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

PubMed

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

2015-11-05

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

Multiconfiguration Pair-Density Functional Theory Outperforms Kohn-Sham Density Functional Theory and Multireference Perturbation Theory for Ground-State and Excited-State Charge Transfer.

PubMed

Ghosh, Soumen; Sonnenberger, Andrew L; Hoyer, Chad E; Truhlar, Donald G; Gagliardi, Laura

2015-08-11

The correct description of charge transfer in ground and excited states is very important for molecular interactions, photochemistry, electrochemistry, and charge transport, but it is very challenging for Kohn-Sham (KS) density functional theory (DFT). KS-DFT exchange-correlation functionals without nonlocal exchange fail to describe both ground- and excited-state charge transfer properly. We have recently proposed a theory called multiconfiguration pair-density functional theory (MC-PDFT), which is based on a combination of multiconfiguration wave function theory with a new type of density functional called an on-top density functional. Here we have used MC-PDFT to study challenging ground- and excited-state charge-transfer processes by using on-top density functionals obtained by translating KS exchange-correlation functionals. For ground-state charge transfer, MC-PDFT performs better than either the PBE exchange-correlation functional or CASPT2 wave function theory. For excited-state charge transfer, MC-PDFT (unlike KS-DFT) shows qualitatively correct behavior at long-range with great improvement in predicted excitation energies.

Theoretical Studies of Chemical Reactions following Electronic Excitation

NASA Technical Reports Server (NTRS)

Chaban, Galina M.

2003-01-01

The use of multi-configurational wave functions is demonstrated for several processes: tautomerization reactions in the ground and excited states of the DNA base adenine, dissociation of glycine molecule after electronic excitation, and decomposition/deformation of novel rare gas molecules HRgF. These processes involve bond brealung/formation and require multi-configurational approaches that include dynamic correlation.

Spin-Multiplet Components and Energy Splittings by Multistate Density Functional Theory.

PubMed

Grofe, Adam; Chen, Xin; Liu, Wenjian; Gao, Jiali

2017-10-05

Kohn-Sham density functional theory has been tremendously successful in chemistry and physics. Yet, it is unable to describe the energy degeneracy of spin-multiplet components with any approximate functional. This work features two contributions. (1) We present a multistate density functional theory (MSDFT) to represent spin-multiplet components and to determine multiplet energies. MSDFT is a hybrid approach, taking advantage of both wave function theory and density functional theory. Thus, the wave functions, electron densities and energy density-functionals for ground and excited states and for different components are treated on the same footing. The method is illustrated on valence excitations of atoms and molecules. (2) Importantly, a key result is that for cases in which the high-spin components can be determined separately by Kohn-Sham density functional theory, the transition density functional in MSDFT (which describes electronic coupling) can be defined rigorously. The numerical results may be explored to design and optimize transition density functionals for configuration coupling in multiconfigurational DFT.

Multiconfiguration calculations of electronic isotope shift factors in Al i

NASA Astrophysics Data System (ADS)

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

2016-12-01

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

Multiconfiguration Pair-Density Functional Theory Is Free From Delocalization Error.

PubMed

Bao, Junwei Lucas; Wang, Ying; He, Xiao; Gagliardi, Laura; Truhlar, Donald G

2017-11-16

Delocalization error has been singled out by Yang and co-workers as the dominant error in Kohn-Sham density functional theory (KS-DFT) with conventional approximate functionals. In this Letter, by computing the vertical first ionization energy for well separated He clusters, we show that multiconfiguration pair-density functional theory (MC-PDFT) is free from delocalization error. To put MC-PDFT in perspective, we also compare it with some Kohn-Sham density functionals, including both traditional and modern functionals. Whereas large delocalization errors are almost universal in KS-DFT (the only exception being the very recent corrected functionals of Yang and co-workers), delocalization error is removed by MC-PDFT, which bodes well for its future as a step forward from KS-DFT.

Unbiased reduced density matrices and electronic properties from full configuration interaction quantum Monte Carlo.

PubMed

Overy, Catherine; Booth, George H; Blunt, N S; Shepherd, James J; Cleland, Deidre; Alavi, Ali

2014-12-28

Properties that are necessarily formulated within pure (symmetric) expectation values are difficult to calculate for projector quantum Monte Carlo approaches, but are critical in order to compute many of the important observable properties of electronic systems. Here, we investigate an approach for the sampling of unbiased reduced density matrices within the full configuration interaction quantum Monte Carlo dynamic, which requires only small computational overheads. This is achieved via an independent replica population of walkers in the dynamic, sampled alongside the original population. The resulting reduced density matrices are free from systematic error (beyond those present via constraints on the dynamic itself) and can be used to compute a variety of expectation values and properties, with rapid convergence to an exact limit. A quasi-variational energy estimate derived from these density matrices is proposed as an accurate alternative to the projected estimator for multiconfigurational wavefunctions, while its variational property could potentially lend itself to accurate extrapolation approaches in larger systems.

Unbiased reduced density matrices and electronic properties from full configuration interaction quantum Monte Carlo

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

Overy, Catherine; Blunt, N. S.; Shepherd, James J.

2014-12-28

Properties that are necessarily formulated within pure (symmetric) expectation values are difficult to calculate for projector quantum Monte Carlo approaches, but are critical in order to compute many of the important observable properties of electronic systems. Here, we investigate an approach for the sampling of unbiased reduced density matrices within the full configuration interaction quantum Monte Carlo dynamic, which requires only small computational overheads. This is achieved via an independent replica population of walkers in the dynamic, sampled alongside the original population. The resulting reduced density matrices are free from systematic error (beyond those present via constraints on the dynamicmore » itself) and can be used to compute a variety of expectation values and properties, with rapid convergence to an exact limit. A quasi-variational energy estimate derived from these density matrices is proposed as an accurate alternative to the projected estimator for multiconfigurational wavefunctions, while its variational property could potentially lend itself to accurate extrapolation approaches in larger systems.« less

Multiconfigurational short-range density-functional theory for open-shell systems

NASA Astrophysics Data System (ADS)

Hedegârd, Erik Donovan; Toulouse, Julien; Jensen, Hans Jørgen Aagaard

2018-06-01

Many chemical systems cannot be described by quantum chemistry methods based on a single-reference wave function. Accurate predictions of energetic and spectroscopic properties require a delicate balance between describing the most important configurations (static correlation) and obtaining dynamical correlation efficiently. The former is most naturally done through a multiconfigurational (MC) wave function, whereas the latter can be done by, e.g., perturbation theory. We have employed a different strategy, namely, a hybrid between multiconfigurational wave functions and density-functional theory (DFT) based on range separation. The method is denoted by MC short-range DFT (MC-srDFT) and is more efficient than perturbative approaches as it capitalizes on the efficient treatment of the (short-range) dynamical correlation by DFT approximations. In turn, the method also improves DFT with standard approximations through the ability of multiconfigurational wave functions to recover large parts of the static correlation. Until now, our implementation was restricted to closed-shell systems, and to lift this restriction, we present here the generalization of MC-srDFT to open-shell cases. The additional terms required to treat open-shell systems are derived and implemented in the DALTON program. This new method for open-shell systems is illustrated on dioxygen and [Fe(H2O)6]3+.

A single-electron picture based on the multiconfiguration time-dependent Hartree-Fock method: application to the anisotropic ionization and subsequent high-harmonic generation of the CO molecule

NASA Astrophysics Data System (ADS)

Ohmura, S.; Kato, T.; Oyamada, T.; Koseki, S.; Ohmura, H.; Kono, H.

2018-02-01

The mechanisms of anisotropic near-IR tunnel ionization and high-order harmonic generation (HHG) in a CO molecule are theoretically investigated by using the multiconfiguration time-dependent Hartree-Fock (MCTDHF) method developed for the simulation of multielectron dynamics of molecules. The multielectron dynamics obtained by numerically solving the equations of motion (EOMs) in the MCTDHF method is converted to a single orbital picture in the natural orbital representation where the first-order reduced density matrix is diagonalized. The ionization through each natural orbital is examined and the process of HHG is classified into different optical paths designated by a combinations of initial, intermediate and final natural orbitals. The EOMs for natural spin-orbitals are also derived within the framework of the MCTDHF, which maintains the first-order reduced density matrix to be a diagonal one throughout the time propagation of a many-electron wave function. The orbital dependent, time-dependent effective potentials that govern the dynamics of respective time-dependent natural orbitals are deduced from the derived EOMs, of which the temporal variation can be used to interpret the motion of the electron density associated with each natural spin-orbital. The roles of the orbital shape, multiorbital ionization, linear Stark effect and multielectron interaction in the ionization and HHG of a CO molecule are revealed by the effective potentials obtained. When the laser electric field points to the nucleus O from C, tunnel ionization from the C atom side is enhanced; a hump structure originating from multielectron interaction is then formed on the top of the field-induced distorted barrier of the HOMO effective potential. This hump formation, responsible for the directional anisotropy of tunnel ionization, restrains the influence of the linear Stark effect on the energy shifts of bound states.

