Data System (ADS)

    Benito, Mónica; Niklas, Michael; Kohler, Sigmund

    2016-11-01

    We develop a scheme for the computation of the full-counting statistics of transport described by Markovian master equations with an arbitrary time dependence. It is based on a hierarchy of generalized density operators, where the trace of each operator yields one cumulant. This direct relation offers a better numerical efficiency than the equivalent number-resolved master equation. The proposed method is particularly useful for conductors with an elaborate time dependence stemming, e.g., from pulses or combinations of slow and fast parameter switching. As a test bench for the evaluation of the numerical stability, we consider time-independent problems for which the full-counting statistics can be computed by other means. As applications, we study cumulants of higher order for two time-dependent transport problems of recent interest, namely steady-state coherent transfer by adiabatic passage (CTAP) and Landau-Zener-Stückelberg-Majorana (LZSM) interference in an open double quantum dot.

  10. Time-Dependent Photodissociation Regions

    NASA Technical Reports Server (NTRS)

    Hollenbach, David; Natta, Antonella

    1995-01-01

    We present theoretical models of the time-dependent thermal and chemical structure of molecular gas suddenly exposed to far-ultraviolet (FUV) (6 eV less than hv less than 13.6 eV) radiation fields and the consequent time- dependent infrared emission of the gas. We focus on the response of molecular hydrogen for cloud densities ranging from n = 10(exp 3) to 10(exp 6)/cu cm and FUV fluxes G(sub 0) = 10(exp 3)-10(exp 6) times the local FUV interstellar flux. For G(sub 0)/n greater than 10(exp -2) cu cm, the emergent H(sub 2) vibrational line intensities are initially larger than the final equilibrium values. The H(sub 2) lines are excited by FUV fluorescence and by collisional excitation in warm gas. Most of the H(sub 2) intensity is generated at a characteristic hydrogen column density of N approximately 10(exp 21)/sq cm, which corresponds to an FUV optical depth of unity caused by dust opacity. The time dependence of the H(sub 2) intensities arises because the initial abundances of H(sub 2) at these depths is much higher than the equilibrium values, so that H(sub 2) initially competes more effectively with dust in absorbing FUV photons. Considerable column densities of warm (T approximately 1000) K H(sub 2) gas can be produced by the FUV pumping of H(sub 2) vibrational levels followed by collisional de-excitation, which transfers the energy to heat. In dense (n greater than or approximately 10(exp 5)/cu cm) gas exposed to high (G(sub 0) greater than or approximately 10(exp 4)) fluxes, this warm gas produces a 2-1 S(1)/1-0 S(l) H(sub 2) line ratio of approximately 0.1, which mimics the ratio found in shocked gas. In lower density regions, the FUV pumping produces a pure-fluorescent ratio of approximately 0.5. We also present calculations of the time dependence of the atomic hydrogen column densities and of the intensities of 0 I 6300 A, S II 6730 A, Fe II 1.64 microns, and rotational OH and H20 emission. Potential applications include star-forming regions, clouds

  11. Quantum-Classical Correspondence of Shortcuts to Adiabaticity

    NASA Astrophysics Data System (ADS)

    Okuyama, Manaka; Takahashi, Kazutaka

    2017-04-01

    We formulate the theory of shortcuts to adiabaticity in classical mechanics. For a reference Hamiltonian, the counterdiabatic term is constructed from the dispersionless Korteweg-de Vries (KdV) hierarchy. Then the adiabatic theorem holds exactly for an arbitrary choice of time-dependent parameters. We use the Hamilton-Jacobi theory to define the generalized action. The action is independent of the history of the parameters and is directly related to the adiabatic invariant. The dispersionless KdV hierarchy is obtained from the classical limit of the KdV hierarchy for the quantum shortcuts to adiabaticity. This correspondence suggests some relation between the quantum and classical adiabatic theorems.

  12. Recent results on time-dependent Hamiltonian oscillators

    NASA Astrophysics Data System (ADS)

    Robnik, M.

    2016-09-01

    Time-dependent Hamilton systems are important in modeling the nondissipative interaction of the system with its environment. We review some recent results and present some new ones. In time-dependent, parametrically driven, one-dimensional linear oscillator, the complete analysis can be performed (in the sense explained below), also using the linear WKB method. In parametrically driven nonlinear oscillators extensive numerical studies have been performed, and the nonlinear WKB-like method can be applied for homogeneous power law potentials (which e.g. includes the quartic oscillator). The energy in time-dependent Hamilton systems is not conserved, and we are interested in its evolution in time, in particular the evolution of the microcanonical ensemble of initial conditions. In the ideal adiabatic limit (infinitely slow parametric driving) the energy changes according to the conservation of the adiabatic invariant, but has a Dirac delta distribution. However, in the general case the initial Dirac delta distribution of the energy spreads and we follow its evolution, especially in the two limiting cases, the slow variation close to the adiabatic regime, and the fastest possible change - a parametric kick, i.e. discontinuous jump (of a parameter), where some exact analytic results are obtained (the so-called PR property, and ABR property). For the linear oscillator the distribution of the energy is always, rigorously, the arcsine distribution, whose variance can in general be calculated by the linear WKB method, while in nonlinear systems there is no such universality. We calculate the Gibbs entropy for the ensembles of noninteracting nonlinear oscillator, which gives the right equipartition and thermostatic laws even for one degree of freedom.

  13. Network-timing-dependent plasticity.

    PubMed

    Delattre, Vincent; Keller, Daniel; Perich, Matthew; Markram, Henry; Muller, Eilif B

    2015-01-01

    Bursts of activity in networks of neurons are thought to convey salient information and drive synaptic plasticity. Here we report that network bursts also exert a profound effect on Spike-Timing-Dependent Plasticity (STDP). In acute slices of juvenile rat somatosensory cortex we paired a network burst, which alone induced long-term depression (LTD), with STDP-induced long-term potentiation (LTP) and LTD. We observed that STDP-induced LTP was either unaffected, blocked or flipped into LTD by the network burst, and that STDP-induced LTD was either saturated or flipped into LTP, depending on the relative timing of the network burst with respect to spike coincidences of the STDP event. We hypothesized that network bursts flip STDP-induced LTP to LTD by depleting resources needed for LTP and therefore developed a resource-dependent STDP learning rule. In a model neural network under the influence of the proposed resource-dependent STDP rule, we found that excitatory synaptic coupling was homeostatically regulated to produce power law distributed burst amplitudes reflecting self-organized criticality, a state that ensures optimal information coding.

  14. Network-timing-dependent plasticity

    PubMed Central

    Delattre, Vincent; Keller, Daniel; Perich, Matthew; Markram, Henry; Muller, Eilif B.

    2015-01-01

    Bursts of activity in networks of neurons are thought to convey salient information and drive synaptic plasticity. Here we report that network bursts also exert a profound effect on Spike-Timing-Dependent Plasticity (STDP). In acute slices of juvenile rat somatosensory cortex we paired a network burst, which alone induced long-term depression (LTD), with STDP-induced long-term potentiation (LTP) and LTD. We observed that STDP-induced LTP was either unaffected, blocked or flipped into LTD by the network burst, and that STDP-induced LTD was either saturated or flipped into LTP, depending on the relative timing of the network burst with respect to spike coincidences of the STDP event. We hypothesized that network bursts flip STDP-induced LTP to LTD by depleting resources needed for LTP and therefore developed a resource-dependent STDP learning rule. In a model neural network under the influence of the proposed resource-dependent STDP rule, we found that excitatory synaptic coupling was homeostatically regulated to produce power law distributed burst amplitudes reflecting self-organized criticality, a state that ensures optimal information coding. PMID:26106298

  15. The Adiabatic Invariance of the Action Variable in Classical Dynamics

    ERIC Educational Resources Information Center

    Wells, Clive G.; Siklos, Stephen T. C.

    2007-01-01

    We consider one-dimensional classical time-dependent Hamiltonian systems with quasi-periodic orbits. It is well known that such systems possess an adiabatic invariant which coincides with the action variable of the Hamiltonian formalism. We present a new proof of the adiabatic invariance of this quantity and illustrate our arguments by means of…

  16. Some Exact Results for the Schroedinger Wave Equation with a Time Dependent Potential

    NASA Technical Reports Server (NTRS)

    Campbell, Joel

    2009-01-01

    The time dependent Schroedinger equation with a time dependent delta function potential is solved exactly for many special cases. In all other cases the problem can be reduced to an integral equation of the Volterra type. It is shown that by knowing the wave function at the origin, one may derive the wave function everywhere. Thus, the problem is reduced from a PDE in two variables to an integral equation in one. These results are used to compare adiabatic versus sudden changes in the potential. It is shown that adiabatic changes in the p otential lead to conservation of the normalization of the probability density.

  17. Time dependence of PEB effects

    NASA Astrophysics Data System (ADS)

    Yanagishita, Yuichiro; Shigematsu, Kazumasa; Yanagida, Kimio

    1990-06-01

    Though simulations of PEB (Post Exposure Bake) on the basis of PAC diffusion mode! have been carried out by a number of researchers '' (2) , it has never been confirmed that those could predict experimental data caused by PEB' s effects accurately . Because no details of chemical reactions thernlly induced by PEB are known, fundamental parameters which determine PEB' s effects must be obtained experimentally. We have acquired the volume of changes of development rate function, RATE(M) by PEB with DRM monitoring for some types of photoresist . The values of diffusion length have been obtained by means of compareing experimental B (exposure ener) vs T (development time to clear) curves with simulated ones which is based on RATEOA) data. Their dependence on the baking time has been investigated with fixed FEB temperature and it has been proved that a progress of the diffusion saturates only in less than a few seconds when the diffusion length is about lO'-l5ncn, which is much shorter than the standing wave length(= 66nm, for G-line). Profiles of low contrast resist patterns can be improved by the decrease in development rate of slightly exposed areas by PEB. The effects on these resists depend on the baking time because the volume of the decrease grows with increasing FEB time. On the other hands, for high contrast resists PEB' s diffusion enhances their resolution while the decreases in development rate have little effect on them. Time dependence cannot be observed for these resists because the diffusion length remains constant with increasing FEB time.

  18. Nuclear inertia from the time dependent pairing equations

    NASA Astrophysics Data System (ADS)

    Mirea, M.

    2016-10-01

    In a dynamical system, the momenta of inertia and the effective masses are not adiabatic quantities, but are dynamical ones that depend on the dissipated energy accumulated during motion. However, these parameters are calculated for adiabatic nuclear systems, leaving no room for dissipated energy. In this work, a formalism is elaborated in order to derive simultaneously the nuclear momenta of inertia and the effective masses by taking into account the appearance of dissipated energy for large amplitude motion of the nuclear system. The expressions that define the inertia are obtained from the variational principle. The same principle manages the time dependent pairing equations, offering estimations of the averaged dissipation energy for large amplitude motions. The model is applied to 232Th fission. The fission barrier was calculated along the least action trajectory. The dissipation energy, effective mass and moment of inertia are determined for different values of the collective velocities. The dissipation increases with the internuclear velocity in binary disintegration processes and modifies the effective mass parameters. We observed that the inertia decreases as long as the collective velocity increases to some moderate values and begins to grow for larger collective velocities. So, a dependence between the cranking mass parameters and the intrinsic excitation energy is evidenced. In order to investigate the overall effect, the half-lives are predicted for adiabatic and dynamics simulations.

  19. Markovian quantum master equation beyond adiabatic regime.

    PubMed

    Yamaguchi, Makoto; Yuge, Tatsuro; Ogawa, Tetsuo

    2017-01-01

    By introducing a temporal change time scale τ_{A}(t) for the time-dependent system Hamiltonian, a general formulation of the Markovian quantum master equation is given to go well beyond the adiabatic regime. In appropriate situations, the framework is well justified even if τ_{A}(t) is faster than the decay time scale of the bath correlation function. An application to the dissipative Landau-Zener model demonstrates this general result. The findings are applicable to a wide range of fields, providing a basis for quantum control beyond the adiabatic regime.

  20. Markovian quantum master equation beyond adiabatic regime

    NASA Astrophysics Data System (ADS)

    Yamaguchi, Makoto; Yuge, Tatsuro; Ogawa, Tetsuo

    2017-01-01

    By introducing a temporal change time scale τA(t ) for the time-dependent system Hamiltonian, a general formulation of the Markovian quantum master equation is given to go well beyond the adiabatic regime. In appropriate situations, the framework is well justified even if τA(t ) is faster than the decay time scale of the bath correlation function. An application to the dissipative Landau-Zener model demonstrates this general result. The findings are applicable to a wide range of fields, providing a basis for quantum control beyond the adiabatic regime.

  1. Optimizing Adiabaticity in NMR

    NASA Astrophysics Data System (ADS)

    Vandermause, Jonathan; Ramanathan, Chandrasekhar

    We demonstrate the utility of Berry's superadiabatic formalism for numerically finding control sequences that implement quasi-adiabatic unitary transformations. Using an iterative interaction picture, we design a shortcut to adiabaticity that reduces the time required to perform an adiabatic inversion pulse in liquid state NMR. We also show that it is possible to extend our scheme to two or more qubits to find adiabatic quantum transformations that are allowed by the control algebra, and demonstrate a two-qubit entangling operation in liquid state NMR. We examine the pulse lengths at which the fidelity of these adiabatic transitions break down and compare with the quantum speed limit.

  2. Spectral methods for time dependent problems

    NASA Technical Reports Server (NTRS)

    Tadmor, Eitan

    1990-01-01

    Spectral approximations are reviewed for time dependent problems. Some basic ingredients from the spectral Fourier and Chebyshev approximations theory are discussed. A brief survey was made of hyperbolic and parabolic time dependent problems which are dealt with by both the energy method and the related Fourier analysis. The ideas presented above are combined in the study of accuracy stability and convergence of the spectral Fourier approximation to time dependent problems.

  3. Time-dependent restricted-active-space self-consistent-field theory for laser-driven many-electron dynamics. II. Extended formulation and numerical analysis

    NASA Astrophysics Data System (ADS)

    Miyagi, Haruhide; Madsen, Lars Bojer

    2014-06-01

    The time-dependent restricted-active-space self-consistent-field (TD-RASSCF) method is formulated based on the TD variational principle. The SCF based TD orbitals contributing to the expansion of the wave function are classified into three groups, between which orbital excitations are considered with the RAS scheme. In analogy with the configuration-interaction singles (CIS), singles-and-doubles (CISD), and singles-doubles-and-triples (CISDT) methods in quantum chemistry, the TD-RASSCF-S, -SD, and -SDT methods are introduced as extensions of the TD-RASSCF-doubles (-D) method [Phys. Rev. A 87, 062511 (2013), 10.1103/PhysRevA.87.062511]. Based on an analysis of the numerical cost and test calculations for one-dimensional (1D) models of atomic helium, beryllium, and carbon, it is shown that the TD-RASSCF-S and -D methods are computationally feasible for systems with many electrons and more accurate than the TD Hartree-Fock (TDHF) and TDCIS methods. In addition to the discussion of methodology, an analysis of electron dynamics in the high-order harmonic generation (HHG) process is presented. For the 1D beryllium atom, a state-resolved analysis of the HHG spectrum based on the time-independent HF orbitals shows that while only single-orbital excitations are needed in the region below the cutoff, single- and double-orbital excitations are essential beyond, where accordingly the single-active-electron (SAE) approximation and the TDCIS method break down. On the other hand, the TD-RASSCF-S and -D methods accurately describe the multiorbital excitation processes throughout the entire region of the HHG spectrum. For the 1D carbon atom, our calculations show that multiorbital excitations are essential in the HHG process even below the cutoff. Hence, in this test system a very accurate treatment of electron correlation is required. The TD-RASSCF-S and -D approaches meet this demand, while the SAE approximation and the TDCIS method are inadequate.

  4. Recent developments and applications of multi-configuration Hartree-Fock methods. NRCC proceedings No. 10

    SciTech Connect

    Dupuis, M.

    1981-02-01

    Twenty-seven papers are included in four sessions titled: generalized Fock operator methods, annihilation of single excitations methods, second-order MCSCF methods, and applications of MCHF methods. Separate abstracts were prepared for eight papers; one of the remaining had been previously abstracted. (DLC)

  5. Predicting bond strength from a single Hartree-Fock ground state using the localized pair model.

    PubMed

    Hennessey, Dylan C; Sheppard, Brendan J H; Mackenzie, Dalton E C K; Pearson, Jason K

    2014-12-14

    We present an application of the recently introduced Localized Pair Model (LPM) [Z. A. Zielinksi and J. K. Pearson, Comput. Theor. Chem., 2013, 1003, 7990] to characterize and quantify properties of the chemical bond in a series of substituted benzoic acid molecules. By computing interelectronic distribution functions for doubly-occupied Edmiston-Ruedenberg localized molecular orbitals (LMOs), we show that chemically intuitive electron pairs may be uniquely classified and bond strength may be predicted with remarkable accuracy. Specifically, the HF/u6-311G(d,p) level (where u denotes a complete uncontraction of the basis set) is used to generate the relevant LMOs and their respective interelectronic distribution functions can be linearly correlated to the well-known Hammett σp or σm parameters with near-unity correlation coefficients.

  6. An open-shell restricted Hartree-Fock perturbation theory based on symmetric spin orbitals

    NASA Technical Reports Server (NTRS)

    Lee, Timothy J.; Jayatilaka, Dylan

    1993-01-01

    A new open-shell perturbation theory is formulated in terms of symmetric spin orbitals. Only one set of spatial orbitals is required, thereby reducing the number of independent coefficients in the perturbed wavefunctions. For second order, the computational cost is shown to be similar to a closed-shell calculation. This formalism is therefore more efficient than the recently developed RMP, ROMP or RMP-MBPT theories. The perturbation theory described herein was designed to have a close correspondence with our recently proposed coupled-cluster theory based on symmetric spin orbitals. The first-order wavefunction contains contributions from only doubly excited determinants. Equilibrium structures and vibrational frequencies determined from second-order perturbation theory are presented for OH, NH, CH, 02, NH2 and CH2.

  7. Kinetic and interaction components of the exact time-dependent correlation potential

    SciTech Connect

    Luo, Kai; Fuks, Johanna I.; Sandoval, Ernesto D.; Maitra, Neepa T.; Elliott, Peter

    2014-05-14

    The exact exchange-correlation (xc) potential of time-dependent density functional theory has been shown to have striking features. For example, step and peak features are generically found when the system is far from its ground-state, and these depend nonlocally on the density in space and time. We analyze the xc potential by decomposing it into kinetic and interaction components and comparing each with their exact-adiabatic counterparts, for a range of dynamical situations in model one-dimensional two-electron systems. We find that often, but not always, the kinetic contribution is largely responsible for these features that are missed by the adiabatic approximation. The adiabatic approximation often makes a smaller error for the interaction component, which we write in two parts, one being the Coulomb potential due to the time-dependent xc hole. Non-adiabatic features of the kinetic component were also larger than those of the interaction component in cases that we studied when there is negligible step structure. In ground-state situations, step and peak structures arise in cases of static correlation, when more than one determinant is essential to describe the interacting state. We investigate the time-dependent natural orbital occupation numbers and find the corresponding relation between these and the dynamical step is more complex than for the ground-state case.

  8. Shortcuts to adiabaticity for quantum annealing

    NASA Astrophysics Data System (ADS)

    Takahashi, Kazutaka

    2017-01-01

    We study the Ising Hamiltonian with a transverse field term to simulate the quantum annealing. Using shortcuts to adiabaticity, we design the time dependence of the Hamiltonian. The dynamical invariant is obtained by the mean-field ansatz, and the Hamiltonian is designed by the inverse engineering. We show that the time dependence of physical quantities such as the magnetization is independent of the speed of the Hamiltonian variation in the infinite-range model. We also show that rotating transverse magnetic fields are useful to achieve the ideal time evolution.

  9. Stability on Time-Dependent Domains

    NASA Astrophysics Data System (ADS)

    Knobloch, E.; Krechetnikov, R.

    2014-06-01

    We explore the key differences in the stability picture between extended systems on time-fixed and time-dependent spatial domains. As a paradigm, we take the complex Swift-Hohenberg equation, which is the simplest nonlinear model with a finite critical wavenumber, and use it to study dynamic pattern formation and evolution on time-dependent spatial domains in translationally invariant systems, i.e., when dilution effects are absent. In particular, we discuss the effects of a time-dependent domain on the stability of spatially homogeneous and spatially periodic base states, and explore its effects on the Eckhaus instability of periodic states. New equations describing the nonlinear evolution of the pattern wavenumber on time-dependent domains are derived, and the results compared with those on fixed domains. Pattern coarsening on time-dependent domains is contrasted with that on fixed domains with the help of the Cahn-Hilliard equation extended here to time-dependent domains. Parallel results for the evolution of the Benjamin-Feir instability on time-dependent domains are also given.

  10. Time-dependent photoelectron angular distributions

    NASA Astrophysics Data System (ADS)

    Wang, Xiangyang

    1999-09-01

    I show that the angular distribution of electrons photoionized from gas phase targets by short light pulses is time-dependent, when the orbital momentum composition of the photocurrent changes with excitation energy so evolves with the time of detection. A theory of time- dependent photoionization is outlined and general formulas of time-dependent photoelectron flux and angular distribution are given. Two general propagator methods suitable to describe the time-dependent photoionization and scattering processes are developed. The photoionization process is viewed as a local excitation followed by a half scattering. The local excitation process is solved theoretically in a small region around the target core. This approach has been generalized to describe the evolution of a wavepacket in an unbound system. An asymptotic propagator theorem is discovered and used to derive analytic expressions for asymptotic propagators. The origin of the time dependence is explored by parameterizing the time delay and orbital momentum coupling in a two channel model. K-shell photoionization of N2 and CO are calculated with this time- dependent photoionization theory, implemented using a multiple scattering model. Numerical results demonstrate that the time dependence of photoelectron angular distributions is a realistic effect.

  11. Birefringence in time-dependent moving media

    NASA Astrophysics Data System (ADS)

    Lin, Shirong; Zhang, Ruoyang; Zhai, Yanwang; Wei, Jianye; Zhao, Qing

    2016-08-01

    Electromagnetic wave propagation in one- and two-dimensional time-dependent moving media is investigated in this paper. We identify another origin of linear birefringence caused by the component of the flow perpendicular to the wave vector. Previously, birefringence is induced by applying external electric and magnetic fields to non-crystalline material. Here it is shown that the time-varying velocity field also contributes to such a phenomenon. Our results indicate that the parallel component, time-dependent or not, will not yield birefringence. Furthermore, the time-dependent flow also results in a frequency shift. One-dimensional simulation is conducted to demonstrate these effects.

  12. Shortcuts to adiabaticity for non-Hermitian systems

    SciTech Connect

    Ibanez, S.; Martinez-Garaot, S.; Torrontegui, E.; Muga, J. G.; Chen Xi

    2011-08-15

    Adiabatic processes driven by non-Hermitian, time-dependent Hamiltonians may be sped up by generalizing inverse engineering techniques based on counter-diabatic (transitionless driving) algorithms or on dynamical invariants. We work out the basic theory and examples described by two-level Hamiltonians: the acceleration of rapid adiabatic passage with a decaying excited level and of the dynamics of a classical particle on an expanding harmonic oscillator.

  13. Topic 5: Time-Dependent Behavior

    SciTech Connect

    Pfeiffer, P.A.; Tanabe, Tada-aki

    1991-12-31

    This chapter is a report of the material presented at the International Workshop on Finite Element Analysis of Reinforced Concrete, Session 4 -- Time Dependent Behavior, held at Columbia University, New York on June 3--6, 1991. Dr. P.A. Pfeiffer presented recent developments in time-dependent behavior of concrete and Professor T. Tanabe presented a review of research in Japan on time-dependent behavior of concrete. The chapter discusses the recent research of time-dependent behavior of concrete in the past few years in both the USA-European and Japanese communities. The author appreciates the valuable information provided by Zdenek P. Bazant in preparing the USA-European Research section.

  14. Invariants for time-dependent Hamiltonian systems.

    PubMed

    Struckmeier, J; Riedel, C

    2001-08-01

    An exact invariant is derived for n-degree-of-freedom Hamiltonian systems with general time-dependent potentials. The invariant is worked out in two equivalent ways. In the first approach, we define a special Ansatz for the invariant and determine its time-dependent coefficients. In the second approach, we perform a two-step canonical transformation of the initially time-dependent Hamiltonian to a time-independent one. The invariant is found to contain a function of time f(2)(t), defined as a solution of a linear third-order differential equation whose coefficients depend in general on the explicitly known configuration space trajectory that follows from the system's time evolution. It is shown that the invariant can be interpreted as the time integral of an energy balance equation. Our result is applied to a one-dimensional, time-dependent, damped non-linear oscillator, and to a three-dimensional system of Coulomb-interacting particles that are confined in a time-dependent quadratic external potential. We finally show that our results can be used to assess the accuracy of numerical simulations of time-dependent Hamiltonian systems.

  15. Adiabatic theory, Liapunov exponents, and rotation number for quadratic Hamiltonians

    NASA Astrophysics Data System (ADS)

    Delyon, François; Foulon, Patrick

    1987-11-01

    We consider the adiabatic problem for general time-dependent quadratic Hamiltonians and develop a method quite different from WKB. In particular, we apply our results to the Schrödinger equation in a strip. We show that there exists a first regular step (avoiding resonance problems) providing one adiabatic invariant, bounds on the Liapunov exponents, and estimates on the rotation number at any order of the perturbation theory. The further step is shown to be equivalent to a quantum adiabatic problem, which, by the usual adiabatic techniques, provides the other possible adiabatic invariants. In the special case of the Schrödinger equation our method is simpler and more powerful than the WKB techniques.

  16. Quantum dynamics by the constrained adiabatic trajectory method

    SciTech Connect

    Leclerc, A.; Jolicard, G.; Guerin, S.; Killingbeck, J. P.

