Molecular Scattering and Born-Oppenheimer Approximation
Vania, Sordoni
2008-01-01
In this paper, we study the scattering wave operators for a diatomic molecules by using the Born-Oppenheimer approximation. Assuming that the ratio h^2 between the electronic and nuclear masses is small, we construct adiabatic wave operators that, under some non trapping conditions, approximate the two-cluster wave operators up to any powers of the parameter h
Entanglement in the Born-Oppenheimer Approximation
Izmaylov, Artur F
2016-01-01
The role of electron-nuclear entanglement on the validity of the Born-Oppenheimer (BO) approximation is investigated. While nonadiabatic couplings generally lead to entanglement and to a failure of the BO approximation, surprisingly the degree of electron-nuclear entanglement is found to be uncorrelated with the degree of validity of the BO approximation. This is because while the degree of entanglement of BO states is determined by their deviation from the corresponding states in the crude BO approximation, the accuracy of the BO approximation is dictated, instead, by the deviation of the BO states from the exact electron-nuclear states. In fact, in the context of a minimal avoided crossing model, extreme cases are identified where an adequate BO state is seen to be maximally entangled, and where the BO approximation fails but the associated BO state remains approximately unentangled. Further, the BO states are found to not preserve the entanglement properties of the exact electron-nuclear eigenstates, and t...
Born-Oppenheimer approximation for a harmonic molecule
Fernandez, Francisco M.
2008-01-01
We apply the Born-Oppenheimer approximation to a harmonic diatomic molecule with one electron. We compare the exact and approximate results not only for the internal degrees of freedom but also for the motion of the center of mass. We address the problem of identical nuclei and discuss other applications of the model and its limitations.
Electronic Flux Density beyond the Born-Oppenheimer Approximation.
Schild, Axel; Agostini, Federica; Gross, E K U
2016-05-19
In the Born-Oppenheimer approximation, the electronic wave function is typically real-valued and hence the electronic flux density (current density) seems to vanish. This is unfortunate for chemistry, because it precludes the possibility to monitor the electronic motion associated with the nuclear motion during chemical rearrangements from a Born-Oppenheimer simulation of the process. We study an electronic flux density obtained from a correction to the electronic wave function. This correction is derived via nuclear velocity perturbation theory applied in the framework of the exact factorization of electrons and nuclei. To compute the correction, only the ground state potential energy surface and the electronic wave function are needed. For a model system, we demonstrate that this electronic flux density approximates the true one very well, for coherent tunneling dynamics as well as for over-the-barrier scattering, and already for mass ratios between electrons and nuclei that are much larger than the true mass ratios. PMID:26878256
On the mathematical treatment of the Born-Oppenheimer approximation
Jecko, Thierry, E-mail: thierry.jecko@u-cergy.fr [AGM, UMR 8088 du CNRS, Université de Cergy-Pontoise, Département de mathématiques, site de Saint Martin, 2 avenue Adolphe Chauvin, F-95000 Pontoise (France)
2014-05-15
Motivated by the paper by Sutcliffe and Woolley [“On the quantum theory of molecules,” J. Chem. Phys. 137, 22A544 (2012)], we present the main ideas used by mathematicians to show the accuracy of the Born-Oppenheimer approximation for molecules. Based on mathematical works on this approximation for molecular bound states, in scattering theory, in resonance theory, and for short time evolution, we give an overview of some rigorous results obtained up to now. We also point out the main difficulties mathematicians are trying to overcome and speculate on further developments. The mathematical approach does not fit exactly to the common use of the approximation in Physics and Chemistry. We criticize the latter and comment on the differences, contributing in this way to the discussion on the Born-Oppenheimer approximation initiated by Sutcliffe and Woolley. The paper neither contains mathematical statements nor proofs. Instead, we try to make accessible mathematically rigourous results on the subject to researchers in Quantum Chemistry or Physics.
Coulomb-Born-Oppenheimer approximation in Ps-H scattering
Hasi Ray
2006-02-01
To improve the Coulomb-Born approximation (CBA) theory of ionization in positronium (Ps) and atom scattering, the effect of exchange is introduced. The nine-dimensional exchange amplitude for ionization of Ps in Ps-H scattering is reduced to a two-dimensional integral using the present Coulomb-Born-Oppenheimer approximation (CBOA). The methodology is extremely useful to evaluate ionization parameters for different target systems and for different types of ionization processes. It is then applied to evaluate the Ps-ionization cross-section and to estimate the effect of exchange on Ps-ionization in Ps-H system. We establish the importance of exchange at lower energy region.
Born-Oppenheimer Approximation for the XYZ Mesons
Braaten, Eric; Smith, D Hudson
2014-01-01
Many of the XYZ mesons discovered in the last decade can be identified as bound states in Born-Oppenheimer (B-O) potentials for a heavy quark and antiquark. They include quarkonium hybrids, which are bound states in excited flavor-singlet B-O potentials, and quarkonium tetraquarks, which are bound states in flavor-nonsinglet B-O potentials. We present simple parameterizations of the deepest flavor-singlet B-O potentials. We infer the deepest flavor-nonsinglet B-O potentials from lattice QCD calculations of static adjoint mesons. Selection rules for hadronic transitions are used to identify XYZ mesons that are candidates for ground-state energy levels in the B-O potentials for charmonium hybrids and tetraquarks. The energies of the lowest-energy charmonium hybrids are predicted by using the results of lattice QCD calculations to calculate the energy splittings between the ground states of different B-O potentials and using the Schroedinger equation to determine the splittings between energy levels within a B-O...
On the mass of atoms in molecules: Beyond the Born-Oppenheimer approximation
Scherrer, Arne; Sebastiani, Daniel; Gross, E K U; Vuilleumier, Rodolphe
2016-01-01
Describing the dynamics of nuclei in molecules requires a potential energy surface, which is traditionally provided by the Born-Oppenheimer or adiabatic approximation. However, we also need to assign masses to the nuclei. There, the Born-Oppenheimer picture does not account for the inertia of the electrons and only bare nuclear masses are considered. Nowadays, experimental accuracy challenges the theoretical predictions of rotational and vibrational spectra and requires to include the participation of electrons in the internal motion of the molecule. More than 80 years after the original work of Born and Oppenheimer, this issue still is not solved in general. Here, we present a theoretical and numerical framework to address this problem in a general and rigorous way. Starting from the exact factorization of the electron-nuclear wave function, we include electronic effects beyond the Born-Oppenheimer regime in a perturbative way via position-dependent corrections to the bare nuclear masses. This maintains an a...
Corrections to the Born-Oppenheimer approximation for a harmonic oscillator
We derive simple expressions for the energy corrections to the Born-Oppenheimer approximation valid for a harmonic oscillator. We apply these corrections to the electronic and rotational ground state of H2+ and show that the diabatic energy corrections are linearly dependent on the vibrational quantum numbers as seen in recent variational calculations [D. A. Kohl and E. J. Shipsey, J. Chem. Phys. 84, 2707 (1986)
Coherent states, quantum gravity and the Born-Oppenheimer approximation, I: General considerations
Stottmeister, Alexander
2015-01-01
This article, as the first of three, aims at establishing the (time-dependent) Born-Oppenheimer approximation, in the sense of space adiabatic perturbation theory, for quantum systems constructed by techniques of the loop quantum gravity framework, especially the canonical formulation of the latter. The analysis presented here fits into a rather general framework, and offers a solution to the problem of applying the usual Born-Oppenheimer ansatz for molecular (or structurally analogous) systems to more general quantum systems (e.g. spin-orbit models) by means of space adiabatic perturbation theory. The proposed solution is applied to a simple, finite dimensional model of interacting spin systems, which serves as a non-trivial, minimal model of the aforesaid problem. Furthermore, it is explained how the content of this article, and its companion, affect the possible extraction of quantum field theory on curved spacetime from loop quantum gravity (including matter fields).
Coherent states, quantum gravity, and the Born-Oppenheimer approximation. I. General considerations
Stottmeister, Alexander; Thiemann, Thomas
2016-06-01
This article, as the first of three, aims at establishing the (time-dependent) Born-Oppenheimer approximation, in the sense of space adiabatic perturbation theory, for quantum systems constructed by techniques of the loop quantum gravity framework, especially the canonical formulation of the latter. The analysis presented here fits into a rather general framework and offers a solution to the problem of applying the usual Born-Oppenheimer ansatz for molecular (or structurally analogous) systems to more general quantum systems (e.g., spin-orbit models) by means of space adiabatic perturbation theory. The proposed solution is applied to a simple, finite dimensional model of interacting spin systems, which serves as a non-trivial, minimal model of the aforesaid problem. Furthermore, it is explained how the content of this article and its companion affect the possible extraction of quantum field theory on curved spacetime from loop quantum gravity (including matter fields).
Coherent Dynamics in Dressed Optical Lattices Beyond the Born-Oppenheimer Approximation
Reeves, Jeremy; Krinner, Ludwig; Stewart, Mike; Pazmino, Arturo; Schneble, Dominik
2015-05-01
Usual treatments of matter-wave diffraction assume that the zero-point energy in the diffracting potential is much smaller than the gap between the dressed levels. However, in near-resonant weak-driving scenarios, zero-point motion can mix the adiabatic dressed states, making the diffracting potentials highly non-adiabatic, such that the usual Born-Oppenheimer approximation for the external and internal degrees of freedom no longer applies. We model the dynamics of a matter wave in a microwave-coupled state-dependent lattice in this regime, and quantify the importance of these effects on recent experiments. Supported by NSF grant PHY-1205894.
Born-Oppenheimer approximation for open quantum systems within the quantum trajectory approach
Using the quantum trajectory approach, we extend the Born-Oppenheimer (BO) approximation from closed to open quantum systems, where the open quantum system is described by a master equation in Lindblad form. The BO approximation is defined and the validity condition is derived. We find that the dissipation in fast variables improves the BO approximation, unlike the dissipation in slow variables. A detailed comparison is presented between this extension and our previous approximation based on the effective Hamiltonian approach [X. L. Huang and X. X. Yi, Phys. Rev. A 80, 032108 (2009)]. Several additional features and advantages are analyzed, which show that the two approximations are complementary to each other. Two examples are described to illustrate our method.
Ahmadi, H; Maghari, A
2016-01-01
The underlying physics behind the molecular harmonic emission in relatively long sin$^2$-like laser pulses is investigated. We numerically solved the full-dimensional electronic time-dependent Schr\\"{o}dinger equation beyond the Born-Oppenheimer approximation for simple molecular ion H$_2^+$. The occurrence and the effect of electron localization, non-adiabatic redshift and spatially asymmetric emission are evaluated to understand better complex patterns appearing in the high-order harmonic generation (HHG) spectrum. Results show that the complex patterns in the HHG spectrum originate mainly from a non-adiabatic response of the molecule to the rapidly changing laser field and also from a spatially asymmetric emission along the polarization direction. The effect of electron localization on the HHG spectrum was not observed as opposed to what is reported in the literature.
Vafaee, Mohsen
2007-01-01
The electronic full dimensional of the time dependent Schr\\"odinger equation of the aligned deuterium molecular ion numerically is solved for the simulation of the complicated dissociative ionization process and compared with the related experimental results. In this work, the R-dependent ionization rate and the enhanced ionization phenomenon beyond the Born-Oppenheimer approximation are introduced and calculated and enhanced ionization is directly related to kinetic energy release (KER) of nuclear energy. The signification of the Coulomb explosion energy and dissociation-ionization energy in the ionization channel are comparatively revealed in the total kinetic energy release. It shows that the dissociation-ionization energy spectra in the ionization channel have significant role in the structure of the KER spectrum.
Stanke, Monika; Adamowicz, Ludwik
2013-10-01
In this work, we describe how the energies obtained in molecular calculations performed without assuming the Born-Oppenheimer (BO) approximation can be augmented with corrections accounting for the leading relativistic effects. Unlike the conventional BO approach, where these effects only concern the relativistic interactions between the electrons, the non-BO approach also accounts for the relativistic effects due to the nuclei and due to the coupling of the coupled electron-nucleus motion. In the numerical sections, the results obtained with the two approaches are compared. The first comparison concerns the dissociation energies of the two-electron isotopologues of the H2 molecule, H2, HD, D2, T2, and the HeH(+) ion. The comparison shows that, as expected, the differences in the relativistic contributions obtained with the two approaches increase as the nuclei become lighter. The second comparison concerns the relativistic corrections to all 23 pure vibrational states of the HD(+) ion. An interesting charge asymmetry caused by the nonadiabatic electron-nucleus interaction appears in this system, and this effect significantly increases with the vibration excitation. The comparison of the non-BO results with the results obtained with the conventional BO approach, which in the lowest order does not describe the charge-asymmetry effect, reveals how this effect affects the values of the relativistic corrections. PMID:23679131
Coherent states, quantum gravity, and the Born- Oppenheimer approximation. II. Compact Lie groups
Stottmeister, Alexander; Thiemann, Thomas
2016-07-01
In this article, the second of three, we discuss and develop the basis of a Weyl quantisation for compact Lie groups aiming at loop quantum gravity-type models. This Weyl quantisation may serve as the main mathematical tool to implement the program of space adiabatic perturbation theory in such models. As we already argued in our first article, space adiabatic perturbation theory offers an ideal framework to overcome the obstacles that hinder the direct implementation of the conventional Born-Oppenheimer approach in the canonical formulation of loop quantum gravity. Additionally, we conjecture the existence of a new form of the Segal-Bargmann-Hall "coherent state" transform for compact Lie groups G, which we prove for G = U(1)n and support by numerical evidence for G = SU(2). The reason for conjoining this conjecture with the main topic of this article originates in the observation that the coherent state transform can be used as a basic building block of a coherent state quantisation (Berezin quantisation) for compact Lie groups G. But, as Weyl and Berezin quantisation for ℝ2d are intimately related by heat kernel evolution, it is natural to ask whether a similar connection exists for compact Lie groups as well. Moreover, since the formulation of space adiabatic perturbation theory requires a (deformation) quantisation as minimal input, we analyse the question to what extent the coherent state quantisation, defined by the Segal-Bargmann-Hall transform, can serve as basis of the former.
All 18 bound pure vibrational levels of the HD molecule have been calculated within the framework that does not assume the Born-Oppenheimer (BO) approximation. The nonrelativistic energies of the states have been corrected for the relativistic effects of the order of α2 (where α is the fine structure constant), calculated using the perturbation theory with the nonrelativistic non-BO wave functions being the zero-order approximation. The calculations were performed by expanding the non-BO wave functions in terms of one-center explicitly correlated Gaussian functions multiplied by even powers of the internuclear distance and by performing extensive optimization of the Gaussian nonlinear parameters. Up to 10 000 basis functions were used for each state.
Study of the structures of four-quark states in terms of the Born-Oppenheimer approximation
In this work, we use the Born-Oppenheimer approximation, where the potential between atoms can be approximated as a function of distance between the two nuclei, to study the four-quark bound states. By this approximation, Heitler and London calculated the spectrum of the hydrogen molecule, which includes two protons (heavy) and two electrons (light). Generally, the observed exotic mesons Zb(10610), Zb(10650), Zc(3900) and Zc(4020) (Zc(4025)) may be molecular states made of two physical mesons and/or diquark-anti-diquark structures. Analogous to the Heitler-London method for calculating the mass of the hydrogen molecule, we investigate whether there exist energy minima for these two structures. Contrary to the hydrogen molecule case where only the spin-triplet possesses an energy minimum, there exist minima for both of these states. This implies that both molecule and tetraquark states can be stable objects. Since they have the same quantum numbers, however, the two states may mix to result in the physical states. A consequence would be that partner exotic states co-existing with Zb (10610), Zb (10650), Zc (3900) and Zc (4020) (Zc (4025)) are predicted and should be experimentally observed
Tolstikhin, Oleg I.; Madsen, Lars Bojer
2013-01-01
result, the BO approximation in the theory of tunneling ionization of molecules breaks down at sufficiently weak fields. We also show that to account for nuclear motion the weak-field asymptotic expansion for the tunneling ionization rate must be restructured. The predictions for the rate using the BO...
A renormalization of the D-dimensional Hamiltonian is developed to ensure that the large-D limit corresponds to a single well at any value of the internuclear distance R. This avoids convergence problems caused by a symmetry-breaking transition that is otherwise expected to occur when R is approximately equal to the equilibrium bond distance Req, with larger R giving a double well. This symmetry breaking has restricted the applicability of large-order perturbation theory in 1/D to cases where R is significantly less than Req. The renormalization greatly extends the range of R for which the large-order expansion can be summed. A numerical demonstration is presented for H2+. The 1/D expansions are summed using Padacute e-Borel approximants with modifications that explicitly model known singularity structure. copyright 1998 The American Physical Society
Graphical abstract: An analytically solvable model was employed to study proton coupled electron transfer reactions. Approximated theories are assessed, and vibrational coherence is observed in case of small reorganization energy. Research highlights: → The Duschinsky rotation effect in PCET reactions. → Assessment of the BO approx. for proton motion using an analytically solvable model. → Vibrational coherence in PCET in the case of small reorganization energy. - Abstract: By employing an analytically solvable model including the Duschinsky rotation effect, we investigated the applicability of the commonly used Born-Oppenheimer (BO) approximation for separating the proton and proton donor-acceptor motions in theories of proton coupled electron transfer (PCET) reactions. Comparison with theories based on the BO approximation shows that, the BO approximation for the proton coordinate is generally valid while some further approximations may become inaccurate in certain range of parameters. We have also investigated the effect of vibrationally coherent tunneling in the case of small reorganization energy, and shown that it plays an important role on the rate constant and kinetic isotope effect.
Marenich, Aleksandr V; Boggs, James E
2007-11-01
This paper addresses some advances in the theoretical description of molecular spectroscopy beyond the Born-Oppenheimer adiabatic approximation. A solution of the nuclear dynamics problem complicated by the EE Jahn-Teller effect and spin-orbit coupling is considered for the case of the CF3O and CF3S radicals, all the model parameters being obtained solely from ab initio calculations without any adjustment to experimental numbers. Vibrational and vibronic model parameters were calculated at the equation-of-motion coupled cluster level of theory with basis sets of triple-zeta quality. The spin-orbit coupling in X 2E CF3O and CF3S was parametrized by means of a perturbative solution of the full Breit-Pauli spin-orbit operator. Spin-vibronic eigenvalues and eigenfunctions were computed in a basis set of products of electronic, electron spin, and vibrational functions. Results demonstrate the importance of explicit inclusion of the spin-orbit coupling and at least cubic Jahn-Teller terms in the model Hamiltonian for the high precision evaluation of spin-vibronic energy levels of CF3O and CF3S. The theoretical results support and complement the spectroscopic data observed for these species. PMID:17469808
We consider tunneling-mediated electron transfer through time dependent bridges. An approach is developed for computing corrections to the time dependent tunneling matrix element that arise from the breakdown of the Born-Oppenheimer Adiabatic approximation. Differences between Franck-Condon and Born-Oppenheimer breakdown are discussed in the context of bridge-mediated tunneling
Quantum heat transfer: A Born Oppenheimer method
Wu, Lian-Ao; Segal, Dvira
2010-01-01
We develop a Born-Oppenheimer type formalism for the description of quantum thermal transport along hybrid nanoscale objects. Our formalism is suitable for treating heat transfer in the off-resonant regime, where e.g., the relevant vibrational modes of the interlocated molecule are high relative to typical bath frequencies, and at low temperatures when tunneling effects dominate. A general expression for the thermal energy current is accomplished, in the form of a generalized Landauer formula...
Adiabatic electronic flux density: a Born-Oppenheimer Broken Symmetry ansatz
Pohl, Vincent
2016-01-01
The Born-Oppenheimer approximation leads to the counterintuitive result of a vanishing electronic flux density upon vibrational dynamics in the electronic ground state. To circumvent this long known issue, we propose using pairwise anti-symmetrically translated vibronic densities to generate a symmetric electronic density that can be forced to satisfy the continuity equation approximately. The so-called Born-Oppenheimer broken symmetry ansatz yields all components of the flux density simultaneously while requiring only knowledge about the nuclear quantum dynamics on the electronic adiabatic ground state potential energy surface. The underlying minimization procedure is transparent and computationally inexpensive, and the solution can be computed from the standard output of any quantum chemistry program. Taylor series expansion reveals that the implicit electron dynamics originates from non-adiabatic coupling to the explicit Born-Oppenheimer nuclear dynamics. The new approach is applied to the ${\\rm H}_2^+$ mo...
Non-Born-Oppenheimer calculations of the BH molecule.
Bubin, Sergiy; Stanke, Monika; Adamowicz, Ludwik
2009-07-28
Variational calculations employing explicitly correlated Gaussian basis functions have been performed for the ground state of the boron monohydride molecule (BH) and for the boron atom (B). Up to 2000 Gaussians were used for each system. The calculations did not assume the Born-Oppenheimer (BO) approximation. In the optimization of the wave function, we employed the analytical energy gradient with respect to the Gaussian exponential parameters. In addition to the total nonrelativistic energies, we computed scalar relativistic corrections (mass-velocity and Darwin). With those added to the total energies, we estimated the dissociation energy of BH. The non-BO wave functions were also used to compute some expectation values involving operators dependent on the interparticle distances. PMID:19655858
Zero-Point Fluctuations in the Nuclear Born-Oppenheimer Ground State
Zettili, Nouredine
The small-amplitude oscillations of rigid nuclei around the equilibrium state are described by means of the nuclear Born-Oppenheimer (NBO) method. In this limit, the method is shown to give back the random phase approximation (RPA) equations of motion. The contribution of the zero-point fluctuations to the ground state are examined, and the NBO ground state energy derived is shown to be identical to the RPA ground state energy.
Higher-order symplectic Born-Oppenheimer molecular dynamics
Niklasson, Anders [Los Alamos National Laboratory; Bock, Nicolas [Los Alamos National Laboratory; Challacombe, Matt [Los Alamos National Laboratory; Odell, Anders [RIT; Delin, Anna [RIT; Johansson, Borje [RIT
2009-01-01
The extended Lagrangian formulation of time-reversible Born-Oppenheimer molecular dynamics (TR-BOMD) enables the use of geometric integrators in the propagation of both the nuclear and the electronic degrees of freedom on the Born-Oppenheimer potential energy surface. Different symplectic integrators up to the 6th order have been adapted and optimized to TR-BOMD in the framework of ab initio self-consistent-field theory. It is shown how the accuracy can be significantly improved compared to a conventional Verlet integration at the same level of computational cost, in particular for the case of very high accuracy requirements.
Analysis of the Time Reversible Born-Oppenheimer Molecular Dynamics
Lin, Lin; Shao, Sihong
2013-01-01
We analyze the time reversible Born-Oppenheimer molecular dynamics (TRBOMD) scheme, which preserves the time reversibility of the Born-Oppenheimer molecular dynamics even with non-convergent self-consistent field iteration. In the linear response regime, we derive the stability condition as well as the accuracy of TRBOMD for computing physical properties such as the phonon frequency obtained from the molecular dynamic simulation. We connect and compare TRBOMD with the Car-Parrinello molecular dynamics in terms of accuracy and stability. We further discuss the accuracy of TRBOMD beyond the linear response regime for non-equilibrium dynamics of nuclei. Our results are demonstrated through numerical experiments using a simplified one dimensional model for Kohn-Sham density functional theory.