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

PubMed

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

2016-04-12

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

Non-adiabatic excited state molecular dynamics of phenylene ethynylene dendrimer using a multiconfigurational Ehrenfest approach

DOE PAGES

Fernandez-Alberti, Sebastian; Makhov, Dmitry V.; Tretiak, Sergei; ...

2016-03-10

Photoinduced dynamics of electronic and vibrational unidirectional energy transfer between meta-linked building blocks in a phenylene ethynylene dendrimer is simulated using a multiconfigurational Ehrenfest in time-dependent diabatic basis (MCE-TDDB) method, a new variant of the MCE approach developed by us for dynamics involving multiple electronic states with numerous abrupt crossings. Excited-state energies, gradients and non-adiabatic coupling terms needed for dynamics simulation are calculated on-the-fly using the Collective Electron Oscillator (CEO) approach. In conclusion, a comparative analysis of our results obtained using MCE-TDDB, the conventional Ehrenfest method and the surface-hopping approach with and without decoherence corrections is presented.

Recent progress in density functional theory

NASA Astrophysics Data System (ADS)

Truhlar, Donald

2014-03-01

Ongoing work involves several areas of density functional theory: new methods for computing electronic excitation energies, including a new way to remove spin contamination in the spin-flip Tamm-Dancoff approximation and a configuration-interaction-corrected Tamm-Dancoff Approximation for treating conical intersections; new ways to treat open-shell states, including a reinterpreted broken-symmetry method and multi-configuration Kohn-Sham theory; a new exchange-correlation functional; new tests of density functional theory against databases for electronic transition energies and molecules and solids containing metal atoms; and applications. A selection of results will be presented. I am grateful to the following collaborators for contributions to the ongoing work: Boris Averkiev, Rebecca Carlson, Laura Fernandez, Laura Gagliardi, Chad Hoyer, Francesc Illas, Miho Isegawa, Shaohong Li, Giovanni Li Manni, Sijie Luo, Dongxia Ma, Remi Maurice, Rubén Means-Pañeda, Roberto Peverati, Nora Planas, Prasenjit Seal, Pragya Verma, Bo Wang, Xuefei Xu, Ke R. Yang, Haoyu Yu, Wenjing Zhang, and Jingjing Zheng. Supported in part by the AFOSR and U.S. DOE.

Multiconfiguration Pair-Density Functional Theory Predicts Spin-State Ordering in Iron Complexes with the Same Accuracy as Complete Active Space Second-Order Perturbation Theory at a Significantly Reduced Computational Cost.

PubMed

Wilbraham, Liam; Verma, Pragya; Truhlar, Donald G; Gagliardi, Laura; Ciofini, Ilaria

2017-05-04

The spin-state orderings in nine Fe(II) and Fe(III) complexes with ligands of diverse ligand-field strength were investigated with multiconfiguration pair-density functional theory (MC-PDFT). The performance of this method was compared to that of complete active space second-order perturbation theory (CASPT2) and Kohn-Sham density functional theory. We also investigated the dependence of CASPT2 and MC-PDFT results on the size of the active-space. MC-PDFT reproduces the CASPT2 spin-state ordering, the dependence on the ligand field strength, and the dependence on active space at a computational cost that is significantly reduced as compared to CASPT2.

An SCF and MCSCF description of the low-lying states of MgO. [Configuration State Functions Multiconfiguration Self Consistent Field

NASA Technical Reports Server (NTRS)

Bauschlicher, C. W., Jr.; Silver, D. M.; Yarkony, D. R.

1980-01-01

The paper presents the multiconfiguration-self-consistent (MCSCF) and configuration state functions (CSF) for the low-lying electronic states of MgO. It was shown that simple description of these states was possible provided the 1 Sigma(+) states are individually optimized at the MCSCF level, noting that the 1(3 Sigma)(+) and 2(1 Sigma)(+) states which nominally result from the same electron occupation are separated energetically. The molecular orbitals obtained at this level of approximation should provide a useful starting point for extended configuration interaction calculations since they have been optimized for the particular states of interest.

Beyond Kohn-Sham Approximation: Hybrid Multistate Wave Function and Density Functional Theory.

PubMed

Gao, Jiali; Grofe, Adam; Ren, Haisheng; Bao, Peng

2016-12-15

A multistate density functional theory (MSDFT) is presented in which the energies and densities for the ground and excited states are treated on the same footing using multiconfigurational approaches. The method can be applied to systems with strong correlation and to correctly describe the dimensionality of the conical intersections between strongly coupled dissociative potential energy surfaces. A dynamic-then-static framework for treating electron correlation is developed to first incorporate dynamic correlation into contracted state functions through block-localized Kohn-Sham density functional theory (KSDFT), followed by diagonalization of the effective Hamiltonian to include static correlation. MSDFT can be regarded as a hybrid of wave function and density functional theory. The method is built on and makes use of the current approximate density functional developed in KSDFT, yet it retains its computational efficiency to treat strongly correlated systems that are problematic for KSDFT but too large for accurate WFT. The results presented in this work show that MSDFT can be applied to photochemical processes involving conical intersections.

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

NASA Astrophysics Data System (ADS)

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

2018-06-01

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

Excitation spectra of retinal by multiconfiguration pair-density functional theory.

PubMed

Dong, Sijia S; Gagliardi, Laura; Truhlar, Donald G

2018-03-07

Retinal is the chromophore in proteins responsible for vision. The absorption maximum of retinal is sensitive to mutations of the protein. However, it is not easy to predict the absorption spectrum of retinal accurately, and questions remain even after intensive investigation. Retinal poses a challenge for Kohn-Sham density functional theory (KS-DFT) because of the charge transfer character in its excitations, and it poses a challenge for wave function theory because the large size of the molecule makes multiconfigurational perturbation theory methods expensive. In this study, we demonstrate that multiconfiguration pair-density functional theory (MC-PDFT) provides an efficient way to predict the vertical excitation energies of 11-Z retinal, and it reproduces the experimentally determined absorption band widths and peak positions better than complete active space second-order perturbation theory (CASPT2). The consistency between complete active space self-consistent field (CASSCF) and KS-DFT dipole moments is demonstrated to be a useful criterion in selecting the active space. We also found that the nature of the terminal groups and the conformations of retinal play a significant role in the absorption spectrum. By considering a thermal distribution of conformations, we predict an absorption spectrum of retinal that is consistent with the experimental gas-phase spectrum. The location of the absorption peak and the spectral broadening based on MC-PDFT calculations agree better with experiments than those of CASPT2.

Multiconfiguration pair-density functional theory for doublet excitation energies and excited state geometries: the excited states of CN.

PubMed

Bao, Jie J; Gagliardi, Laura; Truhlar, Donald G

2017-11-15

Multiconfiguration pair-density functional theory (MC-PDFT) is a post multiconfiguration self-consistent field (MCSCF) method with similar performance to complete active space second-order perturbation theory (CASPT2) but with greater computational efficiency. Cyano radical (CN) is a molecule whose spectrum is well established from experiments and whose excitation energies have been used as a testing ground for theoretical methods to treat excited states of open-shell systems, which are harder and much less studied than excitation energies of closed-shell singlets. In the present work, we studied the adiabatic excitation energies of CN with MC-PDFT. Then we compared this multireference (MR) method to some single-reference (SR) methods, including time-dependent density functional theory (TDDFT) and completely renormalized equation-of-motion coupled-cluster theory with singles, doubles and noniterative triples [CR-EOM-CCSD(T)]; we also compared to some other MR methods, including configuration interaction singles and doubles (MR-CISD) and multistate CASPT2 (MS-CASPT2). Through a comparison between SR and MR methods, we achieved a better appreciation of the need to use MR methods to accurately describe higher excited states, and we found that among the MR methods, MC-PDFT stands out for its accuracy for the first four states out of the five doublet states studied this paper; this shows its efficiency for calculating doublet excited states.

Cross Sections for Electron Impact Excitation of Astrophysically Abundant Atoms and Ions

NASA Technical Reports Server (NTRS)

Tayal, S. S.