    2011-03-15

    We develop the constrained adiabatic trajectory method (CATM), which allows one to solve the time-dependent Schroedinger equation constraining the dynamics to a single Floquet eigenstate, as if it were adiabatic. This constrained Floquet state (CFS) is determined from the Hamiltonian modified by an artificial time-dependent absorbing potential whose forms are derived according to the initial conditions. The main advantage of this technique for practical implementation is that the CFS is easy to determine even for large systems since its corresponding eigenvalue is well isolated from the others through its imaginary part. The properties and limitations of the CATM are explored through simple examples.

  17. Time-dependent density functional theory for strong-field ionization by circularly polarized pulses

    NASA Astrophysics Data System (ADS)

    Chirilă, Ciprian C.; Lein, Manfred

    2017-03-01

    By applying time-dependent density functional theory to a two-dimensional multielectron atom subject to strong circularly polarized light pulses, we confirm that the ionization of p orbitals with defined angular momentum depends on the sense of rotation of the applied field. A simple ad-hoc modification of the adiabatic local-density exchange-correlation functional is proposed to remedy its unphysical behavior under orbital depletion.

  18. Wireless adiabatic power transfer

    SciTech Connect

    Rangelov, A.A.; Suchowski, H.; Silberberg, Y.; Vitanov, N.V.

    2011-03-15

    Research Highlights: > Efficient and robust mid-range wireless energy transfer between two coils. > The adiabatic energy transfer is analogous to adiabatic passage in quantum optics. > Wireless energy transfer is insensitive to any resonant constraints. > Wireless energy transfer is insensitive to noise in the neighborhood of the coils. - Abstract: We propose a technique for efficient mid-range wireless power transfer between two coils, by adapting the process of adiabatic passage for a coherently driven two-state quantum system to the realm of wireless energy transfer. The proposed technique is shown to be robust to noise, resonant constraints, and other interferences that exist in the neighborhood of the coils.

  19. Time-dependent Flare Models with MALI

    NASA Astrophysics Data System (ADS)

    Kašparová, J.; Heinzel, P.; Varady, M.; Karlický, M.

    2003-01-01

    Temporal variations of Hα line profile intensities related to electron beams are presented. We show first results of time dependent simulations of a chromospheric response to a 1 sec monoenergetic electron beam. 1-D hydrodynamic code together with particle representation of the beam have been used to calculate atmospheric evolution. Time dependent radiative transfer problem has been solved for the resulting atmosphere in the MALI approach, using the Crank-Nicholson implicit scheme. Non-thermal collisional rates were included in linearised equations of statistical equilibrium.

  20. Investigations of Low Temperature Time Dependent Cracking

    SciTech Connect

    Van der Sluys, W A; Robitz, E S; Young, B A; Bloom, J

    2002-09-30

    The objective of this project was to investigate metallurgical and mechanical phenomena associated with time dependent cracking of cold bent carbon steel piping at temperatures between 327 C and 360 C. Boiler piping failures have demonstrated that understanding the fundamental metallurgical and mechanical parameters controlling these failures is insufficient to eliminate it from the field. The results of the project consisted of the development of a testing methodology to reproduce low temperature time dependent cracking in laboratory specimens. This methodology was used to evaluate the cracking resistance of candidate heats in order to identify the factors that enhance cracking sensitivity. The resultant data was integrated into current available life prediction tools.

  1. Non-adiabatic effects in near-adiabatic mixed-field orientation and alignment

    NASA Astrophysics Data System (ADS)

    Maan, Anjali; Ahlawat, Dharamvir Singh; Prasad, Vinod

    2016-11-01

    We present a theoretical study of the impact of a pair of moderate electric fields tilted an angle with respect to one another on a molecule. As a prototype, we consider a molecule with large rotational constant (with corresponding small rotational period) and moderate dipole moment. Within rigid-rotor approximation, the time-dependent Schrodinger equation is solved using fourth-order Runge-Kutta method. We have analysed that lower rotational states are significantly influenced by variation in pulse durations, the tilt angle between the fields and also on the electric field strengths. We also suggest a control scheme of how the rotational dynamics, orientation and alignment of a molecule can be enhanced by a combination of near-adiabatic pulses in comparision to non-adiabatic or adiabatic pulses.

  2. TOPICAL REVIEW: The Bloch wave operator: generalizations and applications: II. The time-dependent case

    NASA Astrophysics Data System (ADS)

    Jolicard, Georges; Killingbeck, John P.

    2003-10-01

    Part II of the review shows how the stationary Bloch wave operator of part I can be suitably modified to give a time-dependent wave operator. This operator makes it possible to use a relatively small active space in order to describe the dynamical processes which occur in quantum mechanical systems which have a time-dependent Hamiltonian. A close study is made of the links between the time-dependent and time-independent wave operators at the adiabatic limit; the analysis clarifies the way in which the wave operator formalism allows the time evolution of a system or a wave packet to be described in terms of a fast evolution inside the active space together with weak transitions out of this space which can be treated by perturbation methods. Two alternative wave operator equations of motion are derived and analysed. The first one is a non-linear differential equation in the usual Hilbert space; the second one is a differential equation in an extended Hilbert space with an extra time variable added and becomes equivalent to the usual Bloch equation when the Floquet Hamiltonian is taken in place of the ordinary Hamiltonian. A study is made of the close relationships between the time-dependent wave operator formalism, the Floquet theory and the (t, t') theory. Some original methods of solution of the two forms of wave operator equation are proposed and lead to new techniques of integration for the time-dependent Schrödinger equation (e.g., the generalized Green equation procedure). Mixed procedures involving both the time-independent and time-dependent wave operators are shown to be applicable to the internal eigenstate problem for large complex matrices. A detailed account is given of the description of inelastic and photoreactive processes by means of the time-dependent wave operator formalism, with particular attention to laser-molecule interactions. The emphasis is on projection operator techniques, with special attention being given to the method of selection of

  3. Second quantized scalar QED in homogeneous time-dependent electromagnetic fields

    SciTech Connect

    Kim, Sang Pyo

    2014-12-15

    We formulate the second quantization of a charged scalar field in homogeneous, time-dependent electromagnetic fields, in which the Hamiltonian is an infinite system of decoupled, time-dependent oscillators for electric fields, but it is another infinite system of coupled, time-dependent oscillators for magnetic fields. We then employ the quantum invariant method to find various quantum states for the charged field. For time-dependent electric fields, a pair of quantum invariant operators for each oscillator with the given momentum plays the role of the time-dependent annihilation and the creation operators, constructs the exact quantum states, and gives the vacuum persistence amplitude as well as the pair-production rate. We also find the quantum invariants for the coupled oscillators for the charged field in time-dependent magnetic fields and advance a perturbation method when the magnetic fields change adiabatically. Finally, the quantum state and the pair production are discussed when a time-dependent electric field is present in parallel to the magnetic field.

  4. A Variational Approach to Mass Fluctuations

    NASA Astrophysics Data System (ADS)

    Stevenson, P. D.; Broomfield, J. M. A.

    2009-08-01

    The variational method of Balian and Vénéroni is applied to dynamic simulations of giant resonances using the effective Skyrme interaction. Fluctuations in the mass following the resonance decay are compared in the time-dependent Hartree-Fock and Balian-Vénéroni approaches. The Balian-Vénéroni results are consistly higher than the Time-Dependent Hartree-Fock results.

  5. On time-dependent radiative transfer

    NASA Technical Reports Server (NTRS)

    Streater, A.; Cooper, J.; Sandle, W.

    1987-01-01

    An integral equation is developed for application to time-dependent laboratory experiments in which partial redistribution effects are important. The equation of transport with the Heasly-Kneer (1976) emission coefficient and the equation of statistical equilibrium lead to a time-dependent redistribution function containing an absorption - reemission term which decays exponentially in time and a scattering term which is instantaneous. This integral equation does not agree with an equation written by Payne et al. (1974) that has been used to compare theory with experiments. The difference between the Payne equation and the equation developed here needs to be examined in detail, since it might under some circumstances be on the same order as the difference between partial and complete redistribution.

  6. On time-dependent radiative transfer

    NASA Astrophysics Data System (ADS)

    Streater, A.; Cooper, J.; Sandle, W.

    1987-02-01

    An integral equation is developed for application to time-dependent laboratory experiments in which partial redistribution effects are important. The equation of transport with the Heasly-Kneer (1976) emission coefficient and the equation of statistical equilibrium lead to a time-dependent redistribution function containing an absorption - reemission term which decays exponentially in time and a scattering term which is instantaneous. This integral equation does not agree with an equation written by Payne et al. (1974) that has been used to compare theory with experiments. The difference between the Payne equation and the equation developed here needs to be examined in detail, since it might under some circumstances be on the same order as the difference between partial and complete redistribution.

  7. Time-Dependent Erosion of Ion Optics

    NASA Technical Reports Server (NTRS)

    Wirz, Richard E.; Anderson, John R.; Katz, Ira; Goebel, Dan M.

    2008-01-01

    The accurate prediction of thruster life requires time-dependent erosion estimates for the ion optics assembly. Such information is critical to end-of-life mechanisms such as electron backstreaming. CEX2D was recently modified to handle time-dependent erosion, double ions, and multiple throttle conditions in a single run. The modified code is called "CEX2D-t". Comparisons of CEX2D-t results with LDT and ELT post-tests results show good agreement for both screen and accel grid erosion including important erosion features such as chamfering of the downstream end of the accel grid and reduced rate of accel grid aperture enlargement with time.

  8. Time-dependent species sensitivity distributions.

    PubMed

    Fox, David R; Billoir, Elise

    2013-02-01

    Time is a central component of toxicity assessments. However, current ecotoxicological practice marginalizes time in concentration-response (C-R) modeling and species sensitivity distribution (SSD) analyses. For C-R models, time is invariably fixed, and toxicity measures are estimated from a function fitted to the data at that time. The estimated toxicity measures are used as inputs to the SSD modeling phase, which similarly avoids explicit recognition of the temporal component. The present study extends some commonly employed probability models for SSDs to derive theoretical results that characterize the time-dependent nature of hazardous concentration (HCx) values. The authors' results show that even from very simple assumptions, more complex patterns in the SSD time dependency can be revealed.

  9. Parallelizable adiabatic gate teleportation

    NASA Astrophysics Data System (ADS)

    Nakago, Kosuke; Hajdušek, Michal; Nakayama, Shojun; Murao, Mio

    2015-12-01

    To investigate how a temporally ordered gate sequence can be parallelized in adiabatic implementations of quantum computation, we modify adiabatic gate teleportation, a model of quantum computation proposed by Bacon and Flammia [Phys. Rev. Lett. 103, 120504 (2009), 10.1103/PhysRevLett.103.120504], to a form deterministically simulating parallelized gate teleportation, which is achievable only by postselection. We introduce a twisted Heisenberg-type interaction Hamiltonian, a Heisenberg-type spin interaction where the coordinates of the second qubit are twisted according to a unitary gate. We develop parallelizable adiabatic gate teleportation (PAGT) where a sequence of unitary gates is performed in a single step of the adiabatic process. In PAGT, numeric calculations suggest the necessary time for the adiabatic evolution implementing a sequence of L unitary gates increases at most as O (L5) . However, we show that it has the interesting property that it can map the temporal order of gates to the spatial order of interactions specified by the final Hamiltonian. Using this property, we present a controlled-PAGT scheme to manipulate the order of gates by a control qubit. In the controlled-PAGT scheme, two differently ordered sequential unitary gates F G and G F are coherently performed depending on the state of a control qubit by simultaneously applying the twisted Heisenberg-type interaction Hamiltonians implementing unitary gates F and G . We investigate why the twisted Heisenberg-type interaction Hamiltonian allows PAGT. We show that the twisted Heisenberg-type interaction Hamiltonian has an ability to perform a transposed unitary gate by just modifying the space ordering of the final Hamiltonian implementing a unitary gate in adiabatic gate teleportation. The dynamics generated by the time-reversed Hamiltonian represented by the transposed unitary gate enables deterministic simulation of a postselected event of parallelized gate teleportation in adiabatic

  10. Time-dependent oral absorption models

    NASA Technical Reports Server (NTRS)

    Higaki, K.; Yamashita, S.; Amidon, G. L.

    2001-01-01

    The plasma concentration-time profiles following oral administration of drugs are often irregular and cannot be interpreted easily with conventional models based on first- or zero-order absorption kinetics and lag time. Six new models were developed using a time-dependent absorption rate coefficient, ka(t), wherein the time dependency was varied to account for the dynamic processes such as changes in fluid absorption or secretion, in absorption surface area, and in motility with time, in the gastrointestinal tract. In the present study, the plasma concentration profiles of propranolol obtained in human subjects following oral dosing were analyzed using the newly derived models based on mass balance and compared with the conventional models. Nonlinear regression analysis indicated that the conventional compartment model including lag time (CLAG model) could not predict the rapid initial increase in plasma concentration after dosing and the predicted Cmax values were much lower than that observed. On the other hand, all models with the time-dependent absorption rate coefficient, ka(t), were superior to the CLAG model in predicting plasma concentration profiles. Based on Akaike's Information Criterion (AIC), the fluid absorption model without lag time (FA model) exhibited the best overall fit to the data. The two-phase model including lag time, TPLAG model was also found to be a good model judging from the values of sum of squares. This model also described the irregular profiles of plasma concentration with time and frequently predicted Cmax values satisfactorily. A comparison of the absorption rate profiles also suggested that the TPLAG model is better at prediction of irregular absorption kinetics than the FA model. In conclusion, the incorporation of a time-dependent absorption rate coefficient ka(t) allows the prediction of nonlinear absorption characteristics in a more reliable manner.

  11. Dissipative time-dependent quantum transport theory.

    PubMed

    Zhang, Yu; Yam, Chi Yung; Chen, GuanHua

    2013-04-28

    A dissipative time-dependent quantum transport theory is developed to treat the transient current through molecular or nanoscopic devices in presence of electron-phonon interaction. The dissipation via phonon is taken into account by introducing a self-energy for the electron-phonon coupling in addition to the self-energy caused by the electrodes. Based on this, a numerical method is proposed. For practical implementation, the lowest order expansion is employed for the weak electron-phonon coupling case and the wide-band limit approximation is adopted for device and electrodes coupling. The corresponding hierarchical equation of motion is derived, which leads to an efficient and accurate time-dependent treatment of inelastic effect on transport for the weak electron-phonon interaction. The resulting method is applied to a one-level model system and a gold wire described by tight-binding model to demonstrate its validity and the importance of electron-phonon interaction for the quantum transport. As it is based on the effective single-electron model, the method can be readily extended to time-dependent density functional theory.

  12. Time Dependent Behavior in the Weissenberg Effect

    NASA Astrophysics Data System (ADS)

    Degen, Michael M.; Andereck, C. David

    1997-03-01

    The Weissenberg effect is the climb of a non-Newtonian fluid up a rotating rod. We have found novel transitional effects in the behavior of a particular climbing fluid, STP(STP Oil Treatment distributed by First Brands Corporation.). The first state is a time-independent axisymmetric concave climb. As the rotation rate of the rod is increased, the first transition is to an axisymmetric climb with an ``onion dome'' shape. At higher rotation rates, the flow undergoes a symmetry breaking bifurcation to a time-dependent state. This time-dependent state exhibits an oscillation with a single frequency. Upon further increase of the rod rotation rate, the oscillation becomes modulated by a second frequency. The nature of each transition will be characterized, including the measurement of oscillation amplitudes and the frequency (or frequencies) of the time dependent states. These results will be compared with previous work.(G.S. Beavers, D.D. Joseph, J. Fluid Mech. 69), 475 (1975).(D.D. Joseph, R.L. Fosdick, Arch. Rational Mech. 49), 321 (1973).

  13. Accurate Variational Description of Adiabatic Quantum Optimization

    NASA Astrophysics Data System (ADS)

    Carleo, Giuseppe; Bauer, Bela; Troyer, Matthias

    Adiabatic quantum optimization (AQO) is a quantum computing protocol where a system is driven by a time-dependent Hamiltonian. The initial Hamiltonian has an easily prepared ground-state and the final Hamiltonian encodes some desired optimization problem. An adiabatic time evolution then yields a solution to the optimization problem. Several challenges emerge in the theoretical description of this protocol: on one hand, the exact simulation of quantum dynamics is exponentially complex in the size of the optimization problem. On the other hand, approximate approaches such as tensor network states (TNS) are limited to small instances by the amount of entanglement that can be encoded. I will present here an extension of the time-dependent Variational Monte Carlo approach to problems in AQO. This approach is based on a general class of (Jastrow-Feenberg) entangled states, whose parameters are evolved in time according to a stochastic variational principle. We demonstrate this approach for optimization problems of the Ising spin-glass type. A very good accuracy is achieved when compared to exact time-dependent TNS on small instances. We then apply this approach to larger problems, and discuss the efficiency of the quantum annealing scheme in comparison with its classical counterpart.

  14. Shortcuts to adiabaticity from linear response theory

    SciTech Connect

    Acconcia, Thiago V.; Bonança, Marcus V. S.; Deffner, Sebastian

    2015-10-23

    A shortcut to adiabaticity is a finite-time process that produces the same final state as would result from infinitely slow driving. We show that such shortcuts can be found for weak perturbations from linear response theory. Moreover, with the help of phenomenological response functions, a simple expression for the excess work is found—quantifying the nonequilibrium excitations. For two specific examples, i.e., the quantum parametric oscillator and the spin 1/2 in a time-dependent magnetic field, we show that finite-time zeros of the excess work indicate the existence of shortcuts. We finally propose a degenerate family of protocols, which facilitates shortcuts to adiabaticity for specific and very short driving times.

  15. Shortcuts to adiabaticity from linear response theory

    DOE PAGES

    Acconcia, Thiago V.; Bonança, Marcus V. S.; Deffner, Sebastian

    2015-10-23

    A shortcut to adiabaticity is a finite-time process that produces the same final state as would result from infinitely slow driving. We show that such shortcuts can be found for weak perturbations from linear response theory. Moreover, with the help of phenomenological response functions, a simple expression for the excess work is found—quantifying the nonequilibrium excitations. For two specific examples, i.e., the quantum parametric oscillator and the spin 1/2 in a time-dependent magnetic field, we show that finite-time zeros of the excess work indicate the existence of shortcuts. We finally propose a degenerate family of protocols, which facilitates shortcuts tomore » adiabaticity for specific and very short driving times.« less

  16. Fast forward to the classical adiabatic invariant

    NASA Astrophysics Data System (ADS)

    Jarzynski, Christopher; Deffner, Sebastian; Patra, Ayoti; Subaşı, Yiǧit

    2017-03-01

    We show how the classical action, an adiabatic invariant, can be preserved under nonadiabatic conditions. Specifically, for a time-dependent Hamiltonian H =p2/2 m +U (q ,t ) in one degree of freedom, and for an arbitrary choice of action I0, we construct a so-called fast-forward potential energy function VFF(q ,t ) that, when added to H , guides all trajectories with initial action I0 to end with the same value of action. We use this result to construct a local dynamical invariant J (q ,p ,t ) whose value remains constant along these trajectories. We illustrate our results with numerical simulations. Finally, we sketch how our classical results may be used to design approximate quantum shortcuts to adiabaticity.

  17. Time-dependent Hartree approximation and time-dependent harmonic oscillator model

    NASA Astrophysics Data System (ADS)

    Blaizot, J. P.; Schulz, H.

    1982-03-01

    We present an analytically soluble model for studying nuclear collective motion within the framework of the time-dependent Hartree (TDH) approximation. The model reduces the TDH equations to the Schrödinger equation of a time-dependent harmonic oscillator. Using canonical transformations and coherent states we derive a few properties of the time-dependent harmonic oscillator which are relevant for applications. We analyse the role of the normal modes in the time evolution of a system governed by TDH equations. We show how these modes couple together due to the anharmonic terms generated by the non-linearity of the theory.

  18. Quantum adiabatic machine learning

    NASA Astrophysics Data System (ADS)

    Pudenz, Kristen L.; Lidar, Daniel A.

    2013-05-01

    We develop an approach to machine learning and anomaly detection via quantum adiabatic evolution. This approach consists of two quantum phases, with some amount of classical preprocessing to set up the quantum problems. In the training phase we identify an optimal set of weak classifiers, to form a single strong classifier. In the testing phase we adiabatically evolve one or more strong classifiers on a superposition of inputs in order to find certain anomalous elements in the classification space. Both the training and testing phases are executed via quantum adiabatic evolution. All quantum processing is strictly limited to two-qubit interactions so as to ensure physical feasibility. We apply and illustrate this approach in detail to the problem of software verification and validation, with a specific example of the learning phase applied to a problem of interest in flight control systems. Beyond this example, the algorithm can be used to attack a broad class of anomaly detection problems.

  19. Adiabatic capture and debunching

    SciTech Connect

    Ng, K.Y.; /Fermilab

    2012-03-01

    In the study of beam preparation for the g-2 experiment, adiabatic debunching and adiabatic capture are revisited. The voltage programs for these adiabbatic processes are derived and their properties discussed. Comparison is made with some other form of adiabatic capture program. The muon g-2 experiment at Fermilab calls for intense proton bunches for the creation of muons. A booster batch of 84 bunches is injected into the Recycler Ring, where it is debunched and captured into 4 intense bunches with the 2.5-MHz rf. The experiment requires short bunches with total width less than 100 ns. The transport line from the Recycler to the muon-production target has a low momentum aperture of {approx} {+-}22 MeV. Thus each of the 4 intense proton bunches required to have an emittance less than {approx} 3.46 eVs. The incoming booster bunches have total emittance {approx} 8.4 eVs, or each one with an emittance {approx} 0.1 eVs. However, there is always emittance increase when the 84 booster bunches are debunched. There will be even larger emittance increase during adiabatic capture into the buckets of the 2.5-MHz rf. In addition, the incoming booster bunches may have emittances larger than 0.1 eVs. In this article, we will concentrate on the analysis of the adiabatic capture process with the intention of preserving the beam emittance as much as possible. At this moment, beam preparation experiment is being performed at the Main Injector. Since the Main Injector and the Recycler Ring have roughly the same lattice properties, we are referring to adiabatic capture in the Main Injector instead in our discussions.

  20. On the General Class of Models of Adiabatic Evolution

    NASA Astrophysics Data System (ADS)

    Sun, Jie; Lu, Songfeng; Liu, Fang

    2016-10-01

    The general class of models of adiabatic evolution was proposed to speed up the usual adiabatic computation in the case of quantum search problem. It was shown [8] that, by temporarily increasing the ground state energy of a time-dependent Hamiltonian to a suitable quantity, the quantum computation can perform the calculation in time complexity O(1). But it is also known that if the overlap between the initial and final states of the system is zero, then the computation based on the generalized models of adiabatic evolution can break down completely. In this paper, we find another severe limitation for this class of adiabatic evolution-based algorithms, which should be taken into account in applications. That is, it is still possible that this kind of evolution designed to deal with the quantum search problem fails completely if the interpolating paths in the system Hamiltonian are chosen inappropriately, while the usual adiabatic evolutions can do the same job relatively effectively. This implies that it is not always recommendable to use nonlinear paths in adiabatic computation. On the contrary, the usual simple adiabatic evolution may be sufficient for effective use.

  1. Time-Dependent Protein Thermostability Assay.

    PubMed

    Vandecaetsbeek, Ilse; Vangheluwe, Peter

    2016-01-01

    Membrane protein purification often yields rather unstable proteins impeding functional and structural protein characterization. Low protein stability also leads to low purification yields as a result of protein degradation, aggregation, precipitation, and folding instability. It is often required to optimize buffer conditions through numerous iterations of trial and error to improve the homogeneity, stability, and solubility of the protein sample demanding high amounts of purified protein. Therefore we have set up a fast, simple, and high-throughput time-dependent thermostability-based assay at low protein cost to identify protein stabilizing factors to facilitate the handling and characterization of membrane proteins by subsequent structural and functional studies.

  2. A Time Dependent Transport Equation Solver

    DTIC Science & Technology

    1991-05-01

    Using TWIGL Mesh Spacing ............. 63 11 Initial FEMP2D Flux Using 2X TWIGL Mesh Spacing ........ .. 64 12 Time Dependent Thermal Absorption...energy group, and g = G is the lowest ( thermal ) energy group. ?oo(r, E, t) the coefficient in the P approximation that phys- ically r’iDresents the total...than these MrPs. This suggest that the thermal flux calculations could be suspect. Indeed, both the FEMP2D and FMP2DT calculations showed that the

  3. Adiabatic gate teleportation.

    PubMed

    Bacon, Dave; Flammia, Steven T

    2009-09-18

    The difficulty in producing precisely timed and controlled quantum gates is a significant source of error in many physical implementations of quantum computers. Here we introduce a simple universal primitive, adiabatic gate teleportation, which is robust to timing errors and many control errors and maintains a constant energy gap throughout the computation above a degenerate ground state space. This construction allows for geometric robustness based upon the control of two independent qubit interactions. Further, our piecewise adiabatic evolution easily relates to the quantum circuit model, enabling the use of standard methods from fault-tolerance theory for establishing thresholds.

  4. Exact time dependence of solutions to the time-dependent Schrödinger equation

    NASA Astrophysics Data System (ADS)

    Lohe, M. A.