Analysis of Time Reversible Born-Oppenheimer Molecular Dynamics
Lin Lin
2013-12-01
Full Text Available We analyze the time reversible Born-Oppenheimer molecular dynamics (TRBOMD scheme, which preserves the time reversibility of the Born-Oppenheimer molecular dynamics even with non-convergent self-consistent field iteration. In the linear response regime, we derive the stability condition, as well as the accuracy of TRBOMD for computing physical properties, such as the phonon frequency obtained from the molecular dynamics simulation. We connect and compare TRBOMD with Car-Parrinello molecular dynamics in terms of accuracy and stability. We further discuss the accuracy of TRBOMD beyond the linear response regime for non-equilibrium dynamics of nuclei. Our results are demonstrated through numerical experiments using a simplified one-dimensional model for Kohn-Sham density functional theory.
Darwin and mass-velocity relativistic corrections in non-Born-Oppenheimer variational calculations.
Kedziera, Dariusz; Stanke, Monika; Bubin, Sergiy; Barysz, Maria; Adamowicz, Ludwik
2006-08-28
The Pauli approach to account for the mass-velocity and Darwin relativistic corrections has been applied to the formalism for quantum mechanical molecular calculations that does not assume the Born-Oppenheimer (BO) approximation regarding separability of the electronic and nuclear motions in molecular systems. The corrections are determined using the first order perturbation theory and are derived for the non-BO wave function of a diatomic system expressed in terms of explicitly correlated Gaussian functions with premultipliers in the form of even powers of the internuclear distance. As a numerical example we used calculations of the transition energies for pure vibrational states of the HD(+) ion. PMID:16965008
Lowest vibrational states of 4He3He+: Non-Born-Oppenheimer calculations
Very accurate quantum mechanical calculations of the first five vibrational states of the 4He3He+ molecular ion are reported. The calculations have been performed explicitly including the coupling of the electronic and nuclear motions [i.e., without assuming the Born-Oppenheimer (BO) approximation]. The nonrelativistic non-BO wave functions were used to calculate the α2 relativistic mass velocity, Darwin, and spin-spin interaction corrections. For the lowest vibrational transition, whose experimental energy is established with high precision, the calculated and the experimental results differ by only 0.16 cm-1
Born-Oppenheimer description of two atoms in a combined oscillator and lattice trap
Sørensen, Ole Søe; Mølmer, Klaus
2012-01-01
We analyze the quantum states of two identical bosons in a combined harmonic oscillator and periodic lattice trap in one spatial dimension. In the case of tight-binding and only nearest-neighbor tunneling, the equations of motion are conveniently represented in the momentum representation. We sho...... that in the case of strong attraction between the particles, the different time scales of relative and center-of-mass motions validate a separation of the problem similar to the Born-Oppenheimer approximation applied in the description of electronic and nuclear motions in molecules....
Generalized extended Lagrangian Born-Oppenheimer molecular dynamics
Extended Lagrangian Born-Oppenheimer molecular dynamics based on Kohn-Sham density functional theory is generalized in the limit of vanishing self-consistent field optimization prior to the force evaluations. The equations of motion are derived directly from the extended Lagrangian under the condition of an adiabatic separation between the nuclear and the electronic degrees of freedom. We show how this separation is automatically fulfilled and system independent. The generalized equations of motion require only one diagonalization per time step and are applicable to a broader range of materials with improved accuracy and stability compared to previous formulations
Electric transition dipole moment in pre-Born-Oppenheimer molecular structure theory.
Simmen, Benjamin; Mátyus, Edit; Reiher, Markus
2014-10-21
This paper presents the calculation of the electric transition dipole moment in a pre-Born-Oppenheimer framework. Electrons and nuclei are treated equally in terms of the parametrization of the non-relativistic total wave function, which is written as a linear combination of basis functions constructed from explicitly correlated Gaussian functions and the global vector representation. The integrals of the electric transition dipole moment are derived corresponding to these basis functions in both the length and the velocity representation. The calculations are performed in laboratory-fixed Cartesian coordinates without relying on coordinates which separate the center of mass from the translationally invariant degrees of freedom. The effect of the overall motion is eliminated through translationally invariant integral expressions. The electric transition dipole moment is calculated between two rovibronic levels of the H2 molecule assignable to the lowest rovibrational states of the X (1)Σ(g)(+) and B (1)Σ(u)(+) electronic states in the clamped-nuclei framework. This is the first evaluation of this quantity in a full quantum mechanical treatment without relying on the Born-Oppenheimer approximation. PMID:25338879
Adjustment of Born-Oppenheimer electronic wave functions to simplify close coupling calculations.
Buenker, Robert J; Liebermann, Heinz-Peter; Zhang, Yu; Wu, Yong; Yan, Lingling; Liu, Chunhua; Qu, Yizhi; Wang, Jianguo
2013-04-30
Technical problems connected with use of the Born-Oppenheimer clamped-nuclei approximation to generate electronic wave functions, potential energy surfaces (PES), and associated properties are discussed. A computational procedure for adjusting the phases of the wave functions, as well as their order when potential crossings occur, is presented which is based on the calculation of overlaps between sets of molecular orbitals and configuration interaction eigenfunctions obtained at neighboring nuclear conformations. This approach has significant advantages for theoretical treatments describing atomic collisions and photo-dissociation processes by means of ab initio PES, electronic transition moments, and nonadiabatic radial and rotational coupling matrix elements. It ensures that the electronic wave functions are continuous over the entire range of nuclear conformations considered, thereby greatly simplifying the process of obtaining the above quantities from the results of single-point Born-Oppenheimer calculations. The overlap results are also used to define a diabatic transformation of the wave functions obtained for conical intersections that greatly simplifies the computation of off-diagonal matrix elements by eliminating the need for complex phase factors. PMID:23345171
Stanke, Monika; Kedziera, Dariusz; Bubin, Sergiy; Adamowicz, Ludwik
2007-05-21
In this work the authors present an approach to calculate the leading-order relativistic corrections for ground and excited states of helium isotopomers. In the calculations they used variational wave functions expanded in terms of explicitly correlated Gaussians obtained without assuming the Born-Oppenheimer approximation. PMID:17523809
Falke, Stephan; Friebe, Jan; Riedmann, Matthias; Tiemann, Eberhard; Lisdat, Christian
2008-01-01
We present precision measurements with MHz uncertainty of the energy gap between asymptotic and well bound levels in the electronic ground state X $^1\\Sigma_{\\mathrm{g}}^+$ of the $^{39}$K$_2$ molecule. The molecules are prepared in a highly collimated particle beam and are interrogated in a $\\Lambda$-type excitation scheme of optical transitions to long range levels close to the asymptote of the ground state, using the electronically excited state A $^1\\Sigma^+_{\\rm u}$ as intermediate one. The transition frequencies are measured either by comparison with I$_2$ lines or by absolute measurements using a fs-frequency comb. The determined level energies were used together with Feshbach resonances from cold collisions of $^{39}$K and $^{40}$K reported from other authors to fit new ground state potentials. Precise scattering lengths are determined and tests of the validity of the Born-Oppenheimer approximation for the description of cold collisions at this level of precision are performed.
Stanke, Monika; Adamowicz, Ludwik
2014-10-21
We report very accurate calculations of the complete pure vibrational spectrum of the T2 molecule with an approach where the Born-Oppenheimer (BO) approximation is not assumed. As the considered states correspond to the zero total angular momentum, their non-BO wave functions are spherically symmetric and are expanded in terms of all-particle, one-center, spherically symmetric explicitly correlated Gaussian functions multiplied by even nonnegative powers of the internuclear distance. The nonrelativistic energies of the states obtained in the non-BO calculations are corrected for the relativistic effects of the order of α(2) (where α is the fine structure constant) calculated as expectation values of the operators representing these effects. PMID:25338891
Born--Oppenheimer decomposition for quantum fields on quantum spacetimes
Giesel, Kristina; Thiemann, Thomas
2009-01-01
Quantum Field Theory on Curved Spacetime (QFT on CS) is a well established theoretical framework which intuitively should be a an extremely effective description of the quantum nature of matter when propagating on a given background spacetime. If one wants to take care of backreaction effects, then a theory of quantum gravity is needed. It is now widely believed that such a theory should be formulated in a non-perturbative and therefore background independent fashion. Hence, it is a priori a puzzle how a background dependent QFT on CS should emerge as a semiclassical limit out of a background independent quantum gravity theory. In this article we point out that the Born-Oppenheimer decomposition (BOD) of the Hilbert space is ideally suited in order to establish such a link, provided that the Hilbert space representation of the gravitational field algebra satisfies an important condition. If the condition is satisfied, then the framework of QFT on CS can be, in a certain sense, embedded into a theory of quantu...
Complete α2 relativistic corrections to the pure vibrational non-Born-Oppenheimer energies of HeH+
We report the implementation of the complete set of the lowest-order relativistic corrections of the order of α2 (where α is the fine structure constant) for calculating vibrational states of diatomic molecular systems within the framework that does not assume the Born-Oppenheimer approximation. To test the accuracy of the approach we have performed calculations for all rotationless vibrational states (also called pure vibrational states or S states) of the HeH+ ion in the ground electronic state. For the lowest transitions, where very precise experimental results are available, an excellent agreement with the experimental values has been achieved
Non-Born-Oppenheimer self-consistent field calculations with cubic scaling
Moncada, Felix, E-mail: areyesv@unal.edu.co [Departamento de Quimica, Universidad Nacional de Colombia, Av. Cra. 30 45-03, Bogota (Colombia); Posada, Edwin [Departamento de Quimica, Universidad Nacional de Colombia, Av. Cra. 30 45-03, Bogota (Colombia); Flores-Moreno, Roberto [Departamento de Quimica, Universidad de Guadalajara, Blvd. Marcelino Garcia Barragan 1421, Guadalajara Jal., C.P. 44430 (Mexico); Reyes, Andres [Departamento de Quimica, Universidad Nacional de Colombia, Av. Cra. 30 45-03, Bogota (Colombia)
2012-05-25
Highlights: Black-Right-Pointing-Pointer It is possible to perform cubic-scaling Non-Born-Oppenheimer calculations. Black-Right-Pointing-Pointer The errors introduced by the approximations used in this methodology are small. Black-Right-Pointing-Pointer This method makes possible calculations of molecules with more than a hundred atoms. - Abstract: An efficient nuclear molecular orbital methodology is presented. This approach combines an auxiliary density functional theory for electrons (ADFT) and a localized Hartree product (LHP) representation for the nuclear wave function. A series of test calculations conducted on small molecules exposed that energy and geometry errors introduced by the use of ADFT and LHP approximations are small and comparable to those obtained by the use of electronic ADFT. In addition, sample calculations performed on (HF){sub n} chains disclosed that the combined ADFT/LHP approach scales cubically with system size (n) as opposed to the quartic scaling of Hartree-Fock/LHP or DFT/LHP methods. Even for medium size molecules the improved scaling of the ADFT/LHP approach resulted in speedups of at least 5x with respect to Hartree-Fock/LHP calculations. The ADFT/LHP method opens up the possibility of studying nuclear quantum effects on large size systems that otherwise would be impractical.
Wave function continuity and the diagonal Born-Oppenheimer correction at conical intersections
Meek, Garrett A.; Levine, Benjamin G.
2016-05-01
We demonstrate that though exact in principle, the expansion of the total molecular wave function as a sum over adiabatic Born-Oppenheimer (BO) vibronic states makes inclusion of the second-derivative nonadiabatic energy term near conical intersections practically problematic. In order to construct a well-behaved molecular wave function that has density at a conical intersection, the individual BO vibronic states in the summation must be discontinuous. When the second-derivative nonadiabatic terms are added to the Hamiltonian, singularities in the diagonal BO corrections (DBOCs) of the individual BO states arise from these discontinuities. In contrast to the well-known singularities in the first-derivative couplings at conical intersections, these singularities are non-integrable, resulting in undefined DBOC matrix elements. Though these singularities suggest that the exact molecular wave function may not have density at the conical intersection point, there is no physical basis for this constraint. Instead, the singularities are artifacts of the chosen basis of discontinuous functions. We also demonstrate that continuity of the total molecular wave function does not require continuity of the individual adiabatic nuclear wave functions. We classify nonadiabatic molecular dynamics methods according to the constraints placed on wave function continuity and analyze their formal properties. Based on our analysis, it is recommended that the DBOC be neglected when employing mixed quantum-classical methods and certain approximate quantum dynamical methods in the adiabatic representation.
Wave function continuity and the diagonal Born-Oppenheimer correction at conical intersections.
Meek, Garrett A; Levine, Benjamin G
2016-05-14
We demonstrate that though exact in principle, the expansion of the total molecular wave function as a sum over adiabatic Born-Oppenheimer (BO) vibronic states makes inclusion of the second-derivative nonadiabatic energy term near conical intersections practically problematic. In order to construct a well-behaved molecular wave function that has density at a conical intersection, the individual BO vibronic states in the summation must be discontinuous. When the second-derivative nonadiabatic terms are added to the Hamiltonian, singularities in the diagonal BO corrections (DBOCs) of the individual BO states arise from these discontinuities. In contrast to the well-known singularities in the first-derivative couplings at conical intersections, these singularities are non-integrable, resulting in undefined DBOC matrix elements. Though these singularities suggest that the exact molecular wave function may not have density at the conical intersection point, there is no physical basis for this constraint. Instead, the singularities are artifacts of the chosen basis of discontinuous functions. We also demonstrate that continuity of the total molecular wave function does not require continuity of the individual adiabatic nuclear wave functions. We classify nonadiabatic molecular dynamics methods according to the constraints placed on wave function continuity and analyze their formal properties. Based on our analysis, it is recommended that the DBOC be neglected when employing mixed quantum-classical methods and certain approximate quantum dynamical methods in the adiabatic representation. PMID:27179473
Bubin, Sergiy; Stanke, Monika; Adamowicz, Ludwik
2011-08-21
In this work we report very accurate variational calculations of the complete pure vibrational spectrum of the D(2) molecule performed within the framework where the Born-Oppenheimer (BO) approximation is not assumed. After the elimination of the center-of-mass motion, D(2) becomes a three-particle problem in this framework. As the considered states correspond to the zero total angular momentum, their wave functions are expanded in terms of all-particle, one-center, spherically symmetric explicitly correlated Gaussian functions multiplied by even non-negative powers of the internuclear distance. The nonrelativistic energies of the states obtained in the non-BO calculations are corrected for the relativistic effects of the order of α(2) (where α = 1/c is the fine structure constant) calculated as expectation values of the operators representing these effects. PMID:21861559
Kedziera, Dariusz; Stanke, Monika; Bubin, Sergiy; Barysz, Maria; Adamowicz, Ludwik
2006-07-01
The Darwin and mass-velocity relativistic corrections have been calculated for all pure vibrational states of the H2 using the perturbation theory and very accurate variational wave functions obtained without assuming the Born-Oppenheimer (BO) approximation. Expansions in terms of explicitly correlated Gaussians with premultipliers in the form of even powers of the internuclear distance were used for the wave functions. With the inclusion of the two relativistic corrections to the non-BO energies the transition energies for the highest states agree more with the experimental results. PMID:16863309
Monte Carlo calculation of the Born-Oppenheimer potential between two helium atoms
Fully correlated Hylleraas-type electronic wave functions and a biased-selection Monte Carlo method have been used to find a rigorous upper bound to the Born-Oppenheimer potential between two helium atoms. The potential agrees with the experimental results of Burgmans, Farrar, and Lee (BFL) to within 1.4 Monte Carlo standard deviations for all nuclear separation distances calculated (4.5--15.0a/sub B/). At the potential minimum of 5.6a/sub B/ this bound (-7.10 +- 0.30 Ry) is slightly below the BFL value of -6.70 Ry
Monte Carlo calculation of the Born-Oppenheimer potential between two helium atoms
Lowther, R.E.; Coldwell, R.L.
1980-07-01
Fully correlated Hylleraas-type electronic wave functions and a biased-selection Monte Carlo method have been used to find a rigorous upper bound to the Born-Oppenheimer potential between two helium atoms. The potential agrees with the experimental results of Burgmans, Farrar, and Lee (BFL) to within 1.4 Monte Carlo standard deviations for all nuclear separation distances calculated (4.5--15.0a/sub B/). At the potential minimum of 5.6a/sub B/ this bound (-7.10 +- 0.30 Ry) is slightly below the BFL value of -6.70 Ry.
Imafuku, Yuji; Abe, Minori; Schmidt, Michael W; Hada, Masahiko
2016-04-01
Methodologies beyond the Born-Oppenheimer (BO) approximation are nowadays important to explain high precision spectroscopic measurements. Most previous evaluations of the BO correction are, however, focused on light-element molecules and based on a nonrelativistic Hamiltonian, so no information about the BO approximation (BOA) breakdown in heavy-element molecules is available. The present work is the first to investigate the BOA breakdown for the entire periodic table, by considering scalar relativistic effects in the Diagonal BO correction (DBOC). In closed shell atoms, the relativistic EDBOC scales as Z(1.25) and the nonrelativistic EDBOC scales as Z(1.17), where Z is the atomic number. Hence, we found that EDBOC becomes larger in heavy element atoms and molecules, and the relativistic EDBOC increases faster than nonrelativistic EDBOC. We have further investigated the DBOC effects on properties such as potential energy curves, spectroscopic parameters, and various energetic properties. The DBOC effects for these properties are mostly affected by the lightest atom in the molecule. Hence, in X2 or XAt molecule (X = H, Li, Na, K, Rb, and Cs) the effect of DBOC systematically decreases when X becomes heavier but in HX molecules, the effect of DBOC seems relatively similar among all the molecules. PMID:27003510
Mielke, Steven L; Schwenke, David W; Schatz, George C; Garrett, Bruce C; Peterson, Kirk A
2009-04-23
Multireference configuration interaction (MRCI) calculations of the Born-Oppenheimer diagonal correction (BODC) for H(3) were performed at 1397 symmetry-unique configurations using the Handy-Yamaguchi-Schaefer approach; isotopic substitution leads to 4041 symmetry-unique configurations for the DH(2) mass combination. These results were then fit to a functional form that permits calculation of the BODC for any combination of isotopes. Mean unsigned fitting errors on a test grid of configurations not included in the fitting process were 0.14, 0.12, and 0.65 cm(-1) for the H(3), DH(2), and MuH(2) isotopomers, respectively. This representation can be combined with any Born-Oppenheimer potential energy surface (PES) to yield Born-Huang (BH) PESs; herein, we choose the CCI potential energy surface, the uncertainties of which ( approximately 0.01 kcal/mol) are much smaller than the magnitude of the BODC. Fortran routines to evaluate these BH surfaces are provided. Variational transition state theory calculations are presented comparing thermal rate constants for reactions on the BO and BH surfaces to provide an initial estimate of the significance of the diagonal correction for the dynamics. PMID:19290604
On the inclusion of the diagonal Born-Oppenheimer correction in surface hopping methods
Gherib, Rami; Ryabinkin, Ilya G; Izmaylov, Artur F
2016-01-01
The diagonal Born-Oppenheimer correction (DBOC) stems from the diagonal second derivative coupling term in the adiabatic representation, and it can have an arbitrary large magnitude when a gap between neighbouring Born-Oppenheimer (BO) potential energy surfaces (PESs) is closing. Nevertheless, DBOC is typically neglected in mixed quantum-classical methods of simulating nonadiabatic dynamics (e.g., fewest-switch surface hopping (FSSH) method). A straightforward addition of DBOC to BO PESs in the FSSH method, FSSH+D, has been shown to lead to numerically much inferior results for models containing conical intersections. More sophisticated variation of the DBOC inclusion, phase-space surface-hopping (PSSH) was more successful than FSSH+D but on model problems without conical intersections. This work comprehensively assesses the role of DBOC in nonadiabatic dynamics of two electronic state problems and the performance of FSSH, FSSH+D, and PSSH methods in variety of one- and two-dimensional models. Our results sho...
Deviations from Born-Oppenheimer mass scaling in spectroscopy and ultracold molecular physics
Lutz, Jesse J
2016-01-01
We investigate Born-Oppenheimer breakdown (BOB) effects (beyond the usual mass scaling) for the electronic ground states of a series of homonuclear and heteronuclear alkali-metal diatoms, together with the Sr$_2$ and Yb$_2$ diatomics. Several widely available electronic structure software packages are used to calculate the leading contributions to the total isotope shift for commonly occurring isotopologs of each species. Computed quantities include diagonal Born-Oppenheimer corrections (mass shifts) and isotopic field shifts. Mass shifts dominate for light nuclei up to and including K, but field shifts contribute significantly for Rb and Sr and are dominant for Yb. We compare the {\\em ab initio} mass-shift functions for Li$_2$, LiK and LiRb with spectroscopically derived ground-state BOB functions from the literature. We find good agreement in the values of the functions for LiK and LiRb at their equilibrium geometries, but significant disagreement with the shapes of the functions for all 3 systems. The diff...
Orbit-orbit relativistic corrections to the pure vibrational non-Born-Oppenheimer energies of H(2).
Stanke, Monika; Kedziera, Dariusz; Bubin, Sergiy; Molski, Marcin; Adamowicz, Ludwik
2008-03-21
We report the derivation of the orbit-orbit relativistic correction for calculating pure vibrational states of diatomic molecular systems with sigma electrons within the framework that does not assume the Born-Oppenheimer (BO) approximation. The correction is calculated as the expectation value of the orbit-orbit interaction operator with the non-BO wave function expressed in terms of explicitly correlated Gaussian functions multiplied by even powers of the internuclear distance. With that we can now calculate the complete relativistic correction of the order of alpha(2) (where alpha=1/c). The new algorithm is applied to determine the full set of the rotationless vibrational levels and the corresponding transition frequencies of the H(2) molecule. The results are compared with the previous calculations, as well as with the frequencies obtained from the experimental spectra. The comparison shows the need to include corrections higher than second order in alpha to further improve the agreement between the theory and the experiment. PMID:18361577
Dynamics of electronic motion when the nuclei are clamped is discussed and shown to be always described as a superposition of adiabatic electronic states. These states are stationary when the nuclei are clamped but their superposition leads to multiply periodic motion where the natural frequencies are the differences in the energies of the adiabatic electronic states. When one or more of the frequencies are low and the atoms are allowed to move, the electronic rearrangement is commensurate with the motion of the nuclei. This is the usual breakdown of the Born-Oppenheimer approximation. But when the electronic frequencies are higher there is an electronic motion before the nuclei move. The motion can be demonstrated through expectation values such as the multipole moments of the charge distribution. Such superposition states will be excited when the laser pulse width in energy exceeds the spacings of the states. For low-lying valence excited or low Rydberg states this requires a femtosecond or shorter laser pulse. Since the carrier frequency has to be comparable to the excitation energy, the required laser pulses must span only a few cycles.