2006-01-01

Electron collisional excitation rates and transition probabilities are important for computing electron temperatures and densities, ionization equilibria, and for deriving elemental abundances from emission lines formed in the collisional and photoionized astrophysical plasmas. Accurate representation of target wave functions that properly account for the important correlation and relaxation effects and inclusion of coupling effects including coupling to the continuum are essential components of a reliable collision calculation. Non-orthogonal orbitals technique in multiconfiguration Hartree-Fock approach is used to calculate oscillator strengths and transition probabilities. The effect of coupling to the continuum spectrum is included through the use of pseudostates which are chosen to account for most of the dipole polarizabilities of target states. The B-spline basis is used in the R-matrix approach to calculate electron excitation collision strengths and rates. Results for oscillator strengths and electron excitation collision strengths for transitions in N I, O I, O II, O IV, S X and Fe XIV have been produced

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

PubMed

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

2017-07-11

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

Alternative separation of exchange and correlation energies in multi-configuration range-separated density-functional theory.

PubMed

Stoyanova, Alexandrina; Teale, Andrew M; Toulouse, Julien; Helgaker, Trygve; Fromager, Emmanuel

2013-10-07

The alternative separation of exchange and correlation energies proposed by Toulouse et al. [Theor. Chem. Acc. 114, 305 (2005)] is explored in the context of multi-configuration range-separated density-functional theory. The new decomposition of the short-range exchange-correlation energy relies on the auxiliary long-range interacting wavefunction rather than the Kohn-Sham (KS) determinant. The advantage, relative to the traditional KS decomposition, is that the wavefunction part of the energy is now computed with the regular (fully interacting) Hamiltonian. One potential drawback is that, because of double counting, the wavefunction used to compute the energy cannot be obtained by minimizing the energy expression with respect to the wavefunction parameters. The problem is overcome by using short-range optimized effective potentials (OEPs). The resulting combination of OEP techniques with wavefunction theory has been investigated in this work, at the Hartree-Fock (HF) and multi-configuration self-consistent-field (MCSCF) levels. In the HF case, an analytical expression for the energy gradient has been derived and implemented. Calculations have been performed within the short-range local density approximation on H2, N2, Li2, and H2O. Significant improvements in binding energies are obtained with the new decomposition of the short-range energy. The importance of optimizing the short-range OEP at the MCSCF level when static correlation becomes significant has also been demonstrated for H2, using a finite-difference gradient. The implementation of the analytical gradient for MCSCF wavefunctions is currently in progress.

Gradient-based multiconfiguration Shepard interpolation for generating potential energy surfaces for polyatomic reactions.

PubMed

Tishchenko, Oksana; Truhlar, Donald G

2010-02-28

This paper describes and illustrates a way to construct multidimensional representations of reactive potential energy surfaces (PESs) by a multiconfiguration Shepard interpolation (MCSI) method based only on gradient information, that is, without using any Hessian information from electronic structure calculations. MCSI, which is called multiconfiguration molecular mechanics (MCMM) in previous articles, is a semiautomated method designed for constructing full-dimensional PESs for subsequent dynamics calculations (classical trajectories, full quantum dynamics, or variational transition state theory with multidimensional tunneling). The MCSI method is based on Shepard interpolation of Taylor series expansions of the coupling term of a 2 x 2 electronically diabatic Hamiltonian matrix with the diagonal elements representing nonreactive analytical PESs for reactants and products. In contrast to the previously developed method, these expansions are truncated in the present version at the first order, and, therefore, no input of electronic structure Hessians is required. The accuracy of the interpolated energies is evaluated for two test reactions, namely, the reaction OH+H(2)-->H(2)O+H and the hydrogen atom abstraction from a model of alpha-tocopherol by methyl radical. The latter reaction involves 38 atoms and a 108-dimensional PES. The mean unsigned errors averaged over a wide range of representative nuclear configurations (corresponding to an energy range of 19.5 kcal/mol in the former case and 32 kcal/mol in the latter) are found to be within 1 kcal/mol for both reactions, based on 13 gradients in one case and 11 in the other. The gradient-based MCMM method can be applied for efficient representations of multidimensional PESs in cases where analytical electronic structure Hessians are too expensive or unavailable, and it provides new opportunities to employ high-level electronic structure calculations for dynamics at an affordable cost.

Multi-layer multi-configuration time-dependent Hartree (ML-MCTDH) approach to the correlated exciton-vibrational dynamics in the FMO complex

NASA Astrophysics Data System (ADS)

Schulze, Jan; Shibl, Mohamed F.; Al-Marri, Mohammed J.; Kühn, Oliver

2016-05-01

The coupled quantum dynamics of excitonic and vibrational degrees of freedom is investigated for high-dimensional models of the Fenna-Matthews-Olson complex. This includes a seven- and an eight-site model with 518 and 592 harmonic vibrational modes, respectively. The coupling between local electronic transitions and vibrations is described within the Huang-Rhys model using parameters that are obtained by discretization of an experimental spectral density. Different pathways of excitation energy flow are analyzed in terms of the reduced one-exciton density matrix, focussing on the role of vibrational and vibronic excitations. Distinct features due to both competing time scales of vibrational and exciton motion and vibronically assisted transfer are observed. The question of the effect of initial state preparation is addressed by comparing the case of an instantaneous Franck-Condon excitation at a single site with that of a laser field excitation.

Selection of active spaces for multiconfigurational wavefunctions

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

Keller, Sebastian; Boguslawski, Katharina; Reiher, Markus, E-mail: markus.reiher@phys.chem.ethz.ch

2015-06-28

The efficient and accurate description of the electronic structure of strongly correlated systems is still a largely unsolved problem. The usual procedures start with a multiconfigurational (usually a Complete Active Space, CAS) wavefunction which accounts for static correlation and add dynamical correlation by perturbation theory, configuration interaction, or coupled cluster expansion. This procedure requires the correct selection of the active space. Intuitive methods are unreliable for complex systems. The inexpensive black-box unrestricted natural orbital (UNO) criterion postulates that the Unrestricted Hartree-Fock (UHF) charge natural orbitals with fractional occupancy (e.g., between 0.02 and 1.98) constitute the active space. UNOs generally approximatemore » the CAS orbitals so well that the orbital optimization in CAS Self-Consistent Field (CASSCF) may be omitted, resulting in the inexpensive UNO-CAS method. A rigorous testing of the UNO criterion requires comparison with approximate full configuration interaction wavefunctions. This became feasible with the advent of Density Matrix Renormalization Group (DMRG) methods which can approximate highly correlated wavefunctions at affordable cost. We have compared active orbital occupancies in UNO-CAS and CASSCF calculations with DMRG in a number of strongly correlated molecules: compounds of electronegative atoms (F{sub 2}, ozone, and NO{sub 2}), polyenes, aromatic molecules (naphthalene, azulene, anthracene, and nitrobenzene), radicals (phenoxy and benzyl), diradicals (o-, m-, and p-benzyne), and transition metal compounds (nickel-acetylene and Cr{sub 2}). The UNO criterion works well in these cases. Other symmetry breaking solutions, with the possible exception of spatial symmetry, do not appear to be essential to generate the correct active space. In the case of multiple UHF solutions, the natural orbitals of the average UHF density should be used. The problems of the UNO criterion and their potential solutions are discussed: finding the UHF solutions, discontinuities on potential energy surfaces, and inclusion of dynamical electron correlation and generalization to excited states.« less

Selection of active spaces for multiconfigurational wavefunctions

NASA Astrophysics Data System (ADS)

Keller, Sebastian; Boguslawski, Katharina; Janowski, Tomasz; Reiher, Markus; Pulay, Peter

2015-06-01

The efficient and accurate description of the electronic structure of strongly correlated systems is still a largely unsolved problem. The usual procedures start with a multiconfigurational (usually a Complete Active Space, CAS) wavefunction which accounts for static correlation and add dynamical correlation by perturbation theory, configuration interaction, or coupled cluster expansion. This procedure requires the correct selection of the active space. Intuitive methods are unreliable for complex systems. The inexpensive black-box unrestricted natural orbital (UNO) criterion postulates that the Unrestricted Hartree-Fock (UHF) charge natural orbitals with fractional occupancy (e.g., between 0.02 and 1.98) constitute the active space. UNOs generally approximate the CAS orbitals so well that the orbital optimization in CAS Self-Consistent Field (CASSCF) may be omitted, resulting in the inexpensive UNO-CAS method. A rigorous testing of the UNO criterion requires comparison with approximate full configuration interaction wavefunctions. This became feasible with the advent of Density Matrix Renormalization Group (DMRG) methods which can approximate highly correlated wavefunctions at affordable cost. We have compared active orbital occupancies in UNO-CAS and CASSCF calculations with DMRG in a number of strongly correlated molecules: compounds of electronegative atoms (F2, ozone, and NO2), polyenes, aromatic molecules (naphthalene, azulene, anthracene, and nitrobenzene), radicals (phenoxy and benzyl), diradicals (o-, m-, and p-benzyne), and transition metal compounds (nickel-acetylene and Cr2). The UNO criterion works well in these cases. Other symmetry breaking solutions, with the possible exception of spatial symmetry, do not appear to be essential to generate the correct active space. In the case of multiple UHF solutions, the natural orbitals of the average UHF density should be used. The problems of the UNO criterion and their potential solutions are discussed: finding the UHF solutions, discontinuities on potential energy surfaces, and inclusion of dynamical electron correlation and generalization to excited states.