    2009-01-01

    Solutions of the Schrödinger equation with an exact time dependence are derived as eigenfunctions of dynamical invariants which are constructed from time-independent operators using time-dependent unitary transformations. Exact solutions and a closed form expression for the corresponding time evolution operator are found for a wide range of time-dependent Hamiltonians in d dimensions, including non-Hermitean {\\cal PT} -symmetric Hamiltonians. Hamiltonians are constructed using time-dependent unitary spatial transformations comprising dilatations, translations and rotations and solutions are found in several forms: as eigenfunctions of a quadratic invariant, as coherent state eigenfunctions of boson operators, as plane wave solutions from which the general solution is obtained as an integral transform by means of the Fourier transform, and as distributional solutions for which the initial wavefunction is the Dirac δ-function. For the isotropic harmonic oscillator in d dimensions radial solutions are found which extend known results for d = 1, including Barut-Girardello and Perelomov coherent states (i.e., vector coherent states), which are shown to be related to eigenfunctions of the quadratic invariant by the ζ-transformation. This transformation, which leaves the Ermakov equation invariant, implements SU(1, 1) transformations on linear dynamical invariants. \\mathfrak{su}(1, 1) coherent states are derived also for the time-dependent linear potential. Exact solutions are found for Hamiltonians with electromagnetic interactions in which the time-dependent magnetic and electric fields are not necessarily spatially uniform. As an example, it is shown how to find exact solutions of the time-dependent Schrödinger equation for the Dirac magnetic monopole in the presence of time-dependent magnetic and electric fields of a specified form.

  5. Time-dependent diffusion in stellar atmospheres

    NASA Astrophysics Data System (ADS)

    Alecian, G.; Stift, M. J.; Dorfi, E. A.

    2011-12-01

    The chemical peculiarities of Ap stars are due to abundance stratifications produced by atomic diffusion in their outer layers. Theoretical models can predict such stratifications, but so far only provide equilibrium solutions which correspond to the maximum depth-dependent abundances for each element that can be supported by the radiation field. However, these stratifications are actually built up through a non-linear, time-dependent process which has never been modelled for realistic stellar atmospheres. Here, we present the first numerical simulations of time-dependent diffusion. We solve the continuity equation after having computed, as accurately as possible, atomic diffusion velocities (with and without a magnetic field) for a simplified fictitious - but still realistic - chemical element: cloudium. The direct comparison with existing observations is not the immediate aim of this work but rather a general understanding of how the stratification build-up proceeds in time and space. Our results raise serious questions as to the relevance of equilibrium solutions and reinforce the suspicion that certain accumulations of chemical elements might prove unstable.

  6. Adiabatically implementing quantum gates

    SciTech Connect

    Sun, Jie; Lu, Songfeng Liu, Fang

    2014-06-14

    We show that, through the approach of quantum adiabatic evolution, all of the usual quantum gates can be implemented efficiently, yielding running time of order O(1). This may be considered as a useful alternative to the standard quantum computing approach, which involves quantum gates transforming quantum states during the computing process.

  7. Time-dependent Cooling in Photoionized Plasma

    NASA Astrophysics Data System (ADS)

    Gnat, Orly

    2017-02-01

    I explore the thermal evolution and ionization states in gas cooling from an initially hot state in the presence of external photoionizing radiation. I compute the equilibrium and nonequilibrium cooling efficiencies, heating rates, and ion fractions for low-density gas cooling while exposed to the ionizing metagalactic background radiation at various redshifts (z = 0 ‑ 3), for a range of temperatures (108–104 K), densities (10‑7–103 cm‑3), and metallicities (10‑3–2 times solar). The results indicate the existence of a threshold ionization parameter, above which the cooling efficiencies are very close to those in photoionization equilibrium (so that departures from equilibrium may be neglected), and below which the cooling efficiencies resemble those in collisional time-dependent gas cooling with no external radiation (and are thus independent of density).

  8. Determination of Time Dependent Virus Inactivation Rates

    NASA Astrophysics Data System (ADS)

    Chrysikopoulos, C. V.; Vogler, E. T.

    2003-12-01

    A methodology is developed for estimating temporally variable virus inactivation rate coefficients from experimental virus inactivation data. The methodology consists of a technique for slope estimation of normalized virus inactivation data in conjunction with a resampling parameter estimation procedure. The slope estimation technique is based on a relatively flexible geostatistical method known as universal kriging. Drift coefficients are obtained by nonlinear fitting of bootstrap samples and the corresponding confidence intervals are obtained by bootstrap percentiles. The proposed methodology yields more accurate time dependent virus inactivation rate coefficients than those estimated by fitting virus inactivation data to a first-order inactivation model. The methodology is successfully applied to a set of poliovirus batch inactivation data. Furthermore, the importance of accurate inactivation rate coefficient determination on virus transport in water saturated porous media is demonstrated with model simulations.

  9. Time-dependent landslide probability mapping

    USGS Publications Warehouse

    Campbell, Russell H.; Bernknopf, Richard L.; ,

    1993-01-01

    Case studies where time of failure is known for rainfall-triggered debris flows can be used to estimate the parameters of a hazard model in which the probability of failure is a function of time. As an example, a time-dependent function for the conditional probability of a soil slip is estimated from independent variables representing hillside morphology, approximations of material properties, and the duration and rate of rainfall. If probabilities are calculated in a GIS (geomorphic information system ) environment, the spatial distribution of the result for any given hour can be displayed on a map. Although the probability levels in this example are uncalibrated, the method offers a potential for evaluating different physical models and different earth-science variables by comparing the map distribution of predicted probabilities with inventory maps for different areas and different storms. If linked with spatial and temporal socio-economic variables, this method could be used for short-term risk assessment.

  10. Time-dependence of the holographic spectral function: diverse routes to thermalisation

    NASA Astrophysics Data System (ADS)

    Banerjee, Souvik; Ishii, Takaaki; Joshi, Lata Kh; Mukhopadhyay, Ayan; Ramadevi, P.

    2016-08-01

    We develop a new method for computing the holographic retarded propagator in generic (non-)equilibrium states using the state/geometry map. We check that our method reproduces the thermal spectral function given by the Son-Starinets prescription. The time-dependence of the spectral function of a relevant scalar operator is studied in a class of non-equilibrium states. The latter are represented by AdS-Vaidya geometries with an arbitrary parameter characterising the timescale for the dual state to transit from an initial thermal equilibrium to another due to a homogeneous quench. For long quench duration, the spectral function indeed follows the thermal form at the instantaneous effective temperature adiabatically, although with a slight initial time delay and a bit premature thermalisation. At shorter quench durations, several new non-adiabatic features appear: (i) time-dependence of the spectral function is seen much before than that in the effective temperature (advanced time-dependence), (ii) a big transfer of spectral weight to frequencies greater than the initial temperature occurs at an intermediate time (kink formation) and (iii) new peaks with decreasing amplitudes but in greater numbers appear even after the effective temperature has stabilised (persistent oscillations). We find four broad routes to thermalisation for lower values of spatial momenta. At higher values of spatial momenta, kink formations and persistent oscillations are suppressed, and thermalisation time decreases. The general thermalisation pattern is globally top-down, but a closer look reveals complexities.

  11. Time Dependent Fluid Occurrence Offshore Taiwan

    NASA Astrophysics Data System (ADS)

    Chen, L.

    2010-12-01

    Time Dependent Fluid Occurrence Offshore Taiwan Liwen Chenab, Wu-Cheng Chia, Char-Shine Liuc (mma@earth.sinica.edu.tw)(wchi@gate.sinica.edu.tw) ; aInstitute of Earth Sciences, Academia Sinica, Taipei, Taiwan bInstitute of Geosciences, National Taiwan University, Taipei, Taiwan ; cInstitute of Oceanography, National Taiwan University, Taipei, Taiwan Earthquake-induced groundwater flows have been observed recently. Such fluid flow might temporarily change the temperature field in the crust. Here we used seismically detected gas hydrate under seafloor to study the temperature fields at a few hundred meters subbottom depth before, and after the 2006 Henchuan earthquake (Mw7.0). We used the hydrate-related bottom-simulating-reflector (BSR) in seismic profiles to study the effects of gas/fluid migration on the BSR attributes. We have conducted two seismic experiments before and after the earthquake across the same transects near the hypocenter of the earthquake using similar air gun arrays and streamers. By analyzing this unique dataset, we found enhanced BSR reflectivity in average after the earthquake (~0.03), but the Sea-floor reflectivity is very similar (~0.5). We also found changed amplitudes versus offset (AVO) in the dataset (the gradient of reflection coefficient versus the angles was ~-0.34). We interpret these results as a consequence of earthquake-induced gas and fluid migration, bringing the gases underneath the BSR, thus the enhanced reflection coefficients. Next we will explore new methods to use the BSR as a flow meter. Using time-dependent seismic attribute analyses across transects before and after a large earthquake, we found strong evidences of earthquake-related fluid migrations and possibly associated temperature perturbations. This is among the first studies to document such feature in the offshore region.

  12. Semiconductor adiabatic qubits

    DOEpatents

    Carroll, Malcolm S.; Witzel, Wayne; Jacobson, Noah Tobias; Ganti, Anand; Landahl, Andrew J.; Lilly, Michael; Nguyen, Khoi Thi; Bishop, Nathaniel; Carr, Stephen M.; Bussmann, Ezra; Nielsen, Erik; Levy, James Ewers; Blume-Kohout, Robin J.; Rahman, Rajib

    2016-12-27

    A quantum computing device that includes a plurality of semiconductor adiabatic qubits is described herein. The qubits are programmed with local biases and coupling terms between qubits that represent a problem of interest. The qubits are initialized by way of a tuneable parameter, a local tunnel coupling within each qubit, such that the qubits remain in a ground energy state, and that initial state is represented by the qubits being in a superposition of |0> and |1> states. The parameter is altered over time adiabatically or such that relaxation mechanisms maintain a large fraction of ground state occupation through decreasing the tunnel coupling barrier within each qubit with the appropriate schedule. The final state when tunnel coupling is effectively zero represents the solution state to the problem represented in the |0> and |1> basis, which can be accurately read at each qubit location.

  13. Infrared Blobs : Time-dependent Flags

    NASA Astrophysics Data System (ADS)

    McCullough, P. R.; Mack, J.; Dulude, M.; Hilbert, B.

    2014-10-01

    We describe the creation of time-dependent flags for pixels associated with "blobs" on the WFC3 IR detector. We detect the blobs on flat fields obtained by repeated observations of the night side of the Earth. We provide the most complete census of IR blobs' positions, radii, and times of first appearance. In aggregate, a set of 46 blobs, 27 "strong" and 19 "medium" in their effective scattering cross section, affect slightly less than 1% of the pixels of the detector. A second set of 81 "weak" (and typically smaller) blobs affect another 1% of the pixels. In the past, the "blob" flag, bit 9 (i.e. value = 512) in the data quality (DQ) array described in Table 2.5 of the WFC3 Data Handbook (Rajan et al. 2010) has been a static 2-D array; henceforth a set of such arrays, each associated with a "use after" date corresponding to the appearance of one or more new blobs, can be used. We prepared such DQ arrays using the 46 "strong" and "medium" blobs and discuss why we did not include the fainter blobs therein. As an added data product, we create and test a blob flat field that corrects the effects of blobs on extended emission; however, it should not be applied if stellar photometry is the goal.

  14. Heating liquid dielectrics by time dependent fields

    NASA Astrophysics Data System (ADS)

    Khalife, A.; Pathak, U.; Richert, R.

    2011-10-01

    Steady state and time-resolved dielectric relaxation experiments are performed at high fields on viscous glycerol and the effects of energy absorption from the electric field are studied. Time resolution is obtained by a sinusoidal field whose amplitude is switched from a low to a high level and by recording voltage and current traces with an oscilloscope during this transition. Based on their distinct time and frequency dependences, three sources of modifying the dynamics and dielectric loss via an increase in the effective temperature can be distinguished: electrode temperature, real sample temperature, and configurational temperatures of the modes that absorbed the energy. Isothermal conditions that are desired for focusing on the configurational temperature changes (as in dielectric hole burning and related techniques) are maintained only for very thin samples and for moderate power levels. For high frequencies, say ν > 1 MHz, changes of the real temperature will exceed the effects of configurational temperatures in the case of macroscopic samples. Regarding microwave chemistry, heating via cell phone use, and related situations in which materials are subject to fields involving frequencies beyond the MHz regime, we conclude that changes in the configurational (or fictive) temperatures remain negligible compared with the increase of the real temperature. This simplifies the assessment of how time dependent electric fields modify the properties of materials.

  15. Tunable Time-Dependent Colloidal Interactions

    NASA Astrophysics Data System (ADS)

    Bergman, Andrew M.; Rogers, W. Benjamin; Manoharan, Vinothan N.

    Self-assembly of colloidal particles can be driven by changes in temperature, density, or the concentration of solutes, and it is even possible to program the thermal response and equilibrium phase transitions of such systems. It is still difficult, however, to tune how the self-assembly process varies in time. We demonstrate control over the time-dependence of colloidal interactions, using DNA-functionalized colloidal particles with binding energies that are set by the concentration of a free linker strand in solution. We control the rate at which this free strand is consumed using a catalytic DNA reaction, whose rate is governed by the concentration of a catalyst strand. Varying the concentration of the linker, its competitor, and the catalyst at a fixed temperature, we can tune the rate and degree of the formation of colloidal aggregates and their following disassembly. Close to the colloidal melting point, the timescales of these out-of-equilibrium assembly and disassembly processes are determined by the rate of the catalytic reaction. Far below the colloidal melting point, however, the effects from varying our linker and competitor concentrations dominate.

  16. Time dependent particle emission from fission products

    SciTech Connect

    Holloway, Shannon T; Kawano, Toshihiko; Moller, Peter

    2010-01-01

    Decay heating following nuclear fission is an important factor in the design of nuclear facilities; impacting a variety of aspects ranging from cooling requirements to shielding design. Calculations of decay heat, often assumed to be a simple product of activity and average decay product energy, are complicated by the so called 'pandemonium effect'. Elucidated in the 1970's this complication arises from beta-decays feeding high-energy nuclear levels; redistributing the available energy between betas and gammas. Increased interest in improving the theoretical predictions of decay probabilities has been, in part, motivated by the recent experimental effort utilizing the Total Absorption Gamma-ray Spectrometer (TAGS) to determine individual beta-decay transition probabilities to individual nuclear levels. Accurate predictions of decay heating require a detailed understanding of these transition probabilities, accurate representation of particle decays as well as reliable predictions of temporal inventories from fissioning systems. We will discuss a recent LANL effort to provide a time dependent study of particle emission from fission products through a combination of Quasiparticle Random Phase Approximation (QRPA) predictions of beta-decay probabilities, statistical Hauser-Feshbach techniques to obtain particle and gamma-ray emissions in statistical Hauser-Feshbach and the nuclear inventory code, CINDER.

  17. Time dependent friction in a free gas

    NASA Astrophysics Data System (ADS)

    Fanelli, Cristiano; Sisti, Francesco; Stagno, Gabriele V.

    2016-03-01

    We consider a body moving in a perfect gas, described by the mean-field approximation and interacting elastically with the body, we study the friction exerted by the gas on the body fixed at constant velocities. The time evolution of the body in this setting was studied in Caprino et al. [Math. Phys. 264, 167-189 (2006)], Caprino et al. [Math. Models Methods Appl. Sci. 17, 1369-1403 (2007)], and Cavallaro [Rend. Mat. Appl. 27, 123-145 (2007)] for object with simple shape; the first study where a simple kind of concavity was considered was in Sisti and Ricciuti [SIAM J. Math. Anal. 46, 3759-3611 (2014)], showing new features in the dynamic but not in the friction term. The case of more general shape of the body was left out for further difficulties, and we believe indeed that there are actually non-trivial issues to be faced for these more general cases. To show this and in the spirit of getting a more realistic perspective in the study of friction problems, in this paper, we focused our attention on the friction term itself, studying its behavior on a body with a more general kind of concavity and fixed at constant velocities. We derive the expression of the friction term for constant velocities, we show how it is time dependent, and we give its exact estimate in time. Finally, we use this result to show the absence of a constant velocity in the actual dynamic of such a body.

  18. Non-adiabatic molecular dynamics with complex quantum trajectories. II. The adiabatic representation

    SciTech Connect

    Zamstein, Noa; Tannor, David J.

    2012-12-14

    We present a complex quantum trajectory method for treating non-adiabatic dynamics. Each trajectory evolves classically on a single electronic surface but with complex position and momentum. The equations of motion are derived directly from the time-dependent Schroedinger equation, and the population exchange arises naturally from amplitude-transfer terms. In this paper the equations of motion are derived in the adiabatic representation to complement our work in the diabatic representation [N. Zamstein and D. J. Tannor, J. Chem. Phys. 137, 22A517 (2012)]. We apply our method to two benchmark models introduced by John Tully [J. Chem. Phys. 93, 1061 (1990)], and get very good agreement with converged quantum-mechanical calculations. Specifically, we show that decoherence (spatial separation of wavepackets on different surfaces) is already contained in the equations of motion and does not require ad hoc augmentation.

  19. Time dependence of Hawking radiation entropy

    SciTech Connect

    Page, Don N.

    2013-09-01

    If a black hole starts in a pure quantum state and evaporates completely by a unitary process, the von Neumann entropy of the Hawking radiation initially increases and then decreases back to zero when the black hole has disappeared. Here numerical results are given for an approximation to the time dependence of the radiation entropy under an assumption of fast scrambling, for large nonrotating black holes that emit essentially only photons and gravitons. The maximum of the von Neumann entropy then occurs after about 53.81% of the evaporation time, when the black hole has lost about 40.25% of its original Bekenstein-Hawking (BH) entropy (an upper bound for its von Neumann entropy) and then has a BH entropy that equals the entropy in the radiation, which is about 59.75% of the original BH entropy 4πM{sub 0}{sup 2}, or about 7.509M{sub 0}{sup 2} ≈ 6.268 × 10{sup 76}(M{sub 0}/M{sub s}un){sup 2}, using my 1976 calculations that the photon and graviton emission process into empty space gives about 1.4847 times the BH entropy loss of the black hole. Results are also given for black holes in initially impure states. If the black hole starts in a maximally mixed state, the von Neumann entropy of the Hawking radiation increases from zero up to a maximum of about 119.51% of the original BH entropy, or about 15.018M{sub 0}{sup 2} ≈ 1.254 × 10{sup 77}(M{sub 0}/M{sub s}un){sup 2}, and then decreases back down to 4πM{sub 0}{sup 2} = 1.049 × 10{sup 77}(M{sub 0}/M{sub s}un){sup 2}.

  20. Time dependence of Hawking radiation entropy

    NASA Astrophysics Data System (ADS)

    Page, Don N.

    2013-09-01

    If a black hole starts in a pure quantum state and evaporates completely by a unitary process, the von Neumann entropy of the Hawking radiation initially increases and then decreases back to zero when the black hole has disappeared. Here numerical results are given for an approximation to the time dependence of the radiation entropy under an assumption of fast scrambling, for large nonrotating black holes that emit essentially only photons and gravitons. The maximum of the von Neumann entropy then occurs after about 53.81% of the evaporation time, when the black hole has lost about 40.25% of its original Bekenstein-Hawking (BH) entropy (an upper bound for its von Neumann entropy) and then has a BH entropy that equals the entropy in the radiation, which is about 59.75% of the original BH entropy 4πM02, or about 7.509M02 ≈ 6.268 × 1076(M0/Msolar)2, using my 1976 calculations that the photon and graviton emission process into empty space gives about 1.4847 times the BH entropy loss of the black hole. Results are also given for black holes in initially impure states. If the black hole starts in a maximally mixed state, the von Neumann entropy of the Hawking radiation increases from zero up to a maximum of about 119.51% of the original BH entropy, or about 15.018M02 ≈ 1.254 × 1077(M0/Msolar)2, and then decreases back down to 4πM02 = 1.049 × 1077(M0/Msolar)2.

  1. Exact Time-Dependent Exchange-Correlation Potential for a 2-Electron System

    NASA Astrophysics Data System (ADS)

    D'Amico, Irene; Vignale, Giovanni

    1998-03-01

    We present an exact solution for the Floquet state evolving from the ground state of a 2-electron system confined in a plane by an isotropic parabolic potential whose curvature is periodically modulated in time. >From this solution we extract the exact frequency-dependent exchange correlation potential V_xc which, when used in the time-dependent Kohn-Sham equation (in addition to external and Hartree potentials) generates the exact time-dependent density. The exact V_xc is compared with the V_xc's obtained from the adiabatic local density approximation and from the retarded local current-density approximation (G. Vignale and W. Kohn, Phys. Rev. Lett. 77), 2037 (1996); G. Vignale, C. Ullrich, and S. Conti, Phys. Rev. Lett. 79 (1997)..

  2. Vibrationally resolved UV/Vis spectroscopy with time-dependent density functional based tight binding.

    PubMed

    Rüger, Robert; Niehaus, Thomas; van Lenthe, Erik; Heine, Thomas; Visscher, Lucas

    2016-11-14

    We report a time-dependent density functional based tight-binding (TD-DFTB) scheme for the calculation of UV/Vis spectra, explicitly taking into account the excitation of nuclear vibrations via the adiabatic Hessian Franck-Condon method with a harmonic approximation for the nuclear wavefunction. The theory of vibrationally resolved UV/Vis spectroscopy is first summarized from the viewpoint of TD-DFTB. The method is benchmarked against time-dependent density functional theory (TD-DFT) calculations for strongly dipole allowed excitations in various aromatic and polar molecules. Using the recent 3ob:freq parameter set of Elstner's group, very good agreement with TD-DFT calculations using local functionals was achieved.

  3. Landau levels of scalar QED in time-dependent magnetic fields

    SciTech Connect

    Kim, Sang Pyo

    2014-05-15

    The Landau levels of scalar QED undergo continuous transitions under a homogeneous, time-dependent magnetic field. We analytically formulate the Klein–Gordon equation for a charged spinless scalar as a Cauchy initial value problem in the two-component first order formalism and then put forth a measure that classifies the quantum motions into the adiabatic change, the nonadiabatic change, and the sudden change. We find the exact quantum motion and calculate the pair-production rate when the magnetic field suddenly changes as a step function. -- Highlights: •We study the Landau levels of scalar QED in time-dependent magnetic fields. •Instantaneous Landau levels make continuous transitions but keep parity. •The Klein–Gordon equation is expressed in the two-component first order formalism. •A measure is advanced that characterizes the quantum motions into three categories. •A suddenly changing magnetic field produces pairs of charged scalars from vacuum.

  4. Vibrationally resolved UV/Vis spectroscopy with time-dependent density functional based tight binding

    NASA Astrophysics Data System (ADS)

    Rüger, Robert; Niehaus, Thomas; van Lenthe, Erik; Heine, Thomas; Visscher, Lucas

    2016-11-01

    We report a time-dependent density functional based tight-binding (TD-DFTB) scheme for the calculation of UV/Vis spectra, explicitly taking into account the excitation of nuclear vibrations via the adiabatic Hessian Franck-Condon method with a harmonic approximation for the nuclear wavefunction. The theory of vibrationally resolved UV/Vis spectroscopy is first summarized from the viewpoint of TD-DFTB. The method is benchmarked against time-dependent density functional theory (TD-DFT) calculations for strongly dipole allowed excitations in various aromatic and polar molecules. Using the recent 3ob:freq parameter set of Elstner's group, very good agreement with TD-DFT calculations using local functionals was achieved.

  5. Time-Dependent Rate Phenomenon in Viruses

    PubMed Central

    Aiewsakun, Pakorn

    2016-01-01

    ABSTRACT Among the most fundamental questions in viral evolutionary biology are how fast viruses evolve and how evolutionary rates differ among viruses and fluctuate through time. Traditionally, viruses are loosely classed into two groups: slow-evolving DNA viruses and fast-evolving RNA viruses. As viral evolutionary rate estimates become more available, it appears that the rates are negatively correlated with the measurement timescales and that the boundary between the rates of DNA and RNA viruses might not be as clear as previously thought. In this study, we collected 396 viral evolutionary rate estimates across almost all viral genome types and replication strategies, and we examined their rate dynamics. We showed that the time-dependent rate phenomenon exists across multiple levels of viral taxonomy, from the Baltimore classification viral groups to genera. We also showed that, by taking the rate decay dynamics into account, a clear division between the rates of DNA and RNA viruses as well as reverse-transcribing viruses could be recovered. Surprisingly, despite large differences in their biology, our analyses suggested that the rate decay speed is independent of viral types and thus might be useful for better estimation of the evolutionary time scale of any virus. To illustrate this, we used our model to reestimate the evolutionary timescales of extant lentiviruses, which were previously suggested to be very young by standard phylogenetic analyses. Our analyses suggested that these viruses are millions of years old, in agreement with paleovirological evidence, and therefore, for the first time, reconciled molecular analyses of ancient and extant viruses. IMPORTANCE This work provides direct evidence that viral evolutionary rate estimates decay with their measurement timescales and that the rate decay speeds do not differ significantly among viruses despite the vast differences in their molecular features. After adjustment for the rate decay dynamics, the

  6. A time-dependent variational principle and the time-dependent Hartree approximation in hydrodynamical form

    NASA Astrophysics Data System (ADS)

    Lill, J. V.; Haftel, M. I.; Herling, G. H.

    1989-05-01

    A quantum mechanical time-dependent variational principle is generalized using the classical theory of fluids to obtain a variational principle suitable for the fluid dynamical description of mixed state quantum mechanics. A newly derived set of moment equations, in both standard and renormalized form, can be derived with the aid of this principle through minimization of the error in expressing the total derivative of the Wigner function. Coupled systems are studied in the time-dependent Hartree (TDH) approximation using a novel variational principle, and the renormalization procedure used earlier in the examination of single particle dynamics is extended to the TDH analysis. Use of a local Maxwellian ansatz for each particle results in a particularly simple ``two-fluid'' theory, the TDH/LM approximation, which does not violate the standard and renormalized energy conservation theorems derived earlier for the single particle equations. The fluid dynamical TDH/LM approximation is shown to possess a simple semiclassical interpretation.