Elimination of the Translational Kinetic Energy Contamination in pre-Born-Oppenheimer Calculations
Simmen, Benjamin; Reiher, Markus
2012-01-01
In this paper we present a simple strategy for the elimination of the translational kinetic energy contamination of the total energy in pre-Born--Oppenheimer calculations carried out in laboratory-fixed Cartesian coordinates (LFCCs). The simple expressions for the coordinates and the operators are thus preserved throughout the calculations, while the mathematical form and the parametrisation of the basis functions are chosen so that the translational and rotational invariances are respected. The basis functions are constructed using explicitly correlated Gaussian functions (ECGs) and the global vector representation. First, we observe that it is not possible to parametrise the ECGs so that the system is at rest in LFCCs and at the same time the basis functions are square-integrable with a non-vanishing norm. Then, we work out a practical strategy to circumvent this problem by making use of the properties of the linear transformation between the LFCCs and translationally invariant and center-of-mass Cartesian ...
Electric Transition Dipole Moment in pre-Born-Oppenheimer Molecular Structure Theory
Simmen, Benjamin; Reiher, Markus
2014-01-01
This paper presents the calculation of the electric transition dipole moment in a pre-Born-Oppenheimer framework. Electrons and nuclei are treated equally in terms of the parametrization of the non-relativistic total wave function, which is written as a linear combination of basis functions constructed with explicitly correlated Gaussian functions and the global vector representation. The integrals of the electric transition dipole moment are derived corresponding to these basis functions in both the length and the velocity representation. The complete derivation and the calculations are performed in laboratory-fixed Cartesian coordinates without relying on coordinates which separate the center of mass from the translationally invariant degrees of freedom. The effect of the overall motion is eliminated via translationally invariant integral expressions. As a numerical example the electric transition dipole moment is calculated between two rovibronic levels of the H2 molecule assignable to the lowest rovibrati...
Fang, Jun; Song, Haifeng; Wang, Han
2016-01-01
Wavefunction extrapolation greatly reduces the number of self-consistent field (SCF) iterations and thus the overall computational cost of Born-Oppenheimer molecular dynamics (BOMD) that is based on the Kohn-Sham density functional theory. Going against the intuition that the higher order of extrapolation possesses a better accuracy, we demonstrate, from both theoretical and numerical perspectives, that the extrapolation accuracy firstly increases and then decreases with respect to the order, and an optimal extrapolation order in terms of minimal number of SCF iterations always exists. We also prove that the optimal order tends to be larger when using larger MD time steps or more strict SCF convergence criteria. By example BOMD simulations of a solid copper system, we show that the optimal extrapolation order covers a broad range when varying the MD time step or the SCF convergence criterion. Therefore, we suggest the necessity for BOMD simulation packages to open the user interface and to provide more choice...
The initial chemical events that occur during the shock compression of liquid phenylacetylene have been investigated using self-consistent tight binding molecular dynamics simulations. The extended Lagrangian Born-Oppenheimer molecular dynamics formalism enabled us to compute microcanonical trajectories with precise conservation of the total energy. Our simulations revealed that the first density-increasing step under shock compression arises from the polymerization of phenylacetylene molecules at the acetylene moiety. The application of electronic structure-based molecular dynamics with long-term conservation of the total energy enabled us to identify electronic signatures of reactivity via monitoring changes in the HOMO-LUMO gap, and to capture directly adiabatic shock heating, transient non-equilibrium states, and changes in temperature arising from exothermic chemistry in classical molecular dynamics trajectories
Diagonalization of multicomponent wave equations with a Born-Oppenheimer example
Weigert, S.; Littlejohn, R.G. (Department of Physics and Lawrence Berkeley Laboratory, University of California, Berkeley, California 94720 (United States))
1993-05-01
A general method to decouple multicomponent linear wave equations is presented. First, the Weyl calculus is used to transform operator relations into relations between [ital c]-number valued matrices. Then it is shown that the symbol representing the wave operator can be diagonalized systematically up to arbitrary order in an appropriate expansion parameter. After transforming the symbols back to operators, the original problem is reduced to solving a set of linear uncoupled [ital scalar] wave equations. The procedure is exemplified for a particle with a Born-Oppenheimer-type Hamiltonian valid through second order in [h bar]. The resulting effective scalar Hamiltonians are seen to contain an additional velocity-dependent potential. This contribution has not been reported in recent studies investigating the adiabatic motion of a neutral particle moving in an inhomogeneous magnetic field. Finally, the relation of the general method to standard quantum-mechanical perturbation theory is discussed.
On the inclusion of the diagonal Born-Oppenheimer correction in surface hopping methods
Gherib, Rami; Ye, Liyuan; Ryabinkin, Ilya G.; Izmaylov, Artur F.
2016-04-01
The diagonal Born-Oppenheimer correction (DBOC) stems from the diagonal second derivative coupling term in the adiabatic representation, and it can have an arbitrary large magnitude when a gap between neighbouring Born-Oppenheimer (BO) potential energy surfaces (PESs) is closing. Nevertheless, DBOC is typically neglected in mixed quantum-classical methods of simulating nonadiabatic dynamics (e.g., fewest-switch surface hopping (FSSH) method). A straightforward addition of DBOC to BO PESs in the FSSH method, FSSH+D, has been shown to lead to numerically much inferior results for models containing conical intersections. More sophisticated variation of the DBOC inclusion, phase-space surface-hopping (PSSH) was more successful than FSSH+D but on model problems without conical intersections. This work comprehensively assesses the role of DBOC in nonadiabatic dynamics of two electronic state problems and the performance of FSSH, FSSH+D, and PSSH methods in variety of one- and two-dimensional models. Our results show that the inclusion of DBOC can enhance the accuracy of surface hopping simulations when two conditions are simultaneously satisfied: (1) nuclei have kinetic energy lower than DBOC and (2) PESs are not strongly nonadiabatically coupled. The inclusion of DBOC is detrimental in situations where its energy scale becomes very high or even diverges, because in these regions PESs are also very strongly coupled. In this case, the true quantum formalism heavily relies on an interplay between diagonal and off-diagonal nonadiabatic couplings while surface hopping approaches treat diagonal terms as PESs and off-diagonal ones stochastically.
Topological and AIM analyses beyond the Born-Oppenheimer paradigm: New opportunities
Goli, Mohammad
2014-01-01
The multi-component quantum theory of atoms in molecules (MC-QTAIM) analysis is done on methane, ethylene, acetylene and benzene as selected basic hydrocarbons. This is the first report on applying the MC-QTAIM analysis on polyatomic species. In order to perform the MC-QTAIM analysis, at first step the nuclear-electronic orbital method at Hartree-Fock level (NEO-HF) is used as a non-Born-Oppenheimer (nBO) ab initio computational procedure assuming both electrons and protons as quantum waves while carbon nuclei as point charges in these systems. The ab initio calculations proceed substituting all the protons of each species first with deuterons and then tritons. At the next step, the derived nBO wavefunctions are used for the "atoms in molecules" (AIM) analysis. The results of topological analysis and integration of atomic properties demonstrate that the MC-QTAIM is capable of deciphering the underlying AIM structure of all the considered species. Also, the results of the analysis for each isotopic composition...
Fang, Jun; Gao, Xingyu; Song, Haifeng; Wang, Han
2016-06-01
Wavefunction extrapolation greatly reduces the number of self-consistent field (SCF) iterations and thus the overall computational cost of Born-Oppenheimer molecular dynamics (BOMD) that is based on the Kohn-Sham density functional theory. Going against the intuition that the higher order of extrapolation possesses a better accuracy, we demonstrate, from both theoretical and numerical perspectives, that the extrapolation accuracy firstly increases and then decreases with respect to the order, and an optimal extrapolation order in terms of minimal number of SCF iterations always exists. We also prove that the optimal order tends to be larger when using larger MD time steps or more strict SCF convergence criteria. By example BOMD simulations of a solid copper system, we show that the optimal extrapolation order covers a broad range when varying the MD time step or the SCF convergence criterion. Therefore, we suggest the necessity for BOMD simulation packages to open the user interface and to provide more choices on the extrapolation order. Another factor that may influence the extrapolation accuracy is the alignment scheme that eliminates the discontinuity in the wavefunctions with respect to the atomic or cell variables. We prove the equivalence between the two existing schemes, thus the implementation of either of them does not lead to essential difference in the extrapolation accuracy.
Mniszewski, S M; Cawkwell, M J; Wall, M E; Mohd-Yusof, J; Bock, N; Germann, T C; Niklasson, A M N
2015-10-13
We present an algorithm for the calculation of the density matrix that for insulators scales linearly with system size and parallelizes efficiently on multicore, shared memory platforms with small and controllable numerical errors. The algorithm is based on an implementation of the second-order spectral projection (SP2) algorithm [ Niklasson, A. M. N. Phys. Rev. B 2002 , 66 , 155115 ] in sparse matrix algebra with the ELLPACK-R data format. We illustrate the performance of the algorithm within self-consistent tight binding theory by total energy calculations of gas phase poly(ethylene) molecules and periodic liquid water systems containing up to 15,000 atoms on up to 16 CPU cores. We consider algorithm-specific performance aspects, such as local vs nonlocal memory access and the degree of matrix sparsity. Comparisons to sparse matrix algebra implementations using off-the-shelf libraries on multicore CPUs, graphics processing units (GPUs), and the Intel many integrated core (MIC) architecture are also presented. The accuracy and stability of the algorithm are illustrated with long duration Born-Oppenheimer molecular dynamics simulations of 1000 water molecules and a 303 atom Trp cage protein solvated by 2682 water molecules. PMID:26574255
A Priori Estimation of the Resolvent on Approximation of Born-Oppenheimer
Sabria B. Mentri
2007-01-01
Full Text Available In this study, we estimate the resolvent of the two bodies Shrodinger operator perturbed by a potential of Coulombian type on Hilbert space when h tends to zero. Using the Feschbach method, we first distorted it and then reduced it to a diagonal matrix. We considered a case where two energy levels cross in the classical forbidden region. Under the assumption that the second energy level admits a non degenerate point well and virial conditions on the others levels, a good estimate of the resolvent were observed.
Souvatzis, Petros; Niklasson, Anders M. N.
2013-01-01
We present an efficient general approach to first principles molecular dynamics simulations based on extended Lagrangian Born-Oppenheimer molecular dynamics in the limit of vanishing self-consistent field optimization. The reduction of the optimization requirement reduces the computational cost to a minimum, but without causing any significant loss of accuracy or longterm energy drift. The optimization-free first principles molecular dynamics requires only one single diagonalization per time ...
Exact non-Born-Oppenheimer wave functions for three-particle Hookean systems with arbitrary masses
A Hookean model of a three-body problem for particles with arbitrary masses and charges where two of them interact with each other through a Coulomb potential and with the third through a harmonic potential is presented. It is shown that a condition relating the masses to the harmonic coupling constants must be satisfied in order to render this problem separable. A general exact analytic solution written in terms of the relative interparticle coordinates is given as well as general expressions for the total and binding energies of this three-body system. We apply these results to examine electronic, muonic, antiprotonic, and pionic families of non-Born-Oppenheimer Hookean systems. The first contains the atoms or atomic ions: Ps-(e+e-e-), H-(p+e-e-), D-(d+e-e-), T-(p+e-e-), 4He(he+2e-e-), and the following molecular ions: Ps2+(e-e+e+), H2+(e-p+p+), HD+(e-d+p+), HT+(e-t+p+), DT+(e-d+t+), D2+(e-d+d+), T2+(e-t+t+). The muonic and antiprotonic families are similar to the electronic ones except that the species are formed replacing e- by μ- or p-. The pionic family comprises exotic atoms containing at least one pion. We also apply these results to two-electron three-dimensional spherical quantum dots and for these systems we examine the effect of electronic correlation, particularly on the singlet-triplet transitions and on the collective motion of the electrons and center of mass leading to ''floppy''dynamics
Sharkey, Keeper L.; Adamowicz Team
2014-03-01
The development of highly accurate theoretical quantum mechanics models for atomic and molecular calculations is crucial for the verification of the results of high-resolution experimental spectroscopy. High accuracy in the calculations can be achieved by not assuming the Born-Oppenheimer approximation (non-BO) and by using the variational principle. The non-relativistic Hamiltonian describing the internal state of the considered system used in the approach is obtained by separating out the center-of-mass motion from the laboratory frame Hamiltonian. The wave functions used in the calculations are expanded in terms of explicitly correlated Gaussian (ECG) functions. The optimization of the Gaussian non-linear parameters is aided by the analytical energy gradient determined with respect to these parameters. Examples of some very accurate calculations of small atoms and diatomic molecules will be presented. The presentation will also include a discussion of the extension of the approach to perform non-BO calculations of bound states of small triatomic molecules (e.g. H 3 +). Acknowledgements go to Ludwik Adamowicz for guidance and NSF for funding (DGE1-1143953).
Kain, J S
2001-01-01
The infrared spectrum of water is possibly one of the most well studied and yet portions of it are still poorly understood. Recently, significant advances have been made in assigning water spectra using variational nuclear calculations. The major factor determining the accuracy of ro-vibrational spectra of water is the accuracy of the underlying Potential Energy Surface. Even the most accurate ab initio Potential Energy Surface does not reproduce the Born-Oppenheimer surface to sufficient accuracy for spectroscopic studies. Furthermore, effects beyond this model such as the adiabatic correction, the relativistic correction and the non-adiabatic correction have to be considered. This thesis includes a discussion on how the relativistic correction was calculated, for the water molecule, from first-order perturbation theory. The relativistic correction improved vibrational stretching motion while making the prediction of the bending modes far worse. For rotational motion the relativistic effect had an increasing...
Born Oppenheimer Molecular Dynamics calculation of the νO-H IR spectra for acetic acid cyclic dimers
Both ab initio molecular dynamics simulations based on the Born-Oppenheimer approach calculations and a quantum theoretical model are used in order to study the IR spectrum of the acetic acid dimer in the gas phase. The theoretical model is taking into account the strong anharmonic coupling, Davydov coupling, multiple Fermi resonances between the first harmonics of some bending modes and the first excited state of the symmetric combination of the two vO-H modes and the quantum direct and indirect relaxation. The IR spectra obtained from DFT-based molecular dynamics is compared with our theoretical lineshape and with experiment. Note that in a previous work we have shown that our approach reproduces satisfactorily the main futures of the IR experimental lineshapes of the acetic acid dimer [Mohamed el Amine Benmalti, Paul Blaise, H. T. Flakus, Olivier Henri-Rousseau, Chem Phys, 320(2006) 267-274.
Reimers, Jeffrey R; McKemmish, Laura K; McKenzie, Ross H; Hush, Noel S
2015-10-14
Using a simple model Hamiltonian, the three correction terms for Born-Oppenheimer (BO) breakdown, the adiabatic diagonal correction (DC), the first-derivative momentum non-adiabatic correction (FD), and the second-derivative kinetic-energy non-adiabatic correction (SD), are shown to all contribute to thermodynamic and spectroscopic properties as well as to thermal non-diabatic chemical reaction rates. While DC often accounts for >80% of thermodynamic and spectroscopic property changes, the commonly used practice of including only the FD correction in kinetics calculations is rarely found to be adequate. For electron-transfer reactions not in the inverted region, the common physical picture that diabatic processes occur because of surface hopping at the transition state is proven inadequate as the DC acts first to block access, increasing the transition state energy by (ℏω)(2)λ/16J(2) (where λ is the reorganization energy, J the electronic coupling and ω the vibration frequency). However, the rate constant in the weakly-coupled Golden-Rule limit is identified as being only inversely proportional to this change rather than exponentially damped, owing to the effects of tunneling and surface hopping. Such weakly-coupled long-range electron-transfer processes should therefore not be described as "non-adiabatic" processes as they are easily described by Born-Huang ground-state adiabatic surfaces made by adding the DC to the BO surfaces; instead, they should be called just "non-Born-Oppenheimer" processes. The model system studied consists of two diabatic harmonic potential-energy surfaces coupled linearly through a single vibration, the "two-site Holstein model". Analytical expressions are derived for the BO breakdown terms, and the model is solved over a large parameter space focusing on both the lowest-energy spectroscopic transitions and the quantum dynamics of coherent-state wavepackets. BO breakdown is investigated pertinent to: ammonia inversion, aromaticity
Mielke, Steven L.; Schwenke, David W.; Peterson, Kirk A.
2005-06-01
We present a detailed ab initio study of the effect that the Born-Oppenheimer diagonal correction (BODC) has on the saddle-point properties of the H3 system and its isotopomers. Benchmark values are presented that are estimated to be within 0.1cm-1 of the complete configuration-interaction limit. We consider the basis set and correlation treatment requirements for accurate BODC calculations, and both are observed to be more favorable than for the Born-Oppenheimer energies. The BODC raises the H+H2 barrier height by 0.1532kcal/mol and slightly narrows the barrier—with the imaginary frequency increasing by ˜2%.
Mielke, Steven L; Schwenke, David; Schatz, George C; Garrett, Bruce C; Peterson, Kirk A
2009-04-23
Multireference configuration interaction (MRCI) calculations of the Born-Oppenheimer diagonal correction (BODC) for H_{3} were performed at 1397 symmetry-unique configurations using the Born-Handy approach; isotopic substitution leads to 4041 symmetry-unique configurations for the DH_{2} mass combination. These results were then fit to a functional form that permits calculation of the BODC for any combination of isotopes. Mean unsigned fitting errors on a test grid of configurations not included in the fitting process were 0.14, 0.12, and 0.65 cm^{-1} for the H_{3}, DH_{2}, and MuH_{2} isotopomers, respectively. This representation can be combined with any Born-Oppenheimer potential energy surface (PES) to yield Born-Huang (BH) PESs; herein we choose the CCI potential energy surface, the uncertainties of which (~0.01 kcal/mol) are much smaller than the magnitude of the BODC. FORTRAN routines to evaluate these BH surfaces are provided. Variational transition state theory calculations are presented comparing thermal rate constants for reactions on the BO and BH surfaces to provide an initial estimate of the significance of the diagonal correction for the dynamics.
Ludena, E. V. [Centro de Quimica, Instituto Venezolano de Investigaciones Cientificas, IVIC, Apartado 21827, Caracas 1020-A (Venezuela, Bolivarian Republic of); Echevarria, L. [Departamento de Quimica, Universidad Simon Bolivar, USB, Sartenejas, Caracas (Venezuela, Bolivarian Republic of); Lopez, X.; Ugalde, J. M. [Kimika Fakultatea, Euskal Herriko Unibertsitatea, Posta Kutxa 1072, 20080 Donostia, Euskadi (Spain)
2012-02-28
We consider the calculation of non-Born-Oppenheimer, nBO, one-particle densities for both electrons and nuclei. We show that the nBO one-particle densities evaluated in terms of translationally invariant coordinates are independent of the wavefunction describing the motion of center of mass of the whole system. We show that they depend, however, on an arbitrary reference point from which the positions of the vectors labeling the particles are determined. We examine the effect that this arbitrary choice has on the topology of the one-particle density by selecting the Hooke-Calogero model of a three-body system for which expressions for the one-particle densities can be readily obtained in analytic form. We extend this analysis to the one-particle densities obtained from full Coulomb interaction wavefunctions for three-body systems. We conclude, in view of the fact that there is a close link between the choice of the reference point and the topology of one-particle densities that the molecular structure inferred from the topology of these densities is not unique. We analyze the behavior of one-particle densities for the Hooke-Calogero Born-Oppenheimer, BO, wavefunction and show that topological transitions are also present in this case for a particular mass value of the light particles even though in the BO regime the nuclear masses are infinite. In this vein, we argue that the change in topology caused by variation of the mass ratio between light and heavy particles does not constitute a true indication in the nBO regime of the emergence of molecular structure.
We consider the calculation of non-Born-Oppenheimer, nBO, one-particle densities for both electrons and nuclei. We show that the nBO one-particle densities evaluated in terms of translationally invariant coordinates are independent of the wavefunction describing the motion of center of mass of the whole system. We show that they depend, however, on an arbitrary reference point from which the positions of the vectors labeling the particles are determined. We examine the effect that this arbitrary choice has on the topology of the one-particle density by selecting the Hooke-Calogero model of a three-body system for which expressions for the one-particle densities can be readily obtained in analytic form. We extend this analysis to the one-particle densities obtained from full Coulomb interaction wavefunctions for three-body systems. We conclude, in view of the fact that there is a close link between the choice of the reference point and the topology of one-particle densities that the molecular structure inferred from the topology of these densities is not unique. We analyze the behavior of one-particle densities for the Hooke-Calogero Born-Oppenheimer, BO, wavefunction and show that topological transitions are also present in this case for a particular mass value of the light particles even though in the BO regime the nuclear masses are infinite. In this vein, we argue that the change in topology caused by variation of the mass ratio between light and heavy particles does not constitute a true indication in the nBO regime of the emergence of molecular structure.
Coutinho, Nayara D; Aquilanti, Vincenzo; Silva, Valter H C; Camargo, Ademir J; Mundim, Kleber C; de Oliveira, Heibbe C B
2016-07-14
Among four-atom processes, the reaction OH + HBr → H2O + Br is one of the most studied experimentally: its kinetics has manifested an unusual anti-Arrhenius behavior, namely, a marked decrease of the rate constant as the temperature increases, which has intrigued theoreticians for a long time. Recently, salient features of the potential energy surface have been characterized and most kinetic aspects can be considered as satisfactorily reproduced by classical trajectory simulations. Motivation of the work reported in this paper is the investigation of the stereodirectional dynamics of this reaction as the prominent reason for the peculiar kinetics: we started in a previous Letter ( J. Phys. Chem. Lett. 2015 , 6 , 1553 - 1558 ) a first-principles Born-Oppenheimer "canonical" molecular dynamics approach. Trajectories are step-by-step generated on a potential energy surface quantum mechanically calculated on-the-fly and are thermostatically equilibrated to correspond to a specific temperature. Here, refinements of the method permitted a major increase of the number of trajectories and the consideration of four temperatures -50, +200, +350, and +500 K, for which the sampling of initial conditions allowed us to characterize the stereodynamical effect. The role is documented of the adjustment of the reactants' mutual orientation to encounter the entrance into the "cone of acceptance" for reactivity. The aperture angle of this cone is dictated by a range of directions of approach compatible with the formation of the specific HOH angle of the product water molecule; and consistently the adjustment is progressively less effective the higher the kinetic energy. Qualitatively, this emerging picture corroborates experiments on this reaction, involving collisions of aligned and oriented molecular beams, and covering a range of energies higher than the thermal ones. The extraction of thermal rate constants from this molecular dynamics approach is discussed and the systematic
Cassam-Chenaï, Patrick; Suo, Bingbing; Liu, Wenjian
2015-07-01
We introduce the electron-nucleus mean-field configuration-interaction (EN-MFCI) approach. It consists in building an effective Hamiltonian for the electrons taking into account a mean field due to the nuclear motion and, conversely, in building an effective Hamiltonian for the nuclear motion taking into account a mean field due to the electrons. The eigenvalue problems of these Hamiltonians are solved in basis sets giving partial eigensolutions for the active degrees of freedom (DOF's), that is to say, either for the electrons or for nuclear motion. The process can be iterated or electron and nuclear motion DOF's can be contracted in a CI calculation. In the EN-MFCI reduction of the molecular Schrödinger equation to an electronic and a nuclear problem, the electronic wave functions do not depend parametrically upon nuclear coordinates. So, it is different from traditional adiabatic methods. Furthermore, when contracting electronic and nuclear functions, a direct product basis set is built in contrast with methods which treat electrons and nuclei on the same footing, but where electron-nucleus explicitly correlated coordinates are used. Also, the EN-MFCI approach can make use of the partition of molecular DOF's into translational, rotational, and internal DOF's. As a result, there is no need to eliminate translations and rotations from the calculation, and the convergence of vibrational levels is facilitated by the use of appropriate internal coordinates. The method is illustrated on diatomic molecules.