Assessing the density functional theory-based multireference configuration interaction (DFT/MRCI) method for transition metal complexes

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

Escudero, Daniel, E-mail: escudero@kofo.mpg.de, E-mail: thiel@kofo.mpg.de; Thiel, Walter, E-mail: escudero@kofo.mpg.de, E-mail: thiel@kofo.mpg.de

2014-05-21

We report an assessment of the performance of density functional theory-based multireference configuration interaction (DFT/MRCI) calculations for a set of 3d- and 4d-transition metal (TM) complexes. The DFT/MRCI results are compared to published reference data from reliable high-level multi-configurational ab initio studies. The assessment covers the relative energies of different ground-state minima of the highly correlated CrF{sub 6} complex, the singlet and triplet electronically excited states of seven typical TM complexes (MnO{sub 4}{sup −}, Cr(CO){sub 6}, [Fe(CN){sub 6}]{sup 4−}, four larger Fe and Ru complexes), and the corresponding electronic spectra (vertical excitation energies and oscillator strengths). It includes comparisons withmore » results from different flavors of time-dependent DFT (TD-DFT) calculations using pure, hybrid, and long-range corrected functionals. The DFT/MRCI method is found to be superior to the tested TD-DFT approaches and is thus recommended for exploring the excited-state properties of TM complexes.« less

Relativistic atomic structure calculations and electron impact excitations of Fe23+

NASA Astrophysics Data System (ADS)

El-Maaref, A. A.

2016-02-01

Relativistic calculations using the multiconfiguration Dirac-Fock method for energy levels, oscillator strengths, and electronic dipole transition probabilities of Li-like iron (Fe23+) are presented. A configuration state list with the quantum numbers nl, where n = 2 - 7 and l = s , p , d , f , g , h , i has been considered. Excitations up to three electrons and correlation contributions from higher orbitals up to 7 l have been included. Contributions from core levels have been taken into account, EOL (extended optimal level) type calculations have been applied, and doubly excited levels are considered. The calculations have been executed by using the fully relativistic atomic structure package GRASP2K. The present calculations have been compared with the available experimental and theoretical sources, the comparisons show a good agreement between the present results of energy levels and oscillator strengths with the literature. In the second part of the present study, the atomic data (energy levels, and radiative parameters) have been used to calculate the excitation and deexcitation rates of allowed transitions by electron impact, as well as the population densities of some excited levels at different electron temperatures.

Cooperative Metal+Ligand Oxidative Addition and Sigma-Bond Metathesis: A DFT Study

DOE PAGES

Lopez, Kent G.; Cundari, Thomas R.; Gary, J. Brannon

2018-01-17

A computational study of the experimentally proposed mechanism of alkyne diboration by a PDICo complex yielded two fundamental catalytic steps that undergo remarkable electronic changes, PDI = bis(imino)-pyridine. The reactions are envisaged via DFT (density functional theory) and MCSCF (multi-configuration self-consistent field) simulations as (i) a cooperative metal+ligand oxidative addition, and (ii) a sigma-bond metathesis induced ligand-to-metal charge transfer. Analysis of the bonding of pertinent intermediates/TSs also yielded important insight that may be illuminating with regards to the larger field of green catalysis that seeks to ennoble base metals through synergy with potentially redox non-innocent (RNI) ligands. For the presentmore » case, massive changes in electronic structure do not incur massive energetic penalties. Finally, in conjunction with previous research, one may postulate that structural and energetic “fluidity” among several electronic states of RNI-M 3d along the reaction coordinate is an essential signature of redox cooperativity and thus ennoblement.« less

Cooperative Metal+Ligand Oxidative Addition and Sigma-Bond Metathesis: A DFT Study

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

Lopez, Kent G.; Cundari, Thomas R.; Gary, J. Brannon

A computational study of the experimentally proposed mechanism of alkyne diboration by a PDICo complex yielded two fundamental catalytic steps that undergo remarkable electronic changes, PDI = bis(imino)-pyridine. The reactions are envisaged via DFT (density functional theory) and MCSCF (multi-configuration self-consistent field) simulations as (i) a cooperative metal+ligand oxidative addition, and (ii) a sigma-bond metathesis induced ligand-to-metal charge transfer. Analysis of the bonding of pertinent intermediates/TSs also yielded important insight that may be illuminating with regards to the larger field of green catalysis that seeks to ennoble base metals through synergy with potentially redox non-innocent (RNI) ligands. For the presentmore » case, massive changes in electronic structure do not incur massive energetic penalties. Finally, in conjunction with previous research, one may postulate that structural and energetic “fluidity” among several electronic states of RNI-M 3d along the reaction coordinate is an essential signature of redox cooperativity and thus ennoblement.« less

Systematic theoretical study of non-nuclear electron density maxima in some diatomic molecules.

PubMed

Terrabuio, Luiz A; Teodoro, Tiago Q; Rachid, Marina G; Haiduke, Roberto L A

2013-10-10

First, exploratory calculations were performed to investigate the presence of non-nuclear maxima (NNMs) in ground-state electron densities of homonuclear diatomic molecules from hydrogen up to calcium at their equilibrium geometries. In a second stage, only for the cases in which these features were previously detected, a rigorous analysis was carried out by several combinations of theoretical methods and basis sets in order to ensure that they are not only calculation artifacts. Our best results support that Li2, B2, C2, and P2 are molecules that possess true NNMs. A NNM was found in values obtained from the largest basis sets for Na2, but it disappeared at the experimental geometry because optimized bond lengths are significantly inaccurate for this case (deviations of 0.10 Å). Two of these maxima are also observed in Si2 with CCSD and large basis sets, but they are no longer detected as core-valence correlation or multiconfigurational wave functions are taken into account. Therefore, the NNMs in Si2 can be considered unphysical features due to an incomplete treatment of electron correlation. Finally, we show that a NNM is encountered in LiNa, representing the first discovery of such electron density maxima in a heteronuclear diatomic system at its equilibrium geometry, to our knowledge. Some results for LiNa, found in variations in internuclear distances, suggest that molecular electric moments, such as dipole and quadrupole, are sensitive to the presence of NNMs.

ELECTRONIC STRUCTURE FOR THE GROUND STATE OF T1H FROM RELATIVISTIC MULTICONFIGURATION SCF CALCULATIONS

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

Christiansen, P.A.; Pitzer, K.S.

The dissociation curve for the ground state of TlH was computed using a relativistic {omega}-{omega} coupling formalism. The relativistic effects represented by the Dirac equation were introduced using effective potentials generated from atomic Dirac-Fock wave functions using a generalization of the improved effective potential formulation of Christiansen, Lee, and Pitzer. The multiconfiguration SCF treatment used is a generalization of the two-component molecular spinor formalism of Lee, Ermler, and Pitzer. Using a five configuration wave function we were able to obtain approximately 85% of the experimental dissociation energy. Our computations indicate that the bond is principally sigma in form, despite themore » large spin-orbit splitting in atomic thallium. Furthermore the bond appears to be slightly ionic (Tl{sup +}H{sup -}) with about 0.3 extra electron charge on the hydrogen.« less

Electronic structure for the ground state of TlH from relativistic multiconfiguration SCF calculations

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

Christiansen, P.A.; Pitzer, K.S.

The dissociation curve for the ground state of TlH was computed using a relativistic ..omega..--..omega.. coupling formalism. The relativistic effects represented by the Dirac equation were introduced using effective potentials generated from atomic Dirac--Fock wave functions using a generalization of the improved effective potential formulation of Christiansen, Lee, and Pitzer. The multiconfiguration SCF treatment used is a generalization of the two-component molecular spinor formalism of Lee, Ermler, and Pitzer. Using a five configuration wave function we were able to obtain approximately 85% of the experimental dissociation energy. Our computations indicate that the bond is principally sigma in form, despite themore » large spin--orbit splitting in atomic thallium. Furthermore the bond appears to be slightly ionic (Tl/sup +/H/sup -/) with about 0.3 extra electron charge on the hydrogen.« less

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

NASA Astrophysics Data System (ADS)

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

2015-09-01

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

Ab initio quantum direct dynamics simulations of ultrafast photochemistry with Multiconfigurational Ehrenfest approach

NASA Astrophysics Data System (ADS)

Makhov, Dmitry V.; Symonds, Christopher; Fernandez-Alberti, Sebastian; Shalashilin, Dmitrii V.