  7. Photodissociation dynamics of the pyridinyl radical: Time-dependent quantum wave-packet calculations

    NASA Astrophysics Data System (ADS)

    Ehrmaier, Johannes; Picconi, David; Karsili, Tolga N. V.; Domcke, Wolfgang

    2017-03-01

    The H-atom photodissociation reaction from the pyridinyl radical (C5H5NH ) via the low-lying π σ* excited electronic state is investigated by nonadiabatic time-dependent quantum wave-packet dynamics calculations. A model comprising three electronic states and three nuclear coordinates has been constructed using ab initio multi-configurational self-consistent-field and multi-reference perturbation theory methods. Two conical intersections among the three lowest electronic states have been characterized in the framework of the linear vibronic-coupling model. Time-dependent wave-packet simulations have been performed using the multi-configuration time-dependent Hartree method. The population dynamics of the diabatic and adiabatic electronic states and the time-dependent dissociation behavior are analyzed for various vibrational initial conditions. The results provide detailed mechanistic insight into the photoinduced H-atom dissociation process from a hypervalent aromatic radical and show that an efficient dissociation reaction through two conical intersections is possible.

  8. From Classical Nonlinear Integrable Systems to Quantum Shortcuts to Adiabaticity

    NASA Astrophysics Data System (ADS)

    Okuyama, Manaka; Takahashi, Kazutaka

    2016-08-01

    Using shortcuts to adiabaticity, we solve the time-dependent Schrödinger equation that is reduced to a classical nonlinear integrable equation. For a given time-dependent Hamiltonian, the counterdiabatic term is introduced to prevent nonadiabatic transitions. Using the fact that the equation for the dynamical invariant is equivalent to the Lax equation in nonlinear integrable systems, we obtain the counterdiabatic term exactly. The counterdiabatic term is available when the corresponding Lax pair exists and the solvable systems are classified in a unified and systematic way. Multisoliton potentials obtained from the Korteweg-de Vries equation and isotropic X Y spin chains from the Toda equations are studied in detail.

  9. Time-dependent hygrothermomechanical properties of a structural adhesive

    NASA Astrophysics Data System (ADS)

    You, Jianmin

    This research determines the effect of hygro-thermal environment and strain rate on the tensile properties and develop a method to determine the long-term durability of structural adhesive FM300k. Topics related to structural adhesives are reviewed, including development history, classification, application, and chemical structure. Most high performance structural adhesives are epoxies with viscoelastic behavior which is greatly affected by relative humidity (RH), temperature, and strain rate. Theories for modeling the viscoelastic materials are also investigated. A testing system was developed with which the time-dependent hygro-thermo-mechanical properties of structural adhesives can be measured. This effort consists of building tensiometers and environmental chambers, controlling RH and temperature, preparing and conditioning specimens, applying displacements with a computer-controlled stepper motor, developing C++ and LabVIEW programs, and acquiring data automatically. Tests performed in the present study include thermal expansion and moisture swelling, tensile creep and stress relaxation, monotonic tensile tests, and adiabatic cooling. Tensile stress-strain curves are measured at different RHs (15%, 50% and 85%), temperature (--15°, 30° and 50°C) and strain rate (10-2, 10-4, 10-6 and 10 -8 s-1) to determine the effects of batch, loading method, environment, strain rate, and adhesive. Results from the five series of tests show very good correlation and indicate the excellent performance, high reliability, and reproducibility of the testing system developed in the present study. Mathematical models of creep and stress relaxation are used to predict the long-term durability of structural adhesive FM 300k. The concept of a master stress-strain curve for polymeric materials is introduced based on the results of the monotonic tensile tests. Using a master stress-strain curve, the long-term hygro-thermo-mechanical properties of structural adhesive FM300k can be

  10. Time dependent deformation of Kilauea Volcano, Hawaii

    NASA Astrophysics Data System (ADS)

    Montgomery-Brown, Emily Kvietka Desmarais

    to a decollement structure 8 km under the south flank, and the locations of the microearthquakes suggest that both occur on the same structure. In 2007, Episode 56 of the Pu'u 'O'o-Kupianaha eruption occurred. This episode was exciting both because it was the largest intrusion in the last decade, and because it occurred concurrently with a flank slow-slip event. The intrusion started on Father's day (June 17th), 2007 with increased seismicity and abrupt tilts at the summit and rift zones. Quasi-static models of the total deformation determined from GPS, tilt, and InSAR indicate that the intrusion occurred on two en echelon dike segments in the upper East Rift Zone along with deformation consistent with slow-slip in the same areas of previous events. The ˜ 2 m maximum opening occurred on the eastern segment near Makaopui crater. Unlike previous intrusions in 1997, 1999, and 2000, the dike model was not sufficient to explain deformation on the western flank. Additionally, a coastal tiltmeter installed in anticipation of a slow-slip event recorded tilts consistent with those observed during the 2005 slow-slip event. These observations led to the conclusion that a concurrent slow-slip event occurred. Geodetic models indicate a similar amount of decollement slip occurred as in previous slow-slip events. Sub-daily GPS positions were used to study the spatio-temporal distribution of the dike intrusion. The time-dependent intrusion model shows that the intrusion began on the western en echelon segment before jumping to the eastern segment, which accumulated the majority of the 2 m of opening. Sub-daily GPS positions limit the number of stations available since there are very few continuous stations north of the East Rift Zone, where coverage is critical for separating the intrusion from the slow-slip. However, an ENVISAT interferogram at 08:22 on June 18, 2007 provides additional spatial coverage of deformation up to that point. Combining this image with the GPS and tilt

  11. Geometry of the Adiabatic Theorem

    ERIC Educational Resources Information Center

    Lobo, Augusto Cesar; Ribeiro, Rafael Antunes; Ribeiro, Clyffe de Assis; Dieguez, Pedro Ruas

    2012-01-01

    We present a simple and pedagogical derivation of the quantum adiabatic theorem for two-level systems (a single qubit) based on geometrical structures of quantum mechanics developed by Anandan and Aharonov, among others. We have chosen to use only the minimum geometric structure needed for the understanding of the adiabatic theorem for this case.…

  12. THE APPLICATION OF SOME HARTREE-FOCK MODEL CALCULATION TO THE ANALYSIS OF ATOMIC AND FREE-ION OPTICAL SPECTRA

    SciTech Connect

    Hayhurst, Thomas Laine

    1980-08-06

    Techniques for applying ab-initio calculations to the is of atomic spectra are investigated, along with the relationship between the semi-empirical and ab-initio forms of Slater-Condon theory. Slater-Condon theory is reviewed with a focus on the essential features that lead to the effective Hamiltonians associated with the semi-empirical form of the theory. Ab-initio spectroscopic parameters are calculated from wavefunctions obtained via self-consistent field methods, while multi-configuration Hamiltonian matrices are constructed and diagonalized with computer codes written by Robert Cowan of Los Alamos Scientific Laboratory. Group theoretical analysis demonstrates that wavefunctions more general than Slater determinants (i.e. wavefunctions with radial correlations between electrons) lead to essentially the same parameterization of effective Hamiltonians. In the spirit of this analysis, a strategy is developed for adjusting ab-initio values of the spectroscopic parameters, reproducing parameters obtained by fitting the corresponding effective Hamiltonian. Secondary parameters are used to "screen" the calculated (primary) spectroscopic parameters, their values determined by least squares. Extrapolations of the secondary parameters determined from analyzed spectra are attempted to correct calculations of atoms and ions without experimental levels. The adjustment strategy and extrapolations are tested on the K I sequence from K{sup 0+} through Fe{sup 7+}, fitting to experimental levels for V{sup 4+}, and Cr{sup 5+}; unobserved levels and spectra are predicted for several members of the sequence. A related problem is also discussed: Energy levels of the Uranium hexahalide complexes, (UX{sub 6}){sup 2-} for X= F, Cl, Br, and I, are fit to an effective Hamiltonian (the f{sup 2} configuration in O{sub h} symmetry) with corrections proposed by Brian Judd.

  13. Hartree-Fock Solutions of 2d Interacting Tight-Binding Electrons: Mott Properties and Room Temperature Superconductivity Indications

    NASA Astrophysics Data System (ADS)

    Cabo Montes de Oca, A.; March, N. H.; Cabo-Bizet, A.

    2014-12-01

    Former results for a tight-binding (TB) model of CuO planes in La2CuO4 are reinterpreted here to underline their wider implications. It is noted that physical systems being appropriately described by the TB model can exhibit the main strongly correlated electron system (SCES) properties, when they are solved in the HF approximation, by also allowing crystal symmetry breaking effects and noncollinear spin orientations of the HF orbitals. It is argued how a simple 2D square lattice system of Coulomb interacting electrons can exhibit insulator gaps and pseudogap states, and quantum phase transitions as illustrated by the mentioned former works. A discussion is also presented here indicating the possibility of attaining room temperature superconductivity, by means of a surface coating with water molecules of cleaved planes of graphite, being orthogonal to its c-axis. The possibility that 2D arrays of quantum dots can give rise to the same effect is also proposed to consideration. The analysis also furnishes theoretical insight to solve the Mott-Slater debate, at least for the La2CuO4 and TMO band structures. The idea is to apply a properly noncollinear GW scheme to the electronic structure calculation of these materials. The fact is that the GW approach can be viewed as a HF procedure in which the screening polarization is also determined. This directly indicates the possibility of predicting the assumed dielectric constant in the previous works. Thus, the results seem to identify that the main correlation properties in these materials are determined by screening. Finally, the conclusions also seem to be of help for the description of the experimental observations of metal-insulator transitions and Mott properties in atoms trapped in planar photonic lattices.

  14. Restricted and unrestricted non-Hermitian Hartree-Fock: Theory, practical considerations, and applications to metastable molecular anions.

    PubMed

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

    2015-08-21

    This work describes the implementation and applications of non-Hermitian self-consistent field (NH-SCF) theory with complex basis functions for the ab initio computation of positions and widths of shape resonances in molecules. We utilize both the restricted open-shell and the previously unexplored spin-unrestricted variants to compute Siegert energies of several anionic shape resonances in small diatomic and polyatomic molecules including carbon tetrafluoride which has been the subject of several recent experimental studies. The computation of general molecular properties from a non-Hermitian wavefunction is discussed, and a density-based analysis is applied to the (2)B1 shape resonance in formaldehyde. Spin-unrestricted NH-SCF is used to compute a complex potential energy surface for the carbon monoxide anion which correctly describes dissociation.

  15. Convergent Partially Augmented Basis Sets for Post-Hartree-Fock Calculations of Molecular Properties and Reaction Barrier Heights.

    PubMed

    Papajak, Ewa; Truhlar, Donald G

    2011-01-11

    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", "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.

  16. Convergent Partially Augmented Basis Sets for Post-Hartree-Fock Calculations of Molecular Properties and Reaction Barrier Heights

    SciTech Connect

    Papajak, Ewa; Truhlar, Donald G.

    2011-01-11

    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”, “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.

  17. Energy spectra and electromagnetic transition rates of {sup 160,162,164}Gd in the projected Hartree-Fock model

    SciTech Connect

    Ghorui, S. K.; Raina, P. K.; Praharaj, C. R.; Patra, S. K.; Naik, Z.

    2014-08-14

    Band structure and electromagnetic properties of bands of {sup 160,162,164}Gd are studied theoretically upto high spin values using self-consisstent mean field theory. Predictions for the band structures are made. A K = 6{sup −} isomer at fairly low energy is predicted. Four quasi-particle bands involving i{sub 13/2} neutron and h{sub 11/2} protons are also studied.

  18. Further explorations of Skyrme-Hartree-Fock-Bogoliubov mass formulas. I: Role of density dependence in pairing force

    NASA Astrophysics Data System (ADS)

    Samyn, M.; Goriely, S.; Pearson, J. M.

    2003-09-01

    The HFB-2 mass formula is generalized to make the δ-function pairing force density-dependent. It is shown that the mass data rule out the simple model of a pairing force that vanishes completely in the nuclear interior. Consistency with the mass data is found for a fairly wide range of δ-function pairing forces with a partial weakening in the nuclear interior. In particular, the form of density dependence determined by the realistic nuclear-matter calculations of Garrido et al. is shown to be compatible with the mass data, 2135 measured masses being fitted with an rms error of 0.656 MeV. On this basis we construct a new mass table, HFB-3, running from one drip line to the other. Shell quenching at the neutron-drip line is now somewhat stronger than before, but otherwise the new mass formula does not differ in any conspicuous way from the HFB-2 mass formula.

  19. Post-Hartree-Fock studies of the He/Mg(0001) interaction: Anti-corrugation, screening, and pairwise additivity

    NASA Astrophysics Data System (ADS)

    de Lara-Castells, María Pilar; Fernández-Perea, Ricardo; Madzharova, Fani; Voloshina, Elena

    2016-06-01

    The adsorption of noble gases on metallic surfaces represents a paradigmatic case of van-der-Waals (vdW) interaction due to the role of screening effects on the corrugation of the interaction potential [J. L. F. Da Silva et al., Phys. Rev. Lett. 90, 066104 (2003)]. The extremely small adsorption energy of He atoms on the Mg(0001) surface (below 3 meV) and the delocalized nature and mobility of the surface electrons make the He/Mg(0001) system particularly challenging, even for state-of-the-art vdW-corrected density functional-based (vdW-DFT) approaches [M. P. de Lara-Castells et al., J. Chem. Phys. 143, 194701 (2015)]. In this work, we meet this challenge by applying two different procedures. First, the dispersion-corrected second-order Möller-Plesset perturbation theory (MP2C) approach is adopted, using bare metal clusters of increasing size. Second, the method of increments [H. Stoll, J. Chem. Phys. 97, 8449 (1992)] is applied at coupled cluster singles and doubles and perturbative triples level, using embedded cluster models of the metal surface. Both approaches provide clear evidences of the anti-corrugation of the interaction potential: the He atom prefers on-top sites, instead of the expected hollow sites. This is interpreted as a signature of the screening of the He atom by the metal for the on-top configuration. The strong screening in the metal is clearly reflected in the relative contribution of successively deeper surface layers to the main dispersion contribution. Aimed to assist future dynamical simulations, a pairwise potential model for the He/surface interaction as a sum of effective He-Mg pair potentials is also presented, as an improvement of the approximation using isolated He-Mg pairs.

  20. Quantum and classical non-adiabatic dynamics of Li_{2}^{+}Ne photodissociation

    NASA Astrophysics Data System (ADS)

    Pouilly, Brigitte; Monnerville, Maurice; Zanuttini, David; Gervais, Benoît

    2015-01-01

    The 3D photodissociation dynamics of Li2+Ne system is investigated by quantum calculations using the multi-configuration time-dependent Hartree (MCTDH) method and by classical simulations with the trajectory surface hopping (TSH) approach. Six electronic states of A’ symmetry and two states of A” symmetry are involved in the process. Couplings in the excitation region and two conical intersections in the vicinity of the Franck-Condon zone control the non-adiabatic nuclear dynamics. A diabatic representation including all the states and the couplings is determined. Diabatic and adiabatic populations calculated for initial excitation to pure diabatic and adiabatic states lead to a clear understanding of the mechanisms governing the non-adiabatic photodissociation process. The classical and quantum photodissociation cross-sections for absorption in two adiabatic states of the A’ symmetry are calculated. A remarkable agreement between quantum and classical results is obtained regarding the populations and the absorption cross-sections.

  1. Stochasticity, superadiabaticity, and the theory of adiabatic invariants and guiding center motion

    SciTech Connect

    Dubin, D.H.E.; Krommes, J.A.

    1981-07-01

    The theory of adiabatic invariants is discussed within the modern framework of symplectic Hamiltonian dynamics. The distinctions between exact, adiabatic, and superadiabatic invariants are clarified. The intimate connection between adiabatic (as opposed to exact) invariance and resonant interactions between motions on disparate time scales is elucidated. For the important case of charged particle motion in a strong magnetic field, resonances between gyration, bounce motion, and an external sinusoidal perturbation are described explicitly by introducing a time-dependent symplectic formulation of the guiding center motion. Destruction of invariance is discussed for quite general situations of physical interest, including the case of a trapped particle in a tokamak.

  2. Non-adiabatic Rayleigh-Taylor instability

    NASA Astrophysics Data System (ADS)

    Canfield, Jesse; Denissen, Nicholas; Reisner, Jon

    2016-11-01

    Onset of Rayleigh-Taylor instability (RTI) in a non-adiabatic environment is investigated with the multi-physics numerical model, FLAG. This work was inspired by laboratory experiments of non-adiabatic RTI, where a glass vessel with a layer of tetrahyrdofuran (THF) below a layer of toluene was placed inside a microwave. THF, a polar solvent, readily absorbs electromagnetic energy from microwaves. Toluene, a non-polar solvent, is nearly transparent to microwave heating. The presence of a heat source in the THF layer produced convection and a time-dependent Atwood number (At). The system, initially in stable hydrostatic equilibrium At < 0 , was set into motion by microwave induced, volumetric heating of the THF. The point when At > 0 , indicates that the system is RTI unstable. The observed dominant mode at the onset of RTI was the horizontal length scale of the vessel. This scale is contrary to classical RTI, where the modes start small and increases in scale with time. It is shown that the dominant RTI mode observed in the experiments was determined by the THF length scale prior to RTI. The dominant length scale transitions from the THF to the toluene via the updrafts and downdrafts in the convective cells. This happens when At passes from negative to positive. This work was funded by the Advanced Simulation and Computing Program.

  3. Time-dependent exchange-correlation functional for a Hubbard dimer: Quantifying nonadiabatic effects

    NASA Astrophysics Data System (ADS)

    Fuks, Johanna I.; Farzanehpour, Mehdi; Tokatly, Ilya V.; Appel, Heiko; Kurth, Stefan; Rubio, Angel

    2013-12-01

    We address and quantify the role of nonadiabaticity ("memory effects") in the exchange-correlation (xc) functional of time-dependent density functional theory (TDDFT) for describing nonlinear dynamics of many-body systems. Time-dependent resonant processes are particularly challenging for available TDDFT approximations, due to their strong nonlinear and nonadiabatic character. None of the known approximate density functionals are able to cope with this class of problems in a satisfactory manner. In this work we look at the prototypical example of the resonant processes by considering Rabi oscillations within the exactly soluble two-site Hubbard model. We construct the exact adiabatic xc functional and show that (i) it does not reproduce correctly resonant Rabi dynamics, and (ii) there is a sizable nonadiabatic contribution to the exact xc potential, which turns out to be small only at the beginning and at the end of the Rabi cycle when the ground-state population is dominant. We then propose a "two-level" approximation for the time-dependent xc potential which can capture Rabi dynamics in the two-site problem. It works well both for resonant and for detuned Rabi oscillations and becomes essentially exact in the linear response regime.

  4. Robust exponential acceleration in time-dependent billiards.

    PubMed

    Gelfreich, Vassili; Rom-Kedar, Vered; Shah, Kushal; Turaev, Dmitry

    2011-02-18

    A class of nonrelativistic particle accelerators in which the majority of particles gain energy at an exponential rate is constructed. The class includes ergodic billiards with a piston that moves adiabatically and is removed adiabatically in a periodic fashion. The phenomenon is robust: deformations that keep the chaotic character of the billiard retain the exponential energy growth. The growth rate is found analytically and is, thus, controllable. Numerical simulations corroborate the analytic predictions with good precision. The acceleration mechanism has a natural thermodynamical interpretation and is applied to a hot dilute gas of repelling particles.

  5. LETTER TO THE EDITOR: Exact energy distribution function in a time-dependent harmonic oscillator

    NASA Astrophysics Data System (ADS)

    Robnik, Marko; Romanovski, Valery G.; Stöckmann, Hans-Jürgen

    2006-09-01

    Following a recent work by Robnik and Romanovski (2006 J. Phys. A: Math. Gen. 39 L35, 2006 Open Syst. Inf. Dyn. 13 197-222), we derive an explicit formula for the universal distribution function of the final energies in a time-dependent 1D harmonic oscillator, whose functional form does not depend on the details of the frequency ω(t) and is closely related to the conservation of the adiabatic invariant. The normalized distribution function is P(x) = \\pi^{-1} (2\\mu^2 - x^2)^{-\\frac{1}{2}} , where x=E_1- \\skew3\\bar{E}_1 ; E1 is the final energy, \\skew3\\bar{E}_1 is its average value and µ2 is the variance of E1. \\skew3\\bar{E}_1 and µ2 can be calculated exactly using the WKB approach to all orders.

  6. Charge and heat transport in soft nanosystems in the presence of time-dependent perturbations

    PubMed Central

    Perroni, Carmine Antonio; Ramaglia, Vincenzo Marigliano; Cataudella, Vittorio

    2016-01-01

    Summary Background: Soft nanosystems are electronic nanodevices, such as suspended carbon nanotubes or molecular junctions, whose transport properties are modulated by soft internal degrees of freedom, for example slow vibrational modes. Effects of the electron–vibration coupling on the charge and heat transport of soft nanoscopic systems are theoretically investigated in the presence of time-dependent perturbations, such as a forcing antenna or pumping terms between the leads and the nanosystem. A well-established approach valid for non-equilibrium adiabatic regimes is generalized to the case where external time-dependent perturbations are present. Then, a number of relevant applications of the method are reviewed for systems composed by a quantum dot (or molecule) described by a single electronic level coupled to a vibrational mode. Results: Before introducing time-dependent perturbations, the range of validity of the adiabatic approach is discussed showing that a very good agreement with the results of an exact quantum calculation is obtained in the limit of low level occupation. Then, we show that the interplay between the low frequency vibrational modes and the electronic degrees of freedom affects the thermoelectric properties within the linear response regime finding out that the phonon thermal conductance provides an important contribution to the figure of merit at room temperature. Our work has been stimulated by recent experimental results on carbon nanotube electromechanical devices working in the semiclassical regime (resonator frequencies in the megahertz range compared to an electronic hopping frequency of the order of tens of gigahertz) with extremely high quality factors. The nonlinear vibrational regime induced by the external antenna in such systems has been discussed within the non-perturbative adiabatic approach reproducing quantitatively the characteristic asymmetric shape of the current–frequency curves. Within the same set-up, we have

  7. Failure of geometric electromagnetism in the adiabatic vector Kepler problem

    SciTech Connect

    Anglin, J.R.; Schmiedmayer, J.

    2004-02-01

    The magnetic moment of a particle orbiting a straight current-carrying wire may precess rapidly enough in the wire's magnetic field to justify an adiabatic approximation, eliminating the rapid time dependence of the magnetic moment and leaving only the particle position as a slow degree of freedom. To zeroth order in the adiabatic expansion, the orbits of the particle in the plane perpendicular to the wire are Keplerian ellipses. Higher-order postadiabatic corrections make the orbits precess, but recent analysis of this 'vector Kepler problem' has shown that the effective Hamiltonian incorporating a postadiabatic scalar potential ('geometric electromagnetism') fails to predict the precession correctly, while a heuristic alternative succeeds. In this paper we resolve the apparent failure of the postadiabatic approximation, by pointing out that the correct second-order analysis produces a third Hamiltonian, in which geometric electromagnetism is supplemented by a tensor potential. The heuristic Hamiltonian of Schmiedmayer and Scrinzi is then shown to be a canonical transformation of the correct adiabatic Hamiltonian, to second order. The transformation has the important advantage of removing a 1/r{sup 3} singularity which is an artifact of the adiabatic approximation.

  8. Adiabatic State Conversion and Photon Transmission in Optomechanical Systems

    NASA Astrophysics Data System (ADS)

    Tian, Lin

    2012-02-01

    Light-matter interaction in optomechanical systems in the strong coupling regime can be explored as a tool to transfer cavity states and to transmit photon pulses. Here, we show that quantum state conversion between cavity modes with different wavelengths can be realized with high fidelity by adiabatically varying the effective optomechanical couplings. During this adiabatic process, the quantum state is preserved in the dark mode of the cavities, similar to the adiabatic transfer schemes in EIT systems. The fidelity for gaussian states is derived by solving the Langevin equation in the adiabatic limit and shows negligible dependence on the mechanical noise. We also show that an input pulse can be transmitted to an output channel with a different wavelength via the effective optomechanical couplings. The condition for optimal transmission is derived in the frequency domain. Input pulses with a narrow spectral width can be transmitted with high fidelity. For input pulses with a large spectral width, the shape of the output pulses can be manipulated by applying time-dependent effective couplings. (1) L. Tian, arXiv:1111.2119. (2) L. Tian and H. L. Wang, Phys. Rev. A 82, 053806 (2010).

  9. Growth dynamics of a Bose-Einstein condensate in a dimple trap without cooling

    SciTech Connect

    Garrett, Michael C.; Davis, Matthew J.; Ratnapala, Adrian; Ooijen, Eikbert D. van; Vale, Christopher J.; Weegink, Kristian; Schnelle, Sebastian K.; Vainio, Otto; Heckenberg, Norman R.; Rubinsztein-Dunlop, Halina

    2011-01-15

    We study the formation of a Bose-Einstein condensate in a cigar-shaped three-dimensional harmonic trap, induced by the controlled addition of an attractive ''dimple'' potential along the weak axis. In this manner we are able to induce condensation without cooling due to a localized increase in the phase-space density. We perform a quantitative analysis of the thermodynamic transformation in both the sudden and adiabatic regimes for a range of dimple widths and depths. We find good agreement with equilibrium calculations based on self-consistent semiclassical Hartree-Fock theory describing the condensate and thermal cloud. We observe that there is an optimal dimple depth that results in a maximum in the condensate fraction. We also study the nonequilibrium dynamics of condensate formation in the sudden turn-on regime, finding good agreement for the observed time dependence of the condensate fraction with calculations based on quantum kinetic theory.