Gamallo, Pablo; Akpinar, Sinan; Defazio, Paolo; Petrongolo, Carlo
2015-11-19
The quantum dynamics of three CH(X(2)Π) + D((2)S) reactions is studied by means of the coupled-channel time-dependent real-wavepacket (WP) and flux methods at collision energy Ecol ≤ 0.6 eV and on three potential energy surfaces (PESs): the Born-Oppenheimer (BO) ground PES X̃(3)A″ and the excited ones ã(1)A' and b̃(1)A″, coupled by nonadiabatic (NA) Renner-Teller (RT) effects. This three-state model is suitable for obtaining initial-state-resolved observables, is based on a complete analysis of the correlation diagram of the lowest electronic states of the CHD intermediate and of their NA interactions, and neglects the smaller coupling effects due to the asymptotic electronic angular momenta that become important in state-to-state dynamics. WPs are propagated on each PES at total angular momentum values J ≤ 70, with CH in the two lowest vibrational states v0 and in the ground rotational state j0 = 1. Reaction probabilities are obtained for three possible final products (f): (dP) CH decay and C((3)P) + HD(X(1)Σ(+)) formation that occurs on the uncoupled ground PES, (dD) CH decay and C((1)D) + HD(X(1)Σ(+)) formation that depends on the RT-coupled singlet species, and (ex) exchange to CD(X(2)Π) + H((2)S) available adiabatically from the X̃(3)A″ PES and nonadiabatically from ã(1)A' and b̃(1)A″. Observable cross sections σf,v0j0 and rate constants kf,v0j0 in the temperature range T = 100-2000 K are obtained for (dP), (dD), and (ex) channels. Comparing BO with RT probabilities, we show that NA effects are important at high J values for the (ex) channel at v0 = 1. Real time mechanisms on the three PESs show that RT couplings are opened after some time and clearly point out the formation of the product channels. Both cross sections and rate constants present the same sequence, for example σex,11 > σdP,01 ∼ σex,01 > σdP,11 ≫ σdD,11 ≫ σdD,01, and the CH vibrational excitation enhances the total removal CH+D reactivity by a factor of ∼1
Towards a Philosophy of Approximations in the 'Exact' Sciences
Valentin N. Ostrovsky
2005-11-01
Full Text Available The issue of approximations is mostly neglected in the philosophy of science, and sometimes misinterpreted. The paper demonstrates that approximations are in fact in the core of some recent discussions in the philosophy of chemistry: on the shape of molecules, the Born-Oppenheimer approximation, the role of orbitals, and the physical explanation of the Periodic Table of Elements. The ontological and epistemological significance of approximations in the exact sciences is analyzed. The crucial role of approximations in generating qualitative images and comprehensible models is emphasized. A complementarity relation between numerically 'exact' theories and explanatory approximate approaches is claimed.
Calculational schemes enabling to go beyond crude Condon approximation in non-adiabatic electron transfer reactions are discussed with the use of continuum approximation for the solvent polarization. An algorithm for the self-consistent introduction of an effective reaction coordinate in the adiabatic transition is suggested. Effects due to deviations from the Born-Oppenheimer approximation in bridge-assisted electron transfer reactions are discussed. Interpolation formulae covering limits of coherent and sequential electron transfer in bridge-assisted processes are presented. Simple equations determining a parametric dependence of the transition probability on the reaction free energy in crude Condon approximation are included. (author)
The semiclassical approximation to supersymmetric quantum gravity
Kiefer, C; Moniz, P; Kiefer, Claus; Lueck, Tobias; Moniz, Paulo
2005-01-01
We develop a semiclassical approximation scheme for the constraint equations of supersymmetric canonical quantum gravity. This is achieved by a Born-Oppenheimer type of expansion, in analogy to the case of the usual Wheeler-DeWitt equation. The formalism is only consistent if the states at each order depend on the gravitino field. We recover at consecutive orders the Hamilton-Jacobi equation, the functional Schrodinger equation, and quantum gravitational correction terms to this Schrodinger equation. In particular, the following consequences are found: (i) the Hamilton-Jacobi equation and therefore the background spacetime must involve the gravitino, (ii) a (many fingered) local time parameter has to be present on $SuperRiem \\Sigma$ (the space of all possible tetrad and gravitino fields), (iii) quantum supersymmetric gravitational corrections affect the evolution of the very early universe. The physical meaning of these equations and results, in particular the similarities to and differences from the pure bos...
Static NLO susceptibilities testing approximation schemes against exact results
Del Freo, L; Painelli, A; Freo, Luca Del; Terenziani, Francesca; Painelli, Anna
2001-01-01
The reliability of the approximations commonly adopted in the calculation of static optical (hyper)polarizabilities is tested against exact results obtained for an interesting toy-model. The model accounts for the principal features of typical nonlinear organic materials with mobile electrons strongly coupled to molecular vibrations. The approximations introduced in sum over states and finite field schemes are analyzed in detail. Both the Born-Oppenheimer and the clamped nucleus approximations turn out to be safe for molecules, whereas for donor-acceptor charge transfer complexes deviations from adiabaticity are expected. In the regime of low vibrational frequency, static susceptibilities are strongly dominated by the successive derivatives of the potential energy and large vibrational contributions to hyperpolarizabilities are found. In this regime anharmonic corrections to hyperpolarizabilities are very large, and the harmonic approximation, exact for the linear polarizability, turns out totally inadequate ...
Wave packet dynamics in the optimal superadiabatic approximation
Betz, Volker; Manthe, Uwe
2016-01-01
We explain the concept of superadiabatic approximations and show how in the context of the Born- Oppenheimer approximation they lead to an explicit formula that can be used to predict transitions at avoided crossings. Based on this formula, we present a simple method for computing wave packet dynamics across avoided crossings. Only knowledge of the adiabatic electronic energy levels near the avoided crossing is required for the computation. In particular, this means that no diabatization procedure is necessary, the adiabatic energy levels can be computed on the fly, and they only need to be computed to higher accuracy when an avoided crossing is detected. We test the quality of our method on the paradigmatic example of photo-dissociation of NaI, finding very good agreement with results of exact wave packet calculations.
Semiclassical approximation to supersymmetric quantum gravity
Kiefer, Claus; Lück, Tobias; Moniz, Paulo
2005-08-01
We develop a semiclassical approximation scheme for the constraint equations of supersymmetric canonical quantum gravity. This is achieved by a Born-Oppenheimer type of expansion, in analogy to the case of the usual Wheeler-DeWitt equation. The formalism is only consistent if the states at each order depend on the gravitino field. We recover at consecutive orders the Hamilton-Jacobi equation, the functional Schrödinger equation, and quantum gravitational correction terms to this Schrödinger equation. In particular, the following consequences are found: (i) the Hamilton-Jacobi equation and therefore the background spacetime must involve the gravitino, (ii) a (many-fingered) local time parameter has to be present on super Riem Σ (the space of all possible tetrad and gravitino fields), (iii) quantum supersymmetric gravitational corrections affect the evolution of the very early Universe. The physical meaning of these equations and results, in particular, the similarities to and differences from the pure bosonic case, are discussed.
Bond selective chemistry beyond the adiabatic approximation
Butler, L.J. [Univ. of Chicago, IL (United States)
1993-12-01
One of the most important challenges in chemistry is to develop predictive ability for the branching between energetically allowed chemical reaction pathways. Such predictive capability, coupled with a fundamental understanding of the important molecular interactions, is essential to the development and utilization of new fuels and the design of efficient combustion processes. Existing transition state and exact quantum theories successfully predict the branching between available product channels for systems in which each reaction coordinate can be adequately described by different paths along a single adiabatic potential energy surface. In particular, unimolecular dissociation following thermal, infrared multiphoton, or overtone excitation in the ground state yields a branching between energetically allowed product channels which can be successfully predicted by the application of statistical theories, i.e. the weakest bond breaks. (The predictions are particularly good for competing reactions in which when there is no saddle point along the reaction coordinates, as in simple bond fission reactions.) The predicted lack of bond selectivity results from the assumption of rapid internal vibrational energy redistribution and the implicit use of a single adiabatic Born-Oppenheimer potential energy surface for the reaction. However, the adiabatic approximation is not valid for the reaction of a wide variety of energetic materials and organic fuels; coupling between the electronic states of the reacting species play a a key role in determining the selectivity of the chemical reactions induced. The work described below investigated the central role played by coupling between electronic states in polyatomic molecules in determining the selective branching between energetically allowed fragmentation pathways in two key systems.
Diagonalization of multicomponent wave equations with a Born-Oppenheimer example
Weigert, S.; Littlejohn, Robert
1993-01-01
A general method to decouple multicomponent linear wave equations is presented. First, the Weyl calculus is used to transform operator relations into relations between c-number valued matrices. Then it is shown that the symbol representing the wave operator can be diagonalized systematically up to arbitrary order in an appropriate expansion parameter. After transforming the symbols back to operators, the original problem is reduced to solving a set of linear uncoupled scalar wave equations. T...
Szalay, Viktor
1999-11-01
The reconstruction of a function from knowing only its values on a finite set of grid points, that is the construction of an analytical approximation reproducing the function with good accuracy everywhere within the sampled volume, is an important problem in all branches of sciences. One such problem in chemical physics is the determination of an analytical representation of Born-Oppenheimer potential energy surfaces by ab initio calculations which give the value of the potential at a finite set of grid points in configuration space. This article describes the rudiments of iterative and direct methods of potential surface reconstruction. The major new results are the derivation, numerical demonstration, and interpretation of a reconstruction formula. The reconstruction formula derived approximates the unknown function, say V, by linear combination of functions obtained by discretizing the continuous distributed approximating functional (DAF) approximation of V over the grid of sampling. The simplest of contracted and ordinary Hermite-DAFs are shown to be sufficient for reconstruction. The linear combination coefficients can be obtained either iteratively or directly by finding the minimal norm least-squares solution of a linear system of equations. Several numerical examples of reconstructing functions of one and two variables, and very different shape are given. The examples demonstrate the robustness, high accuracy, as well as the caveats of the proposed method. As to the mathematical foundation of the method, it is shown that the reconstruction formula can be interpreted as, and in fact is, frame expansion. By recognizing the relevance of frames in determining analytical approximation to potential energy surfaces, an extremely rich and beautiful toolbox of mathematics has come to our disposal. Thus, the simple reconstruction method derived in this paper can be refined, extended, and improved in numerous ways.
De Backer, A.; Sand, A.; Ortiz, C. J.; Domain, C.; Olsson, P.; Berthod, E.; Becquart, C. S.
2016-02-01
The damage produced by primary knock-on atoms (PKA) in W has been investigated from the threshold displacement energy (TDE) where it produces one self interstitial atom-vacancy pair to larger energies, up to 100 keV, where a large molten volume is formed. The TDE has been determined in different crystal directions using the Born-Oppenheimer density functional molecular dynamics (DFT-MD). A significant difference has been observed without and with the semi-core electrons. Classical MD has been used with two different empirical potentials characterized as ‘soft’ and ‘hard’ to obtain statistics on TDEs. Cascades of larger energy have been calculated, with these potentials, using a model that accounts for electronic losses (Sand et al 2013 Europhys. Lett. 103 46003). Two other sets of cascades have been produced using the binary collision approximation (BCA): a Monte Carlo BCA using SDTrimSP (Eckstein et al 2011 SDTrimSP: Version 5.00. Report IPP 12/8) (similar to SRIM www.srim.org) and MARLOWE (RSICC Home Page. (https://rsicc.ornl.gov/codes/psr/psr1/psr-137.html) (accessed May, 2014)). The comparison of these sets of cascades gave a recombination distance equal to 12 Å which is significantly larger from the one we reported in Hou et al (2010 J. Nucl. Mater. 403 89) because, here, we used bulk cascades rather than surface cascades which produce more defects (Stoller 2002 J. Nucl. Mater. 307 935, Nordlund et al 1999 Nature 398 49). Investigations on the defect clustering aspect showed that the difference between BCA and MD cascades is considerably reduced after the annealing of the cascade debris at 473 K using our Object Kinetic Monte Carlo model, LAKIMOCA (Domain et al 2004 J. Nucl. Mater. 335 121).
Vibrational Energies of the Hydrogen Bonds of H_3O_2^- and H_5O_2^+
Gamble, Stephanie Nicole
2016-01-01
We approximate the vibrational energies of the symmetric and asymmetric stretches of the hydrogen bonds of the molecules H_3O_2^- and H_5O_2^+ by applying an improvement to the standard time-independent Born-Oppenheimer approximation. These two molecules are symmetric around a central hydrogen which participates in hydrogen bonding. Unlike the standard Born-Oppenheimer approximation, this approximation appropriately scales the hydrogen nuclei differently than the heavier oxygen nuclei. This r...
Niven, Ivan
2008-01-01
This self-contained treatment originated as a series of lectures delivered to the Mathematical Association of America. It covers basic results on homogeneous approximation of real numbers; the analogue for complex numbers; basic results for nonhomogeneous approximation in the real case; the analogue for complex numbers; and fundamental properties of the multiples of an irrational number, for both the fractional and integral parts.The author refrains from the use of continuous fractions and includes basic results in the complex case, a feature often neglected in favor of the real number discuss
Approximate Representations and Approximate Homomorphisms
Moore, Cristopher; Russell, Alexander
2010-01-01
Approximate algebraic structures play a defining role in arithmetic combinatorics and have found remarkable applications to basic questions in number theory and pseudorandomness. Here we study approximate representations of finite groups: functions f:G -> U_d such that Pr[f(xy) = f(x) f(y)] is large, or more generally Exp_{x,y} ||f(xy) - f(x)f(y)||^2$ is small, where x and y are uniformly random elements of the group G and U_d denotes the unitary group of degree d. We bound these quantities i...
CERN. Geneva
2015-01-01
Most physics results at the LHC end in a likelihood ratio test. This includes discovery and exclusion for searches as well as mass, cross-section, and coupling measurements. The use of Machine Learning (multivariate) algorithms in HEP is mainly restricted to searches, which can be reduced to classification between two fixed distributions: signal vs. background. I will show how we can extend the use of ML classifiers to distributions parameterized by physical quantities like masses and couplings as well as nuisance parameters associated to systematic uncertainties. This allows for one to approximate the likelihood ratio while still using a high dimensional feature vector for the data. Both the MEM and ABC approaches mentioned above aim to provide inference on model parameters (like cross-sections, masses, couplings, etc.). ABC is fundamentally tied Bayesian inference and focuses on the “likelihood free” setting where only a simulator is available and one cannot directly compute the likelihood for the dat...
Schmidt, Wolfgang M
1980-01-01
"In 1970, at the U. of Colorado, the author delivered a course of lectures on his famous generalization, then just established, relating to Roth's theorem on rational approxi- mations to algebraic numbers. The present volume is an ex- panded and up-dated version of the original mimeographed notes on the course. As an introduction to the author's own remarkable achievements relating to the Thue-Siegel-Roth theory, the text can hardly be bettered and the tract can already be regarded as a classic in its field."(Bull.LMS) "Schmidt's work on approximations by algebraic numbers belongs to the deepest and most satisfactory parts of number theory. These notes give the best accessible way to learn the subject. ... this book is highly recommended." (Mededelingen van het Wiskundig Genootschap)
Diophantine approximation and badly approximable sets
Kristensen, S.; Thorn, R.; Velani, S.
2006-01-01
Let (X,d) be a metric space and (Omega, d) a compact subspace of X which supports a non-atomic finite measure m. We consider `natural' classes of badly approximable subsets of Omega. Loosely speaking, these consist of points in Omega which `stay clear' of some given set of points in X....... The classical set Bad of `badly approximable' numbers in the theory of Diophantine approximation falls within our framework as do the sets Bad(i,j) of simultaneously badly approximable numbers. Under various natural conditions we prove that the badly approximable subsets of Omega have full Hausdorff dimension...
Isotopic scaling in strong-field dissociation by few-cycle pulses
Madsen, Lars Bojer
2009-01-01
Within the Born-Oppenheimer approximation, scaling laws are derived for isotopic homonuclear diatomic molecules interacting with strong few-cycles laser pulses. As a consequence of an approximate scaling of the transition dipole moment function between charge-resonant states, the Schrödinger...... equation describing the nuclear dynamics on the initial bonding Born-Oppenheimer curve for a given isotope can approximately be mapped to a reference molecule within that isotope. For other channels the presence of the external field inhibits a scaling even though in the field-free case scaling can be...
Comment on “On the quantum theory of molecules” [J. Chem. Phys. 137, 22A544 (2012)
Sutcliffe, Brian T., E-mail: bsutclif@ulb.ac.be [Service de Chimie quantique et Photophysique, Université Libre de Bruxelles, B-1050 Bruxelles (Belgium); Woolley, R. Guy [School of Science and Technology, Nottingham Trent University, Nottingham NG11 8NS (United Kingdom)
2014-01-21
In our previous paper [B. T. Sutcliffe and R. G. Woolley, J. Chem. Phys. 137, 22A544 (2012)] we argued that the Born-Oppenheimer approximation could not be based on an exact transformation of the molecular Schrödinger equation. In this Comment we suggest that the fundamental reason for the approximate nature of the Born-Oppenheimer model is the lack of a complete set of functions for the electronic space, and the need to describe the continuous spectrum using spectral projection.
Bin Qin
2014-01-01
Relationships between fuzzy relations and fuzzy topologies are deeply researched. The concept of fuzzy approximating spaces is introduced and decision conditions that a fuzzy topological space is a fuzzy approximating space are obtained.
Stochastic approximation: invited paper
Lai, Tze Leung
2003-01-01
Stochastic approximation, introduced by Robbins and Monro in 1951, has become an important and vibrant subject in optimization, control and signal processing. This paper reviews Robbins' contributions to stochastic approximation and gives an overview of several related developments.
Rasin, A
1994-01-01
We discuss the idea of approximate flavor symmetries. Relations between approximate flavor symmetries and natural flavor conservation and democracy models is explored. Implications for neutrino physics are also discussed.
Approximate iterative algorithms
Almudevar, Anthony Louis
2014-01-01
Iterative algorithms often rely on approximate evaluation techniques, which may include statistical estimation, computer simulation or functional approximation. This volume presents methods for the study of approximate iterative algorithms, providing tools for the derivation of error bounds and convergence rates, and for the optimal design of such algorithms. Techniques of functional analysis are used to derive analytical relationships between approximation methods and convergence properties for general classes of algorithms. This work provides the necessary background in functional analysis a
Approximation of distributed delays
Lu, Hao; Eberard, Damien; Simon, Jean-Pierre
2010-01-01
We address in this paper the approximation problem of distributed delays. Such elements are convolution operators with kernel having bounded support, and appear in the control of time-delay systems. From the rich literature on this topic, we propose a general methodology to achieve such an approximation. For this, we enclose the approximation problem in the graph topology, and work with the norm defined over the convolution Banach algebra. The class of rational approximates is described, and a constructive approximation is proposed. Analysis in time and frequency domains is provided. This methodology is illustrated on the stabilization control problem, for which simulations results show the effectiveness of the proposed methodology.
Sparse approximation with bases
2015-01-01
This book systematically presents recent fundamental results on greedy approximation with respect to bases. Motivated by numerous applications, the last decade has seen great successes in studying nonlinear sparse approximation. Recent findings have established that greedy-type algorithms are suitable methods of nonlinear approximation in both sparse approximation with respect to bases and sparse approximation with respect to redundant systems. These insights, combined with some previous fundamental results, form the basis for constructing the theory of greedy approximation. Taking into account the theoretical and practical demand for this kind of theory, the book systematically elaborates a theoretical framework for greedy approximation and its applications. The book addresses the needs of researchers working in numerical mathematics, harmonic analysis, and functional analysis. It quickly takes the reader from classical results to the latest frontier, but is written at the level of a graduate course and do...
An isotopic mass effect on the intermolecular potential
Herman, Michael F.; Currier, Robert P.; Clegg, Samuel M.
2015-10-01
The impact of isotopic variation on the electronic energy and intermolecular potentials is often suppressed when calculating isotopologue thermodynamics. Intramolecular potential energy surfaces for distinct isotopologues are in fact equivalent under the Born-Oppenheimer approximation, which is sometimes used to imply that the intermolecular interactions are independent of isotopic mass. In this communication, the intermolecular dipole-dipole interaction between hetero-nuclear diatomic molecules is considered. It is shown that the intermolecular potential contains mass-dependent terms even though each nucleus moves on a Born-Oppenheimer surface. The analysis suggests that mass dependent variations in intermolecular potentials should be included in comprehensive descriptions of isotopologue thermodynamics.
Nonadiabatic coupling in antiprotonic pHe+ atomcule
Metastable states of the pHe+ system are studied in the adiabatic and the united atom representations. The upper and lower estimations of energy shifts with respect to Born-Oppenheimer approximation are given taking into account the nonadiabatic coupling of the states belong both to discrete and continuous parts of the electron spectrum. The limits within which the Born-Oppenheimer picture is valid for the description of the metastable states are established. An efficient scheme for calculation of energy levels and wave functions is implemented
YueShihong; ZhangKecun
2002-01-01
In a dot product space with the reproducing kernel (r. k. S. ) ,a fuzzy system with the estimation approximation errors is proposed ,which overcomes the defect that the existing fuzzy control system is difficult to estimate the errors of approximation for a desired function,and keeps the characteristics of fuzzy system as an inference approach. The structure of the new fuzzy approximator benefits a course got by other means.
Malvina Baica
1985-01-01
The author uses a new modification of Jacobi-Perron Algorithm which holds for complex fields of any degree (abbr. ACF), and defines it as Generalized Euclidean Algorithm (abbr. GEA) to approximate irrationals.This paper deals with approximation of irrationals of degree n=2,3,5. Though approximations of these irrationals in a variety of patterns are known, the results are new and practical, since there is used an algorithmic method.
Expectation Consistent Approximate Inference
Opper, Manfred; Winther, Ole
2005-01-01
We propose a novel framework for approximations to intractable probabilistic models which is based on a free energy formulation. The approximation can be understood from replacing an average over the original intractable distribution with a tractable one. It requires two tractable probability distributions which are made consistent on a set of moments and encode different features of the original intractable distribution. In this way we are able to use Gaussian approximations for models with ...
Approximation techniques for engineers
Komzsik, Louis
2006-01-01
Presenting numerous examples, algorithms, and industrial applications, Approximation Techniques for Engineers is your complete guide to the major techniques used in modern engineering practice. Whether you need approximations for discrete data of continuous functions, or you''re looking for approximate solutions to engineering problems, everything you need is nestled between the covers of this book. Now you can benefit from Louis Komzsik''s years of industrial experience to gain a working knowledge of a vast array of approximation techniques through this complete and self-contained resource.
Expectation Consistent Approximate Inference
Opper, Manfred; Winther, Ole
2005-01-01
We propose a novel framework for approximations to intractable probabilistic models which is based on a free energy formulation. The approximation can be understood from replacing an average over the original intractable distribution with a tractable one. It requires two tractable probability dis...