2017-08-01

The Multiconfigurational Ehrenfest (MCE) method is a quantum dynamics technique which allows treatment of a large number of quantum nuclear degrees of freedom. This paper presents a review of MCE and its recent applications, providing a summary of the formalisms, including its ab initio direct dynamics versions and also giving a summary of recent results. Firstly, we describe the Multiconfigurational Ehrenfest version 2 (MCEv2) method and its applicability to direct dynamics and report new calculations which show that the approach converges to the exact result in model systems with tens of degrees of freedom. Secondly, we review previous ;on the fly; ab initio Multiple Cloning (AIMC-MCE) MCE dynamics results obtained for systems of a similar size, in which the calculations treat every electron and every nucleus of a polyatomic molecule on a fully quantum basis. We also review the Time Dependent Diabatic Basis (TDDB) version of the technique and give an example of its application. We summarise the details of the sampling techniques and interpolations used for calculation of the matrix elements, which make our approach efficient. Future directions of work are outlined.

Multiconfiguration Pair-Density Functional Theory and Complete Active Space Second Order Perturbation Theory. Bond Dissociation Energies of FeC, NiC, FeS, NiS, FeSe, and NiSe.

PubMed

Sharkas, Kamal; Gagliardi, Laura; Truhlar, Donald G

2017-12-07

We investigate the performance of multiconfiguration pair-density functional theory (MC-PDFT) and complete active space second-order perturbation theory for computing the bond dissociation energies of the diatomic molecules FeC, NiC, FeS, NiS, FeSe, and NiSe, for which accurate experimental data have become recently available [Matthew, D. J.; Tieu, E.; Morse, M. D. J. Chem. Phys. 2017, 146, 144310-144320]. We use three correlated participating orbital (CPO) schemes (nominal, moderate, and extended) to define the active spaces, and we consider both the complete active space (CAS) and the separated-pair (SP) schemes to specify the configurations included for a given active space. We found that the moderate SP-PDFT scheme with the tPBE on-top density functional has the smallest mean unsigned error (MUE) of the methods considered. This level of theory provides a balanced treatment of the static and dynamic correlation energies for the studied systems. This is encouraging because the method is low in cost even for much more complicated systems.

Two-Dimensional Electronic Spectroscopy of Benzene, Phenol, and Their Dimer: An Efficient First-Principles Simulation Protocol.

PubMed

Nenov, Artur; Mukamel, Shaul; Garavelli, Marco; Rivalta, Ivan

2015-08-11

First-principles simulations of two-dimensional electronic spectroscopy in the ultraviolet region (2DUV) require computationally demanding multiconfigurational approaches that can resolve doubly excited and charge transfer states, the spectroscopic fingerprints of coupled UV-active chromophores. Here, we propose an efficient approach to reduce the computational cost of accurate simulations of 2DUV spectra of benzene, phenol, and their dimer (i.e., the minimal models for studying electronic coupling of UV-chromophores in proteins). We first establish the multiconfigurational recipe with the highest accuracy by comparison with experimental data, providing reference gas-phase transition energies and dipole moments that can be used to construct exciton Hamiltonians involving high-lying excited states. We show that by reducing the active spaces and the number of configuration state functions within restricted active space schemes, the computational cost can be significantly decreased without loss of accuracy in predicting 2DUV spectra. The proposed recipe has been successfully tested on a realistic model proteic system in water. Accounting for line broadening due to thermal and solvent-induced fluctuations allows for direct comparison with experiments.

Multi-layer multi-configuration time-dependent Hartree (ML-MCTDH) approach to the correlated exciton-vibrational dynamics in the FMO complex

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

Schulze, Jan; Kühn, Oliver, E-mail: oliver.kuehn@uni-rostock.de; Shibl, Mohamed F., E-mail: mfshibl@qu.edu.qa

2016-05-14

The coupled quantum dynamics of excitonic and vibrational degrees of freedom is investigated for high-dimensional models of the Fenna-Matthews-Olson complex. This includes a seven- and an eight-site model with 518 and 592 harmonic vibrational modes, respectively. The coupling between local electronic transitions and vibrations is described within the Huang-Rhys model using parameters that are obtained by discretization of an experimental spectral density. Different pathways of excitation energy flow are analyzed in terms of the reduced one-exciton density matrix, focussing on the role of vibrational and vibronic excitations. Distinct features due to both competing time scales of vibrational and exciton motionmore » and vibronically assisted transfer are observed. The question of the effect of initial state preparation is addressed by comparing the case of an instantaneous Franck-Condon excitation at a single site with that of a laser field excitation.« less

Anharmonic frequencies of CX2Y2 (X, Y = O, N, F, H, D) isomers and related systems obtained from vibrational multiconfiguration self-consistent field theory.

PubMed

Pfeiffer, Florian; Rauhut, Guntram

2011-10-13

Accurate anharmonic frequencies are provided for molecules of current research, i.e., diazirines, diazomethane, the corresponding fluorinated and deuterated compounds, their dioxygen analogs, and others. Vibrational-state energies were obtained from state-specific vibrational multiconfiguration self-consistent field theory (VMCSCF) based on multilevel potential energy surfaces (PES) generated from explicitly correlated coupled cluster, CCSD(T)-F12a, and double-hybrid density functional calculations, B2PLYP. To accelerate the vibrational structure calculations, a configuration selection scheme as well as a polynomial representation of the PES have been exploited. Because experimental data are scarce for these systems, many calculated frequencies of this study are predictions and may guide experiments to come.

Vibrational Properties of Hydrogen-Bonded Systems Using the Multireference Generalization to the "On-the-Fly" Electronic Structure within Quantum Wavepacket ab Initio Molecular Dynamics (QWAIMD).

PubMed

Li, Junjie; Li, Xiaohu; Iyengar, Srinivasan S

2014-06-10

We discuss a multiconfigurational treatment of the "on-the-fly" electronic structure within the quantum wavepacket ab initio molecular dynamics (QWAIMD) method for coupled treatment of quantum nuclear effects with electronic structural effects. Here, multiple single-particle electronic density matrices are simultaneously propagated with a quantum nuclear wavepacket and other classical nuclear degrees of freedom. The multiple density matrices are coupled through a nonorthogonal configuration interaction (NOCI) procedure to construct the instantaneous potential surface. An adaptive-mesh-guided set of basis functions composed of Gaussian primitives are used to simplify the electronic structure calculations. Specifically, with the replacement of the atom-centered basis functions positioned on the centers of the quantum-mechanically treated nuclei by a mesh-guided band of basis functions, the two-electron integrals used to compute the electronic structure potential surface become independent of the quantum nuclear variable and hence reusable along the entire Cartesian grid representing the quantum nuclear coordinates. This reduces the computational complexity involved in obtaining a potential surface and facilitates the interpretation of the individual density matrices as representative diabatic states. The parametric nuclear position dependence of the diabatic states is evaluated at the initial time-step using a Shannon-entropy-based sampling function that depends on an approximation to the quantum nuclear wavepacket and the potential surface. This development is meant as a precursor to an on-the-fly fully multireference electronic structure procedure embedded, on-the-fly, within a quantum nuclear dynamics formalism. We benchmark the current development by computing structural, dynamic, and spectroscopic features for a series of bihalide hydrogen-bonded systems: FHF(-), ClHCl(-), BrHBr(-), and BrHCl(-). We find that the donor-acceptor structural features are in good agreement with experiments. Spectroscopic features are computed using a unified velocity/flux autocorrelation function and include vibrational fundamentals and combination bands. These agree well with experiments and other theories.

Predicting Bond Dissociation Energies of Transition-Metal Compounds by Multiconfiguration Pair-Density Functional Theory and Second-Order Perturbation Theory Based on Correlated Participating Orbitals and Separated Pairs.