  10. Dynamical nucleus-nucleus potential at short distances

    SciTech Connect

    Jiang Yongying; Wang Ning; Li Zhuxia; Scheid, Werner

    2010-04-15

    The dynamical nucleus-nucleus potentials for fusion reactions {sup 40}Ca+{sup 40}Ca, {sup 48}Ca+{sup 208}Pb, and {sup 126}Sn+{sup 130}Te are studied with the improved quantum molecular dynamics model together with the extended Thomas-Fermi approximation for the kinetic energies of nuclei. The obtained fusion barrier for {sup 40}Ca+{sup 40}Ca is in good agreement with the extracted fusion barrier from the measured fusion excitation function, and the depths of the fusion pockets are close to the results of time-dependent Hartree-Fock calculations. The energy dependence of the fusion barrier is also investigated. The fusion pocket becomes shallow for a heavy fusion system and almost disappears for heavy nearly symmetric systems, and the obtained potential at short distances is higher than the adiabatic potential.

  11. Interaction of a Single-Mode Laser With a Generalized Sturmian Description of Helium: Application of a Space-Time Basis Time Propagation Algorithm

    NASA Astrophysics Data System (ADS)

    McDowell, Justin; Red, Eddie; Wynn, Albert, III; Weatherford, Charles

    2006-05-01

    The method of Generalized Sturmians is applied to the calculation of the ground and excited states of the helium atom. In the process, the screening constant of each one-electron Sturmian orbital is non- iteratively uniquely determined. Also, the usual Hartree-Fock calculation is avoided. The entire helium spectrum is thus calculated with approximately the same accuracy for the excited and ground states. The interaction of a single-mode laser with helium is then simulated by solving the time-dependent Schr"odinger equation using a space-time basis propagation algorithm. The method is implicit and is quite stable. The STIRAP (Stimulated Raman Adiabatic Passage) noniterative control scheme will be used to manipulate the helium excitation by the laser.

  12. Nonadiabatic electron dynamics in time-dependent density-functional theory

    NASA Astrophysics Data System (ADS)

    Ullrich, C. A.; Tokatly, I. V.

    2006-06-01

    Time-dependent density-functional theory (TDDFT) treats dynamical exchange and correlation (xc) via a single-particle potential, Vxc(r,t) , defined as a nonlocal functional of the density n(r',t') . The popular adiabatic local-density approximation (ALDA) for Vxc(r,t) uses only densities at the same space-time point (r,t) . To go beyond the ALDA, two local approximations have been proposed based on quantum hydrodynamics and elasticity theory: (a) using the current as the basic variable (C-TDDFT) [G. Vignale, C. A. Ullrich, and S. Conti, Phys. Rev. Lett. 79, 4847 (1997)], (b) working in a comoving Lagrangian reference frame (L-TDDFT) [I. V. Tokatly, Phys. Rev. B 71, 165105 (2005)]. In this paper we illustrate, compare, and analyze both nonadiabatic theories for simple time-dependent model densities in the linear and nonlinear regime, for a broad range of time and frequency scales. C- and L-TDDFT are identical in certain limits, but, in general, exhibit qualitative and quantitative differences in their respective treatment of elastic and dissipative electron dynamics. In situations where the electronic density rapidly undergoes large deformations, it is found that nonadiabatic effects can become significant, causing the ALDA to break down.

  13. Theoretical study of time-dependent, ultrasound-induced acoustic streaming in microchannels.

    PubMed

    Muller, Peter Barkholt; Bruus, Henrik

    2015-12-01

    Based on first- and second-order perturbation theory, we present a numerical study of the temporal buildup and decay of unsteady acoustic fields and acoustic streaming flows actuated by vibrating walls in the transverse cross-sectional plane of a long straight microchannel under adiabatic conditions and assuming temperature-independent material parameters. The unsteady streaming flow is obtained by averaging the time-dependent velocity field over one oscillation period, and as time increases, it is shown to converge towards the well-known steady time-averaged solution calculated in the frequency domain. Scaling analysis reveals that the acoustic resonance builds up much faster than the acoustic streaming, implying that the radiation force may dominate over the drag force from streaming even for small particles. However, our numerical time-dependent analysis indicates that pulsed actuation does not reduce streaming significantly due to its slow decay. Our analysis also shows that for an acoustic resonance with a quality factor Q, the amplitude of the oscillating second-order velocity component is Q times larger than the usual second-order steady time-averaged velocity component. Consequently, the well-known criterion v(1)≪c(s) for the validity of the perturbation expansion is replaced by the more restrictive criterion v(1)≪c(s)/Q. Our numerical model is available as supplemental material in the form of comsol model files and matlab scripts.

  14. The Floquet Adiabatic Theorem revisited

    NASA Astrophysics Data System (ADS)

    Weinberg, Phillip; Bukov, Marin; D'Alessio, Luca; Kolodrubetz, Michael; Davidson, Shainen; Polkovnikov, Anatoli

    2015-03-01

    The existance of the adiabatic theorem for Floquet systems has been the subject of an active debate with different articles reaching opposite conclusions over the years. In this talk we clarify the situation by deriving a systematic expansion in the time-derivatives of a slow parameter for the occupation probabilities of the Floque states. Our analysis shows that the in a certain limit the transition between Floquet eigenstates are suppressed and it is possible to define an adiabatic theorem for Floquet systems. Crucially we observe however that the conditions for adiabaticity in ordinary and Floquet systems are different and that this difference can become important when the amplitude of the periodic driving is large. We illustrate our results with specific examples of a periodically driven harmonic oscillator and cold atoms in optical lattices which are relevant in current experiments.

  15. Adiabatic losses in Stirling refrigerators

    SciTech Connect

    Bauwens, L.

    1996-06-01

    The Stirling cycle has been used very effectively in cryocoolers; but efficiencies relative to the Carnot limit are typically observed to peak for absolute temperature ratios of about two, which makes it less suitable for low-life refrigeration. The adiabatic loss appears to be responsible for poor performance at small temperature differences. In this paper, adiabatic losses are evaluated, for a temperature ratio of 2/3, taking into account the effect of phase angle between pistons, of volume ratio, of the distribution of the dead volume necessary to reduce the volume ratio, and of the distribution of displacement between expansion and compression spaces. The study is carried out numerically, using an adiabatic Stirling engine model in which cylinder flow is assumed to be stratified. Results show that the best location for the cylinder dead volume is on the compression side. Otherwise, all strategies used to trade off refrigeration for coefficient of performance are found to be roughly equivalent.

  16. Time Dependent Studies of Reactive Shocks in the Gas Phase

    DTIC Science & Technology

    1978-11-16

    1 LEVEL NRL Memorandum Report 3W tO Time Dependent Studies of Reactive Shocks in the Gas Phase E.S. ORAN, ’T.R. YOUNG and J.P. BORIS Laboratory for...34-• TIME DEPENDENT STUDIES OF REACTIVE SHOCKS IN THE GAS PHASE I. Introduction This paper presents results obtained from a detailed numerical...chemical kinetics, reaction products, and intermediates produced in reactive gas mixtures ignited by the propagation of a shock front. The model is based

  17. One Dimensional Time-Dependent Tunnelling of Excitons

    NASA Astrophysics Data System (ADS)

    Kilcullen, Patrick; Salayka-Ladouceur, Logan; Malmgren, Kevin; Reid, Matthew; Shegelski, Mark R. A.

    2017-03-01

    We study the time-dependent tunnelling of excitons in one dimension using numerical integration based on the Crank-Nicholson method. A complete development of the time-dependent simulator is provided. External barriers studied include single and double delta barriers. We find that the appearance of transmission resonances depends strongly on the dielectric constant, relative effective masses, and initial spatial spread of the wavefunction. A discussion regarding applications to realistic systems is provided.

  18. Adiabatic evolution of plasma equilibrium

    PubMed Central

    Grad, H.; Hu, P. N.; Stevens, D. C.

    1975-01-01

    A new theory of plasma equilibrium is introduced in which adiabatic constraints are specified. This leads to a mathematically nonstandard structure, as compared to the usual equilibrium theory, in which prescription of pressure and current profiles leads to an elliptic partial differential equation. Topologically complex configurations require further generalization of the concept of adiabaticity to allow irreversible mixing of plasma and magnetic flux among islands. Matching conditions across a boundary layer at the separatrix are obtained from appropriate conservation laws. Applications are made to configurations with planned islands (as in Doublet) and accidental islands (as in Tokamaks). Two-dimensional, axially symmetric, helically symmetric, and closed line equilibria are included. PMID:16578729

  19. Adiabatic invariants in stellar dynamics. 2: Gravitational shocking

    NASA Technical Reports Server (NTRS)

    Weinberg, Martin D.

    1994-01-01

    A new theory of gravitational shocking based on time-dependent perturbation theory shows that the changes in energy and angular momentum due to a slowly varying disturbance are not exponentially small for stellar dynamical systems in general. It predicts significant shock heating by slowly varying perturbations previously thought to be negligible according to the adiabatic criterion. The theory extends the scenarios traditionally computed only with the impulse approximation and is applicable to a wide class of disturbances. The approach is applied specifically to the problem of disk shocking of star clusters.

  20. Towards time-dependent current-density-functional theory in the non-linear regime

    SciTech Connect

    Escartín, J. M.; Vincendon, M.; Dinh, P. M.; Suraud, E.; Romaniello, P.; Reinhard, P.-G.

    2015-02-28

    Time-Dependent Density-Functional Theory (TDDFT) is a well-established theoretical approach to describe and understand irradiation processes in clusters and molecules. However, within the so-called adiabatic local density approximation (ALDA) to the exchange-correlation (xc) potential, TDDFT can show insufficiencies, particularly in violently dynamical processes. This is because within ALDA the xc potential is instantaneous and is a local functional of the density, which means that this approximation neglects memory effects and long-range effects. A way to go beyond ALDA is to use Time-Dependent Current-Density-Functional Theory (TDCDFT), in which the basic quantity is the current density rather than the density as in TDDFT. This has been shown to offer an adequate account of dissipation in the linear domain when the Vignale-Kohn (VK) functional is used. Here, we go beyond the linear regime and we explore this formulation in the time domain. In this case, the equations become very involved making the computation out of reach; we hence propose an approximation to the VK functional which allows us to calculate the dynamics in real time and at the same time to keep most of the physics described by the VK functional. We apply this formulation to the calculation of the time-dependent dipole moment of Ca, Mg and Na{sub 2}. Our results show trends similar to what was previously observed in model systems or within linear response. In the non-linear domain, our results show that relaxation times do not decrease with increasing deposited excitation energy, which sets some limitations to the practical use of TDCDFT in such a domain of excitations.

  1. Pressure Oscillations in Adiabatic Compression

    ERIC Educational Resources Information Center

    Stout, Roland

    2011-01-01

    After finding Moloney and McGarvey's modified adiabatic compression apparatus, I decided to insert this experiment into my physical chemistry laboratory at the last minute, replacing a problematic experiment. With insufficient time to build the apparatus, we placed a bottle between two thick textbooks and compressed it with a third textbook forced…

  2. Information theories for time-dependent harmonic oscillator

    SciTech Connect

    Choi, Jeong Ryeol; Kim, Min-Soo; Kim, Daeyeoul; Maamache, Mustapha; Menouar, Salah; Nahm, In Hyun

    2011-06-15

    Highlights: > Information theories for the general time-dependent harmonic oscillator based on invariant operator method. > Time dependence of entropies and entropic uncertainty relation. > Characteristics of Shannon information and Fisher information. > Application of information theories to particular systems that have time-dependent behavior. - Abstract: Information theories for the general time-dependent harmonic oscillator are described on the basis of invariant operator method. We obtained entropic uncertainty relation of the system and discussed whether it is always larger than or equal to the physically allowed minimum value. Shannon information and Fisher information are derived by means of density operator that satisfies Liouville-von Neumann equation and their characteristics are investigated. Shannon information is independent of time, but Fisher information is explicitly dependent on time as the time functions of the Hamiltonian vary. We can regard that the Fisher information is a local measure since its time behavior is largely affected by local arrangements of the density, whilst the Shannon information plays the role of a global measure of the spreading of density. To promote the understanding, our theory is applied to special systems, the so-called quantum oscillator with time-dependent frequency and strongly pulsating mass system.

  3. Watching excitons move: the time-dependent transition density matrix

    NASA Astrophysics Data System (ADS)

    Ullrich, Carsten

    2012-02-01

    Time-dependent density-functional theory allows one to calculate excitation energies and the associated transition densities in principle exactly. The transition density matrix (TDM) provides additional information on electron-hole localization and coherence of specific excitations of the many-body system. We have extended the TDM concept into the real-time domain in order to visualize the excited-state dynamics in conjugated molecules. The time-dependent TDM is defined as an implicit density functional, and can be approximately obtained from the time-dependent Kohn-Sham orbitals. The quality of this approximation is assessed in simple model systems. A computational scheme for real molecular systems is presented: the time-dependent Kohn-Sham equations are solved with the OCTOPUS code and the time-dependent Kohn-Sham TDM is calculated using a spatial partitioning scheme. The method is applied to show in real time how locally created electron-hole pairs spread out over neighboring conjugated molecular chains. The coupling mechanism, electron-hole coherence, and the possibility of charge separation are discussed.

  4. Digital waveguide adiabatic passage part 1: theory

    NASA Astrophysics Data System (ADS)

    Vaitkus, Jesse A.; Steel, M. J.; Greentree, Andrew D.

    2017-03-01

    Spatial adiabatic passage represents a new way to design integrated photonic devices. In conventional adiabatic passage designs require smoothly varying waveguide separations. Here we show modelling of adiabatic passage devices where the waveguide separation is varied digitally. Despite digitisation, our designs show robustness against variations in the input wavelength and refractive index contrast of the waveguides relative to the cladding. This approach to spatial adiabatic passage opens new design strategies and hence the potential for new photonics devices.

  5. Time-dependent density-functional tight-binding method with the third-order expansion of electron density

    SciTech Connect

    Nishimoto, Yoshio

    2015-09-07

    We develop a formalism for the calculation of excitation energies and excited state gradients for the self-consistent-charge density-functional tight-binding method with the third-order contributions of a Taylor series of the density functional theory energy with respect to the fluctuation of electron density (time-dependent density-functional tight-binding (TD-DFTB3)). The formulation of the excitation energy is based on the existing time-dependent density functional theory and the older TD-DFTB2 formulae. The analytical gradient is computed by solving Z-vector equations, and it requires one to calculate the third-order derivative of the total energy with respect to density matrix elements due to the inclusion of the third-order contributions. The comparison of adiabatic excitation energies for selected small and medium-size molecules using the TD-DFTB2 and TD-DFTB3 methods shows that the inclusion of the third-order contributions does not affect excitation energies significantly. A different set of parameters, which are optimized for DFTB3, slightly improves the prediction of adiabatic excitation energies statistically. The application of TD-DFTB for the prediction of absorption and fluorescence energies of cresyl violet demonstrates that TD-DFTB3 reproduced the experimental fluorescence energy quite well.

  6. Time-dependent perturbation theory for inelastic scattering

    NASA Astrophysics Data System (ADS)

    Cross, R. J.

    1982-08-01

    We show by numerical integration that the first-order, time-dependent, Magnus approximation agrees with the first-order, exponential, distorted-wave approximation to within a few percent, provided that the trajectory used for the time-dependent calculation is characterized by the arithmetic mean of the initial and final velocities and the arithmetic mean of the initial and final orbital angular momenta. Calculations are done for rotational energy transfer from an exponentially repulsive potential characteristic of He+H2 and for a Lennard-Jones potential characteristic of Ar+N2.

  7. Time-dependent Bragg diffraction by multilayer gratings

    NASA Astrophysics Data System (ADS)

    André, Jean-Michel; Jonnard, Philippe

    2016-01-01

    Time-dependent Bragg diffraction by multilayer gratings working by reflection or by transmission is investigated. The study is performed by generalizing the time-dependent coupled-wave theory previously developed for one-dimensional photonic crystals (André J-M and Jonnard P 2015 J. Opt. 17 085609) and also by extending the Takagi-Taupin approach of the dynamical theory of diffraction. The indicial response is calculated. It presents a time delay with a transient time that is a function of the extinction length for reflection geometry and of the extinction length combined with the thickness of the grating for transmission geometry.

  8. Vacuum radiation induced by time dependent electric field

    NASA Astrophysics Data System (ADS)

    Zhang, Bo; Zhang, Zhi-meng; Hong, Wei; He, Shu-Kai; Teng, Jian; Gu, Yu-qiu

    2017-04-01

    Many predictions of new phenomena given by strong field quantum electrodynamics (SFQED) will be tested on next generation multi-petawatt laser facilities in the near future. These new phenomena are basis to understand physics in extremely strong electromagnetic fields therefore have attracted wide research interest. Here we discuss a new SFQED phenomenon that is named as vacuum radiation. In vacuum radiation, a virtual electron loop obtain energy from time dependent external electric field and radiate an entangled photon pair. Features of vacuum radiation in a locally time dependent electric field including spectrum, characteristic temperature, production rate and power are given.

  9. Enhanced thermopower under a time-dependent gate voltage

    NASA Astrophysics Data System (ADS)

    Crépieux, Adeline; Šimkovic, Fedor; Cambon, Benjamin; Michelini, Fabienne

    2011-04-01

    We derive formal expressions of time-dependent energy and heat currents through a nanoscopic device using the Keldysh nonequilibrium Green function technique. Numerical results are reported for a metal-dot-metal junction where the dot level energy is abruptly changed by a step-shaped voltage pulse. Analytical linear responses are obtained for the time-dependent thermoelectric coefficients. We show that in the transient regime the Seebeck coefficient can be enhanced by an amount (as much as 40%) controlled by both the dot energy and the height of the voltage step.

  10. Two-stream instability with time-dependent drift velocity

    DOE PAGES

    Qin, Hong; Davidson, Ronald C.

    2014-06-26

    The classical two-stream instability driven by a constant relative drift velocity between two plasma components is extended to the case with time-dependent drift velocity. A solution method is developed to rigorously define and calculate the instability growth rate for linear perturbations relative to the time-dependent unperturbed two-stream motions. The stability diagrams for the oscillating two-stream instability are presented over a large region of parameter space. It is shown that the growth rate for the classical two-stream instability can be significantly reduced by adding an oscillatory component to the relative drift velocity.

  11. Choice of Variables and Preconditioning for Time Dependent Problems

    NASA Technical Reports Server (NTRS)

    Turkel, Eli; Vatsa, Verr N.

    2003-01-01

    We consider the use of low speed preconditioning for time dependent problems. These are solved using a dual time step approach. We consider the effect of this dual time step on the parameter of the low speed preconditioning. In addition, we compare the use of two sets of variables, conservation and primitive variables, to solve the system. We show the effect of these choices on both the convergence to a steady state and the accuracy of the numerical solutions for low Mach number steady state and time dependent flows.

  12. Particle in a box with a time-dependent δ -function potential

    NASA Astrophysics Data System (ADS)

    Baek, Seung Ki; Yi, Su Do; Kim, Minjae

    2016-11-01

    In quantum information processing, one often considers inserting a barrier into a box containing a particle to generate one bit of Shannon entropy. We formulate this problem as a one-dimensional Schrödinger equation with a time-dependent δ -function potential. It is a natural generalization of the particle in a box, a canonical example of quantum mechanics, and we present analytic and numerical investigations on this problem. After deriving an exact Volterra-type integral equation, composed of an infinite sum of modes, we show that approximate formulas with the lowest-frequency modes correctly capture the qualitative behavior of the wave function. If we take into account hundreds of modes, our numerical calculation shows that the quantum adiabatic theorem actually gives a very good approximation even if the barrier height diverges within finite time, as long as it is sufficiently longer than the characteristic time scale of the particle. In particular, if the barrier is slowly inserted at an asymmetric position, the particle is localized by the insertion itself, in accordance with a prediction of the adiabatic theorem. On the other hand, when the barrier is inserted quickly, the wave function becomes rugged after the insertion because of the energy transfer to the particle. Regardless of the position of the barrier, the fast insertion leaves the particle unlocalized so that we can obtain meaningful information by a which-side measurement. Our numerical procedure provides a precise way to calculate the wave function throughout the process, from which one can estimate the amount of this information for an arbitrary insertion protocol.

  13. Adjoint-Based Methodology for Time-Dependent Optimization

    NASA Technical Reports Server (NTRS)

    Yamaleev, N. K.; Diskin, B.; Nielsen, E. J.

    2008-01-01

    This paper presents a discrete adjoint method for a broad class of time-dependent optimization problems. The time-dependent adjoint equations are derived in terms of the discrete residual of an arbitrary finite volume scheme which approximates unsteady conservation law equations. Although only the 2-D unsteady Euler equations are considered in the present analysis, this time-dependent adjoint method is applicable to the 3-D unsteady Reynolds-averaged Navier-Stokes equations with minor modifications. The discrete adjoint operators involving the derivatives of the discrete residual and the cost functional with respect to the flow variables are computed using a complex-variable approach, which provides discrete consistency and drastically reduces the implementation and debugging cycle. The implementation of the time-dependent adjoint method is validated by comparing the sensitivity derivative with that obtained by forward mode differentiation. Our numerical results show that O(10) optimization iterations of the steepest descent method are needed to reduce the objective functional by 3-6 orders of magnitude for test problems considered.

  14. Time-Dependent Interfacial Properties and DNAPL Mobility

    SciTech Connect

    Tuck, D.M.

    1999-03-10

    Interfacial properties play a major role in governing where and how dense nonaqueous phase liquids (DNAPLs) move in the subsurface. Interfacial tension and contact angle measurements were obtained for a simple, single component DNAPL (tetrachloroethene, PCE), complex laboratory DNAPLs (PCE plus Sudan IV dye), and a field DNAPL from the Savannah River Site (SRS) M-Area DNAPL (PCE, trichloroethene [TCE], and maching oils). Interfacial properties for complex DNAPLs were time-dependent, a phenomenon not observed for PCE alone. Drainage capillary pressure-saturation curves are strongly influenced by interfacial properties. Therefore time-dependence will alter the nature of DNAPL migration and penetration. Results indicate that the time-dependence of PCE with relatively high Sudan IV dye concentrations is comparable to that of the field DNAPL. Previous DNAPL mobility experiments in which the DNAPL was dyed should be reviewed to determine whether time-dependent properties influenced the resutls. Dyes appear to make DNAPL more complex, and therefore a more realistic analog for field DNAPLs than single component DNAPLs.

  15. Stability on time-dependent domains: convective and dilution effects

    NASA Astrophysics Data System (ADS)

    Krechetnikov, R.; Knobloch, E.

    2017-03-01

    We explore near-critical behavior of spatially extended systems on time-dependent spatial domains with convective and dilution effects due to domain flow. As a paradigm, we use the Swift-Hohenberg equation, which is the simplest nonlinear model with a non-zero critical wavenumber, to study dynamic pattern formation on time-dependent domains. A universal amplitude equation governing weakly nonlinear evolution of patterns on time-dependent domains is derived and proves to be a generalization of the standard Ginzburg-Landau equation. Its key solutions identified here demonstrate a substantial variety-spatially periodic states with a time-dependent wavenumber, steady spatially non-periodic states, and pulse-train solutions-in contrast to extended systems on time-fixed domains. The effects of domain flow, such as bifurcation delay due to domain growth and destabilization due to oscillatory domain flow, on the Eckhaus instability responsible for phase slips in spatially periodic states are analyzed with the help of both local and global stability analyses. A nonlinear phase equation describing the approach to a phase-slip event is derived. Detailed analysis of a phase slip using multiple time scale methods demonstrates different mechanisms governing the wavelength changing process at different stages.

  16. Advances in time-dependent methods for multiphoton processes

    SciTech Connect

    Kulander, K.C.; Schafer, K.J.; Krause, J.L.

    1990-09-01

    This paper discusses recent theoretical results on above threshold ionization harmonic generation and high-frequency, high intensity suppression of ionization. These studies of multiphoton processes in atoms and molecules for short, intense pulsed optical lasers have been carried out using techniques which involve the explicit solution of the time-dependent Schroedinger equation. 43 refs., 5 figs.

  17. Time dependent solution for acceleration of tau-leaping

    SciTech Connect

    Fu, Jin; Wu, Sheng; Petzold, Linda R.

    2013-02-15

    The tau-leaping method is often effective for speeding up discrete stochastic simulation of chemically reacting systems. However, when fast reactions are involved, the speed-up for this method can be quite limited. One way to address this is to apply a stochastic quasi-steady state assumption. However we must be careful when using this assumption. If the fast subsystem cannot reach a steady distribution fast enough, the quasi-steady-state assumption will propagate error into the simulation. To avoid these errors, we propose to use the time dependent solution rather than the quasi-steady-state. Generally speaking, the time dependent solution is not easy to derive for an arbitrary network. However, for some common motifs we do have time dependent solutions. We derive the time dependent solutions for these motifs, and then show how they can be used with tau-leaping to achieve substantial speed-ups, including for a realistic model of blood coagulation. Although the method is complicated, we have automated it.

  18. Student Understanding of Time Dependence in Quantum Mechanics

    ERIC Educational Resources Information Center

    Emigh, Paul J.; Passante, Gina; Shaffer, Peter S.