Ordered cones and approximation
Keimel, Klaus
1992-01-01
This book presents a unified approach to Korovkin-type approximation theorems. It includes classical material on the approximation of real-valuedfunctions as well as recent and new results on set-valued functions and stochastic processes, and on weighted approximation. The results are notonly of qualitative nature, but include quantitative bounds on the order of approximation. The book is addressed to researchers in functional analysis and approximation theory as well as to those that want to applythese methods in other fields. It is largely self- contained, but the readershould have a solid background in abstract functional analysis. The unified approach is based on a new notion of locally convex ordered cones that are not embeddable in vector spaces but allow Hahn-Banach type separation and extension theorems. This concept seems to be of independent interest.
Approximate Modified Policy Iteration
Scherrer, Bruno; Ghavamzadeh, Mohammad; Geist, Matthieu
2012-01-01
Modified policy iteration (MPI) is a dynamic programming (DP) algorithm that contains the two celebrated policy and value iteration methods. Despite its generality, MPI has not been thoroughly studied, especially its approximation form which is used when the state and/or action spaces are large or infinite. In this paper, we propose three approximate MPI (AMPI) algorithms that are extensions of the well-known approximate DP algorithms: fitted-value iteration, fitted-Q iteration, and classification-based policy iteration. We provide an error propagation analysis for AMPI that unifies those for approximate policy and value iteration. We also provide a finite-sample analysis for the classification-based implementation of AMPI (CBMPI), which is more general (and somehow contains) than the analysis of the other presented AMPI algorithms. An interesting observation is that the MPI's parameter allows us to control the balance of errors (in value function approximation and in estimating the greedy policy) in the fina...
Approximations to toroidal harmonics
Toroidal harmonics P/sub n-1/2/1(cosh μ) and Q/sub n-1/2/1(cosh μ) are useful in solutions to Maxwell's equations in toroidal coordinates. In order to speed their computation, a set of approximations has been developed that is valid over the range 0 -10. The simple method used to determine the approximations is described. Relative error curves are also presented, obtained by comparing approximations to the more accurate values computed by direct summation of the hypergeometric series
Approximations in Inspection Planning
Engelund, S.; Sørensen, John Dalsgaard; Faber, M. H.; Bloch, Allan
2000-01-01
. One of the more important of these approximations is the assumption that all inspections will reveal no defects. Using this approximation the optimal inspection plan may be determined on the basis of conditional probabilities, i.e. the probability of failure given no defects have been found by the......Planning of inspections of civil engineering structures may be performed within the framework of Bayesian decision analysis. The effort involved in a full Bayesian decision analysis is relatively large. Therefore, the actual inspection planning is usually performed using a number of approximations...... inspection. In this paper the quality of this approximation is investigated. The inspection planning is formulated both as a full Bayesian decision problem and on the basis of the assumption that the inspection will reveal no defects....
The Karlqvist approximation revisited
Tannous, C.
2015-01-01
The Karlqvist approximation signaling the historical beginning of magnetic recording head theory is reviewed and compared to various approaches progressing from Green, Fourier, Conformal mapping that obeys the Sommerfeld edge condition at angular points and leads to exact results.
Approximation Behooves Calibration
da Silva Ribeiro, André Manuel; Poulsen, Rolf
2013-01-01
Calibration based on an expansion approximation for option prices in the Heston stochastic volatility model gives stable, accurate, and fast results for S&P500-index option data over the period 2005–2009.......Calibration based on an expansion approximation for option prices in the Heston stochastic volatility model gives stable, accurate, and fast results for S&P500-index option data over the period 2005–2009....
Gautschi, Walter; Rassias, Themistocles M
2011-01-01
Approximation theory and numerical analysis are central to the creation of accurate computer simulations and mathematical models. Research in these areas can influence the computational techniques used in a variety of mathematical and computational sciences. This collection of contributed chapters, dedicated to renowned mathematician Gradimir V. Milovanovia, represent the recent work of experts in the fields of approximation theory and numerical analysis. These invited contributions describe new trends in these important areas of research including theoretic developments, new computational alg
Dutta, Soumitra
1988-01-01
Much of human reasoning is approximate in nature. Formal models of reasoning traditionally try to be precise and reject the fuzziness of concepts in natural use and replace them with non-fuzzy scientific explicata by a process of precisiation. As an alternate to this approach, it has been suggested that rather than regard human reasoning processes as themselves approximating to some more refined and exact logical process that can be carried out with mathematical precision, the essence and power of human reasoning is in its capability to grasp and use inexact concepts directly. This view is supported by the widespread fuzziness of simple everyday terms (e.g., near tall) and the complexity of ordinary tasks (e.g., cleaning a room). Spatial reasoning is an area where humans consistently reason approximately with demonstrably good results. Consider the case of crossing a traffic intersection. We have only an approximate idea of the locations and speeds of various obstacles (e.g., persons and vehicles), but we nevertheless manage to cross such traffic intersections without any harm. The details of our mental processes which enable us to carry out such intricate tasks in such apparently simple manner are not well understood. However, it is that we try to incorporate such approximate reasoning techniques in our computer systems. Approximate spatial reasoning is very important for intelligent mobile agents (e.g., robots), specially for those operating in uncertain or unknown or dynamic domains.
Multidimensional effects on dissociation of N-2 on Ru(0001)
Diaz, C.; Vincent, J.K.; Krishnamohan, G.P.;
2006-01-01
The applicability of the Born-Oppenheimer approximation to molecule-metal surface reactions is presently a topic of intense debate. We have performed classical trajectory calculations on a prototype activated dissociation reaction, of N-2 on Ru(0001), using a potential energy surface based on den...
Tunneling Ionization of Diatomic Molecules
Svensmark, Jens Søren Sieg
2016-01-01
of tunneling ionizaion of molecules is presented and the results of numerical calculations are shown. One perhaps surprising result is, that the frequently used Born-Oppenheimer approximation breaks down for weak fields when describing tunneling ionization. An analytic theory applicable in the weak...
Efimov States of Heavy Impurities in a Bose-Einstein Condensate
Zinner, Nikolaj Thomas
2013-01-01
We consider the problem of two heavy impurity particles embedded in a gas of weakly-interacting light mass bosonic particles in the condensed state. Using the Bogoliubov approach to describe the bosonic gas and the Born-Oppenheimer approximation for the three-body dynamics, we calculate the modif...
Time resolved four- and six-wave mixing in liquids .1. Theory
Steffen, T; Fourkas, J.T.; Duppen, K.
1996-01-01
Low-frequency intermolecular dynamics in liquids is studied by ultrafast four- and six-wave mixing. The theory of these nonlinear optical processes is given for electronically nonresonant optical interactions up to fifth order in the electric field. The Born-Oppenheimer approximation is used to sepa
A Cartoon in One Dimension of the Hydrogen Molecular Ion
Dutta, Sourav; Ganguly, Shreemoyee; Dutta-Roy, Binayak
2008-01-01
To illustrate the basic methodology involved in the quantum mechanics of molecules, a one-dimensional caricature of the hydrogen molecular ion (H[superscript +][subscript 2]) is presented, which is exactly solvable, in the Born-Oppenheimer approximation, in terms of elementary functions. The purpose of the exercise is to elucidate in a simple…
On the Origin of the Intensity Deficit in Neutron Compton Scattering
Reiter, G. F.; Platzman, P. M.
2004-01-01
Neutron Compton Scattering measurements in a variety of materials have shown a relative deficit in the total signal from hydrogen compared to deuterium and heavier ions. We show here that a breakdown in the Born-Oppenheimer approximation in the final states of the scattering process leads to such a deficit, and may be responsible for the effect.
Diophantine approximations on fractals
Einsiedler, Manfred; Shapira, Uri
2009-01-01
We exploit dynamical properties of diagonal actions to derive results in Diophantine approximations. In particular, we prove that the continued fraction expansion of almost any point on the middle third Cantor set (with respect to the natural measure) contains all finite patterns (hence is well approximable). Similarly, we show that for a variety of fractals in [0,1]^2, possessing some symmetry, almost any point is not Dirichlet improvable (hence is well approximable) and has property C (after Cassels). We then settle by similar methods a conjecture of M. Boshernitzan saying that there are no irrational numbers x in the unit interval such that the continued fraction expansions of {nx mod1 : n is a natural number} are uniformly eventually bounded.
Covariant approximation averaging
Shintani, Eigo; Blum, Thomas; Izubuchi, Taku; Jung, Chulwoo; Lehner, Christoph
2014-01-01
We present a new class of statistical error reduction techniques for Monte-Carlo simulations. Using covariant symmetries, we show that correlation functions can be constructed from inexpensive approximations without introducing any systematic bias in the final result. We introduce a new class of covariant approximation averaging techniques, known as all-mode averaging (AMA), in which the approximation takes account of contributions of all eigenmodes through the inverse of the Dirac operator computed from the conjugate gradient method with a relaxed stopping condition. In this paper we compare the performance and computational cost of our new method with traditional methods using correlation functions and masses of the pion, nucleon, and vector meson in $N_f=2+1$ lattice QCD using domain-wall fermions. This comparison indicates that AMA significantly reduces statistical errors in Monte-Carlo calculations over conventional methods for the same cost.
Accuracy of Approximate Eigenstates
Lucha, Wolfgang; Lucha, Wolfgang
2000-01-01
Besides perturbation theory, which requires, of course, the knowledge of the exact unperturbed solution, variational techniques represent the main tool for any investigation of the eigenvalue problem of some semibounded operator H in quantum theory. For a reasonable choice of the employed trial subspace of the domain of H, the lowest eigenvalues of H usually can be located with acceptable precision whereas the trial-subspace vectors corresponding to these eigenvalues approximate, in general, the exact eigenstates of H with much less accuracy. Accordingly, various measures for the accuracy of the approximate eigenstates derived by variational techniques are scrutinized. In particular, the matrix elements of the commutator of the operator H and (suitably chosen) different operators, with respect to degenerate approximate eigenstates of H obtained by some variational method, are proposed here as new criteria for the accuracy of variational eigenstates. These considerations are applied to that Hamiltonian the eig...
Synthesis of approximation errors
Bareiss, E.H.; Michel, P.
1977-07-01
A method is developed for the synthesis of the error in approximations in the large of regular and irregular functions. The synthesis uses a small class of dimensionless elementary error functions which are weighted by the coefficients of the expansion of the regular part of the function. The question is answered whether a computer can determine the analytical nature of a solution by numerical methods. It is shown that continuous least-squares approximations of irregular functions can be replaced by discrete least-squares approximation and how to select the discrete points. The elementary error functions are used to show how the classical convergence criterions can be markedly improved. There are eight numerical examples included, 30 figures and 74 tables.
White, Martin
2014-01-01
This year marks the 100th anniversary of the birth of Yakov Zel'dovich. Amongst his many legacies is the Zel'dovich approximation for the growth of large-scale structure, which remains one of the most successful and insightful analytic models of structure formation. We use the Zel'dovich approximation to compute the two-point function of the matter and biased tracers, and compare to the results of N-body simulations and other Lagrangian perturbation theories. We show that Lagrangian perturbation theories converge well and that the Zel'dovich approximation provides a good fit to the N-body results except for the quadrupole moment of the halo correlation function. We extend the calculation of halo bias to 3rd order and also consider non-local biasing schemes, none of which remove the discrepancy. We argue that a part of the discrepancy owes to an incorrect prediction of inter-halo velocity correlations. We use the Zel'dovich approximation to compute the ingredients of the Gaussian streaming model and show that ...
Prestack wavefield approximations
Alkhalifah, Tariq
2013-09-01
The double-square-root (DSR) relation offers a platform to perform prestack imaging using an extended single wavefield that honors the geometrical configuration between sources, receivers, and the image point, or in other words, prestack wavefields. Extrapolating such wavefields, nevertheless, suffers from limitations. Chief among them is the singularity associated with horizontally propagating waves. I have devised highly accurate approximations free of such singularities which are highly accurate. Specifically, I use Padé expansions with denominators given by a power series that is an order lower than that of the numerator, and thus, introduce a free variable to balance the series order and normalize the singularity. For the higher-order Padé approximation, the errors are negligible. Additional simplifications, like recasting the DSR formula as a function of scattering angle, allow for a singularity free form that is useful for constant-angle-gather imaging. A dynamic form of this DSR formula can be supported by kinematic evaluations of the scattering angle to provide efficient prestack wavefield construction. Applying a similar approximation to the dip angle yields an efficient 1D wave equation with the scattering and dip angles extracted from, for example, DSR ray tracing. Application to the complex Marmousi data set demonstrates that these approximations, although they may provide less than optimal results, allow for efficient and flexible implementations. © 2013 Society of Exploration Geophysicists.
Madsen, Rasmus Elsborg
2005-01-01
The Dirichlet compound multinomial (DCM), which has recently been shown to be well suited for modeling for word burstiness in documents, is here investigated. A number of conceptual explanations that account for these recent results, are provided. An exponential family approximation of the DCM that...
Prestack traveltime approximations
Alkhalifah, Tariq Ali
2011-01-01
Most prestack traveltime relations we tend work with are based on homogeneous (or semi-homogenous, possibly effective) media approximations. This includes the multi-focusing or double square-root (DSR) and the common reflection stack (CRS) equations. Using the DSR equation, I analyze the associated eikonal form in the general source-receiver domain. Like its wave-equation counterpart, it suffers from a critical singularity for horizontally traveling waves. As a result, I derive expansion based solutions of this eikonal based on polynomial expansions in terms of the reflection and dip angles in a generally inhomogenous background medium. These approximate solutions are free of singularities and can be used to estimate travetimes for small to moderate offsets (or reflection angles) in a generally inhomogeneous medium. A Marmousi example demonstrates the usefulness of the approach. © 2011 Society of Exploration Geophysicists.
Richtárik, Peter
2008-01-01
In this paper we propose and analyze a variant of the level method [4], which is an algorithm for minimizing nonsmooth convex functions. The main work per iteration is spent on 1) minimizing a piecewise-linear model of the objective function and on 2) projecting onto the intersection of the feasible region and a polyhedron arising as a level set of the model. We show that by replacing exact computations in both cases by approximate computations, in relative scale, the theoretical ...
Approximate Bayesian recursive estimation
Kárný, Miroslav
2014-01-01
Roč. 285, č. 1 (2014), s. 100-111. ISSN 0020-0255 R&D Projects: GA ČR GA13-13502S Institutional support: RVO:67985556 Keywords : Approximate parameter estimation * Bayesian recursive estimation * Kullback–Leibler divergence * Forgetting Subject RIV: BB - Applied Statistics, Operational Research Impact factor: 4.038, year: 2014 http://library.utia.cas.cz/separaty/2014/AS/karny-0425539.pdf
Local approximate inference algorithms
Jung, Kyomin; Shah, Devavrat
2006-01-01
We present a new local approximation algorithm for computing Maximum a Posteriori (MAP) and log-partition function for arbitrary exponential family distribution represented by a finite-valued pair-wise Markov random field (MRF), say $G$. Our algorithm is based on decomposition of $G$ into {\\em appropriately} chosen small components; then computing estimates locally in each of these components and then producing a {\\em good} global solution. We show that if the underlying graph $G$ either excl...
Fragments of approximate counting
Buss, S.R.; Kolodziejczyk, L.. A.; Thapen, Neil
2014-01-01
Roč. 79, č. 2 (2014), s. 496-525. ISSN 0022-4812 R&D Projects: GA AV ČR IAA100190902 Institutional support: RVO:67985840 Keywords : approximate counting * bounded arithmetic * ordering principle Subject RIV: BA - General Mathematics Impact factor: 0.541, year: 2014 http://journals.cambridge.org/action/displayAbstract?fromPage=online&aid=9287274&fileId=S0022481213000376
Highlights: • Development of optimization rules for S2 quadrature sets. • Studying the dependency of optimized S2 quadratures on composition and geometry. • Demonstrating S2 procedures preserving the features of higher approximations. - Abstract: Discrete ordinates method relies on approximating the integral term of the transport equation with the aid of quadrature summation rules. These quadratures are usually based on certain assumptions which assure specific symmetry rules and transport/diffusion limits. Generally, these assumptions are not problem-dependent which results in inaccuracies in some instances. Here, various methods have been developed for more accurate estimation of the independent angle in S2 approximation, as it is tightly related to valid estimation of the diffusion coefficient/length. We proposed and examined a method to reduce a complicated problem that usually is consisting many energy groups and discrete directions (SN) to an equivalent one-group S2 problem while it mostly preserves general features of the original model. Some numerical results are demonstrated to show the accuracy of proposed method
Chalasani, P.; Saias, I. [Los Alamos National Lab., NM (United States); Jha, S. [Carnegie Mellon Univ., Pittsburgh, PA (United States)
1996-04-08
As increasingly large volumes of sophisticated options (called derivative securities) are traded in world financial markets, determining a fair price for these options has become an important and difficult computational problem. Many valuation codes use the binomial pricing model, in which the stock price is driven by a random walk. In this model, the value of an n-period option on a stock is the expected time-discounted value of the future cash flow on an n-period stock price path. Path-dependent options are particularly difficult to value since the future cash flow depends on the entire stock price path rather than on just the final stock price. Currently such options are approximately priced by Monte carlo methods with error bounds that hold only with high probability and which are reduced by increasing the number of simulation runs. In this paper the authors show that pricing an arbitrary path-dependent option is {number_sign}-P hard. They show that certain types f path-dependent options can be valued exactly in polynomial time. Asian options are path-dependent options that are particularly hard to price, and for these they design deterministic polynomial-time approximate algorithms. They show that the value of a perpetual American put option (which can be computed in constant time) is in many cases a good approximation to the value of an otherwise identical n-period American put option. In contrast to Monte Carlo methods, the algorithms have guaranteed error bounds that are polynormally small (and in some cases exponentially small) in the maturity n. For the error analysis they derive large-deviation results for random walks that may be of independent interest.
A simple approach employing properties of solutions of differential equations is adopted to derive an appropriate extension of the WKBJ method. Some of the earlier techniques that are commonly in use are unified, whereby the general approximate solution to a second-order homogeneous linear differential equation is presented in a standard form that is valid for all orders. In comparison to other methods, the present one is shown to be leading in the order of iteration, and thus possibly has the ability of accelerating the convergence of the solution. The method is also extended for the solution of inhomogeneous equations. (author)
Approximation by Cylinder Surfaces
Randrup, Thomas
1997-01-01
We present a new method for approximation of a given surface by a cylinder surface. It is a constructive geometric method, leading to a monorail representation of the cylinder surface. By use of a weighted Gaussian image of the given surface, we determine a projection plane. In the orthogonal...... projection of the surface onto this plane, a reference curve is determined by use of methods for thinning of binary images. Finally, the cylinder surface is constructed as follows: the directrix of the cylinder surface is determined by a least squares method minimizing the distance to the points in the...
Finite elements and approximation
Zienkiewicz, O C
2006-01-01
A powerful tool for the approximate solution of differential equations, the finite element is extensively used in industry and research. This book offers students of engineering and physics a comprehensive view of the principles involved, with numerous illustrative examples and exercises.Starting with continuum boundary value problems and the need for numerical discretization, the text examines finite difference methods, weighted residual methods in the context of continuous trial functions, and piecewise defined trial functions and the finite element method. Additional topics include higher o
Approximations to Euler's constant
We study a problem of finding good approximations to Euler's constant γ=lim→∞ Sn, where Sn = Σk=Ln (1)/k-log(n+1), by linear forms in logarithms and harmonic numbers. In 1995, C. Elsner showed that slow convergence of the sequence Sn can be significantly improved if Sn is replaced by linear combinations of Sn with integer coefficients. In this paper, considering more general linear transformations of the sequence Sn we establish new accelerating convergence formulae for γ. Our estimates sharpen and generalize recent Elsner's, Rivoal's and author's results. (author)
Chen, Dan
2012-01-01
We consider the problem of approximating the majority depth (Liu and Singh, 1993) of a point q with respect to an n-point set, S, by random sampling. At the heart of this problem is a data structures question: How can we preprocess a set of n lines so that we can quickly test whether a randomly selected vertex in the arrangement of these lines is above or below the median level. We describe a Monte-Carlo data structure for this problem that can be constructed in O(nlog n$ time, can answer queries O((log n)^{4/3}) expected time, and answers correctly with high probability.
The Compact Approximation Property does not imply the Approximation Property
Willis, George A.
1992-01-01
It is shown how to construct, given a Banach space which does not have the approximation property, another Banach space which does not have the approximation property but which does have the compact approximation property.
Prestack traveltime approximations
Alkhalifah, Tariq Ali
2012-05-01
Many of the explicit prestack traveltime relations used in practice are based on homogeneous (or semi-homogenous, possibly effective) media approximations. This includes the multifocusing, based on the double square-root (DSR) equation, and the common reflection stack (CRS) approaches. Using the DSR equation, I constructed the associated eikonal form in the general source-receiver domain. Like its wave-equation counterpart, it suffers from a critical singularity for horizontally traveling waves. As a result, I recasted the eikonal in terms of the reflection angle, and thus, derived expansion based solutions of this eikonal in terms of the difference between the source and receiver velocities in a generally inhomogenous background medium. The zero-order term solution, corresponding to ignoring the lateral velocity variation in estimating the prestack part, is free of singularities and can be used to estimate traveltimes for small to moderate offsets (or reflection angles) in a generally inhomogeneous medium. The higher-order terms include limitations for horizontally traveling waves, however, we can readily enforce stability constraints to avoid such singularities. In fact, another expansion over reflection angle can help us avoid these singularities by requiring the source and receiver velocities to be different. On the other hand, expansions in terms of reflection angles result in singularity free equations. For a homogenous background medium, as a test, the solutions are reasonably accurate to large reflection and dip angles. A Marmousi example demonstrated the usefulness and versatility of the formulation. © 2012 Society of Exploration Geophysicists.
Interacting boson approximation
Lectures notes on the Interacting Boson Approximation are given. Topics include: angular momentum tensors; properties of T/sub i//sup (n)/ matrices; T/sub i//sup (n)/ matrices as Clebsch-Gordan coefficients; construction of higher rank tensors; normalization: trace of products of two s-rank tensors; completeness relation; algebra of U(N); eigenvalue of the quadratic Casimir operator for U(3); general result for U(N); angular momentum content of U(3) representation; p-Boson model; Hamiltonian; quadrupole transitions; S,P Boson model; expectation value of dipole operator; S-D model: U(6); quadratic Casimir operator; an O(5) subgroup; an O(6) subgroup; properties of O(5) representations; quadratic Casimir operator; quadratic Casimir operator for U(6); decomposition via SU(5) chain; a special O(3) decomposition of SU(3); useful identities; a useful property of D/sub αβγ/(α,β,γ = 4-8) as coupling coefficients; explicit construction of T/sub x//sup (2)/ and d/sub αβγ/; D-coefficients; eigenstates of T3; and summary of T = 2 states
Operators of Approximations and Approximate Power Set Spaces
ZHANG Xian-yong; MO Zhi-wen; SHU Lan
2004-01-01
Boundary inner and outer operators are introduced; and union, intersection, complement operators of approximations are redefined. The approximation operators have a good property of maintaining union, intersection, complement operators, so the rough set theory has been enriched from the operator-oriented and set-oriented views. Approximate power set spaces are defined, and it is proved that the approximation operators are epimorphisms from power set space to approximate power set spaces. Some basic properties of approximate power set space are got by epimorphisms in contrast to power set space.