PubMed

Bao, Junwei Lucas; Odoh, Samuel O; Gagliardi, Laura; Truhlar, Donald G

2017-02-14

We study the performance of multiconfiguration pair-density functional theory (MC-PDFT) and multireference perturbation theory for the computation of the bond dissociation energies in 12 transition-metal-containing diatomic molecules and three small transition-metal-containing polyatomic molecules and in two transition-metal dimers. The first step is a multiconfiguration self-consistent-field calculation, for which two choices must be made: (i) the active space and (ii) its partition into subspaces, if the generalized active space formulation is used. In the present work, the active space is chosen systematically by using three correlated-participating-orbitals (CPO) schemes, and the partition is chosen by using the separated-pair (SP) approximation. Our calculations show that MC-PDFT generally has similar accuracy to CASPT2, and the active-space dependence of MC-PDFT is not very great for transition-metal-ligand bond dissociation energies. We also find that the SP approximation works very well, and in particular SP with the fully translated BLYP functional SP-ftBLYP is more accurate than CASPT2. SP greatly reduces the number of configuration state functions relative to CASSCF. For the cases of FeO and NiO with extended-CPO active space, for which complete active space calculations are unaffordable, SP calculations are not only affordable but also of satisfactory accuracy. All of the MC-PDFT results are significantly better than the corresponding results with broken-symmetry spin-unrestricted Kohn-Sham density functional theory. Finally we test a perturbation theory method based on the SP reference and find that it performs slightly worse than CASPT2 calculations, and for most cases of the nominal-CPO active space, the approximate SP perturbation theory calculations are less accurate than the much less expensive SP-PDFT calculations.

Multiconfigurational nature of 5f orbitals in uranium and plutonium intermetallics

PubMed Central

Booth, C.H.; Jiang, Yu; Wang, D.L.; Mitchell, J.N.; Tobash, P.H.; Bauer, E.D.; Wall, M.A.; Allen, P.G.; Sokaras, D.; Nordlund, D.; Weng, T.-C.; Torrez, M.A.; Sarrao, J.L.

2012-01-01

Uranium and plutonium’s 5f electrons are tenuously poised between strongly bonding with ligand spd-states and residing close to the nucleus. The unusual properties of these elements and their compounds (e.g., the six different allotropes of elemental plutonium) are widely believed to depend on the related attributes of f-orbital occupancy and delocalization for which a quantitative measure is lacking. By employing resonant X-ray emission spectroscopy (RXES) and X-ray absorption near-edge structure (XANES) spectroscopy and making comparisons to specific heat measurements, we demonstrate the presence of multiconfigurational f-orbital states in the actinide elements U and Pu and in a wide range of uranium and plutonium intermetallic compounds. These results provide a robust experimental basis for a new framework toward understanding the strongly-correlated behavior of actinide materials. PMID:22706643

Extended multi-configuration quasi-degenerate perturbation theory: the new approach to multi-state multi-reference perturbation theory.

PubMed

Granovsky, Alexander A

2011-06-07

The distinctive desirable features, both mathematically and physically meaningful, for all partially contracted multi-state multi-reference perturbation theories (MS-MR-PT) are explicitly formulated. The original approach to MS-MR-PT theory, called extended multi-configuration quasi-degenerate perturbation theory (XMCQDPT), having most, if not all, of the desirable properties is introduced. The new method is applied at the second order of perturbation theory (XMCQDPT2) to the 1(1)A(')-2(1)A(') conical intersection in allene molecule, the avoided crossing in LiF molecule, and the 1(1)A(1) to 2(1)A(1) electronic transition in cis-1,3-butadiene. The new theory has several advantages compared to those of well-established approaches, such as second order multi-configuration quasi-degenerate perturbation theory and multi-state-second order complete active space perturbation theory. The analysis of the prevalent approaches to the MS-MR-PT theory performed within the framework of the XMCQDPT theory unveils the origin of their common inherent problems. We describe the efficient implementation strategy that makes XMCQDPT2 an especially useful general-purpose tool in the high-level modeling of small to large molecular systems. © 2011 American Institute of Physics

Quantum dynamical simulation of photoinduced electron transfer processes in dye-semiconductor systems: theory and application to coumarin 343 at TiO₂.

PubMed

Li, Jingrui; Kondov, Ivan; Wang, Haobin; Thoss, Michael

2015-04-10

A recently developed methodology to simulate photoinduced electron transfer processes at dye-semiconductor interfaces is outlined. The methodology employs a first-principles-based model Hamiltonian and accurate quantum dynamics simulations using the multilayer multiconfiguration time-dependent Hartree approach. This method is applied to study electron injection in the dye-semiconductor system coumarin 343-TiO2. Specifically, the influence of electronic-vibrational coupling is analyzed. Extending previous work, we consider the influence of Dushinsky rotation of the normal modes as well as anharmonicities of the potential energy surfaces on the electron transfer dynamics.

Photoionization of atomic barium subshells in the 4 d threshold region using the relativistic multiconfiguration Tamm-Dancoff approximation

NASA Astrophysics Data System (ADS)

Ganesan, Aarthi; Deshmukh, P. C.; Manson, S. T.

2017-03-01

Photoionization cross sections and photoelectron angular distribution asymmetry parameters are calculated for the 4 d10, 5 s2, 5 p6 , and 6 s2 subshells of atomic barium as a test of the relativistic multiconfiguration Tamm-Dancoff (RMCTD) method. The shape resonance present in the near-threshold region of the 4 d subshell is studied in detail in the 4 d photoionization along with the 5 s , 5 p , and 6 s subshells in the region of the 4 d thresholds, as the 4 d shape resonance strongly influences these subshells in its vicinity. The results are compared with available experiment and other many-body theoretical results in an effort to assess the capabilities of the RMCTD methodology. The electron correlations addressed in the RMCTD method give relatively good agreement with the experimental data, indicating that the important many-body correlations are included correctly.

Nonadiabatic Dynamics of Photoinduced Proton-Coupled Electron Transfer Processes

DTIC Science & Technology

devices and photoelectrochemical cells. Theoretical methodology for simulating the nonadiabatic dynamics of photoinduced PCET reactions in solution has...tuning and control of the ultrafast dynamics is crucial for designing renewable and sustainable energy sources, such as artificial photosynthesis...describes the solute with a multiconfigurational method in a bath of explicit solvent molecules. The transferring hydrogen nucleus is represented as a

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

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

Kato, Tsuyoshi; Ide, Yoshihiro; Yamanouchi, Kaoru

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

Molcas 8: New capabilities for multiconfigurational quantum chemical calculations across the periodic table.

PubMed

Aquilante, Francesco; Autschbach, Jochen; Carlson, Rebecca K; Chibotaru, Liviu F; Delcey, Mickaël G; De Vico, Luca; Fdez Galván, Ignacio; Ferré, Nicolas; Frutos, Luis Manuel; Gagliardi, Laura; Garavelli, Marco; Giussani, Angelo; Hoyer, Chad E; Li Manni, Giovanni; Lischka, Hans; Ma, Dongxia; Malmqvist, Per Åke; Müller, Thomas; Nenov, Artur; Olivucci, Massimo; Pedersen, Thomas Bondo; Peng, Daoling; Plasser, Felix; Pritchard, Ben; Reiher, Markus; Rivalta, Ivan; Schapiro, Igor; Segarra-Martí, Javier; Stenrup, Michael; Truhlar, Donald G; Ungur, Liviu; Valentini, Alessio; Vancoillie, Steven; Veryazov, Valera; Vysotskiy, Victor P; Weingart, Oliver; Zapata, Felipe; Lindh, Roland

2016-02-15

In this report, we summarize and describe the recent unique updates and additions to the Molcas quantum chemistry program suite as contained in release version 8. These updates include natural and spin orbitals for studies of magnetic properties, local and linear scaling methods for the Douglas-Kroll-Hess transformation, the generalized active space concept in MCSCF methods, a combination of multiconfigurational wave functions with density functional theory in the MC-PDFT method, additional methods for computation of magnetic properties, methods for diabatization, analytical gradients of state average complete active space SCF in association with density fitting, methods for constrained fragment optimization, large-scale parallel multireference configuration interaction including analytic gradients via the interface to the Columbus package, and approximations of the CASPT2 method to be used for computations of large systems. In addition, the report includes the description of a computational machinery for nonlinear optical spectroscopy through an interface to the QM/MM package Cobramm. Further, a module to run molecular dynamics simulations is added, two surface hopping algorithms are included to enable nonadiabatic calculations, and the DQ method for diabatization is added. Finally, we report on the subject of improvements with respects to alternative file options and parallelization. © 2015 Wiley Periodicals, Inc.

Ultrafast Independent N-H and N-C Bond Deformation Investigated with Resonant Inelastic X-Ray Scattering

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

Eckert, Sebastian; Norell, Jesper; Miedema, Piter S.

Here, the femtosecond excited-state dynamics following resonant photoexcitation enable the selective deformation of N-H and N-C chemical bonds in 2-thiopyridone in aqueous solution with optical or X-ray pulses. In combination with multiconfigurational quantum-chemical calculations, the orbital-specific electronic structure and its ultrafast dynamics accessed with resonant inelastic X-ray scattering at the N 1s level using synchrotron radiation and the soft X-ray free-electron laser LCLS provide direct evidence for this controlled photoinduced molecular deformation and its ultrashort timescale.