    2015-01-01

    The time evolution of quantum states is arguably one of the more difficult ideas in quantum mechanics. In this article, we report on results from an investigation of student understanding of this topic after lecture instruction. We demonstrate specific problems that students have in applying time dependence to quantum systems and in recognizing…

  19. Shoulder pain and time dependent structure in wheelchair propulsion variability.

    PubMed

    Jayaraman, Chandrasekaran; Moon, Yaejin; Sosnoff, Jacob J

    2016-07-01

    Manual wheelchair propulsion places considerable repetitive mechanical strain on the upper limbs leading to shoulder injury and pain. While recent research indicates that the amount of variability in wheelchair propulsion and shoulder pain may be related. There has been minimal inquiry into the fluctuation over time (i.e. time-dependent structure) in wheelchair propulsion variability. Consequently the purpose of this investigation was to examine if the time-dependent structure in the wheelchair propulsion parameters are related to shoulder pain. 27 experienced wheelchair users manually propelled their own wheelchair fitted with a SMARTWheel on a roller at 1.1m/s for 3min. Time-dependent structure of cycle-to-cycle fluctuations in contact angle and inter push time interval was quantified using sample entropy (SampEn) and compared between the groups with/without shoulder pain using non-parametric statistics. Overall findings were, (1) variability observed in contact angle fluctuations during manual wheelchair propulsion is structured (Z=3.15;p<0.05), (2) individuals with shoulder pain exhibited higher SampEn magnitude for contact angle during wheelchair propulsion than those without pain (χ(2)(1)=6.12;p<0.05); and (3) SampEn of contact angle correlated significantly with self-reported shoulder pain (rs (WUSPI) =0.41;rs (VAS)=0.56;p<0.05). It was concluded that the time-dependent structure in wheelchair propulsion may provide novel information for tracking and monitoring shoulder pain.

  20. Jet methods in time-dependent Lagrangian biomechanics

    NASA Astrophysics Data System (ADS)

    Ivancevic, Tijana T.

    2010-10-01

    In this paper we propose the time-dependent generalization of an ‘ordinary’ autonomous human biomechanics, in which total mechanical + biochemical energy is not conserved. We introduce a general framework for time-dependent biomechanics in terms of jet manifolds associated to the extended musculo-skeletal configuration manifold, called the configuration bundle. We start with an ordinary configuration manifold of human body motion, given as a set of its all active degrees of freedom (DOF) for a particular movement. This is a Riemannian manifold with a material metric tensor given by the total mass-inertia matrix of the human body segments. This is the base manifold for standard autonomous biomechanics. To make its time-dependent generalization, we need to extend it with a real time axis. By this extension, using techniques from fibre bundles, we defined the biomechanical configuration bundle. On the biomechanical bundle we define vector-fields, differential forms and affine connections, as well as the associated jet manifolds. Using the formalism of jet manifolds of velocities and accelerations, we develop the time-dependent Lagrangian biomechanics. Its underlying geometric evolution is given by the Ricci flow equation.

  1. Jet methods in time-dependent Lagrangian biomechanics

    NASA Astrophysics Data System (ADS)

    Ivancevic, Tijana

    2010-10-01

    In this paper we propose the time-dependent generalization of an `ordinary' autonomous human biomechanics, in which total mechanical + biochemical energy is not conserved. We introduce a general framework for time-dependent biomechanics in terms of jet manifolds associated to the extended musculo-skeletal configuration manifold, called the configuration bundle. We start with an ordinary configuration manifold of human body motion, given as a set of its all active degrees of freedom (DOF) for a particular movement. This is a Riemannian manifold with a material metric tensor given by the total mass-inertia matrix of the human body segments. This is the base manifold for standard autonomous biomechanics. To make its time-dependent generalization, we need to extend it with a real time axis. By this extension, using techniques from fibre bundles, we defined the biomechanical configuration bundle. On the biomechanical bundle we define vector-fields, differential forms and affine connections, as well as the associated jet manifolds. Using the formalism of jet manifolds of velocities and accelerations, we develop the time-dependent Lagrangian biomechanics. Its underlying geometric evolution is given by the Ricci flow equation.

  2. Noncommutative quantum mechanics in a time-dependent background

    NASA Astrophysics Data System (ADS)

    Dey, Sanjib; Fring, Andreas

    2014-10-01

    We investigate a quantum mechanical system on a noncommutative space for which the structure constant is explicitly time dependent. Any autonomous Hamiltonian on such a space acquires a time-dependent form in terms of the conventional canonical variables. We employ the Lewis-Riesenfeld method of invariants to construct explicit analytical solutions for the corresponding time-dependent Schrödinger equation. The eigenfunctions are expressed in terms of the solutions of variants of the nonlinear Ermakov-Pinney equation and discussed in detail for various types of background fields. We utilize the solutions to verify a generalized version of Heisenberg's uncertainty relations for which the lower bound becomes a time-dependent function of the background fields. We study the variance for various states, including standard Glauber coherent states with their squeezed versions and Gaussian Klauder coherent states resembling a quasiclassical behavior. No type of coherent state appears to be optimal in general with regard to achieving minimal uncertainties, as this feature turns out to be background field dependent.

  3. Time dependent solution for acceleration of tau-leaping

    NASA Astrophysics Data System (ADS)

    Fu, Jin; Wu, Sheng; Petzold, Linda R.

    2013-02-01

    The tau-leaping method is often effective for speeding up discrete stochastic simulation of chemically reacting systems. However, when fast reactions are involved, the speed-up for this method can be quite limited. One way to address this is to apply a stochastic quasi-steady state assumption. However we must be careful when using this assumption. If the fast subsystem cannot reach a steady distribution fast enough, the quasi-steady-state assumption will propagate error into the simulation. To avoid these errors, we propose to use the time dependent solution rather than the quasi-steady-state. Generally speaking, the time dependent solution is not easy to derive for an arbitrary network. However, for some common motifs we do have time dependent solutions. We derive the time dependent solutions for these motifs, and then show how they can be used with tau-leaping to achieve substantial speed-ups, including for a realistic model of blood coagulation. Although the method is complicated, we have automated it.

  4. Pedagogical Aspects of Time-Dependent Rotation Operators.

    ERIC Educational Resources Information Center

    Leubner, C.

    1980-01-01

    Describes the reformulation of a classical magnetic moment interacting with various magnetic field configurations in terms of coordinate-free, time-dependent rotation operators. This approach provides useful exercises for the manipulation of three-dimensional rotation operators and provides examples for a number of quantum-mechanics related…

  5. A quantum time-dependent wave-packet study of intersystem crossing effects in the O(3P0, 1, 2) + D2(v = 0, j = 0) reaction

    NASA Astrophysics Data System (ADS)

    Zhao, Juan

    2013-04-01

    We investigated spin-orbit-induced intersystem crossing effects in the title reaction by the time-dependent wave-packet method combined with an extended split operator scheme. We performed non-adiabatic calculations of the fine-structure-resolved cross section and adiabatic calculations of integral cross section. The calculations are based on the potential energy surfaces of 3A' and the two degenerate 3A'' states [S. Rogers, D. Wang, A. Kuppermann, and S. Walch, J. Phys. Chem. A 104, 2308 (2000)], 10.1021/jp992985g, together with the spin-orbit coupling matrix [B. Maiti and G. C. Schatz, J. Chem. Phys. 119, 12360 (2003)], 10.1063/1.1623481 and singlet 1A' potential energy surface [J. Dobbyn and P. J. Knowles, Faraday Discuss. 110, 247 (1998)]. The results of the O(3P) + D2 are similar to those of the O(3P) + H2 reaction. The product spin state-resolved reaction cross section and the total reaction cross section both show that the adiabatic channel is dominant in all cases, and the non-adiabatic channels have cross sections of several orders of magnitude smaller than the adiabatic channels at high collision energy. Although the cross sections caused by the intersystem crossing effects in the O(3P) + D2 reaction are larger than those in the O(3P) + H2 reaction, the differences in non-adiabaticity between these two reaction systems are quite modest. Based on the results of the O(3P) + H2 reaction, we can predict that the influence of spin-orbit on the total reaction cross sections of the O(3P) + D2 reaction is also insignificant. However, these non-adiabatic effects can be reflected in the presence of some forward-scattering in the angular distribution for the OD product.

  6. Time-Dependent SSC Cooling Effects on Blazar Emission

    NASA Astrophysics Data System (ADS)

    Zacharias, Michael; Schlickeiser, Reinhard

    2014-03-01

    Blazars are among the most violent sources in the cosmos exhibiting flaring states with remarkably different variability time scales. Especially rapid flares with flux doubling time scales of the order of minutes have been puzzling for quite some time. Many modeling attempts use the well known linear and steady-state scenario for the cooling and emission processes in the jet, albeit the obvious strongly time-dependent nature of flares. Due to the feedback of the self-produced synchrotron radiation with additional scattering by the relativistic electrons, the synchrotron-self Compton (SSC) effect is inherently time-dependent. Recently, an analytical analysis on the effects of this nonlinear behavior has been presented. Here, we summarize these results concerning the effect of the time-dependent SSC cooling on the spectral energy distribution (SED), and the synchrotron lightcurves of blazars. For that, we calculated analytically the synchrotron, SSC and external Compton (EC) component of the SED, giving remarkably different spectral features compared to the standard linear approach. The resulting fluxes strongly depend on the parameters, and SSC might have a strong effect even in sources with strong external photon fields (such as FSRQs). For the synchrotron lightcurve we considered the effects of retardation, including the geometry of the source. The retardation might smear out some effects of the time-dependent cooling, but since lightcurves and SEDs have to be fitted simultaneously with the same set of parameters, the results give nonetheless important clues about the source. Thus, we argue for a wide utilization of the time-dependent treatment in modeling (especially rapid) blazar flares, since it accounts for features in the SED and the lightcurves that are usually accounted for by introducing several breaks in the electron distribution without any physical justification.

  7. Time-dependent magnetohydrodynamic simulations of the inner heliosphere

    NASA Astrophysics Data System (ADS)

    Merkin, V. G.; Lyon, J. G.; Lario, D.; Arge, C. N.; Henney, C. J.

    2016-04-01

    This paper presents results from a simulation study exploring heliospheric consequences of time-dependent changes at the Sun. We selected a 2 month period in the beginning of year 2008 that was characterized by very low solar activity. The heliosphere in the equatorial region was dominated by two coronal holes whose changing structure created temporal variations distorting the classical steady state picture of the heliosphere. We used the Air Force Data Assimilate Photospheric Flux Transport (ADAPT) model to obtain daily updated photospheric magnetograms and drive the Wang-Sheeley-Arge (WSA) model of the corona. This leads to a formulation of a time-dependent boundary condition for our three-dimensional (3-D) magnetohydrodynamic (MHD) model, LFM-helio, which is the heliospheric adaptation of the Lyon-Fedder-Mobarry MHD simulation code. The time-dependent coronal conditions were propagated throughout the inner heliosphere, and the simulation results were compared with the spacecraft located near 1 astronomical unit (AU) heliocentric distance: Advanced Composition Explorer (ACE), Solar Terrestrial Relations Observatory (STEREO-A and STEREO-B), and the MErcury Surface, Space ENvironment, GEochemistry, and Ranging (MESSENGER) spacecraft that was in cruise phase measuring the heliospheric magnetic field between 0.35 and 0.6 AU. In addition, during the selected interval MESSENGER and ACE aligned radially allowing minimization of the effects of temporal variation at the Sun versus radial evolution of structures. Our simulations show that time-dependent simulationsreproduce the gross-scale structure of the heliosphere with higher fidelity, while on smaller spatial and faster time scales (e.g., 1 day) they provide important insights for interpretation of the data. The simulations suggest that moving boundaries of slow-fast wind transitions at 0.1 AU may result in the formation of inverted magnetic fields near pseudostreamers which is an intrinsically time-dependent process

  8. Invalidity of the quantitative adiabatic condition and general conditions for adiabatic approximations

    NASA Astrophysics Data System (ADS)

    Li, Dafa

    2016-05-01

    The adiabatic theorem was proposed about 90 years ago and has played an important role in quantum physics. The quantitative adiabatic condition constructed from eigenstates and eigenvalues of a Hamiltonian is a traditional tool to estimate adiabaticity and has proven to be the necessary and sufficient condition for adiabaticity. However, recently the condition has become a controversial subject. In this paper, we list some expressions to estimate the validity of the adiabatic approximation. We show that the quantitative adiabatic condition is invalid for the adiabatic approximation via the Euclidean distance between the adiabatic state and the evolution state. Furthermore, we deduce general necessary and sufficient conditions for the validity of the adiabatic approximation by different definitions.

  9. Chromospheric extents predicted by time-dependent acoustic wave models

    NASA Astrophysics Data System (ADS)

    Cuntz, Manfred

    1990-01-01

    Theoretical models for chromospheric structures of late-type giant stars are computed, including the time-dependent propagation of acoustic waves. Models with short-period monochromatic shock waves as well as a spectrum of acoustic waves are discussed, and the method is applied to the stars Arcturus, Aldebaran, and Betelgeuse. Chromospheric extent, defined as the monotonic decrease with height of the time-averaged electron densities, are found to be 1.12, 1.13, and 1.22 stellar radii for the three stars, respectively; this corresponds to a time-averaged electron density of 10 to the 7th/cu cm. Predictions of the extended chromospheric obtained using a simple scaling law agree well with those obtained by the time-dependent wave models; thus, the chromospheres of all stars for which the scaling law is valid consist of the same number of pressure scale heights.

  10. Chromospheric extents predicted by time-dependent acoustic wave models

    SciTech Connect

    Cuntz, M. Heidelberg Universitaet )

    1990-01-01

    Theoretical models for chromospheric structures of late-type giant stars are computed, including the time-dependent propagation of acoustic waves. Models with short-period monochromatic shock waves as well as a spectrum of acoustic waves are discussed, and the method is applied to the stars Arcturus, Aldebaran, and Betelgeuse. Chromospheric extent, defined as the monotonic decrease with height of the time-averaged electron densities, are found to be 1.12, 1.13, and 1.22 stellar radii for the three stars, respectively; this corresponds to a time-averaged electron density of 10 to the 7th/cu cm. Predictions of the extended chromospheric obtained using a simple scaling law agree well with those obtained by the time-dependent wave models; thus, the chromospheres of all stars for which the scaling law is valid consist of the same number of pressure scale heights. 74 refs.

  11. Time dependent flare model with non-LTE radiative transfer

    NASA Astrophysics Data System (ADS)

    Varady, M.; Karlický, M.; Kašparová, J.; Heinzel, P.

    2002-12-01

    The first results of a time dependent simulation of chromospheric response to a high energy electron beam are presented. The hybrid code, i.e. a combination of a 1-D hydrodynamic code and a test particle code, has been used to calculate the energy losses of a high energy electron beam propagating through the solar atmosphere and the consequent response of the ambient solar plasma to the energy deposition. The resulting time evolution of the solar plasma temperature, density, velocity and energy deposit on hydrogen has then been used as an input for a time dependent radiative transfer code in the MALI approach to determine the time variation of the Hα line profile. Non-thermal collisional rates have been included in the linearised ESE.

  12. Time-dependent response of filamentary composite spherical pressure vessels

    NASA Technical Reports Server (NTRS)

    Dozier, J. D.

    1983-01-01

    A filamentary composite spherical pressure vessel is modeled as a pseudoisotropic (or transversely isotropic) composite shell, with the effects of the liner and fill tubes omitted. Equations of elasticity, macromechanical and micromechanical formulations, and laminate properties are derived for the application of an internally pressured spherical composite vessel. Viscoelastic properties for the composite matrix are used to characterize time-dependent behavior. Using the maximum strain theory of failure, burst pressure and critical strain equations are formulated, solved in the Laplace domain with an associated elastic solution, and inverted back into the time domain using the method of collocation. Viscoelastic properties of HBFR-55 resin are experimentally determined and a Kevlar/HBFR-55 system is evaluated with a FORTRAN program. The computed reduction in burst pressure with respect to time indicates that the analysis employed may be used to predict the time-dependent response of a filamentary composite spherical pressure vessel.

  13. Statistical time-dependent model for the interstellar gas

    NASA Technical Reports Server (NTRS)

    Gerola, H.; Kafatos, M.; Mccray, R.

    1974-01-01

    We present models for temperature and ionization structure of low, uniform-density (approximately 0.3 per cu cm) interstellar gas in a galactic disk which is exposed to soft X rays from supernova outbursts occurring randomly in space and time. The structure was calculated by computing the time record of temperature and ionization at a given point by Monte Carlo simulation. The calculation yields probability distribution functions for ionized fraction, temperature, and their various observable moments. These time-dependent models predict a bimodal temperature distribution of the gas that agrees with various observations. Cold regions in the low-density gas may have the appearance of clouds in 21-cm absorption. The time-dependent model, in contrast to the steady-state model, predicts large fluctuations in ionization rate and the existence of cold (approximately 30 K), ionized (ionized fraction equal to about 0.1) regions.

  14. Transcriptional dynamics with time-dependent reaction rates

    NASA Astrophysics Data System (ADS)

    Nandi, Shubhendu; Ghosh, Anandamohan

    2015-02-01

    Transcription is the first step in the process of gene regulation that controls cell response to varying environmental conditions. Transcription is a stochastic process, involving synthesis and degradation of mRNAs, that can be modeled as a birth-death process. We consider a generic stochastic model, where the fluctuating environment is encoded in the time-dependent reaction rates. We obtain an exact analytical expression for the mRNA probability distribution and are able to analyze the response for arbitrary time-dependent protocols. Our analytical results and stochastic simulations confirm that the transcriptional machinery primarily act as a low-pass filter. We also show that depending on the system parameters, the mRNA levels in a cell population can show synchronous/asynchronous fluctuations and can deviate from Poisson statistics.

  15. Time-dependent buoyant puff model for explosive sources

    SciTech Connect

    Kansa, E.J.

    1997-01-01

    Several models exist to predict the time dependent behavior of bouyant puffs that result from explosions. This paper presents a new model that is derived from the strong conservative form of the conservation partial differential equations that are integrated over space to yield a coupled system of time dependent nonlinear ordinary differential equations. This model permits the cloud to evolve from an intial spherical shape not an ellipsoidal shape. It ignores the Boussinesq approximation, and treats the turbulence that is generated by the puff itself and the ambient atmospheric tubulence as separate mechanisms in determining the puff history. The puff cloud rise history was found to depend no only on the mass and initial temperature of the explosion, but also upon the stability conditions of the ambient atmosphere. This model was calibrated by comparison with the Roller Coaster experiments.

  16. Boosting thermoelectric efficiency using time-dependent control

    PubMed Central

    Zhou, Hangbo; Thingna, Juzar; Hänggi, Peter; Wang, Jian-Sheng; Li, Baowen

    2015-01-01

    Thermoelectric efficiency is defined as the ratio of power delivered to the load of a device to the rate of heat flow from the source. Till date, it has been studied in presence of thermodynamic constraints set by the Onsager reciprocal relation and the second law of thermodynamics that severely bottleneck the thermoelectric efficiency. In this study, we propose a pathway to bypass these constraints using a time-dependent control and present a theoretical framework to study dynamic thermoelectric transport in the far from equilibrium regime. The presence of a control yields the sought after substantial efficiency enhancement and importantly a significant amount of power supplied by the control is utilised to convert the wasted-heat energy into useful-electric energy. Our findings are robust against nonlinear interactions and suggest that external time-dependent forcing, which can be incorporated with existing devices, provides a beneficial scheme to boost thermoelectric efficiency. PMID:26464021

  17. Sublinear scaling for time-dependent stochastic density functional theory

    SciTech Connect

    Gao, Yi; Neuhauser, Daniel; Baer, Roi; Rabani, Eran

    2015-01-21

    A stochastic approach to time-dependent density functional theory is developed for computing the absorption cross section and the random phase approximation (RPA) correlation energy. The core idea of the approach involves time-propagation of a small set of stochastic orbitals which are first projected on the occupied space and then propagated in time according to the time-dependent Kohn-Sham equations. The evolving electron density is exactly represented when the number of random orbitals is infinite, but even a small number (≈16) of such orbitals is enough to obtain meaningful results for absorption spectrum and the RPA correlation energy per electron. We implement the approach for silicon nanocrystals using real-space grids and find that the overall scaling of the algorithm is sublinear with computational time and memory.

  18. Coherent states and their time dependence in fractional dimensions

    NASA Astrophysics Data System (ADS)

    Thilagam, A.; Lohe, M. A.

    2007-08-01

    We construct representations of the Lie algebra \\mathfrak{su}(1,1) using representations of the momentum and position operators satisfying the R-deformed Heisenberg relations, in which the fractional dimension d and angular momentum ell appear as parameters. The Bargmann index κ, which characterizes representations of the positive discrete series of \\mathfrak{su}(1,1) , can take any positive value. We construct coherent states in fractional dimensions, in particular we extend the two well-known analytic representations of coherent states for \\mathfrak{su}(1,1) , Perelomov and Barut-Girardello states, from dimension one to any dimension d. We generalize this construction to time-dependent coherent states by means of the \\mathfrak{su}(1,1) symmetries of the quantum time-dependent harmonic oscillator in fractional dimensions. We investigate the uncertainty relations of the momentum and position operators with respect to these coherent states, and their dependence on the dimension.

  19. Holonomic Quantum Computation by Time dependent Decoherence Free Subspaces

    NASA Astrophysics Data System (ADS)

    Lin, J. N.; Liang, Y.; Yang, H. D.; Gui, J.; Wu, S. L.

    2017-01-01

    We show how to realize nonadiabatic holonomic quantum computation in time-dependent decoherence free subspaces (TDFSs). In our scheme, the holonomy is not generated by computational bases in DFSs but time-dependent bases of TDFSs. Therefore, different from the traditional DFSs, the ancillary systems are not necessary in inducing holonomy, which saves qubits used in the holonomic quantum computation. We also analyze the symmetry of the N-qubits system which couples to a common squeezed field. The results show that, there are several independent DFSs presented in Hilbert space, which is determined by eigenvalues of Lindblad operators. Combining the scheme and the model proposed in this paper, we show that, the one-qubit controllable phase gate can be realized by only two physical qubits.

  20. Generalization of DT equations for time dependent sources.

    PubMed

    Neri, Lorenzo; Tudisco, Salvatore; Musumeci, Francesco; Scordino, Agata; Fallica, Giorgio; Mazzillo, Massimo; Zimbone, Massimo

    2010-01-01

    New equations for paralyzable, non paralyzable and hybrid DT models, valid for any time dependent sources are presented. We show how such new equations include the equations already used for constant rate sources, and how it's is possible to correct DT losses in the case of time dependent sources. Montecarlo simulations were performed to compare the equations behavior with the three DT models. Excellent accordance between equations predictions and Montecarlo simulation was found. We also obtain good results in the experimental validation of the new hybrid DT equation. Passive quenched SPAD device was chosen as a device affected by hybrid DT losses and active quenched SPAD with 50 ns DT was used as DT losses free device.

  1. Time dependent electromagnetic fields and 4-dimensional Stokes' theorem

    NASA Astrophysics Data System (ADS)

    Andosca, Ryan; Singleton, Douglas

    2016-11-01

    Stokes' theorem is central to many aspects of physics—electromagnetism, the Aharonov-Bohm effect, and Wilson loops to name a few. However, the pedagogical examples and research work almost exclusively focus on situations where the fields are time-independent so that one need only deal with purely spatial line integrals (e.g., ∮ A . d x ) and purely spatial area integrals (e.g., ∫ ( ∇ × A ) . d a = ∫ B . d a ). Here, we address this gap by giving some explicit examples of how Stokes' theorem plays out with time-dependent fields in a full 4-dimensional spacetime context. We also discuss some unusual features of Stokes' theorem with time-dependent fields related to gauge transformations and non-simply connected topology.

  2. Holonomic Quantum Computation by Time dependent Decoherence Free Subspaces

    NASA Astrophysics Data System (ADS)

    Lin, J. N.; Liang, Y.; Yang, H. D.; Gui, J.; Wu, S. L.

    2017-04-01

    We show how to realize nonadiabatic holonomic quantum computation in time-dependent decoherence free subspaces (TDFSs). In our scheme, the holonomy is not generated by computational bases in DFSs but time-dependent bases of TDFSs. Therefore, different from the traditional DFSs, the ancillary systems are not necessary in inducing holonomy, which saves qubits used in the holonomic quantum computation. We also analyze the symmetry of the N-qubits system which couples to a common squeezed field. The results show that, there are several independent DFSs presented in Hilbert space, which is determined by eigenvalues of Lindblad operators. Combining the scheme and the model proposed in this paper, we show that, the one-qubit controllable phase gate can be realized by only two physical qubits.

  3. The Role of Environment on Time Dependent Crack Growth

    DTIC Science & Technology

    1981-12-01

    reaction control and transport control terms. More recently, Wei and Shim (41) have extended these terms to represent frequency and temperature effects in...accelerate time dependent crack growth under either static loading (SCC or HE) or dynamic loading conditions. In some cases, the rate controlling ...processes of these phenomena have been related to surface controlled reactions, while in other cases bulk reactions such as diffusion appear to be rate

  4. Autoionization in time-dependent density-functional theory

    NASA Astrophysics Data System (ADS)

    Kapoor, V.

    2016-06-01

    We compute the exact exchange-correlation potential of the time-dependent density-functional theory (TDDFT) for the correlated process of autoionization. The potential develops barriers which regulate the autoionization rate. TDDFT employing known and practicable exchange-correlation potentials does not capture any autoionization dynamics. Approximate exchange-correlation potentials capturing such dynamics would necessarily require memory effects and are unlikely to be developed, as will be illustrated.

  5. Excitons in Time-Dependent Density-Functional Theory.

    PubMed

    Ullrich, Carsten A; Yang, Zeng-hui

    2016-01-01

    This chapter gives an overview of the description of the optical and dielectric properties of bulk insulators and semiconductors in time-dependent density-functional theory (TDDFT), with an emphasis on excitons. We review the linear-response formalism for periodic solids, discuss excitonic exchange-correlation kernels, calculate exciton binding energies for various materials, and compare the treatment of excitons with TDDFT and with the Bethe-Salpeter equation.

  6. Quasinormal modes in a time-dependent black hole background

    SciTech Connect

    Shao Chenggang; Wang Bin; Abdalla, Elcio; Su Rukeng

    2005-02-15

    We have studied the evolution of the massless scalar field propagating in a time-dependent charged Vaidya black hole background. A generalized tortoise coordinate transformation was used to study the evolution of the massless scalar field. It is shown that, for the slowest damped quasinormal modes, the approximate formulas in the stationary Reissner-Nordstroem black hole turn out to be a reasonable prescription, showing that results from quasinormal mode analysis are rather robust.