Approximation algorithms and hardness of approximation for knapsack problems
Buhrman, H.; Loff, B.; Torenvliet, L.
2012-01-01
We show various hardness of approximation algorithms for knapsack and related problems; in particular we will show that unless the Exponential-Time Hypothesis is false, then subset-sum cannot be approximated any better than with an FPTAS. We also give a simple new algorithm for approximating knapsac
Approximate nonlinear self-adjointness and approximate conservation laws
In this paper, approximate nonlinear self-adjointness for perturbed PDEs is introduced and its properties are studied. Consequently, approximate conservation laws which cannot be obtained by the approximate Noether theorem are constructed by means of the method. As an application, a class of perturbed nonlinear wave equations is considered to illustrate the effectiveness. (paper)
$\\sigma $ -Approximately Contractible Banach Algebras
Momeni, M; Yazdanpanah, T.; Mardanbeigi, M. R.
2012-01-01
We investigate $\\sigma $ -approximate contractibility and $\\sigma $ -approximate amenability of Banach algebras, which are extensions of usual notions of contractibility and amenability, respectively, where $\\sigma $ is a dense range or an idempotent bounded endomorphism of the corresponding Banach algebra.
Approximation by planar elastic curves
Brander, David; Gravesen, Jens; Nørbjerg, Toke Bjerge
2015-01-01
We give an algorithm for approximating a given plane curve segment by a planar elastic curve. The method depends on an analytic representation of the space of elastic curve segments, together with a geometric method for obtaining a good initial guess for the approximating curve. A gradient......-driven optimization is then used to find the approximating elastic curve....
Approximate sine-Gordon solitons
Stratopoulos, G.N. (Dept. of Mathematical Sciences, Durham Univ. (United Kingdom)); Zakrzewski, W.J. (Dept. of Mathematical Sciences, Durham Univ. (United Kingdom))
1993-08-01
We look at the recently proposed scheme of approximating a sine-Gordon soliton by an expression derived from two dimensional instantons. We point out that the scheme of Sutcliffe in which he uses two dimensional instantons can be generalised to higher dimensions and that these generalisations produce even better approximations than the original approximation. We also comment on generalisations to other models. (orig.)
Exact constants in approximation theory
Korneichuk, N
1991-01-01
This book is intended as a self-contained introduction for non-specialists, or as a reference work for experts, to the particular area of approximation theory that is concerned with exact constants. The results apply mainly to extremal problems in approximation theory, which in turn are closely related to numerical analysis and optimization. The book encompasses a wide range of questions and problems: best approximation by polynomials and splines; linear approximation methods, such as spline-approximation; optimal reconstruction of functions and linear functionals. Many of the results are base
International Conference Approximation Theory XIV
Schumaker, Larry
2014-01-01
This volume developed from papers presented at the international conference Approximation Theory XIV, held April 7–10, 2013 in San Antonio, Texas. The proceedings contains surveys by invited speakers, covering topics such as splines on non-tensor-product meshes, Wachspress and mean value coordinates, curvelets and shearlets, barycentric interpolation, and polynomial approximation on spheres and balls. Other contributed papers address a variety of current topics in approximation theory, including eigenvalue sequences of positive integral operators, image registration, and support vector machines. This book will be of interest to mathematicians, engineers, and computer scientists working in approximation theory, computer-aided geometric design, numerical analysis, and related approximation areas.
Matthews, Charles
2013-01-01
Molecular dynamics (MD) computations aim to simulate materials at the atomic level by approximating molecular interactions classically, relying on the Born-Oppenheimer approximation and semi-empirical potential energy functions as an alternative to solving the difficult time-dependent Schrodinger equation. An approximate solution is obtained by discretization in time, with an appropriate algorithm used to advance the state of the system between successive timesteps. Modern MD s...
Approximate solutions for the skyrmion
Ponciano, J A; Fanchiotti, H; Canal-Garcia, C A
2001-01-01
We reconsider the Euler-Lagrange equation for the Skyrme model in the hedgehog ansatz and study the analytical properties of the solitonic solution. In view of the lack of a closed form solution to the problem, we work on approximate analytical solutions. We show that Pade approximants are well suited to continue analytically the asymptotic representation obtained in terms of a power series expansion near the origin, obtaining explicit approximate solutions for the Skyrme equations. We improve the approximations by applying the 2-point Pade approximant procedure whereby the exact behaviour at spatial infinity is incorporated. An even better convergence to the exact solution is obtained by introducing a modified form for the approximants. The new representations share the same analytical properties with the exact solution at both small and large values of the radial variable r.
The Smoothed Approximate Linear Program
Desai, V V; Moallemi, C C
2009-01-01
We present a novel linear program for the approximation of the dynamic programming cost-to-go function in high-dimensional stochastic control problems. LP approaches to approximate DP have typically relied on a natural `projection' of a well studied linear program for exact dynamic programming. Such programs restrict attention to approximations that are lower bounds to the optimal cost-to-go function. Our program--the `smoothed approximate linear program'--is distinct from such approaches and relaxes the restriction to lower bounding approximations in an appropriate fashion while remaining computationally tractable. Doing so appears to have several advantages: First, we demonstrate substantially superior bounds on the quality of approximation to the optimal cost-to-go function afforded by our approach. Second, experiments with our approach on a challenging problem (the game of Tetris) show that the approach outperforms the existing LP approach (which has previously been shown to be competitive with several AD...
Approximate Grammar for Information Extraction
Sriram, V; Reddy, B. Ravi Sekar; Sangal, R.
2003-01-01
In this paper, we present the concept of Approximate grammar and how it can be used to extract information from a documemt. As the structure of informational strings cannot be defined well in a document, we cannot use the conventional grammar rules to represent the information. Hence, the need arises to design an approximate grammar that can be used effectively to accomplish the task of Information extraction. Approximate grammars are a novel step in this direction. The rules of an approximat...
BDD Minimization for Approximate Computing
Soeken, Mathias; Grosse, Daniel; Chandrasekharan, Arun; Drechsler, Rolf
2016-01-01
We present Approximate BDD Minimization (ABM) as a problem that has application in approximate computing. Given a BDD representation of a multi-output Boolean function, ABM asks whether there exists another function that has a smaller BDD representation but meets a threshold w.r.t. an error metric. We present operators to derive approximated functions and present algorithms to exactly compute the error metrics directly on the BDD representation. An experimental evaluation demonstrates the app...
Beyond the random phase approximation
Olsen, Thomas; Thygesen, Kristian S.
2013-01-01
We assess the performance of a recently proposed renormalized adiabatic local density approximation (rALDA) for ab initio calculations of electronic correlation energies in solids and molecules. The method is an extension of the random phase approximation (RPA) derived from time-dependent density...
Matrix-Free Approximate Equilibration
Bradley, Andrew M.; Murray, Walter
2011-01-01
The condition number of a diagonally scaled matrix, for appropriately chosen scaling matrices, is often less than that of the original. Equilibration scales a matrix so that the scaled matrix's row and column norms are equal. Scaling can be approximate. We develop approximate equilibration algorithms for nonsymmetric and symmetric matrices having signed elements that access a matrix only by matrix-vector products.
Approximate circuits for increased reliability
Hamlet, Jason R.; Mayo, Jackson R.
2015-08-18
Embodiments of the invention describe a Boolean circuit having a voter circuit and a plurality of approximate circuits each based, at least in part, on a reference circuit. The approximate circuits are each to generate one or more output signals based on values of received input signals. The voter circuit is to receive the one or more output signals generated by each of the approximate circuits, and is to output one or more signals corresponding to a majority value of the received signals. At least some of the approximate circuits are to generate an output value different than the reference circuit for one or more input signal values; however, for each possible input signal value, the majority values of the one or more output signals generated by the approximate circuits and received by the voter circuit correspond to output signal result values of the reference circuit.
Approximate circuits for increased reliability
Hamlet, Jason R.; Mayo, Jackson R.
2015-12-22
Embodiments of the invention describe a Boolean circuit having a voter circuit and a plurality of approximate circuits each based, at least in part, on a reference circuit. The approximate circuits are each to generate one or more output signals based on values of received input signals. The voter circuit is to receive the one or more output signals generated by each of the approximate circuits, and is to output one or more signals corresponding to a majority value of the received signals. At least some of the approximate circuits are to generate an output value different than the reference circuit for one or more input signal values; however, for each possible input signal value, the majority values of the one or more output signals generated by the approximate circuits and received by the voter circuit correspond to output signal result values of the reference circuit.
N-variable rational approximants
''Desirable properties'' of a two-variable generalization of Pade approximants are laid down. The ''Chisholm approximants'' are defined and are shown to obey nearly all of these properties; the alternative ways of completing a unique definition are discussed, and the ''prong structure'' of the defining equations is elucidated. Several generalizations and variants of Chisholm approximants are described: N-variable diagonal, 2-variable simple off-diagonal, N-variable simple and general off-diagonal, and rotationally covariant 2-variable approximants. All of the 2-variable approximants are capable of representing singularities of functions of two variables, and of analytically continuing beyond the polycylinder of convergence of the double series. 8 figures
Chebyshev polynomial approximation to approximate partial differential equations
Caporale, Guglielmo Maria; Cerrato, Mario
2008-01-01
This pa per suggests a simple method based on Chebyshev approximation at Chebyshev nodes to approximate partial differential equations. The methodology simply consists in determining the value function by using a set of nodes and basis functions. We provide two examples. Pricing an European option and determining the best policy for chatting down a machinery. The suggested method is flexible, easy to program and efficient. It is also applicable in other fields, providing efficient solutions t...
Adiabatic Invariant Treatment of a Collapsing Sphere of Quantized Dust
Roberto CasadioDipartimento di Fisica, Universita' di Bologna and INFN, Bologna; Fabio Finelli(Dipartimento di Fisica, Universita' di Bologna and INFN, Bologna); Giovanni Venturi(Department of Physics, University of Bologna, and Istituto Nazionale di Fisica Nucleare, Sezione di Bologna, Italy)
2015-01-01
The semiclassical collapse of a sphere of quantized dust is studied. A Born-Oppenheimer decomposition is performed for the wave function of the system and the semiclassical limit is considered for the gravitational part. The method of adiabatic invariants for time dependent Hamiltonians is then employed to find (approximate) solutions to the quantum dust equations of motions. This allows us to obtain corrections to the adiabatic approximation of the dust states associated with the time evolut...
The efficiency of Flory approximation
The Flory approximation for the self-avoiding chain problem is compared with a conventional perturbation theory expansion. While in perturbation theory each term is averaged over the unperturbed set of configurations, the Flory approximation is equivalent to the perturbation theory with the averaging over the stretched set of configurations. This imposes restrictions on the integration domain in higher order terms and they can be treated self-consistently. The accuracy δν/ν of Flory approximation for self-avoiding chain problems is estimated to be 2-5% for 1 < d < 4. (orig.)
Approximate Reanalysis in Topology Optimization
Amir, Oded; Bendsøe, Martin P.; Sigmund, Ole
2009-01-01
In the nested approach to structural optimization, most of the computational effort is invested in the solution of the finite element analysis equations. In this study, the integration of an approximate reanalysis procedure into the framework of topology optimization of continuum structures is...... investigated. The nested optimization problem is re-formulated to accommodate the use of an approximate displacement vector and the design sensitivities are derived accordingly. It is shown that relatively rough approximations are acceptable since the errors are taken into account in the sensitivity analysis...
Topological Issues In Effective Quantum Theories (skyrmions, Doublet Structure)
Vaidya, S M
1998-01-01
The Born-Oppenheimer (B-O) approximation is an intuitively appealing as well as an efficient scheme to discuss quantum theories that allow a natural separation of degrees of freedom according to energy scales. This dissertation studies a subtle and remarkable interaction between two topological effects in certain effective quantum theories, one being the violation of parity ${\\cal P}$ and time-reversal ${\\cal T}$ symmetries in the quantum description of shapes, the other being the geometric phase arising from the Born-Oppenheimer approximation. There are numerous examples of approximately degenerate states of opposite parity in molecular and nuclear physics. It has also been suggested that such doubles occur in certain heavy baryons. We discuss the theoretical foundations of these doubles in detail, emphasizing their topological and bundle-theoretical underpinnings...
Weighted approximation with varying weight
Totik, Vilmos
1994-01-01
A new construction is given for approximating a logarithmic potential by a discrete one. This yields a new approach to approximation with weighted polynomials of the form w"n"(" "= uppercase)P"n"(" "= uppercase). The new technique settles several open problems, and it leads to a simple proof for the strong asymptotics on some L p(uppercase) extremal problems on the real line with exponential weights, which, for the case p=2, are equivalent to power- type asymptotics for the leading coefficients of the corresponding orthogonal polynomials. The method is also modified toyield (in a sense) uniformly good approximation on the whole support. This allows one to deduce strong asymptotics in some L p(uppercase) extremal problems with varying weights. Applications are given, relating to fast decreasing polynomials, asymptotic behavior of orthogonal polynomials and multipoint Pade approximation. The approach is potential-theoretic, but the text is self-contained.
Approximate maximizers of intricacy functionals
Buzzi, Jerome
2009-01-01
G. Edelman, O. Sporns, and G. Tononi introduced in theoretical biology the neural complexity of a family of random variables. This functional is a special case of intricacy, i.e., an average of the mutual information of subsystems whose weights have good mathematical properties. Moreover, its maximum value grows at a definite speed with the size of the system. In this work, we compute exactly this speed of growth by building "approximate maximizers" subject to an entropy condition. These approximate maximizers work simultaneously for all intricacies. We also establish some properties of arbitrary approximate maximizers, in particular the existence of a threshold in the size of subsystems of approximate maximizers: most smaller subsystems are almost equidistributed, most larger subsystems determine the full system. The main ideas are a random construction of almost maximizers with a high statistical symmetry and the consideration of entropy profiles, i.e., the average entropies of sub-systems of a given size. ...
Metrical Diophantine approximation for quaternions
Dodson, Maurice
2011-01-01
The metrical theory of Diophantine approximation for quaternions is developed using recent results in the general theory. In particular, Quaternionic analogues of the classical theorems of Khintchine, Jarnik and Jarnik-Besicovitch are established.
Metrical Diophantine approximation for quaternions
Dodson, Maurice; Everitt, Brent
2014-11-01
Analogues of the classical theorems of Khintchine, Jarnik and Jarnik-Besicovitch in the metrical theory of Diophantine approximation are established for quaternions by applying results on the measure of general `lim sup' sets.
Reinforcement Learning via AIXI Approximation
Veness, Joel; Ng, Kee Siong; Hutter, Marcus; Silver, David
2010-01-01
This paper introduces a principled approach for the design of a scalable general reinforcement learning agent. This approach is based on a direct approximation of AIXI, a Bayesian optimality notion for general reinforcement learning agents. Previously, it has been unclear whether the theory of AIXI could motivate the design of practical algorithms. We answer this hitherto open question in the affirmative, by providing the first computationally feasible approximation to the AIXI agent. To deve...
Binary nucleation beyond capillarity approximation
Kalikmanov, V.I.
2010-01-01
Large discrepancies between binary classical nucleation theory (BCNT) and experiments result from adsorption effects and inability of BCNT, based on the phenomenological capillarity approximation, to treat small clusters. We propose a model aimed at eliminating both of these deficiencies. Adsorption is taken into account within Gibbsian approximation. Binary clusters are treated by means of statistical-mechanical considerations: tracing out the molecular degrees of freedom of the more volatil...
Approximate factorization with source terms
Shih, T. I.-P.; Chyu, W. J.
1991-01-01
A comparative evaluation is made of three methodologies with a view to that which offers the best approximate factorization error. While two of these methods are found to lead to more efficient algorithms in cases where factors which do not contain source terms can be diagonalized, the third method used generates the lowest approximate factorization error. This method may be preferred when the norms of source terms are large, and transient solutions are of interest.
Chebyshev approximation for multivariate functions
Sukhorukova, Nadezda; Ugon, Julien; Yost, David
2015-01-01
In this paper, we derive optimality conditions (Chebyshev approximation) for multivariate functions. The theory of Chebyshev (uniform) approximation for univariate functions is very elegant. The optimality conditions are based on the notion of alternance (maximal deviation points with alternating deviation signs). It is not very straightforward, however, how to extend the notion of alternance to the case of multivariate functions. There have been several attempts to extend the theory of Cheby...
Analytic Approximations for Spread Options
Carol Alexander; Aanand Venkatramanan
2007-01-01
Even in the simple case that two price processes follow correlated geometric Brownian motions with constant volatility no analytic formula for the price of a standard European spread option has been derived, except when the strike is zero in which case the option becomes an exchange option. This paper expresses the price of a spread option as the price of a compound exchange option and hence derives a new analytic approximation for its price and hedge ratios. This approximation has several ad...
Wavelet Sparse Approximate Inverse Preconditioners
Chan, Tony F.; Tang, W.-P.; Wan, W. L.
1996-01-01
There is an increasing interest in using sparse approximate inverses as preconditioners for Krylov subspace iterative methods. Recent studies of Grote and Huckle and Chow and Saad also show that sparse approximate inverse preconditioner can be effective for a variety of matrices, e.g. Harwell-Boeing collections. Nonetheless a drawback is that it requires rapid decay of the inverse entries so that sparse approximate inverse is possible. However, for the class of matrices that, come from elliptic PDE problems, this assumption may not necessarily hold. Our main idea is to look for a basis, other than the standard one, such that a sparse representation of the inverse is feasible. A crucial observation is that the kind of matrices we are interested in typically have a piecewise smooth inverse. We exploit this fact, by applying wavelet techniques to construct a better sparse approximate inverse in the wavelet basis. We shall justify theoretically and numerically that our approach is effective for matrices with smooth inverse. We emphasize that in this paper we have only presented the idea of wavelet approximate inverses and demonstrated its potential but have not yet developed a highly refined and efficient algorithm.
Shearlets and Optimally Sparse Approximations
Kutyniok, Gitta; Lim, Wang-Q
2011-01-01
Multivariate functions are typically governed by anisotropic features such as edges in images or shock fronts in solutions of transport-dominated equations. One major goal both for the purpose of compression as well as for an efficient analysis is the provision of optimally sparse approximations of such functions. Recently, cartoon-like images were introduced in 2D and 3D as a suitable model class, and approximation properties were measured by considering the decay rate of the $L^2$ error of the best $N$-term approximation. Shearlet systems are to date the only representation system, which provide optimally sparse approximations of this model class in 2D as well as 3D. Even more, in contrast to all other directional representation systems, a theory for compactly supported shearlet frames was derived which moreover also satisfy this optimality benchmark. This chapter shall serve as an introduction to and a survey about sparse approximations of cartoon-like images by band-limited and also compactly supported sh...
Relativistic regular approximations revisited: An infinite-order relativistic approximation
The concept of the regular approximation is presented as the neglect of the energy dependence of the exact Foldy - Wouthuysen transformation of the Dirac Hamiltonian. Expansion of the normalization terms leads immediately to the zeroth-order regular approximation (ZORA) and first-order regular approximation (FORA) Hamiltonians as the zeroth- and first-order terms of the expansion. The expansion may be taken to infinite order by using an un-normalized Foldy - Wouthuysen transformation, which results in the ZORA Hamiltonian and a non-unit metric. This infinite-order regular approximation, IORA, has eigenvalues which differ from the Dirac eigenvalues by order E3/c4 for a hydrogen-like system, which is a considerable improvement over the ZORA eigenvalues, and similar to the non-variational FORA energies. A further perturbation analysis yields a third-order correction to the IORA energies, TIORA. Results are presented for several systems including the neutral U atom. The IORA eigenvalues for all but the 1s spinor of the neutral system are superior even to the scaled ZORA energies, which are exact for the hydrogenic system. The third-order correction reduces the IORA error for the inner orbitals to a very small fraction of the Dirac eigenvalue. copyright 1999 American Institute of Physics
How large are nonadiabatic effects in atomic and diatomic systems?
Yang, Yubo; Kylänpää, Ilkka; Tubman, Norm M; Krogel, Jaron T; Hammes-Schiffer, Sharon; Ceperley, David M
2015-09-28
With recent developments in simulating nonadiabatic systems to high accuracy, it has become possible to determine how much energy is attributed to nuclear quantum effects beyond zero-point energy. In this work, we calculate the non-relativistic ground-state energies of atomic and molecular systems without the Born-Oppenheimer approximation. For this purpose, we utilize the fixed-node diffusion Monte Carlo method, in which the nodes depend on both the electronic and ionic positions. We report ground-state energies for all systems studied, ionization energies for the first-row atoms and atomization energies for the first-row hydrides. We find the ionization energies of the atoms to be nearly independent of the Born-Oppenheimer approximation, within the accuracy of our results. The atomization energies of molecular systems, however, show small effects of the nonadiabatic coupling between electrons and nuclei. PMID:26429012
How large are nonadiabatic effects in atomic and diatomic systems?
With recent developments in simulating nonadiabatic systems to high accuracy, it has become possible to determine how much energy is attributed to nuclear quantum effects beyond zero-point energy. In this work, we calculate the non-relativistic ground-state energies of atomic and molecular systems without the Born-Oppenheimer approximation. For this purpose, we utilize the fixed-node diffusion Monte Carlo method, in which the nodes depend on both the electronic and ionic positions. We report ground-state energies for all systems studied, ionization energies for the first-row atoms and atomization energies for the first-row hydrides. We find the ionization energies of the atoms to be nearly independent of the Born-Oppenheimer approximation, within the accuracy of our results. The atomization energies of molecular systems, however, show small effects of the nonadiabatic coupling between electrons and nuclei
We theoretically investigate the photon-echo spectroscopy of coupled electron-nuclear quantum dynamics. Two situations are treated. In the first case, the Born-Oppenheimer (adiabatic) approximation holds. It is then possible to interpret the two-dimensional (2D) spectra in terms of vibrational motion taking place in different electronic states. In particular, pure vibrational coherences which are related to oscillations in the time-dependent third-order polarization can be identified. This concept fails in the second case, where strong non-adiabatic coupling leads to the breakdown of the Born-Oppenheimer-approximation. Then, the 2D-spectra reveal a complicated vibronic structure and vibrational coherences cannot be disentangled from the electronic motion
How large are nonadiabatic effects in atomic and diatomic systems?
Yang, Yubo, E-mail: yyang173@illinois.edu, E-mail: normantubman2015@u.northwestern.edu; Tubman, Norm M., E-mail: yyang173@illinois.edu, E-mail: normantubman2015@u.northwestern.edu; Ceperley, David M. [Department of Physics, University of Illinois, Urbana, Illinois 61801 (United States); Kylänpää, Ilkka [Department of Physics, University of Illinois, Urbana, Illinois 61801 (United States); Department of Physics, Tampere University of Technology, P.O. Box 692, FI-33101 Tampere (Finland); Krogel, Jaron T. [Oak Ridge National Laboratory, Materials Sciences & Technology Division, Oak Ridge, Tennessee 37831 (United States); Hammes-Schiffer, Sharon [Department of Chemistry, University of Illinois, Urbana, Illinois 61801 (United States)
2015-09-28
With recent developments in simulating nonadiabatic systems to high accuracy, it has become possible to determine how much energy is attributed to nuclear quantum effects beyond zero-point energy. In this work, we calculate the non-relativistic ground-state energies of atomic and molecular systems without the Born-Oppenheimer approximation. For this purpose, we utilize the fixed-node diffusion Monte Carlo method, in which the nodes depend on both the electronic and ionic positions. We report ground-state energies for all systems studied, ionization energies for the first-row atoms and atomization energies for the first-row hydrides. We find the ionization energies of the atoms to be nearly independent of the Born-Oppenheimer approximation, within the accuracy of our results. The atomization energies of molecular systems, however, show small effects of the nonadiabatic coupling between electrons and nuclei.