Ultrafast Independent N-H and N-C Bond Deformation Investigated with Resonant Inelastic X-Ray Scattering

DOE PAGES

Eckert, Sebastian; Norell, Jesper; Miedema, Piter S.; ...

2017-04-04

Here, the femtosecond excited-state dynamics following resonant photoexcitation enable the selective deformation of N-H and N-C chemical bonds in 2-thiopyridone in aqueous solution with optical or X-ray pulses. In combination with multiconfigurational quantum-chemical calculations, the orbital-specific electronic structure and its ultrafast dynamics accessed with resonant inelastic X-ray scattering at the N 1s level using synchrotron radiation and the soft X-ray free-electron laser LCLS provide direct evidence for this controlled photoinduced molecular deformation and its ultrashort timescale.

Vibrational multiconfiguration self-consistent field theory: implementation and test calculations.

PubMed

Heislbetz, Sandra; Rauhut, Guntram

2010-03-28

A state-specific vibrational multiconfiguration self-consistent field (VMCSCF) approach based on a multimode expansion of the potential energy surface is presented for the accurate calculation of anharmonic vibrational spectra. As a special case of this general approach vibrational complete active space self-consistent field calculations will be discussed. The latter method shows better convergence than the general VMCSCF approach and must be considered the preferred choice within the multiconfigurational framework. Benchmark calculations are provided for a small set of test molecules.

Ultrafast Processes in Atoms and Molecules: Integrated treatment of electronic and nuclear motion in ultrashort XUV pulses

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

McCurdy, C. William

This project made use of Multiconfiguration Time-Dependent Hartree-Fock method developed earlier in the McCurdy group in a series of novel applications of the method to ultrafast spectroscopic processes. MCTDHF treats the dynamics of a molecule or atom under the influence of an external field in manner that has all electrons active. That property distinguishes this method from the more popular (and much less computationally demanding) approaches for treating the electron dynamics of atoms and molecules in fields, such as the time-dependent “Configuration Interaction Singles” approximation or approaches that limit the treatment to either one or two-electron models.

Outstanding performance of configuration interaction singles and doubles using exact exchange Kohn-Sham orbitals in real-space numerical grid method

NASA Astrophysics Data System (ADS)

Lim, Jaechang; Choi, Sunghwan; Kim, Jaewook; Kim, Woo Youn

2016-12-01

To assess the performance of multi-configuration methods using exact exchange Kohn-Sham (KS) orbitals, we implemented configuration interaction singles and doubles (CISD) in a real-space numerical grid code. We obtained KS orbitals with the exchange-only optimized effective potential under the Krieger-Li-Iafrate (KLI) approximation. Thanks to the distinctive features of KLI orbitals against Hartree-Fock (HF), such as bound virtual orbitals with compact shapes and orbital energy gaps similar to excitation energies; KLI-CISD for small molecules shows much faster convergence as a function of simulation box size and active space (i.e., the number of virtual orbitals) than HF-CISD. The former also gives more accurate excitation energies with a few dominant configurations than the latter, even with many more configurations. The systematic control of basis set errors is straightforward in grid bases. Therefore, grid-based multi-configuration methods using exact exchange KS orbitals provide a promising new way to make accurate electronic structure calculations.

Theoretical Investigation of the Electronic Structure of Fe(II) Complexes at Spin-State Transitions

PubMed Central

2013-01-01

The electronic structure relevant to low spin (LS)↔high spin (HS) transitions in Fe(II) coordination compounds with a FeN6 core are studied. The selected [Fe(tz)6]2+ (1) (tz = 1H-tetrazole), [Fe(bipy)3]2+ (2) (bipy = 2,2′-bipyridine), and [Fe(terpy)2]2+ (3) (terpy = 2,2′:6′,2″-terpyridine) complexes have been actively studied experimentally, and with their respective mono-, bi-, and tridentate ligands, they constitute a comprehensive set for theoretical case studies. The methods in this work include density functional theory (DFT), time-dependent DFT (TD-DFT), and multiconfigurational second order perturbation theory (CASPT2). We determine the structural parameters as well as the energy splitting of the LS–HS states (ΔEHL) applying the above methods and comparing their performance. We also determine the potential energy curves representing the ground and low-energy excited singlet, triplet, and quintet d6 states along the mode(s) that connect the LS and HS states. The results indicate that while DFT is well suited for the prediction of structural parameters, an accurate multiconfigurational approach is essential for the quantitative determination of ΔEHL. In addition, a good qualitative agreement is found between the TD-DFT and CASPT2 potential energy curves. Although the TD-DFT results might differ in some respect (in our case, we found a discrepancy at the triplet states), our results suggest that this approach, with due care, is very promising as an alternative for the very expensive CASPT2 method. Finally, the two-dimensional (2D) potential energy surfaces above the plane spanned by the two relevant configuration coordinates in [Fe(terpy)2]2+ were computed at both the DFT and CASPT2 levels. These 2D surfaces indicate that the singlet–triplet and triplet–quintet states are separated along different coordinates, i.e., different vibration modes. Our results confirm that in contrast to the case of complexes with mono- and bidentate ligands, the singlet–quintet transitions in [Fe(terpy)2]2+ cannot be described using a single configuration coordinate. PMID:25821416

Exploring biorthonormal transformations of pair-correlation functions in atomic structure variational calculations

NASA Astrophysics Data System (ADS)

Verdebout, S.; Jönsson, P.; Gaigalas, G.; Godefroid, M.; Froese Fischer, C.

2010-04-01

Multiconfiguration expansions frequently target valence correlation and correlation between valence electrons and the outermost core electrons. Correlation within the core is often neglected. A large orbital basis is needed to saturate both the valence and core-valence correlation effects. This in turn leads to huge numbers of configuration state functions (CSFs), many of which are unimportant. To avoid the problems inherent to the use of a single common orthonormal orbital basis for all correlation effects in the multiconfiguration Hartree-Fock (MCHF) method, we propose to optimize independent MCHF pair-correlation functions (PCFs), bringing their own orthonormal one-electron basis. Each PCF is generated by allowing single- and double-excitations from a multireference (MR) function. This computational scheme has the advantage of using targeted and optimally localized orbital sets for each PCF. These pair-correlation functions are coupled together and with each component of the MR space through a low dimension generalized eigenvalue problem. Nonorthogonal orbital sets being involved, the interaction and overlap matrices are built using biorthonormal transformation of the coupled basis sets followed by a counter-transformation of the PCF expansions. Applied to the ground state of beryllium, the new method gives total energies that are lower than the ones from traditional complete active space (CAS)-MCHF calculations using large orbital active sets. It is fair to say that we now have the possibility to account for, in a balanced way, correlation deep down in the atomic core in variational calculations.

Towards a multiconfigurational method of increments

NASA Astrophysics Data System (ADS)

Fertitta, E.; Koch, D.; Paulus, B.; Barcza, G.; Legeza, Ö.

2018-06-01

The method of increments (MoI) allows one to successfully calculate cohesive energies of bulk materials with high accuracy, but it encounters difficulties when calculating dissociation curves. The reason is that its standard formalism is based on a single Hartree-Fock (HF) configuration whose orbitals are localised and used for the many-body expansion. In situations where HF does not allow a size-consistent description of the dissociation, the MoI cannot be guaranteed to yield proper results either. Herein, we address the problem by employing a size-consistent multiconfigurational reference for the MoI formalism. This leads to a matrix equation where a coupling derived by the reference itself is employed. In principle, such an approach allows one to evaluate approximate values for the ground as well as excited states energies. While the latter are accurate close to the avoided crossing only, the ground state results are very promising for the whole dissociation curve, as shown by the comparison with density matrix renormalisation group benchmarks. We tested this two-state constant-coupling MoI on beryllium rings of different sizes and studied the error introduced by the constant coupling.

Ionic scattering factors of atoms that compose biological molecules

PubMed Central

Matsuoka, Rei; Yamashita, Yoshiki; Yamane, Tsutomu; Kidera, Akinori; Maki-Yonekura, Saori

2018-01-01

Ionic scattering factors of atoms that compose biological molecules have been computed by the multi-configuration Dirac–Fock method. These ions are chemically unstable and their scattering factors had not been reported except for O−. Yet these factors are required for the estimation of partial charges in protein molecules and nucleic acids. The electron scattering factors of these ions are particularly important as the electron scattering curves vary considerably between neutral and charged atoms in the spatial-resolution range explored in structural biology. The calculated X-ray and electron scattering factors have then been parameterized for the major scattering curve models used in X-ray and electron protein crystallography and single-particle cryo-EM. The X-ray and electron scattering factors and the fitting parameters are presented for future reference. PMID:29755750

Dynamics of Coupled Electron-Boson Systems with the Multiple Davydov D1 Ansatz and the Generalized Coherent State.