  7. Relating Time-Dependent Acceleration and Height Using an Elevator

    ERIC Educational Resources Information Center

    Kinser, Jason M.

    2015-01-01

    A simple experiment in relating a time-dependent linear acceleration function to height is explored through the use of a smartphone and an elevator. Given acceleration as a function of time, a(t), the velocity function and position functions are determined through integration as in v(t)=? a(t) dt (1) and x(t)=? v(t) dt. Mobile devices such as…

  8. Spectral methods for time dependent partial differential equations

    NASA Technical Reports Server (NTRS)

    Gottlieb, D.; Turkel, E.

    1983-01-01

    The theory of spectral methods for time dependent partial differential equations is reviewed. When the domain is periodic Fourier methods are presented while for nonperiodic problems both Chebyshev and Legendre methods are discussed. The theory is presented for both hyperbolic and parabolic systems using both Galerkin and collocation procedures. While most of the review considers problems with constant coefficients the extension to nonlinear problems is also discussed. Some results for problems with shocks are presented.

  9. Time Dependent Models of Grain Formation Around Carbon Stars

    NASA Technical Reports Server (NTRS)

    Egan, M. P.; Shipman, R. F.

    1996-01-01

    Carbon-rich Asymptotic Giant Branch stars are sites of dust formation and undergo mass loss at rates ranging from 10(exp -7) to 10(exp -4) solar mass/yr. The state-of-the-art in modeling these processes is time-dependent models which simultaneously solve the grain formation and gas dynamics problem. We present results from such a model, which also includes an exact solution of the radiative transfer within the system.

  10. Time-Dependent 5D Solutions of the Einstein Equations

    SciTech Connect

    Lopez, L. A.

    2010-07-12

    In this work are obtained 5D time-dependent solutions of Einstein equations, one is obtained by means of equiping a cylindrically symmetry solution (JEKK) with a scalar field, then lifting it to a fifth dimension. The other is obtained transforming the Myers-Perry solution via Wick rotation. The two solutions can be interpreted as gravitational waves in some cases. The singularities and C-energy are addressed.

  11. The time dependence of molecular iodine emission from Laminaria digitata

    NASA Astrophysics Data System (ADS)

    Dixneuf, S.; Ruth, A. A.; Vaughan, S.; Varma, R. M.; Orphal, J.

    2009-02-01

    We present the first in situ detection of molecular iodine emitted from the brown macroalga Laminaria digitata under natural stress conditions. We show that the release of I2 occurs in short, strong bursts with a complex time signature. The new data indicate that algal control of I2 release in the form of an oscillatory time-dependence may be based on a nonlinear autocatalytic reaction scheme which is closely linked to the production of H2O2.

  12. The time dependence of molecular iodine emission from Laminaria digitata

    NASA Astrophysics Data System (ADS)

    Dixneuf, S.; Ruth, A. A.; Vaughan, S.; Varma, R. M.; Orphal, J.

    2008-08-01

    We present the first in situ detection of molecular iodine emitted from the brown macroalga Laminaria digitata under natural stress conditions. We show that the release of I2 occurs in short, strong bursts with a complex time signature. The new data indicate that algal control of I2 release in the form of an oscillatory time-dependence may be based on a nonlinear autocatalytic reaction scheme which is closely linked to the production of H2O2.

  13. Brans-Dicke cosmology with time-dependent cosmological term

    NASA Astrophysics Data System (ADS)

    Berman, Marcelo Samuel

    1990-12-01

    Berman and Som's solution for a Brans-Dicke cosmology with time-dependent cosmological term, Robertson-Walker metric, perfect fluid, and perfect gas law of state solves the horizon, homogeneity, and isotropy problems without requiring any unnatural fine tuning in the very early universe, thus being an alternative model to inflation. The model also does not need recourse to quantum cosmology, and solves the flatness and magnetic monopole problems.

  14. Time-Dependent Effect of Chlorhexidine Surgical Prep

    DTIC Science & Technology

    2011-10-15

    Time-dependent effect of chlorhexidine surgical prep D.J. Stinner*, C.A. Krueger, B.D. Masini, J.C. Wenke United States Army Institute of Surgical ...2011 by J.A. Child Available online 15 October 2011 Keywords: Chlorhexidine Surgical site infection s u m m a r y Despite continued advances in...preoperative preventive measures and aseptic technique, surgical site infections remain a problem. The purpose of this study was to evaluate the time

  15. Stochastic protein production and time-dependent current fluctuations

    NASA Astrophysics Data System (ADS)

    Gorissen, Mieke; Vanderzande, Carlo

    2011-03-01

    Translation is the cellular process in which ribosomes make proteins from information encoded on messenger RNA. We model this process using driven lattice gases and take into account the finite lifetime of mRNA. The stochastic properties of the translation process can then be determined from the time-dependent current fluctuations of the lattice gas model. We illustrate our ideas with a totally asymmetric exclusion process with extended objects.

  16. Gamma time-dependency in Blaxter's compartmental model.

    NASA Technical Reports Server (NTRS)

    Matis, J. H.

    1972-01-01

    A new two-compartment model for the passage of particles through the gastro-intestinal tract of ruminants is proposed. In this model, a gamma distribution of lifetimes is introduced in the first compartment; thereby, passage from that compartment becomes time-dependent. This modification is strongly suggested by the physical alteration which certain substances, e.g. hay particles, undergo in the digestive process. The proposed model is applied to experimental data.

  17. Adiabatic principles in atom-diatom collisional energy transfer

    SciTech Connect

    Hovingh, W.J.

    1993-01-01

    This work describes the application of numerical methods to the solution of the time dependent Schroedinger equation for non-reactive atom-diatom collisions in which only one of the degrees of freedom has been removed. The basic method involves expanding the wave function in a basis set in two of the diatomic coordinates in a body-fixed frame (with respect to the triatomic complex) and defining the coefficients in that expansion as functions on a grid in the collision coordinate. The wave function is then propagated in time using a split operator method. The bulk of this work is devoted to the application of this formalism to the study of internal rotational predissociation in NeHF, in which quasibound states of the triatom predissociate through the transfer of energy from rotation of the diatom into translational energy in the atom-diatom separation coordinate. The author analyzes the computed time dependent wave functions to calculate the lifetimes for several quasibound states; these are in agreement with time independent quantum calculations using the same potential. Moreover, the time dependent behavior of the wave functions themselves sheds light on the dynamics of the predissociation processes. Finally, the partial cross sections of the products in those processes is determined with multiple exit channels. These show strong selectivity in the orbital angular momentum of the outgoing fragments, which the author explains with an adiabatic channel interpretation of the wave function's dynamics. The author also suggests that the same formalism might profitably be used to investigate the quantum dynamics of [open quotes]quasiresonant vibration-rotation transfer[close quotes], in which remarkably strong propensity rules in certain inelastic atom-diatom collision arise from classical adiabatic invariance theory.

  18. Time-dependent neutron and photon dose-field analysis

    NASA Astrophysics Data System (ADS)

    Wooten, Hasani Omar

    2005-11-01

    A unique tool is developed that allows the user to model physical representations of complicated glovebox facilities in two dimensions and determine neutral-particle flux and ambient dose-equivalent fields throughout that geometry. The code Pandemonium, originally designed to determine flux and dose rates only, has been improved to include realistic glovebox geometries, time-dependent source and detector positions, time-dependent shielding thickness calculations, time-integrated doses, a representative criticality accident scenario based on time-dependent reactor kinetics, and more rigorous photon treatment. The photon model has been significantly enhanced by expanding the energy range to 10 MeV to include fission photons, and by including a set of new buildup factors, the result of an extensive study into the previously unknown "purely-angular effect" on photon buildup. Purely-angular photon buildup factors are determined using discrete ordinates and coupled electron-photon cross sections to account for coherent and incoherent scattering and secondary photon effects of bremsstrahlung and florescence. Improvements to Pandemonium result in significant modeling capabilities for processing facilities using intense neutron and photon sources, and the code obtains comparable results to Monte Carlo calculations but within a fraction of the time required to run such codes as MCNPX.

  19. Time dependent inelastic deformation of shocked soda-lime glass

    NASA Astrophysics Data System (ADS)

    Gupta, Y. M.

    2005-07-01

    Shock wave compression of soda-lime glass (SLG) has received considerable attention in recent years. To understand inelastic deformation in shocked soda-lime glass between 3 and 10.8 GPa, we have carried out plate impact experiments. In-material, time-resolved, measurements were obtained using longitudinal and lateral stress gauges (4.6 to 10.8 GPa), and electromagnetic particle velocity gauges (2.9 to 6 GPa) at comparable sample thicknesses. The 4.6 and 6 GPa experiments revealed time-dependent inelastic response along with time-dependent loss of material strength. The combination of our experimental results and related analyses demonstrate that previous interpretations of shocked SLG response in terms of a propagating failure wave are not valid. At higher peak stresses (˜ 10GPa), the SLG results do not display time-dependent strength loss. The shock response of SLG over the 4-10GPa range is complex and depends significantly on the peak stress. The experimental results and simulations from a phenomenological continuum model will be discussed. Work supported by DOE. Much of this work was carried out by Dr. Hari Simha.

  20. Eisenhart lifts and symmetries of time-dependent systems

    NASA Astrophysics Data System (ADS)

    Cariglia, M.; Duval, C.; Gibbons, G. W.; Horváthy, P. A.

    2016-10-01

    Certain dissipative systems, such as Caldirola and Kannai's damped simple harmonic oscillator, may be modelled by time-dependent Lagrangian and hence time dependent Hamiltonian systems with n degrees of freedom. In this paper we treat these systems, their projective and conformal symmetries as well as their quantisation from the point of view of the Eisenhart lift to a Bargmann spacetime in n + 2 dimensions, equipped with its covariantly constant null Killing vector field. Reparametrisation of the time variable corresponds to conformal rescalings of the Bargmann metric. We show how the Arnold map lifts to Bargmann spacetime. We contrast the greater generality of the Caldirola-Kannai approach with that of Arnold and Bateman. At the level of quantum mechanics, we are able to show how the relevant Schrödinger equation emerges naturally using the techniques of quantum field theory in curved spacetimes, since a covariantly constant null Killing vector field gives rise to well defined one particle Hilbert space. Time-dependent Lagrangians arise naturally also in cosmology and give rise to the phenomenon of Hubble friction. We provide an account of this for Friedmann-Lemaître and Bianchi cosmologies and how it fits in with our previous discussion in the non-relativistic limit.

  1. Spike-timing-dependent synaptic plasticity depends on dendritic location

    NASA Astrophysics Data System (ADS)

    Froemke, Robert C.; Poo, Mu-ming; Dan, Yang

    2005-03-01

    In the neocortex, each neuron receives thousands of synaptic inputs distributed across an extensive dendritic tree. Although postsynaptic processing of each input is known to depend on its dendritic location, it is unclear whether activity-dependent synaptic modification is also location-dependent. Here we report that both the magnitude and the temporal specificity of spike-timing-dependent synaptic modification vary along the apical dendrite of rat cortical layer 2/3 pyramidal neurons. At the distal dendrite, the magnitude of long-term potentiation is smaller, and the window of pre-/postsynaptic spike interval for long-term depression (LTD) is broader. The spike-timing window for LTD correlates with the window of action potential-induced suppression of NMDA (N-methyl-D-aspartate) receptors; this correlation applies to both their dendritic location-dependence and pharmacological properties. Presynaptic stimulation with partial blockade of NMDA receptors induced LTD and occluded further induction of spike-timing-dependent LTD, suggesting that NMDA receptor suppression underlies LTD induction. Computer simulation studies showed that the dendritic inhomogeneity of spike-timing-dependent synaptic modification leads to differential input selection at distal and proximal dendrites according to the temporal characteristics of presynaptic spike trains. Such location-dependent tuning of inputs, together with the dendritic heterogeneity of postsynaptic processing, could enhance the computational capacity of cortical pyramidal neurons.

  2. The multi-configurational time-dependent Hartree approach revisited.

    PubMed

    Manthe, Uwe

    2015-06-28

    The multi-configurational time-dependent Hartree (MCTDH) approach facilitates accurate high-dimensional quantum dynamics simulations. In the approach, the wavefunction is expanded in a direct product of self-adapting time-dependent single-particle functions (SPFs). The equations of motion for the expansion coefficients and the SPFs are obtained via the Dirac-Frenkel variational principle. While this derivation yields well-defined differential equations for the motion of occupied SPFs, singularities in the working equations resulting from unoccupied SPFs have to be removed by a regularization procedure. Here, an alternative derivation of the MCTDH equations of motion is presented. It employs an analysis of the time-dependence of the single-particle density matrices up to second order. While the analysis of the first order terms yields the known equations of motion for the occupied SPFs, the analysis of the second order terms provides new equations which allow one to identify optimal choices for the unoccupied SPFs. The effect of the optimal choice of the unoccupied SPFs on the structure of the MCTDH equations of motion and their regularization is discussed. Generalized equations applicable in the multi-layer MCTDH framework are presented. Finally, the effects resulting from the initial choice of the unoccupied SPFs are illustrated by a simple numerical example.

  3. The multi-configurational time-dependent Hartree approach revisited

    SciTech Connect

    Manthe, Uwe

    2015-06-28

    The multi-configurational time-dependent Hartree (MCTDH) approach facilitates accurate high-dimensional quantum dynamics simulations. In the approach, the wavefunction is expanded in a direct product of self-adapting time-dependent single-particle functions (SPFs). The equations of motion for the expansion coefficients and the SPFs are obtained via the Dirac-Frenkel variational principle. While this derivation yields well-defined differential equations for the motion of occupied SPFs, singularities in the working equations resulting from unoccupied SPFs have to be removed by a regularization procedure. Here, an alternative derivation of the MCTDH equations of motion is presented. It employs an analysis of the time-dependence of the single-particle density matrices up to second order. While the analysis of the first order terms yields the known equations of motion for the occupied SPFs, the analysis of the second order terms provides new equations which allow one to identify optimal choices for the unoccupied SPFs. The effect of the optimal choice of the unoccupied SPFs on the structure of the MCTDH equations of motion and their regularization is discussed. Generalized equations applicable in the multi-layer MCTDH framework are presented. Finally, the effects resulting from the initial choice of the unoccupied SPFs are illustrated by a simple numerical example.

  4. Time-Dependent Delayed Signatures From Energetic Photon Interrogations

    SciTech Connect

    D. R. Norman; J. L. Jones; B. W. Blackburn; S. M. Watson; K. J. Haskell

    2006-08-01

    A pulsed photonuclear interrogation environment is rich with time-dependent, material specific, radiation signatures. Exploitation of these signatures in the delayed time regime (>1us after the photon flash) has been explored through various detection schemes to identify both shielded nuclear material and nitrogen-based explosives. Prompt emission may also be invaluable for these detection methods. Numerical and experimental results, which utilize specially modified neutron and HpGe detectors, are presented which illustrate the efficacy of utilizing these time-dependent signatures. Optimal selection of the appropriate delayed time window is essential to these pulsed inspection systems. For explosive (ANFO surrogate) detection, both numerical models and experimental results illustrate that nearly all 14N(n,y) reactions have occurred within l00 us after the flash. In contrast, however, gamma-ray and neutron signals for nuclear material detection require a delay of several milliseconds after the photon pulse. In this case, any data collected too close to the photon flash results in a spectrum dominated by high energy signals which make it difficult to discern signatures from nuclear material. Specifically, two short-lived, high-energy fission fragments (97Ag(T1/2=5.1 s) and 94Sr(T1/2=75.2 s)) were measured and identified as indicators of the presence of fissionable material. These developments demonstrate that a photon inspection environment can be exploited for time-dependent, material specific signatures through the proper operation of specially modified detectors.

  5. Analytic controllability of time-dependent quantum control systems

    NASA Astrophysics Data System (ADS)

    Lan, Chunhua; Tarn, Tzyh-Jong; Chi, Quo-Shin; Clark, John W.

    2005-05-01

    The question of controllability is investigated for a quantum control system in which the Hamiltonian operator components carry explicit time dependence which is not under the control of an external agent. We consider the general situation in which the state moves in an infinite-dimensional Hilbert space, a drift term is present, and the operators driving the state evolution may be unbounded. However, considerations are restricted by the assumption that there exists an analytic domain, dense in the state space, on which solutions of the controlled Schrödinger equation may be expressed globally in exponential form. The issue of controllability then naturally focuses on the ability to steer the quantum state on a finite-dimensional submanifold of the unit sphere in Hilbert space—and thus on analytic controllability. A relatively straightforward strategy allows the extension of Lie-algebraic conditions for strong analytic controllability derived earlier for the simpler, time-independent system in which the drift Hamiltonian and the interaction Hamiltonian have no intrinsic time dependence. Enlarging the state space by one dimension corresponding to the time variable, we construct an augmented control system that can be treated as time independent. Methods developed by Kunita can then be implemented to establish controllability conditions for the one-dimension-reduced system defined by the original time-dependent Schrödinger control problem. The applicability of the resulting theorem is illustrated with selected examples.

  6. Analytic controllability of time-dependent quantum control systems

    SciTech Connect

    Lan Chunhua; Tarn, T.-J.; Chi, Q.-S.; Clark, John W.

    2005-05-01

    The question of controllability is investigated for a quantum control system in which the Hamiltonian operator components carry explicit time dependence which is not under the control of an external agent. We consider the general situation in which the state moves in an infinite-dimensional Hilbert space, a drift term is present, and the operators driving the state evolution may be unbounded. However, considerations are restricted by the assumption that there exists an analytic domain, dense in the state space, on which solutions of the controlled Schroedinger equation may be expressed globally in exponential form. The issue of controllability then naturally focuses on the ability to steer the quantum state on a finite-dimensional submanifold of the unit sphere in Hilbert space--and thus on analytic controllability. A relatively straightforward strategy allows the extension of Lie-algebraic conditions for strong analytic controllability derived earlier for the simpler, time-independent system in which the drift Hamiltonian and the interaction Hamiltonian have no intrinsic time dependence. Enlarging the state space by one dimension corresponding to the time variable, we construct an augmented control system that can be treated as time independent. Methods developed by Kunita can then be implemented to establish controllability conditions for the one-dimension-reduced system defined by the original time-dependent Schroedinger control problem. The applicability of the resulting theorem is illustrated with selected examples.

  7. Maximum time-dependent space-charge limited diode currents

    SciTech Connect

    Griswold, M. E.; Fisch, N. J.

    2016-01-15

    Recent papers claim that a one dimensional (1D) diode with a time-varying voltage drop can transmit current densities that exceed the Child-Langmuir (CL) limit on average, apparently contradicting a previous conjecture that there is a hard limit on the average current density across any 1D diode, as t → ∞, that is equal to the CL limit. However, these claims rest on a different definition of the CL limit, namely, a comparison between the time-averaged diode current and the adiabatic average of the expression for the stationary CL limit. If the current were considered as a function of the maximum applied voltage, rather than the average applied voltage, then the original conjecture would not have been refuted.

  8. Maximum time-dependent space-charge limited diode currents

    NASA Astrophysics Data System (ADS)

    Griswold, M. E.; Fisch, N. J.

    2016-01-01

    Recent papers claim that a one dimensional (1D) diode with a time-varying voltage drop can transmit current densities that exceed the Child-Langmuir (CL) limit on average, apparently contradicting a previous conjecture that there is a hard limit on the average current density across any 1D diode, as t → ∞, that is equal to the CL limit. However, these claims rest on a different definition of the CL limit, namely, a comparison between the time-averaged diode current and the adiabatic average of the expression for the stationary CL limit. If the current were considered as a function of the maximum applied voltage, rather than the average applied voltage, then the original conjecture would not have been refuted.

  9. A numerical model of the time-dependent wintertime circulation of the New York Bight

    NASA Astrophysics Data System (ADS)

    Hsueh, Y.; Chen, K. C.; Marmorino, G. O.

    1984-01-01

    The time-dependent flow in the New York Bight from March 7 to April 30, 1975, is calculated from approximations to the barotropic vorticity equation subject to forcing by winds observed at the John F. Kennedy airport and by an upstream flow across the Long Island shelf. Comparisons of major axis velocities to observations throughout the bight show reasonable agreement. There is also considerable model skill in the prediction of alongshore variations in the major axis velocity with relatively low absolute errors. In general, associated with northeastward winds are northeastward shelf flows and upvalley currents in the Hudson Shelf Valley (HSV). Downvalley flows in the HSV occur when the northeastward wind abates and the flow on the shelf turns southwestward. The mechanism responsible for the behavior of the valley flow appears to be topographic steering with moderation due to bottom friction. The time rate of change of relative vorticity does not appear to have large net effect over the duration of an event Consequently, steady state models represent well the dynamics for an event-averaged flow. Discrepancies between model results and observation suggest that there is indeed a southwestward pressure gradient force operating in the New York Bight, and an adiabatic pressure condition offshore may be an over simplification that need be removed.

  10. Progress Report on Alloy 617 Time Dependent Allowables

    SciTech Connect

    Wright, Julie Knibloe

    2015-06-01

    Time dependent allowable stresses are required in the ASME Boiler and Pressure Vessel Code for design of components in the temperature range where time dependent deformation (i.e., creep) is expected to become significant. There are time dependent allowable stresses in Section IID of the Code for use in the non-nuclear construction codes, however, there are additional criteria that must be considered in developing time dependent allowables for nuclear components. These criteria are specified in Section III NH. St is defined as the lesser of three quantities: 100% of the average stress required to obtain a total (elastic, plastic, primary and secondary creep) strain of 1%; 67% of the minimum stress to cause rupture; and 80% of the minimum stress to cause the initiation of tertiary creep. The values are reported for a range of temperatures and for time increments up to 100,000 hours. These values are determined from uniaxial creep tests, which involve the elevated temperature application of a constant load which is relatively small, resulting in deformation over a long time period prior to rupture. The stress which is the minimum resulting from these criteria is the time dependent allowable stress St. In this report data from a large number of creep and creep-rupture tests on Alloy 617 are analyzed using the ASME Section III NH criteria. Data which are used in the analysis are from the ongoing DOE sponsored high temperature materials program, form Korea Atomic Energy Institute through the Generation IV VHTR Materials Program and historical data from previous HTR research and vendor data generated in developing the alloy. It is found that the tertiary creep criterion determines St at highest temperatures, while the stress to cause 1% total strain controls at low temperatures. The ASME Section III Working Group on Allowable Stress Criteria has recommended that the uncertainties associated with determining the onset of tertiary creep and the lack of significant

  11. Solvable time-dependent models in quantum mechanics

    NASA Astrophysics Data System (ADS)

    Cordero-Soto, Ricardo J.

    In the traditional setting of quantum mechanics, the Hamiltonian operator does not depend on time. While some Schrodinger equations with time-dependent Hamiltonians have been solved, explicitly solvable cases are typically scarce. This thesis is a collection of papers in which this first author along with Suslov, Suazo, and Lopez, has worked on solving a series of Schrodinger equations with a time-dependent quadratic Hamiltonian that has applications in problems of quantum electrodynamics, lasers, quantum devices such as quantum dots, and external varying fields. In particular the author discusses a new completely integrable case of the time-dependent Schrodinger equation in Rn with variable coefficients for a modified oscillator, which is dual with respect to the time inversion to a model of the quantum oscillator considered by Meiler, Cordero-Soto, and Suslov. A second pair of dual Hamiltonians is found in the momentum representation. Our examples show that in mathematical physics and quantum mechanics a change in the direction of time may require a total change of the system dynamics in order to return the system back to its original quantum state. The author also considers several models of the damped oscillators in nonrelativistic quantum mechanics in a framework of a general approach to the dynamics of the time-dependent Schrodinger equation with variable quadratic Hamiltonians. The Green functions are explicitly found in terms of elementary functions and the corresponding gauge transformations are discussed. The factorization technique is applied to the case of a shifted harmonic oscillator. The time-evolution of the expectation values of the energy related operators is determined for two models of the quantum damped oscillators under consideration. The classical equations of motion for the damped oscillations are derived for the corresponding expectation values of the position operator. Finally, the author constructs integrals of motion for several models

  12. Temperature-Driven and Electrochemical-Potential-Driven Adiabatic Pumping via a Quantum Dot

    NASA Astrophysics Data System (ADS)

    Hasegawa, Masahiro; Kato, Takeo

    2017-02-01

    We investigate adiabatic pumping via a single level quantum dot induced by periodic modulation of thermodynamic variables of reservoirs, i.e., temperatures and electrochemical potentials. We consider the impurity Anderson model and derive analytical formulas for coherent adiabatic charge pumping applicable to the strong dot-reservoir coupling within the first-order perturbation with respect to Coulomb interaction. We show that charge pumping is induced by rectification effect due to delayed response of the quantum dot to time-dependent reservoir parameters. The presence of interaction is necessary because this delayed response rectifies charge current via Coulomb interaction. For temperature-driven charge pumping, one-way pumping is realized regardless of reservoir temperatures when an energy level of the quantum dot locates near the Fermi level. We clarify that this new feature of adiabatic pumping is caused by level broadening effect of the quantum dot due to strong dot-reservoir coupling.

  13. Geometric phase of an atom inside an adiabatic radio-frequency potential

    SciTech Connect

    Zhang, P.; You, L.

    2007-09-15

    We investigate the geometric phase of an atom inside an adiabatic radio-frequency (rf) potential created from a static magnetic field (B field) and a time-dependent rf field. The spatial motion of the atomic center of mass is shown to give rise to a geometric phase, or Berry's phase, in the adiabatically evolving atomic hyperfine spin along the local B field. This phase is found to depend on both the static B field along the semiclassical trajectory of the atomic center of mass and an effective magnetic field consisting of the total B field, including the oscillating rf field. Specific calculations are provided for several recent atom interferometry experiments and proposals utilizing adiabatic rf potentials.