How Large are Nonadiabatic Effects in Atomic and Diatomic Systems?
Yang, Yubo; Tubman, Norm; Krogel, Jaron; Hammes-Schiffer, Sharon; Ceperley, David
2015-01-01
With recent developments in simulating nonadiabatic systems to high accuracy, it has become possible to determine how much energy is attributed to nuclear quantum effects beyond zero-point energy. In this work we calculate the non-relativistic ground-state energies of atomic and molecular systems without the Born-Oppenheimer approximation. For this purpose we utilize the fixed-node diffusion Monte Carlo method, in which the nodes depend on both the electronic and ionic positions. We report ground-state energies for all systems studied, ionization energies for the first-row atoms and atomization energies for the first-row hydrides. We find the ionization energies of the atoms to be nearly independent of the Born-Oppenheimer approximation, within the accuracy of our results. The atomization energies of molecular systems, however, show small effects of the nonadiabatic coupling between electrons and nuclei.
How large are nonadiabatic effects in atomic and diatomic systems?
Yang, Yubo; Kylänpää, Ilkka; Tubman, Norm M.; Krogel, Jaron T.; Hammes-Schiffer, Sharon; Ceperley, David M.
2015-09-01
With recent developments in simulating nonadiabatic systems to high accuracy, it has become possible to determine how much energy is attributed to nuclear quantum effects beyond zero-point energy. In this work, we calculate the non-relativistic ground-state energies of atomic and molecular systems without the Born-Oppenheimer approximation. For this purpose, we utilize the fixed-node diffusion Monte Carlo method, in which the nodes depend on both the electronic and ionic positions. We report ground-state energies for all systems studied, ionization energies for the first-row atoms and atomization energies for the first-row hydrides. We find the ionization energies of the atoms to be nearly independent of the Born-Oppenheimer approximation, within the accuracy of our results. The atomization energies of molecular systems, however, show small effects of the nonadiabatic coupling between electrons and nuclei.
Electron-vibration coupling induced renormalization in the photoemission spectrum of diamondoids
Gali, Adam; Demján, Tamás; Vörös, Márton; Thiering, Gergő; Cannuccia, Elena; Marini, Andrea
2016-04-01
The development of theories and methods devoted to the accurate calculation of the electronic quasi-particle states and levels of molecules, clusters and solids is of prime importance to interpret the experimental data. These quantum systems are often modelled by using the Born-Oppenheimer approximation where the coupling between the electrons and vibrational modes is not fully taken into account, and the electrons are treated as pure quasi-particles. Here, we show that in small diamond cages, called diamondoids, the electron-vibration coupling leads to the breakdown of the electron quasi-particle picture. More importantly, we demonstrate that the strong electron-vibration coupling is essential to properly describe the overall lineshape of the experimental photoemission spectrum. This cannot be obtained by methods within Born-Oppenheimer approximation. Moreover, we deduce a link between the vibronic states found by our many-body perturbation theory approach and the well-known Jahn-Teller effect.
Albert, Julian; Falge, Mirjam; Hildenbrand, Heiko; Engel, Volker [Universität Würzburg, Institut für Physikalische und Theoretische Chemie, Emil-Fischer-Str. 42, Campus Nord, Am Hubland, 97074 Würzburg (Germany); Gomez, Sandra; Sola, Ignacio R. [Departamento de Quimica Fisica, Universidad Complutense, 28040 Madrid (Spain)
2015-07-28
We theoretically investigate the photon-echo spectroscopy of coupled electron-nuclear quantum dynamics. Two situations are treated. In the first case, the Born-Oppenheimer (adiabatic) approximation holds. It is then possible to interpret the two-dimensional (2D) spectra in terms of vibrational motion taking place in different electronic states. In particular, pure vibrational coherences which are related to oscillations in the time-dependent third-order polarization can be identified. This concept fails in the second case, where strong non-adiabatic coupling leads to the breakdown of the Born-Oppenheimer-approximation. Then, the 2D-spectra reveal a complicated vibronic structure and vibrational coherences cannot be disentangled from the electronic motion.
Approximation methods in probability theory
Čekanavičius, Vydas
2016-01-01
This book presents a wide range of well-known and less common methods used for estimating the accuracy of probabilistic approximations, including the Esseen type inversion formulas, the Stein method as well as the methods of convolutions and triangle function. Emphasising the correct usage of the methods presented, each step required for the proofs is examined in detail. As a result, this textbook provides valuable tools for proving approximation theorems. While Approximation Methods in Probability Theory will appeal to everyone interested in limit theorems of probability theory, the book is particularly aimed at graduate students who have completed a standard intermediate course in probability theory. Furthermore, experienced researchers wanting to enlarge their toolkit will also find this book useful.
Concept Approximation between Fuzzy Ontologies
无
2006-01-01
Fuzzy ontologies are efficient tools to handle fuzzy and uncertain knowledge on the semantic web; but there are heterogeneity problems when gaining interoperability among different fuzzy ontologies. This paper uses concept approximation between fuzzy ontologies based on instances to solve the heterogeneity problems. It firstly proposes an instance selection technology based on instance clustering and weighting to unify the fuzzy interpretation of different ontologies and reduce the number of instances to increase the efficiency. Then the paper resolves the problem of computing the approximations of concepts into the problem of computing the least upper approximations of atom concepts. It optimizes the search strategies by extending atom concept sets and defining the least upper bounds of concepts to reduce the searching space of the problem. An efficient algorithm for searching the least upper bounds of concept is given.
An Approximation Ratio for Biclustering
Puolamäki, Kai; Hanhijärvi, Sami; Garriga, Gemma C
2007-01-01
The problem of biclustering consists of the simultaneous clustering of rows and columns of a matrix such that each of the submatrices induced by a pair of row and column clusters is as uniform as possible. In this paper we approximate the optimal biclustering by applying one-way clustering algorithms independently on the rows and on the columns of the input matrix. We show that such a solution yields a worst-case approximation ratio of 1+sqrt(2) under L1-norm for 0-1 valued matrices, and of 2...
An Approximation Ratio for Biclustering
Puolamäki, Kai; Garriga, Gemma C
2007-01-01
The problem of biclustering consists of the simultaneous clustering of rows and columns of a matrix such that each of the submatrices induced by a pair of row and column clusters is as uniform as possible. In this paper we approximate the optimal biclustering by applying one-way clustering algorithms independently on the rows and on the columns of the input matrix. We show that such a solution yields a worst-case approximation ratio of 1+sqrt(2) under L1-norm for 0-1 valued matrices, and of 2 under L2-norm for real valued matrices.
Shearlets and Optimally Sparse Approximations
Kutyniok, Gitta; Lemvig, Jakob; Lim, Wang-Q
Multivariate functions are typically governed by anisotropic features such as edges in images or shock fronts in solutions of transport-dominated equations. One major goal both for the purpose of compression as well as for an efficient analysis is the provision of optimally sparse approximations of...... provide optimally sparse approximations of this model class in 2D as well as 3D. Even more, in contrast to all other directional representation systems, a theory for compactly supported shearlet frames was derived which moreover also satisfy this optimality benchmark. This chapter shall serve as an...
Approximate Reasoning with Fuzzy Booleans
Broek, van den P.M.; Noppen, J.A.R.
2004-01-01
This paper introduces, in analogy to the concept of fuzzy numbers, the concept of fuzzy booleans, and examines approximate reasoning with the compositional rule of inference using fuzzy booleans. It is shown that each set of fuzzy rules is equivalent to a set of fuzzy rules with singleton crisp ante
Truthful approximations to range voting
Filos-Ratsika, Aris; Miltersen, Peter Bro
We consider the fundamental mechanism design problem of approximate social welfare maximization under general cardinal preferences on a finite number of alternatives and without money. The well-known range voting scheme can be thought of as a non-truthful mechanism for exact social welfare maximi...
Analytical Approximations to Galaxy Clustering
Mo, H. J.
1997-01-01
We discuss some recent progress in constructing analytic approximations to the galaxy clustering. We show that successful models can be constructed for the clustering of both dark matter and dark matter haloes. Our understanding of galaxy clustering and galaxy biasing can be greatly enhanced by these models.
Ultrafast Approximation for Phylogenetic Bootstrap
Bui Quang Minh, [No Value; Nguyen, Thi; von Haeseler, Arndt
2013-01-01
Nonparametric bootstrap has been a widely used tool in phylogenetic analysis to assess the clade support of phylogenetic trees. However, with the rapidly growing amount of data, this task remains a computational bottleneck. Recently, approximation methods such as the RAxML rapid bootstrap (RBS) and
Approximation by Penultimate Stable Laws
L.F.M. de Haan (Laurens); L. Peng (Liang); H. Iglesias Pereira
1997-01-01
textabstractIn certain cases partial sums of i.i.d. random variables with finite variance are better approximated by a sequence of stable distributions with indices \\\\alpha_n \\\\to 2 than by a normal distribution. We discuss when this happens and how much the convergence rate can be improved by using
Approximation properties of haplotype tagging
Dreiseitl Stephan
2006-01-01
Full Text Available Abstract Background Single nucleotide polymorphisms (SNPs are locations at which the genomic sequences of population members differ. Since these differences are known to follow patterns, disease association studies are facilitated by identifying SNPs that allow the unique identification of such patterns. This process, known as haplotype tagging, is formulated as a combinatorial optimization problem and analyzed in terms of complexity and approximation properties. Results It is shown that the tagging problem is NP-hard but approximable within 1 + ln((n2 - n/2 for n haplotypes but not approximable within (1 - ε ln(n/2 for any ε > 0 unless NP ⊂ DTIME(nlog log n. A simple, very easily implementable algorithm that exhibits the above upper bound on solution quality is presented. This algorithm has running time O((2m - p + 1 ≤ O(m(n2 - n/2 where p ≤ min(n, m for n haplotypes of size m. As we show that the approximation bound is asymptotically tight, the algorithm presented is optimal with respect to this asymptotic bound. Conclusion The haplotype tagging problem is hard, but approachable with a fast, practical, and surprisingly simple algorithm that cannot be significantly improved upon on a single processor machine. Hence, significant improvement in computatational efforts expended can only be expected if the computational effort is distributed and done in parallel.
Low Rank Approximation in $G_0W_0$ Approximation
Shao, Meiyue; Yang, Chao; Liu, Fang; da Jornada, Felipe H; Deslippe, Jack; Louie, Steven G
2016-01-01
The single particle energies obtained in a Kohn--Sham density functional theory (DFT) calculation are generally known to be poor approximations to electron excitation energies that are measured in transport, tunneling and spectroscopic experiments such as photo-emission spectroscopy. The correction to these energies can be obtained from the poles of a single particle Green's function derived from a many-body perturbation theory. From a computational perspective, the accuracy and efficiency of such an approach depends on how a self energy term that properly accounts for dynamic screening of electrons is approximated. The $G_0W_0$ approximation is a widely used technique in which the self energy is expressed as the convolution of a non-interacting Green's function ($G_0$) and a screened Coulomb interaction ($W_0$) in the frequency domain. The computational cost associated with such a convolution is high due to the high complexity of evaluating $W_0$ at multiple frequencies. In this paper, we discuss how the cos...
Wave Mechanics of a Two Wire Atomic Beamsplitter
Bortolotti, Daniele C. E.; Bohn, John L.
2003-01-01
We consider the problem of an atomic beam propagating quantum mechanically through an atom beam splitter. Casting the problem in an adiabatic representation (in the spirit of the Born-Oppenheimer approximation in molecular physics) sheds light on explicit effects due to non-adiabatic passage of the atoms through the splitter region. We are thus able to probe the fully three dimensional structure of the beam splitter, gathering quantitative information about mode-mixing, splitting ratios,and r...
Wave Mechanics of a Two Wire Atomic Beamsplitter
Bortolotti, D C E; Bortolotti, Daniele C. E.; Bohn, John L.
2004-01-01
We consider the problem of an atomic beam propagating quantum mechanically through an atom beam splitter. Casting the problem in an adiabatic representation (in the spirit of the Born-Oppenheimer approximation in molecular physics) sheds light on explicit effects due to non-adiabatic passage of the atoms through the splitter region. We are thus able to probe the fully three dimensional structure of the beam splitter, gathering quantitative information about mode-mixing, splitting ratios,and reflection and transmission probabilities.
Wave mechanics of a two-wire atomic beam splitter
We consider the problem of an atomic beam propagating quantum mechanically through an atom beam splitter. Casting the problem in an adiabatic representation (in the spirit of the Born-Oppenheimer approximation in molecular physics) sheds light on explicit effects due to nonadiabatic passage of the atoms through the splitter region. We are thus able to probe the fully three-dimensional structure of the beam splitter, gathering quantitative information about mode mixing, splitting ratios, and reflection and transmission probabilities
Semiclassical collapse of a sphere of dust
Roberto CasadioDepartment of Physics University of Bologna and Istituto Nazionale di Fisica Nucleare, Sezione di Bologna; Giovanni Venturi(Department of Physics, University of Bologna, and Istituto Nazionale di Fisica Nucleare, Sezione di Bologna, Italy)
2015-01-01
The semiclassical collapse of a homogeneous sphere of dust is studied. After identifying the independent dynamical variables, the system is canonically quantised and coupled equations describing matter (dust) and gravitation are obtained. The conditions for the validity of the adiabatic (Born--Oppenheimer) and semiclassical approximations are derived. Further on neglecting back--reaction effects, it is shown that in the vicinity of the horizon and inside the dust the Wightman function for a c...
Dirichlet eigenvalues of cones in the small aperture limit
Ourmières-Bonafos, Thomas
2014-01-01
We are interested in finite cones of fixed height 1 parametrized by their opening angle. We study the eigenpairs of the Dirichlet Laplacian in such domains when their apertures tend to 0. We provide multi-scale asymptotics for eigenpairs associated with the lowest eigenvalues of each fiber of the Dirichlet Laplacian. In order to do this, we investigate the family of their one-dimensional Born-Oppenheimer approximations. The eigenvalue asymptotics involves powers of the cube root of the apertu...
A mathematical and computational review of Hartree-Fock SCF methods in Quantum Chemistry
Echenique, Pablo; Alonso, José Luis
2007-01-01
Abstract We present here a review of the fundamental topics of Hartree-Fock theory in Quantum Chemistry. From the molecular Hamiltonian, using and discussing the Born-Oppenheimer approximation, we arrive to the Hartree and Hartree-Fock equations for the electronic problem. Special emphasis is placed in the most relevant mathematical aspects of the theoretical derivation of the final equations, as well as in the results regarding the existence and uniqueness of the...
Neutron Resonances in Systems of Few Nuclei and Their Possible Role in Radiation of Overdense Stars
Exact analytical solutions of three- and four-body systems made of one light particle and other heavy particles have been obtained in the model of Born-Oppenheimer approximation with two-body separable interactions. In the case of neutron scattering on a subsystem of few fixed nuclei the appearance of new resonance quantum states has been shown as well as their dependence on distances between heavy nuclei. The applications of new phenomena to overdense stars radiation are considered. (author)
Variational calculations on the hydrogen molecular ion
Taylor, J. M.; Yan, Zong-Chao; Dalgarno, A.; Babb, J. F.
1998-01-01
We present high-precision non-relativistic variational calculations of bound vibrational-rotational state energies for the $H_2^+$ and $D_2^+$ molecular ions in each of the lowest electronic states of $\\Sigma_g$, $\\Sigma_u$, and $\\Pi_u$ symmetry. The calculations are carried out including coupling between $\\Sigma$ and $\\Pi$ states but without using the Born-Oppenheimer or any adiabatic approximation. Convergence studies are presented which indicate that the resulting energies for low-lying le...
Photodissociation of the HeH+ molecular ion
The photodissociation cross section of the molecular ion HeH+ was calculated within the Born-Oppenheimer approximation for a parallel, a perpendicular, and an isotropic orientation of the molecular axis with respect to the field, considering also different initial vibrational and rotational states. The results were compared to recent data from a free-electron laser experiment performed at the FLASH facility. Within the experimental uncertainties theoretical and experimental results are compatible with each other.
The effect of dressing on high-order harmonic generation in vibrating H$_2$ molecules
Chirila, C. C.; Lein, M.
2008-01-01
We develop the strong-field approximation for high-order harmonic generation in hydrogen molecules, including the vibrational motion and the laser-induced coupling of the lowest two Born-Oppenheimer states in the molecular ion that is created by the initial ionization of the molecule. We show that the field dressing becomes important at long laser wavelengths ($\\approx 2 \\mu$m), leading to an overall reduction of harmonic generation and modifying the ratio of harmonic signals from different i...
Approximate Matching of Hierarchial Data
Augsten, Nikolaus
formally proof that the pq-gram index can be incrementally updated based on the log of edit operations without reconstructing intermediate tree versions. The incremental update is independent of the data size and scales to a large number of changes in the data. We introduce windowed pq-grams for the......-gram based distance between streets, introduces a global greedy matching that guarantees stable pairs, and links addresses that are stored with different granularity. The connector has been successfully tested with public administration databases. Our extensive experiments on both synthetic and real world......The goal of this thesis is to design, develop, and evaluate new methods for the approximate matching of hierarchical data represented as labeled trees. In approximate matching scenarios two items should be matched if they are similar. Computing the similarity between labeled trees is hard as in...
Approximate Privacy: Foundations and Quantification
Feigenbaum, Joan; Schapira, Michael
2009-01-01
Increasing use of computers and networks in business, government, recreation, and almost all aspects of daily life has led to a proliferation of online sensitive data about individuals and organizations. Consequently, concern about the privacy of these data has become a top priority, particularly those data that are created and used in electronic commerce. There have been many formulations of privacy and, unfortunately, many negative results about the feasibility of maintaining privacy of sensitive data in realistic networked environments. We formulate communication-complexity-based definitions, both worst-case and average-case, of a problem's privacy-approximation ratio. We use our definitions to investigate the extent to which approximate privacy is achievable in two standard problems: the second-price Vickrey auction and the millionaires problem of Yao. For both the second-price Vickrey auction and the millionaires problem, we show that not only is perfect privacy impossible or infeasibly costly to achieve...
Hydrogen: Beyond the Classic Approximation
The classical nucleus approximation is the most frequently used approach for the resolution of problems in condensed matter physics.However, there are systems in nature where it is necessary to introduce the nuclear degrees of freedom to obtain a correct description of the properties.Examples of this, are the systems with containing hydrogen.In this work, we have studied the resolution of the quantum nuclear problem for the particular case of the water molecule.The Hartree approximation has been used, i.e. we have considered that the nuclei are distinguishable particles.In addition, we have proposed a model to solve the tunneling process, which involves the resolution of the nuclear problem for configurations of the system away from its equilibrium position
Concentration Bounds for Stochastic Approximations
Frikha, Noufel
2012-01-01
We obtain non asymptotic concentration bounds for two kinds of stochastic approximations. We first consider the deviations between the expectation of a given function of the Euler scheme of some diffusion process at a fixed deterministic time and its empirical mean obtained by the Monte-Carlo procedure. We then give some estimates concerning the deviation between the value at a given time-step of a stochastic approximation algorithm and its target. Under suitable assumptions both concentration bounds turn out to be Gaussian. The key tool consists in exploiting accurately the concentration properties of the increments of the schemes. For the first case, as opposed to the previous work of Lemaire and Menozzi (EJP, 2010), we do not have any systematic bias in our estimates. Also, no specific non-degeneracy conditions are assumed.
Waveless Approximation Theories of Gravity
Isenberg, J A
2007-01-01
The analysis of a general multibody physical system governed by Einstein's equations in quite difficult, even if numerical methods (on a computer) are used. Some of the difficulties -- many coupled degrees of freedom, dynamic instability -- are associated with the presence of gravitational waves. We have developed a number of ``waveless approximation theories'' (WAT) which repress the gravitational radiation and thereby simplify the analysis. The matter, according to these theories, evolves dynamically. The gravitational field, however, is determined at each time step by a set of elliptic equations with matter sources. There is reason to believe that for many physical systems, the WAT-generated system evolution is a very accurate approximation to that generated by the full Einstein theory.
On Approximability of Block Sorting
Narayanaswamy, N S
2011-01-01
Block Sorting is a well studied problem, motivated by its applications in Optical Character Recognition (OCR), and Computational Biology. Block Sorting has been shown to be NP-Hard, and two separate polynomial time 2-approximation algorithms have been designed for the problem. But questions like whether a better approximation algorithm can be designed, and whether the problem is APX-Hard have been open for quite a while now. In this work we answer the latter question by proving Block Sorting to be Max-SNP-Hard (APX-Hard). The APX-Hardness result is based on a linear reduction of Max-3SAT to Block Sorting. We also provide a new lower bound for the problem via a new parametrized problem k-Block Merging.
Variance approximation under balanced sampling
Deville, Jean-Claude; Tillé, Yves
2016-01-01
A balanced sampling design has the interesting property that Horvitz–Thompson estimators of totals for a set of balancing variables are equal to the totals we want to estimate, therefore the variance of Horvitz–Thompson estimators of variables of interest are reduced in function of their correlations with the balancing variables. Since it is hard to derive an analytic expression for the joint inclusion probabilities, we derive a general approximation of variance based on a residual technique....
Approximating Metal-Insulator Transitions
Danieli, C.; Rayanov, K.; Pavlov, B.; Martin, G.; Flach, S
2014-01-01
We consider quantum wave propagation in one-dimensional quasiperiodic lattices. We propose an iterative construction of quasiperiodic potentials from sequences of potentials with increasing spatial period. At each finite iteration step the eigenstates reflect the properties of the limiting quasiperiodic potential properties up to a controlled maximum system size. We then observe approximate metal-insulator transitions (MIT) at the finite iteration steps. We also report evidence on mobility ed...
Saddlepoint approximations to option prices
Rogers, L. C. G.; Zane, O.
1999-01-01
The use of saddlepoint approximations in statistics is a well-established technique for computing the distribution of a random variable whose moment generating function is known. In this paper, we apply the methodology to computing the prices of various European-style options, whose returns processes are not the Brownian motion with drift assumed in the Black-Scholes paradigm. Through a number of examples, we show that the methodology is generally accurate and fast.
Approximate maximizers of intricacy functionals
Buzzi, Jerome; Zambotti, Lorenzo
2009-01-01
G. Edelman, O. Sporns, and G. Tononi introduced in theoretical biology the neural complexity of a family of random variables. This functional is a special case of intricacy, i.e., an average of the mutual information of subsystems whose weights have good mathematical properties. Moreover, its maximum value grows at a definite speed with the size of the system. In this work, we compute exactly this speed of growth by building "approximate maximizers" subject to an entropy condition. These appr...
Stochastic approximation algorithms and applications
Kushner, Harold J
1997-01-01
In recent years algorithms of the stochastic approximation type have found applications in new and diverse areas, and new techniques have been developed for proofs of convergence and rate of convergence. The actual and potential applications in signal processing have exploded. New challenges have arisen in applications to adaptive control. This book presents a thorough coverage of the ODE method used to analyze these algorithms.
Quantum Tunneling Beyond Semiclassical Approximation
Banerjee, Rabin; Majhi, Bibhas Ranjan
2008-01-01
Hawking radiation as tunneling by Hamilton-Jacobi method beyond semiclassical approximation is analysed. We compute all quantum corrections in the single particle action revealing that these are proportional to the usual semiclassical contribution. We show that a simple choice of the proportionality constants reproduces the one loop back reaction effect in the spacetime, found by conformal field theory methods, which modifies the Hawking temperature of the black hole. Using the law of black h...
Approximate quantum and acoustic cloaking
Greenleaf, Allan; Lassas, Matti; Uhlmann, Gunther
2008-01-01
At any energy E > 0, we construct a sequence of bounded potentials $V^E_{n}, n\\in\\N$, supported in an annular region $B_{out}\\setminus B_{inn}$ in three-space, which act as approximate cloaks for solutions of Schr\\"odinger's equation: For any potential $V_0\\in L^\\infty(B_{inn})$ such that E is not a Neumann eigenvalue of $-\\Delta+V_0$ in $B_{inn}$, the scattering amplitudes $a_{V_0+V_n^E}(E,\\theta,\\omega)\\to 0$ as $n\\to\\infty$. The $V^E_{n}$ thus not only form a family of approximately transparent potentials, but also function as approximate invisibility cloaks in quantum mechanics. On the other hand, for $E$ close to interior eigenvalues, resonances develop and there exist {\\it almost trapped states} concentrated in $B_{inn}$. We derive the $V_n^E$ from singular, anisotropic transformation optics-based cloaks by a de-anisotropization procedure, which we call \\emph{isotropic transformation optics}. This technique uses truncation, inverse homogenization and spectral theory to produce nonsingular, isotropic app...
Computer Experiments for Function Approximations
Chang, A; Izmailov, I; Rizzo, S; Wynter, S; Alexandrov, O; Tong, C
2007-10-15
This research project falls in the domain of response surface methodology, which seeks cost-effective ways to accurately fit an approximate function to experimental data. Modeling and computer simulation are essential tools in modern science and engineering. A computer simulation can be viewed as a function that receives input from a given parameter space and produces an output. Running the simulation repeatedly amounts to an equivalent number of function evaluations, and for complex models, such function evaluations can be very time-consuming. It is then of paramount importance to intelligently choose a relatively small set of sample points in the parameter space at which to evaluate the given function, and then use this information to construct a surrogate function that is close to the original function and takes little time to evaluate. This study was divided into two parts. The first part consisted of comparing four sampling methods and two function approximation methods in terms of efficiency and accuracy for simple test functions. The sampling methods used were Monte Carlo, Quasi-Random LP{sub {tau}}, Maximin Latin Hypercubes, and Orthogonal-Array-Based Latin Hypercubes. The function approximation methods utilized were Multivariate Adaptive Regression Splines (MARS) and Support Vector Machines (SVM). The second part of the study concerned adaptive sampling methods with a focus on creating useful sets of sample points specifically for monotonic functions, functions with a single minimum and functions with a bounded first derivative.
Product Approximation of Grade and Precision
ZHANG Xian-yong; MO Zhi-wen
2005-01-01
The normal graded approximation and variable precision approximation are defined in approximate space. The relationship between graded approximation and variable precision approximation is studied, and an important formula of conversion between them is achieved. The product approximation of gradeand precision is defined and its basic properties are studied.
Generalized gradient approximation made simple
Generalized gradient approximations Exc = ∫ d3 r f(n↑, n↓, triangledown n↑, triangledown n↓) for the exchange-correlation energy typically surpass the accuracy of the local spin density approximation and compete with standard quantum-chemical methods in electronic-structure calculations. But the derivation and analytic expression for the integrand f tend to be complicated and over-parametrized. We present a simple derivation of a simple but accurate expression for f, involving no parameter other than fundamental-constants. The derivation invoices only general ideas (not details) of the real-space cutoff construction, and agrees closely with the result of this construction. Besides its greater simplicity, this PBE96 functional has other advantages over PW91: (1) The correct behavior of the correlation energy is recovered under uniform scaling to the high-density limit. (2) The linear response of the uniform electron gas agrees with the accurate local spin density prediction. 96:006128*1 Paper TuI 6 Many-body effects are hidden in the universal density functional. The interaction of degenerate states via two-body operators, such as the electron-electron repulsion (for describing multiplets or the interaction of molecular fragments at large separations) are thus not explicitly considered in the Kohn-Sham scheme. In practice the density functionals have to be approximated, and there is a fundamental difficulty which arises in the case of degeneracy. While density functionals should be universal, the effect of degeneracy is linked to the potential characteristic to the atom, molecule, or crystal. There are, however, several possibilities to treat degeneracy effects within density functional theory, a few of which will be discussed. These take profit of the use of two-body operators, which can be, but must not be, the physical electron-electron interaction
Quantum Tunneling Beyond Semiclassical Approximation
Banerjee, Rabin
2008-01-01
Hawking radiation as tunneling by Hamilton-Jacobi method beyond semiclassical approximation is analysed. We compute all quantum corrections in the single particle action revealing that these are proportional to the usual semiclassical contribution. We show that a simple choice of the proportionality constants reproduces the one loop back reaction effect in the spacetime, found by conformal field theory methods, which modifies the Hawking temperature of the black hole. Using the law of black hole mechanics we give the corrections to the Bekenstein-Hawking area law following from the modified Hawking temperature. Some examples are explicitly worked out.
Quantum tunneling beyond semiclassical approximation
Banerjee, Rabin; Ranjan Majhi, Bibhas
2008-06-01
Hawking radiation as tunneling by Hamilton-Jacobi method beyond semiclassical approximation is analysed. We compute all quantum corrections in the single particle action revealing that these are proportional to the usual semiclassical contribution. We show that a simple choice of the proportionality constants reproduces the one loop back reaction effect in the spacetime, found by conformal field theory methods, which modifies the Hawking temperature of the black hole. Using the law of black hole mechanics we give the corrections to the Bekenstein-Hawking area law following from the modified Hawking temperature. Some examples are explicitly worked out.
Fermion Tunneling Beyond Semiclassical Approximation
Majhi, Bibhas Ranjan
2008-01-01
Applying the Hamilton-Jacobi method beyond the semiclassical approximation prescribed in \\cite{Majhi3} for the scalar particle, Hawking radiation as tunneling of Dirac particle through an event horizon is analysed. We show that, as before, all quantum corrections in the single particle action are proportional to the usual semiclassical contribution. We also compute the modifications to the Hawking temperature and Bekenstein-Hawking entropy for the Schwarzschild black hole. Finally, the coefficient of the logarithmic correction to entropy is shown to be related with the trace anomaly.
Fermion tunneling beyond semiclassical approximation
Majhi, Bibhas Ranjan
2009-02-01
Applying the Hamilton-Jacobi method beyond the semiclassical approximation prescribed in R. Banerjee and B. R. Majhi, J. High Energy Phys.JHEPFG1029-8479 06 (2008) 09510.1088/1126-6708/2008/06/095 for the scalar particle, Hawking radiation as tunneling of the Dirac particle through an event horizon is analyzed. We show that, as before, all quantum corrections in the single particle action are proportional to the usual semiclassical contribution. We also compute the modifications to the Hawking temperature and Bekenstein-Hawking entropy for the Schwarzschild black hole. Finally, the coefficient of the logarithmic correction to entropy is shown to be related with the trace anomaly.
Rollout Sampling Approximate Policy Iteration
Dimitrakakis, Christos
2008-01-01
Several researchers have recently investigated the connection between reinforcement learning and classification. We are motivated by proposals of approximate policy iteration schemes without value functions which focus on policy representation using classifiers and address policy learning as a supervised learning problem. This paper proposes variants of an improved policy iteration scheme which addresses the core sampling problem in evaluating a policy through simulation as a multi-armed bandit machine. The resulting algorithm offers comparable performance to the previous algorithm achieved, however, with significantly less computational effort. An order of magnitude improvement is demonstrated experimentally in two standard reinforcement learning domains: inverted pendulum and mountain-car.
The distorted wave Glauber approximation
A solution of the Pauli equation with non-zero potentials defines quantum scalar and vector potentials and magnetic fields and quantum trajectories. If a line integral of perturbing potentials and fields along these quantum trajectories is added to the phase of this solution, an approximate solution of the perturbed equation is found. Glauber theory is a special case and the conditions of applicability are similar. Applications given start from the harmonic oscillator and from a homogeneous magnetic field and add a perturbation. (author)
The structural physical approximation conjecture
Shultz, Fred
2016-01-01
It was conjectured that the structural physical approximation (SPA) of an optimal entanglement witness is separable (or equivalently, that the SPA of an optimal positive map is entanglement breaking). This conjecture was disproved, first for indecomposable maps and more recently for decomposable maps. The arguments in both cases are sketched along with important related results. This review includes background material on topics including entanglement witnesses, optimality, duality of cones, decomposability, and the statement and motivation for the SPA conjecture so that it should be accessible for a broad audience.
Rotating wave approximation and entropy
This Letter studies composite quantum systems, like atom-cavity systems and coupled optical resonators, in the absence of external driving by resorting to methods from quantum field theory. Going beyond the rotating wave approximation, it is shown that the usually neglected counter-rotating part of the Hamiltonian relates to the entropy operator and generates an irreversible time evolution. The vacuum state of the system is shown to evolve into a generalized coherent state exhibiting entanglement of the modes in which the counter-rotating terms are expressed. Possible consequences at observational level in quantum optics experiments are currently under study.
Approximation of Surfaces by Cylinders
Randrup, Thomas
1998-01-01
We present a new method for approximation of a given surface by a cylinder surface. It is a constructive geometric method, leading to a monorail representation of the cylinder surface. By use of a weighted Gaussian image of the given surface, we determine a projection plane. In the orthogonal...... projection of the surface onto this plane, a reference curve is determined by use of methods for thinning of binary images. Finally, the cylinder surface is constructed as follows: the directrix of the cylinder surface is determined by a least squares method minimizing the distance to the points in the...
Wavelet Approximation in Data Assimilation
Tangborn, Andrew; Atlas, Robert (Technical Monitor)
2002-01-01
Estimation of the state of the atmosphere with the Kalman filter remains a distant goal because of high computational cost of evolving the error covariance for both linear and nonlinear systems. Wavelet approximation is presented here as a possible solution that efficiently compresses both global and local covariance information. We demonstrate the compression characteristics on the the error correlation field from a global two-dimensional chemical constituent assimilation, and implement an adaptive wavelet approximation scheme on the assimilation of the one-dimensional Burger's equation. In the former problem, we show that 99%, of the error correlation can be represented by just 3% of the wavelet coefficients, with good representation of localized features. In the Burger's equation assimilation, the discrete linearized equations (tangent linear model) and analysis covariance are projected onto a wavelet basis and truncated to just 6%, of the coefficients. A nearly optimal forecast is achieved and we show that errors due to truncation of the dynamics are no greater than the errors due to covariance truncation.
Simple approximations for condensational growth
Kostinski, A B [Michigan Technological University, 1400 Townsend Drive, Houghton, MI 49931-1200 (United States)], E-mail: alex.kostinski@mtu.edu
2009-01-15
A simple geometric argument relating to the liquid water content of clouds is given. The phase relaxation time and the nature of the quasi-steady approximation for the diffusional growth of cloud drops are elucidated directly in terms of water vapor concentration. Spatial gradients of vapor concentration, inherent in the notion of quasi-steady growth, are discussed and we argue for an occasional reversal of the traditional point of view: rather than a drop growing in response to a given supersaturation, the observed values of the supersaturation in clouds are the result of a vapor field adjusting to droplet growth. Our perspective is illustrated by comparing the exponential decay of condensation trails with a quasi-steady regime of cirrus clouds. The role of aerosol loading in decreasing relaxation times and increasing the rate of growth of the liquid water content is also discussed.
Strong shock implosion, approximate solution
Fujimoto, Y.; Mishkin, E. A.; Alejaldre, C.
1983-01-01
The self-similar, center-bound motion of a strong spherical, or cylindrical, shock wave moving through an ideal gas with a constant, γ= cp/ cv, is considered and a linearized, approximate solution is derived. An X, Y phase plane of the self-similar solution is defined and the representative curved of the system behind the shock front is replaced by a straight line connecting the mappings of the shock front with that of its tail. The reduced pressure P(ξ), density R(ξ) and velocity U1(ξ) are found in closed, quite accurate, form. Comparison with numerically obtained results, for γ= {5}/{3} and γ= {7}/{5}, is shown.
Stochastic Approximation with Averaging Innovation
Laruelle, Sophie
2010-01-01
The aim of the paper is to establish a convergence theorem for multi-dimensional stochastic approximation in a setting with innovations satisfying some averaging properties and to study some applications. The averaging assumptions allow us to unify the framework where the innovations are generated (to solve problems from Numerical Probability) and the one with exogenous innovations (market data, output of "device" $e.g.$ an Euler scheme) with stationary or ergodic properties. We propose several fields of applications with random innovations or quasi-random numbers. In particular we provide in both setting a rule to tune the step of the algorithm. At last we illustrate our results on five examples notably in Finance.
Benchmarking Declarative Approximate Selection Predicates
Hassanzadeh, Oktie
2009-01-01
Declarative data quality has been an active research topic. The fundamental principle behind a declarative approach to data quality is the use of declarative statements to realize data quality primitives on top of any relational data source. A primary advantage of such an approach is the ease of use and integration with existing applications. Several similarity predicates have been proposed in the past for common quality primitives (approximate selections, joins, etc.) and have been fully expressed using declarative SQL statements. In this thesis, new similarity predicates are proposed along with their declarative realization, based on notions of probabilistic information retrieval. Then, full declarative specifications of previously proposed similarity predicates in the literature are presented, grouped into classes according to their primary characteristics. Finally, a thorough performance and accuracy study comparing a large number of similarity predicates for data cleaning operations is performed.
Narrow-width approximation accuracy
A study of general properties of the narrow-width approximation (NWA) with polarization/spin decorrelation is presented. We prove for sufficiently inclusive differential rates of arbitrary resonant decay or scattering processes with an on-shell intermediate state decaying via a cubic or quartic vertex that decorrelation effects vanish and the NWA is of order Γ. Its accuracy is then determined numerically for all resonant 3-body decays involving scalars, spin-1/2 fermions or vector bosons. We specialize the general results to MSSM benchmark scenarios. Significant off-shell corrections can occur - similar in size to QCD corrections. We qualify the configurations in which a combined consideration is advisable. For this purpose, we also investigate process-independent methods to improve the NWA
Reconstruction within the Zeldovich approximation
White, Martin
2015-01-01
The Zeldovich approximation, 1st order Lagrangian perturbation theory, provides a good description of the clustering of matter and galaxies on large scales. The acoustic feature in the large-scale correlation function of galaxies imprinted by sound waves in the early Universe has been successfully used as a `standard ruler' to constrain the expansion history of the Universe. The standard ruler can be improved if a process known as density field reconstruction is employed. In this paper we develop the Zeldovich formalism to compute the correlation function of biased tracers in both real- and redshift-space using the simplest reconstruction algorithm with a Gaussian kernel and compare to N-body simulations. The model qualitatively describes the effects of reconstruction on the simulations, though its quantitative success depends upon how redshift-space distortions are handled in the reconstruction algorithm.
Approximating metal-insulator transitions
Danieli, Carlo; Rayanov, Kristian; Pavlov, Boris; Martin, Gaven; Flach, Sergej
2015-12-01
We consider quantum wave propagation in one-dimensional quasiperiodic lattices. We propose an iterative construction of quasiperiodic potentials from sequences of potentials with increasing spatial period. At each finite iteration step, the eigenstates reflect the properties of the limiting quasiperiodic potential properties up to a controlled maximum system size. We then observe approximate Metal-Insulator Transitions (MIT) at the finite iteration steps. We also report evidence on mobility edges, which are at variance to the celebrated Aubry-André model. The dynamics near the MIT shows a critical slowing down of the ballistic group velocity in the metallic phase, similar to the divergence of the localization length in the insulating phase.
Diophantine approximations and Diophantine equations
Schmidt, Wolfgang M
1991-01-01
"This book by a leading researcher and masterly expositor of the subject studies diophantine approximations to algebraic numbers and their applications to diophantine equations. The methods are classical, and the results stressed can be obtained without much background in algebraic geometry. In particular, Thue equations, norm form equations and S-unit equations, with emphasis on recent explicit bounds on the number of solutions, are included. The book will be useful for graduate students and researchers." (L'Enseignement Mathematique) "The rich Bibliography includes more than hundred references. The book is easy to read, it may be a useful piece of reading not only for experts but for students as well." Acta Scientiarum Mathematicarum
Dodgson's Rule Approximations and Absurdity
McCabe-Dansted, John C
2010-01-01
With the Dodgson rule, cloning the electorate can change the winner, which Young (1977) considers an "absurdity". Removing this absurdity results in a new rule (Fishburn, 1977) for which we can compute the winner in polynomial time (Rothe et al., 2003), unlike the traditional Dodgson rule. We call this rule DC and introduce two new related rules (DR and D&). Dodgson did not explicitly propose the "Dodgson rule" (Tideman, 1987); we argue that DC and DR are better realizations of the principle behind the Dodgson rule than the traditional Dodgson rule. These rules, especially D&, are also effective approximations to the traditional Dodgson's rule. We show that, unlike the rules we have considered previously, the DC, DR and D& scores differ from the Dodgson score by no more than a fixed amount given a fixed number of alternatives, and thus these new rules converge to Dodgson under any reasonable assumption on voter behaviour, including the Impartial Anonymous Culture assumption.
Approximate analytic solutions to the NPDD: Short exposure approximations
Close, Ciara E.; Sheridan, John T.
2014-04-01
There have been many attempts to accurately describe the photochemical processes that take places in photopolymer materials. As the models have become more accurate, solving them has become more numerically intensive and more 'opaque'. Recent models incorporate the major photochemical reactions taking place as well as the diffusion effects resulting from the photo-polymerisation process, and have accurately described these processes in a number of different materials. It is our aim to develop accessible mathematical expressions which provide physical insights and simple quantitative predictions of practical value to material designers and users. In this paper, starting with the Non-Local Photo-Polymerisation Driven Diffusion (NPDD) model coupled integro-differential equations, we first simplify these equations and validate the accuracy of the resulting approximate model. This new set of governing equations are then used to produce accurate analytic solutions (polynomials) describing the evolution of the monomer and polymer concentrations, and the grating refractive index modulation, in the case of short low intensity sinusoidal exposures. The physical significance of the results and their consequences for holographic data storage (HDS) are then discussed.
Multidimensional stochastic approximation Monte Carlo.
Zablotskiy, Sergey V; Ivanov, Victor A; Paul, Wolfgang
2016-06-01
Stochastic Approximation Monte Carlo (SAMC) has been established as a mathematically founded powerful flat-histogram Monte Carlo method, used to determine the density of states, g(E), of a model system. We show here how it can be generalized for the determination of multidimensional probability distributions (or equivalently densities of states) of macroscopic or mesoscopic variables defined on the space of microstates of a statistical mechanical system. This establishes this method as a systematic way for coarse graining a model system, or, in other words, for performing a renormalization group step on a model. We discuss the formulation of the Kadanoff block spin transformation and the coarse-graining procedure for polymer models in this language. We also apply it to a standard case in the literature of two-dimensional densities of states, where two competing energetic effects are present g(E_{1},E_{2}). We show when and why care has to be exercised when obtaining the microcanonical density of states g(E_{1}+E_{2}) from g(E_{1},E_{2}). PMID:27415383
Decision analysis with approximate probabilities
Whalen, Thomas
1992-01-01
This paper concerns decisions under uncertainty in which the probabilities of the states of nature are only approximately known. Decision problems involving three states of nature are studied. This is due to the fact that some key issues do not arise in two-state problems, while probability spaces with more than three states of nature are essentially impossible to graph. The primary focus is on two levels of probabilistic information. In one level, the three probabilities are separately rounded to the nearest tenth. This can lead to sets of rounded probabilities which add up to 0.9, 1.0, or 1.1. In the other level, probabilities are rounded to the nearest tenth in such a way that the rounded probabilities are forced to sum to 1.0. For comparison, six additional levels of probabilistic information, previously analyzed, were also included in the present analysis. A simulation experiment compared four criteria for decisionmaking using linearly constrained probabilities (Maximin, Midpoint, Standard Laplace, and Extended Laplace) under the eight different levels of information about probability. The Extended Laplace criterion, which uses a second order maximum entropy principle, performed best overall.
Function approximation in inhibitory networks.
Tripp, Bryan; Eliasmith, Chris
2016-05-01
In performance-optimized artificial neural networks, such as convolutional networks, each neuron makes excitatory connections with some of its targets and inhibitory connections with others. In contrast, physiological neurons are typically either excitatory or inhibitory, not both. This is a puzzle, because it seems to constrain computation, and because there are several counter-examples that suggest that it may not be a physiological necessity. Parisien et al. (2008) showed that any mixture of excitatory and inhibitory functional connections could be realized by a purely excitatory projection in parallel with a two-synapse projection through an inhibitory population. They showed that this works well with ratios of excitatory and inhibitory neurons that are realistic for the neocortex, suggesting that perhaps the cortex efficiently works around this apparent computational constraint. Extending this work, we show here that mixed excitatory and inhibitory functional connections can also be realized in networks that are dominated by inhibition, such as those of the basal ganglia. Further, we show that the function-approximation capacity of such connections is comparable to that of idealized mixed-weight connections. We also study whether such connections are viable in recurrent networks, and find that such recurrent networks can flexibly exhibit a wide range of dynamics. These results offer a new perspective on computation in the basal ganglia, and also perhaps on inhibitory networks within the cortex. PMID:26963256
Graphical abstract: Available rotational and vibrational-rotational spectral lines of DF and HF are analyzed simultaneously using a non-Born-Oppenheimer effective Hamiltonian. Research highlights: → Simultaneous analysis of DF and HF spectral data. → Application of a non-Born-Oppenheimer effective Hamiltonian. → Twenty irreducible molecular constants for HF have been determined. - Abstract: Analytic expressions of corrections for the breakdown of the Born-Oppenheimer approximation to Dunham's Yij with optimal parameters, i.e., determinable clusters of expansion coefficients, are applied to a data analysis of the rotational and vibrational-rotational transitions of HF reported in the literature. All the available spectral lines of the two isotopologues, DF and HF, are simultaneously fitted to a single set of molecular parameters of HF within experimental errors. Fitting of a data set of 595 spectral transitions for DF and HF has generated only 20 minimal independent parameter values, i.e., 'irreducible' molecular constants of HF, that are sufficient to precisely generate 82 Yij coefficients and 144 band constants in total: 41 Yij and 72 band constants each for DF and HF.