  14. Unphysical divergences in response theory.

    PubMed

    Parker, Shane M; Roy, Saswata; Furche, Filipp

    2016-10-07

    Transition densities between excited states are key for nonlinear theoretical spectroscopy and multi-state non-adiabatic molecular dynamics (NAMD) simulations. In the framework of response theory, these transition densities are accessible from poles of the quadratic response function. It was shown recently that the thus obtained transition densities within time-dependent Hartree-Fock (TDHF) and adiabatic time-dependent density functional theory (TDDFT) exhibit unphysical divergences when the difference in excitation energy of the two states of interest matches another excitation energy. This unphysical behavior is a consequence of spurious poles in the quadratic response function. We show that the incorrect pole structure of the quadratic response is not limited to TDHF and adiabatic TDDFT, but is also present in many other approximate many-electron response functions, including those from coupled cluster and multiconfigurational self-consistent field response theory. The divergences appear in regions of the potential energy surface where the ground state is perfectly well behaved, and they are frequently encountered in NAMD simulations of photochemical reactions. The origin of the divergences is traced to an incorrect instantaneous time-dependence of the effective Hamiltonian. The implications for computations of frequency-dependent response properties are considerable and call into question the validity of conventional approximate many-electron response theories beyond linear response.

  15. First-order derivative couplings between excited states from adiabatic TDDFT response theory

    SciTech Connect

    Ou, Qi; Subotnik, Joseph E.; Bellchambers, Gregory D.; Furche, Filipp

    2015-02-14

    We present a complete derivation of derivative couplings between excited states in the framework of adiabatic time-dependent density functional response theory. Explicit working equations are given and the resulting derivative couplings are compared with derivative couplings from a pseudo-wavefunction ansatz. For degenerate excited states, i.e., close to a conical intersection (CI), the two approaches are identical apart from an antisymmetric overlap term. However, if the difference between two excitation energies equals another excitation energy, the couplings from response theory exhibit an unphysical divergence. This spurious behavior is a result of the adiabatic or static kernel approximation of time-dependent density functional theory leading to an incorrect analytical structure of the quadratic response function. Numerical examples for couplings close to a CI and for well-separated electronic states are given.

  16. First-order derivative couplings between excited states from adiabatic TDDFT response theory.

    PubMed

    Ou, Qi; Bellchambers, Gregory D; Furche, Filipp; Subotnik, Joseph E

    2015-02-14

    We present a complete derivation of derivative couplings between excited states in the framework of adiabatic time-dependent density functional response theory. Explicit working equations are given and the resulting derivative couplings are compared with derivative couplings from a pseudo-wavefunction ansatz. For degenerate excited states, i.e., close to a conical intersection (CI), the two approaches are identical apart from an antisymmetric overlap term. However, if the difference between two excitation energies equals another excitation energy, the couplings from response theory exhibit an unphysical divergence. This spurious behavior is a result of the adiabatic or static kernel approximation of time-dependent density functional theory leading to an incorrect analytical structure of the quadratic response function. Numerical examples for couplings close to a CI and for well-separated electronic states are given.

  17. Theory of Adiabatic Fountain Resonance

    NASA Astrophysics Data System (ADS)

    Williams, Gary A.

    2017-01-01

    The theory of "Adiabatic Fountain Resonance" with superfluid ^4{He} is clarified. In this geometry a film region between two silicon wafers bonded at their outer edge opens up to a central region with a free surface. We find that the resonance in this system is not a Helmholtz resonance as claimed by Gasparini et al., but in fact is a fourth sound resonance. We postulate that it occurs at relatively low frequency because the thin silicon wafers flex appreciably from the pressure oscillations of the sound wave.

  18. Adiabatic Wankel type rotary engine

    NASA Technical Reports Server (NTRS)

    Kamo, R.; Badgley, P.; Doup, D.

    1988-01-01

    This SBIR Phase program accomplished the objective of advancing the technology of the Wankel type rotary engine for aircraft applications through the use of adiabatic engine technology. Based on the results of this program, technology is in place to provide a rotor and side and intermediate housings with thermal barrier coatings. A detailed cycle analysis of the NASA 1007R Direct Injection Stratified Charge (DISC) rotary engine was performed which concluded that applying thermal barrier coatings to the rotor should be successful and that it was unlikely that the rotor housing could be successfully run with thermal barrier coatings as the thermal stresses were extensive.

  19. Time-dependent tomographic reconstruction of the solar corona

    NASA Astrophysics Data System (ADS)

    Vibert, D.; Peillon, C.; Lamy, P.; Frazin, R. A.; Wojak, J.

    2016-10-01

    Solar rotational tomography (SRT) applied to white-light coronal images observed at multiple aspect angles has been the preferred approach for determining the three-dimensional (3D) electron density structure of the solar corona. However, it is seriously hampered by the restrictive assumption that the corona is time-invariant which introduces significant errors in the reconstruction. We first explore several methods to mitigate the temporal variation of the corona by decoupling the "fast-varying" inner corona from the "slow-moving" outer corona using multiple masking (either by juxtaposition or recursive combination) and radial weighting. Weighting with a radial exponential profile provides some improvement over a classical reconstruction but only beyond ≈ 3R⊙. We next consider a full time-dependent tomographic reconstruction involving spatio-temporal regularization and further introduce a co-rotating regularization aimed at preventing concentration of reconstructed density in the plane of the sky. Crucial to testing our procedure and properly tuning the regularization parameters is the introduction of a time-dependent MHD model of the corona based on observed magnetograms to build a time-series of synthetic images of the corona. Our procedure, which successfully reproduces the time-varying model corona, is finally applied to a set of 53 LASCO-C2 pB images roughly evenly spaced in time from 15 to 29 March 2009. Our procedure paves the way to a time-dependent tomographic reconstruction of the coronal electron density to the whole set of LASCO-C2 images presently spanning 20 years.

  20. Time-Dependent Neutron and Photon Dose-Field Analysis

    SciTech Connect

    Wooten, Hasani Omar

    2005-08-01

    A unique tool is developed that allows the user to model physical representations of complicated glovebox facilities in two dimensions and determine neutral-particle flux and ambient dose-equivalent fields throughout that geometry. The Pandemonium code, originally designed to determine flux and dose-rates only, is improved to include realistic glovebox geometries, time-dependent source and detector positions, time-dependent shielding thickness calculations, time-integrated doses, a representative criticality accident scenario based on time-dependent reactor kinetics, and more rigorous photon treatment. A primary benefit of this work has been an extensive analysis and improvement of the photon model that is not limited to the application described in this thesis. The photon model has been extended in energy range to 10 MeV to include photons from fission and new photon buildup factors have been included that account for the effects of photon buildup at slant-path thicknesses as a function of angle, where the mean free path thickness has been preserved. The overall system of codes is user-friendly and it is directly applicable to facilities such as the plutonium facility at Los Alamos National Laboratory, where high-intensity neutron and photon emitters are regularly used. The codes may be used to determine a priori doses for given work scenarios in an effort to supply dose information to process models which will in turn assist decision makers on ensuring as low as reasonably achievable (ALARA) compliance. In addition, coupling the computational results of these tools with the process model visualization tools will help to increase worker safety and radiological safety awareness.

  1. Time-dependent radiation dose estimations during interplanetary space flights

    NASA Astrophysics Data System (ADS)

    Dobynde, M. I.; Shprits, Y.; Drozdov, A.

    2015-12-01

    Time-dependent radiation dose estimations during interplanetary space flights 1,2Dobynde M.I., 2,3Drozdov A.Y., 2,4Shprits Y.Y.1Skolkovo institute of science and technology, Moscow, Russia 2University of California Los Angeles, Los Angeles, USA 3Lomonosov Moscow State University Skobeltsyn Institute of Nuclear Physics, Moscow, Russia4Massachusetts Institute of Technology, Cambridge, USASpace radiation is the main restriction for long-term interplanetary space missions. It induces degradation of external components and propagates inside providing damage to internal environment. Space radiation particles and induced secondary particle showers can lead to variety of damage to astronauts in short- and long- term perspective. Contribution of two main sources of space radiation- Sun and out-of-heliosphere space varies in time in opposite phase due to the solar activity state. Currently the only habituated mission is the international interplanetary station that flights on the low Earth orbit. Besides station shell astronauts are protected with the Earth magnetosphere- a natural shield that prevents significant damage for all humanity. Current progress in space exploration tends to lead humanity out of magnetosphere bounds. With the current study we make estimations of spacecraft parameters and astronauts damage for long-term interplanetary flights. Applying time dependent model of GCR spectra and data on SEP spectra we show the time dependence of the radiation in a human phantom inside the shielding capsule. We pay attention to the shielding capsule design, looking for an optimal geometry parameters and materials. Different types of particles affect differently on the human providing more or less harm to the tissues. Incident particles provide a large amount of secondary particles while propagating through the shielding capsule. We make an attempt to find an optimal combination of shielding capsule parameters, namely material and thickness, that will effectively decrease

  2. Painlevé V and time-dependent Jacobi polynomials

    NASA Astrophysics Data System (ADS)

    Basor, Estelle; Chen, Yang; Ehrhardt, Torsten

    2010-01-01

    In this paper we study the simplest deformation on a sequence of orthogonal polynomials. This in turn induces a deformation on the moment matrix of the polynomials and associated Hankel determinant. We replace the original (or reference) weight w0(x) (supported on \\mathbb {R} or subsets of \\mathbb {R}) by w0(x) e-tx. It is a well-known fact that under such a deformation the recurrence coefficients denoted as αn and βn evolve in t according to the Toda equations, giving rise to the time-dependent orthogonal polynomials and time-dependent determinants, using Sogo's terminology. If w0 is the normal density e^{-x^2},\\;x\\in \\mathbb {R}, or the gamma density xα e-x, x\\in \\mathbb {R}_{+}, α > -1, then the initial value problem of the Toda equations can be trivially solved. This is because under elementary scaling and translation the orthogonality relations reduce to the original ones. However, if w0 is the beta density (1 - x)α(1 + x)β, x in [ - 1, 1], α, β > -1, the resulting 'time-dependent' Jacobi polynomials will again satisfy a linear second-order ode, but no longer in the Sturm-Liouville form, which is to be expected. This deformation induces an irregular singular point at infinity in addition to three regular singular points of the hypergeometric equation satisfied by the Jacobi polynomials. We will show that the coefficients of this ode, as well as the Hankel determinant, are intimately related to a particular Painlevé V. In particular we show that \\\\textsf {p}_1(n,t), where \\\\textsf {p}_1(n,t) is the coefficient of zn-1 of the monic orthogonal polynomials associated with the 'time-dependent' Jacobi weight, satisfies, up to a translation in t, the Jimbo-Miwa σ-form of the same PV; while a recurrence coefficient αn(t) is up to a translation in t and a linear fractional transformation PV(α2/2, - β2/2, 2n + 1 + α + β, - 1/2). These results are found from combining a pair of nonlinear difference equations and a pair of Toda equations. This

  3. Deterministic methods for time-dependent stochastic neutron transport

    SciTech Connect

    Baker, Randal S

    2009-01-01

    A numerical method is presented for solving the time-dependent survival probability equation in general (lD/2D/3D) geometries using the multi group SNmethod. Although this equation was first formulated by Bell in the early 1960's, it has only been applied to stationary systems (for other than idealized point models) until recently, and detailed descriptions of numerical solution techniques are lacking in the literature. This paper presents such a description and applies it to a dynamic system representative of a figurative criticality accident scenario.

  4. Time-dependent scalar fields as candidates for dark matter

    NASA Astrophysics Data System (ADS)

    Malakolkalami, B.; Mahmoodzadeh, A.

    2016-11-01

    In this paper, we study some properties of what is called the oscillaton, a spherically symmetric object made of a real time-dependent scalar field. Using an exponential scalar potential instead of a quadratic one discussed in previous works, as a new choice, we investigate the oscillaton properties with this potential. Solving the differential equation system resulting from the Einstein-Klein-Gordon equations reveals the importance of the oscillatons as candidates for dark matter. Meanwhile, a simplification called the stationary limit procedure is also carried out.

  5. Efficient auxiliary-mode approach for time-dependent nanoelectronics

    NASA Astrophysics Data System (ADS)

    Popescu, Bogdan Stefan; Croy, Alexander

    2016-09-01

    A new scheme for numerically solving the equations arising in the time-dependent non-equilibrium Green's function formalism is developed. It is based on an auxiliary-mode expansion of the self-energies which convert the complicated set of integro-differential equations into a set of ordinary differential equations. In the new scheme all auxiliary matrices are replaced by vectors or scalars. This drastically reduces the computational effort and memory requirements of the method, rendering it applicable to topical problems in electron quantum optics and molecular electronics. As an illustrative example we consider the dynamics of a Leviton wave-packet in a 1D wire.

  6. Advances in time-dependent current-density functional theory

    NASA Astrophysics Data System (ADS)

    Berger, Arjan

    In this work we solve the problem of the gauge dependence of molecular magnetic properties (magnetizabilities, circular dichroism) using time-dependent current-density functional theory [1]. We also present a new functional that accurately describes the optical absorption spectra of insulators, semiconductors and metals [2] N. Raimbault, P.L. de Boeij, P. Romaniello, and J.A. Berger Phys. Rev. Lett. 114, 066404 (2015) J.A. Berger, Phys. Rev. Lett. 115, 137402 (2015) This study has been partially supported through the Grant NEXT No. ANR-10-LABX-0037 in the framework of the Programme des Investissements d'Avenir.

  7. Optimal moving grids for time-dependent partial differential equations

    NASA Technical Reports Server (NTRS)

    Wathen, A. J.

    1992-01-01

    Various adaptive moving grid techniques for the numerical solution of time-dependent partial differential equations were proposed. The precise criterion for grid motion varies, but most techniques will attempt to give grids on which the solution of the partial differential equation can be well represented. Moving grids are investigated on which the solutions of the linear heat conduction and viscous Burgers' equation in one space dimension are optimally approximated. Precisely, the results of numerical calculations of optimal moving grids for piecewise linear finite element approximation of PDE solutions in the least-squares norm are reported.

  8. Optimal moving grids for time-dependent partial differential equations

    NASA Technical Reports Server (NTRS)

    Wathen, A. J.

    1989-01-01

    Various adaptive moving grid techniques for the numerical solution of time-dependent partial differential equations were proposed. The precise criterion for grid motion varies, but most techniques will attempt to give grids on which the solution of the partial differential equation can be well represented. Moving grids are investigated on which the solutions of the linear heat conduction and viscous Burgers' equation in one space dimension are optimally approximated. Precisely, the results of numerical calculations of optimal moving grids for piecewise linear finite element approximation of partial differential equation solutions in the least squares norm.

  9. Time-dependent correlations in quantum magnets at finite temperature

    NASA Astrophysics Data System (ADS)

    Fauseweh, B.; Groitl, F.; Keller, T.; Rolfs, K.; Tennant, D. A.; Habicht, K.; Uhrig, G. S.

    2016-11-01

    In this Rapid Communication we investigate the time dependence of the gap mode of copper nitrate at various temperatures. We combine state-of-the-art theoretical calculations with high precision neutron resonance spin-echo measurements to understand the anomalous decoherence effects found previously in this material. It is shown that the time domain offers a complementary view on this phenomenon, which allows us to directly compare experimental data and theoretical predictions without the need of further intensive data analysis, such as (de)convolution.

  10. Time-dependent Kohn-Sham approach to quantum electrodynamics

    SciTech Connect

    Ruggenthaler, M.; Mackenroth, F.; Bauer, D.

    2011-10-15

    We prove a generalization of the van Leeuwen theorem toward quantum electrodynamics, providing the formal foundations of a time-dependent Kohn-Sham construction for coupled quantized matter and electromagnetic fields. We circumvent the symmetry-causality problems associated with the action-functional approach to Kohn-Sham systems. We show that the effective external four-potential and four-current of the Kohn-Sham system are uniquely defined and that the effective four-current takes a very simple form. Further we rederive the Runge-Gross theorem for quantum electrodynamics.

  11. Perspective: Fundamental aspects of time-dependent density functional theory

    NASA Astrophysics Data System (ADS)

    Maitra, Neepa T.

    2016-06-01

    In the thirty-two years since the birth of the foundational theorems, time-dependent density functional theory has had a tremendous impact on calculations of electronic spectra and dynamics in chemistry, biology, solid-state physics, and materials science. Alongside the wide-ranging applications, there has been much progress in understanding fundamental aspects of the functionals and the theory itself. This Perspective looks back to some of these developments, reports on some recent progress and current challenges for functionals, and speculates on future directions to improve the accuracy of approximations used in this relatively young theory.

  12. Time-dependent thermoelectric transport for nanoscale thermal machines

    NASA Astrophysics Data System (ADS)

    Daré, A.-M.; Lombardo, P.

    2016-01-01

    We analyze an electronic nanoscale thermal machine driven by time-dependent environment: besides bias and gate voltage variations, we consider also the less prevailing time modulation of the couplings between leads and dot. We provide energy and heat current expressions in such situations, as well as expressions for the power exchanged between the dot+leads system and its outside. Calculations are made in the Keldysh nonequilibrium Green's function framework. We apply these results to design a cyclic refrigerator, circumventing the ambiguity of defining energy flows between subsystems in the case of strong coupling. For fast lead-dot coupling modulation, we observe transient currents which cannot be ascribed to charge tunneling.

  13. Time-dependent, lattice approach to atomic collisions

    SciTech Connect

    Schultz, D.R.

    1995-12-31

    Recent progress in developing and applying methods of direct numerical solution of atomic collision problems is described. Various forms of the three-body problem are used to illustrate these techniques. Specifically, the process of ionization in proton-, antiproton-, and electron-impact of atomic hydrogen is considered in applications ranging in computational intensity from collisions simulated in two spatial dimensions to treatment of the three-dimensional, fully correlated two-electron Schroedinger equation. These examples demonstrate the utility and feasibility of treating strongly interacting atomic systems through time-dependent, lattice approaches.

  14. Ultrafast adiabatic second harmonic generation

    NASA Astrophysics Data System (ADS)

    Dahan, Asaf; Levanon, Assaf; Katz, Mordechai; Suchowski, Haim

    2017-03-01

    We introduce a generalization of the adiabatic frequency conversion method for an efficient conversion of ultrashort pulses in the full nonlinear regime. Our analysis takes into account dispersion as well as two-photon processes and Kerr effect, allowing complete analysis of any three waves with arbitrary phase mismatched design and any nonlinear optical process. We use this analysis to design an efficient and robust second harmonic generation, the most widely used nonlinear process for both fundamental and applied research. We experimentally show that such design not only allows for very efficient conversion of various of ultrashort pulses, but is also very robust to variations in the parameters of both the nonlinear crystal and the incoming light. These include variation of more than 100 °C in the crystal temperature, a wide bandwidth of up to 75 nm and a chirp variation of 300 fs to 3.5 ps of the incoming pulse. Also, we show the dependency of the adiabatic second harmonic generation design on the pump intensity and the crystal length. Our study shows that two photon absorption plays a critical role in such high influence nonlinear dynamics, and that it must be considered in order to achieve agreement with experimental results.

  15. Ultrafast adiabatic second harmonic generation.

    PubMed

    Dahan, Asaf; Levanon, Assaf; Katz, Mordechai; Suchowski, Haim

    2017-03-01

    We introduce a generalization of the adiabatic frequency conversion method for an efficient conversion of ultrashort pulses in the full nonlinear regime. Our analysis takes into account dispersion as well as two-photon processes and Kerr effect, allowing complete analysis of any three waves with arbitrary phase mismatched design and any nonlinear optical process. We use this analysis to design an efficient and robust second harmonic generation, the most widely used nonlinear process for both fundamental and applied research. We experimentally show that such design not only allows for very efficient conversion of various of ultrashort pulses, but is also very robust to variations in the parameters of both the nonlinear crystal and the incoming light. These include variation of more than 100 °C in the crystal temperature, a wide bandwidth of up to 75 nm and a chirp variation of 300 fs to 3.5 ps of the incoming pulse. Also, we show the dependency of the adiabatic second harmonic generation design on the pump intensity and the crystal length. Our study shows that two photon absorption plays a critical role in such high influence nonlinear dynamics, and that it must be considered in order to achieve agreement with experimental results.

  16. Rayleigh-Taylor mixing with time-dependent acceleration

    NASA Astrophysics Data System (ADS)

    Abarzhi, Snezhana

    2016-10-01

    We extend the momentum model to describe Rayleigh-Taylor (RT) mixing driven by a time-dependent acceleration. The acceleration is a power-law function of time, similarly to astrophysical and plasma fusion applications. In RT flow the dynamics of a fluid parcel is driven by a balance per unit mass of the rates of momentum gain and loss. We find analytical solutions in the cases of balanced and imbalanced gains and losses, and identify their dependence on the acceleration exponent. The existence is shown of two typical regimes of self-similar RT mixing-acceleration-driven Rayleigh-Taylor-type and dissipation-driven Richtymer-Meshkov-type with the latter being in general non-universal. Possible scenarios are proposed for transitions from the balanced dynamics to the imbalanced self-similar dynamics. Scaling and correlations properties of RT mixing are studied on the basis of dimensional analysis. Departures are outlined of RT dynamics with time-dependent acceleration from canonical cases of homogeneous turbulence as well as blast waves with first and second kind self-similarity. The work is supported by the US National Science Foundation.

  17. Time-dependent Models of Magnetospheric Accretion onto Young Stars

    NASA Astrophysics Data System (ADS)

    Robinson, C. E.; Owen, J. E.; Espaillat, C. C.; Adams, F. C.

    2017-04-01

    Accretion onto Classical T Tauri stars is thought to take place through the action of magnetospheric processes, with gas in the inner disk being channeled onto the star’s surface by the stellar magnetic field lines. Young stars are known to accrete material in a time-variable manner, and the source of this variability remains an open problem, particularly on the shortest (∼day) timescales. Using one-dimensional time-dependent numerical simulations that follow the field line geometry, we find that for plausibly realistic young stars, steady-state transonic accretion occurs naturally in the absence of any other source of variability. However, we show that if the density in the inner disk varies smoothly in time with ∼day-long timescales (e.g., due to turbulence), this complication can lead to the development of shocks in the accretion column. These shocks propagate along the accretion column and ultimately hit the star, leading to rapid, large amplitude changes in the accretion rate. We argue that when these shocks hit the star, the observed time dependence will be a rapid increase in accretion luminosity, followed by a slower decline, and could be an explanation for some of the short-period variability observed in accreting young stars. Our one-dimensional approach bridges previous analytic work to more complicated multi-dimensional simulations and observations.

  18. Time-dependent depolarization of aligned HD molecules.

    PubMed

    Bartlett, Nate C-M; Miller, Daniel J; Zare, Richard N; Alexander, Andrew J; Sofikitis, Dimitris; Rakitzis, T Peter

    2009-01-07

    An aligned sample of HD(v = 1, J = 2, M(J) = 0) molecules is prepared under collision-free conditions using the S(0) stimulated Raman pumping transition. Subsequent coupling to the spins of the deuteron I(D) and the proton I(H) causes the initial degree of alignment to oscillate and decrease as monitored over the time range from 0-13 mus via the O2 line of the [2 + 1] REMPI E,F(1)Sigma-X(1)Sigma (0,1) band. The time dependence of the rotational alignment is also calculated using both a hierarchical coupling scheme in which the rotational angular momentum J is regarded first to couple to I(D), and then the resultant F(i) to couple to I(H), to form the total angular momentum F and a non-hierarchical coupling scheme in which the HD energy level structure is not assumed to be diagonal in the |I(H)(JI(D))F(i)FM(F)> basis set. The experimental data is in good agreement with the non-hierarchical calculation but not with the hierarchical calculation, as expected for this system. Additionally, we calculate the time dependence of the H and D nuclear spin polarizations.

  19. A time-dependent embedding calculation of surface electron emission.

    PubMed

    Inglesfield, J E

    2011-08-03

    The Dirac-Frenkel variational principle is used to derive the embedding method for solving the time-dependent Schrödinger equation. Embedding allows the time evolution of the wavefunction to be calculated explicitly in a limited region of space, the region of physical interest, the embedding potential ensuring that the wavefunction satisfies the correct boundary conditions for matching on to the rest of the system. This is applied to a study of the excitation of electrons at a metal surface, represented by a one-dimensional model potential for Cu(111). Time-dependent embedding potentials are derived for replacing the bulk substrate, and the image potential and vacuum region outside the surface, so that the calculation of electron excitation by a surface perturbation can be restricted to the surface itself. The excitation of the Shockley surface state and a continuum bulk state is studied, and the time structure of the resulting currents analysed. There is a distinction between emission from the localized surface state, where the charge is steadily depleted, and the extended continuum state, where the current emitted into the vacuum is compensated by current approaching the surface from the bulk. The time taken for the current to arrive outside the surface is studied.

  20. Equivalent emergence of time dependence in classical and quantum mechanics

    NASA Astrophysics Data System (ADS)

    Briggs, John S.

    2015-05-01

    Beginning with the principle that a closed mechanical composite system is timeless, time can be defined by the regular changes in a suitable position coordinate (clock) in the observing part, when one part of the closed composite observes another part. Translating this scenario into both classical and quantum mechanics allows a transition to be made from a time-independent mechanics for the closed composite to a time-dependent description of the observed part alone. The use of Hamilton-Jacobi theory yields a very close parallel between the derivations in classical and quantum mechanics. The time-dependent equations, Hamilton-Jacobi or Schrödinger, appear as approximations since no observed system is truly closed. The quantum case has an additional feature in the condition that the observing environment must become classical in order to define a real classical time variable. This condition leads to a removal of entanglement engendered by the interaction between the observed system and the observing environment. Comparison is made to the similar emergence of time in quantum gravity theory.