PubMed

Chen, Lipeng; Borrelli, Raffaele; Zhao, Yang

2017-11-22

The dynamics of a coupled electron-boson system is investigated by employing a multitude of the Davydov D 1 trial states, also known as the multi-D 1 Ansatz, and a second trial state based on a superposition of the time-dependent generalized coherent state (GCS Ansatz). The two Ansätze are applied to study population dynamics in the spin-boson model and the Holstein molecular crystal model, and a detailed comparison with numerically exact results obtained by the (multilayer) multiconfiguration time-dependent Hartree method and the hierarchy equations of motion approach is drawn. It is found that the two methodologies proposed here have significantly improved over that with the single D 1 Ansatz, yielding quantitatively accurate results even in the critical cases of large energy biases and large transfer integrals. The two methodologies provide new effective tools for accurate, efficient simulation of many-body quantum dynamics thanks to a relatively small number of parameters which characterize the electron-nuclear wave functions. The wave-function-based approaches are capable of tracking explicitly detailed bosonic dynamics, which is absent by construct in approaches based on the reduced density matrix. The efficiency and flexibility of our methods are also advantages as compared with numerically exact approaches such as QUAPI and HEOM, especially at low temperatures and in the strong coupling regime.

Influence of Plasma Environment on K-Line Emission in Highly Ionized Iron Atoms Evaluated Using a Debye-Huckel Model

NASA Technical Reports Server (NTRS)

Deprince, J.; Fritzsche, S.; Kallman, T. R.; Palmeri, P.; Quinet, P.

2017-01-01

The influence of plasma environment on the atomic parameters associated with the K-vacancy states has been investigated theoretically for several iron ions. To do this, a time-averaged Debye-Huckel potential for both the electron-nucleus and electron-electron interactions has been considered in the framework of relativistic multiconfiguration Dirac-Fock computations. More particularly, the plasma screening effects on ionization potentials, K-thresholds, transition energies, and radiative rates have been estimated in the astrophysical context of accretion disks around black holes. In the present paper, we describe the behavior of those atomic parameters for Ne-, Na-, Ar-, and K-like iron ions.

Double Photoionization of helium atom using Screening Potential Approach

NASA Astrophysics Data System (ADS)

Saha, Haripada

2014-05-01

The triple differential cross section for double Photoionization of helium atom will be investigated using our recently extended MCHF method. It is well known that electron correlation effects in both the initial and the final states are very important. To incorporate these effects we will use the multi-configuration Hartree-Fock method to account for electron correlation in the initial state. The electron correlation in the final state will be taken into account using the angle-dependent screening potential approximation. The triple differential cross section (TDCS) will be calculated for 20 eV photon energy, which has experimental results. Our results will be compared with available experimental and the theoretical observations.

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

PubMed

Granovsky, Alexander A

2015-12-21

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

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

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

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

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

A theoretical study of three gas-phase reactions involving the production or loss of methane cations.

PubMed

Baptista, Leonardo; da Silveira, Enio F

2014-10-21

Hydrocarbon ions are important species in flames, spectroscopy and the interstellar medium. Their importance is reflected in the extensive body of literature on the structure and reactivity of carbocations. However, the geometry, electronic structure and reactivity of carbocations are difficult to assess. This study aims to contribute to the current knowledge of this subject by presenting a quantum mechanics description of methane cation dissociation using multiconfigurational methods. The geometric and electronic parameters of the minimum structure were determined for three main reaction paths: the dissociation CH4(+)→ CH2(+) + H2 and the dissociation-recombination processes CH4(+)↔ CH3(+) + H. The electronic and energetic effects of these reactions were analyzed, and it was found that each reaction path has a strong dependence on the methodology used as well as a strong multiconfigurational character during dissociation. The first doublet excited states are inner-shell excited states and may correspond to the ions that are expected to be formed after electron detachment. The rate coefficient for each reaction path was determined using variational transition state theory and RRKM/master equation calculations. The major dissociation paths, with their rate coefficients at the high-pressure limit, are CH4(+)(X(~)(2)B1) → CH3(+)(A(2)A1') + H((2)S) (k∞(T) = 1.42 × 10(+14) s(-1) exp(-37.12/RT)) and CH4(+)(X(~)(2)B1) → CH2(+)(A(2)A1) + H2((2)Σg(+)) (k∞(T) = 9.18 × 10(+14) s(-1) exp(-55.77/RT)). Our findings help to explain the abundance of ions formed from CH4 in the interstellar medium and to build models of chemical evolution.

Multiconfiguration Molecular Mechanics Based on Combined Quantum Mechanical and Molecular Mechanical Calculations.

PubMed

Lin, Hai; Zhao, Yan; Tishchenko, Oksana; Truhlar, Donald G

2006-09-01

The multiconfiguration molecular mechanics (MCMM) method is a general algorithm for generating potential energy surfaces for chemical reactions by fitting high-level electronic structure data with the help of molecular mechanical (MM) potentials. It was previously developed as an extension of standard MM to reactive systems by inclusion of multidimensional resonance interactions between MM configurations corresponding to specific valence bonding patterns, with the resonance matrix element obtained from quantum mechanical (QM) electronic structure calculations. In particular, the resonance matrix element is obtained by multidimensional interpolation employing a finite number of geometries at which electronic-structure calculations of the energy, gradient, and Hessian are carried out. In this paper, we present a strategy for combining MCMM with hybrid quantum mechanical molecular mechanical (QM/MM) methods. In the new scheme, electronic-structure information for obtaining the resonance integral is obtained by means of hybrid QM/MM calculations instead of fully QM calculations. As such, the new strategy can be applied to the studies of very large reactive systems. The new MCMM scheme is tested for two hydrogen-transfer reactions. Very encouraging convergence is obtained for rate constants including tunneling, suggesting that the new MCMM method, called QM/MM-MCMM, is a very general, stable, and efficient procedure for generating potential energy surfaces for large reactive systems. The results are found to converge well with respect to the number of Hessians. The results are also compared to calculations in which the resonance integral data are obtained by pure QM, and this illustrates the sensitivity of reaction rate calculations to the treatment of the QM-MM border. For the smaller of the two systems, comparison is also made to direct dynamics calculations in which the potential energies are computed quantum mechanically on the fly.

Self-Interaction Error in Density Functional Theory: An Appraisal.

PubMed

Bao, Junwei Lucas; Gagliardi, Laura; Truhlar, Donald G

2018-05-03

Self-interaction error (SIE) is considered to be one of the major sources of error in most approximate exchange-correlation functionals for Kohn-Sham density-functional theory (KS-DFT), and it is large with all local exchange-correlation functionals and with some hybrid functionals. In this work, we consider systems conventionally considered to be dominated by SIE. For these systems, we demonstrate that by using multiconfiguration pair-density functional theory (MC-PDFT), the error of a translated local density-functional approximation is significantly reduced (by a factor of 3) when using an MCSCF density and on-top density, as compared to using KS-DFT with the parent functional; the error in MC-PDFT with local on-top functionals is even lower than the error in some popular KS-DFT hybrid functionals. Density-functional theory, either in MC-PDFT form with local on-top functionals or in KS-DFT form with some functionals having 50% or more nonlocal exchange, has smaller errors for SIE-prone systems than does CASSCF, which has no SIE.

Computationally Efficient Multiconfigurational Reactive Molecular Dynamics

PubMed Central

Yamashita, Takefumi; Peng, Yuxing; Knight, Chris; Voth, Gregory A.

2012-01-01

It is a computationally demanding task to explicitly simulate the electronic degrees of freedom in a system to observe the chemical transformations of interest, while at the same time sampling the time and length scales required to converge statistical properties and thus reduce artifacts due to initial conditions, finite-size effects, and limited sampling. One solution that significantly reduces the computational expense consists of molecular models in which effective interactions between particles govern the dynamics of the system. If the interaction potentials in these models are developed to reproduce calculated properties from electronic structure calculations and/or ab initio molecular dynamics simulations, then one can calculate accurate properties at a fraction of the computational cost. Multiconfigurational algorithms model the system as a linear combination of several chemical bonding topologies to simulate chemical reactions, also sometimes referred to as “multistate”. These algorithms typically utilize energy and force calculations already found in popular molecular dynamics software packages, thus facilitating their implementation without significant changes to the structure of the code. However, the evaluation of energies and forces for several bonding topologies per simulation step can lead to poor computational efficiency if redundancy is not efficiently removed, particularly with respect to the calculation of long-ranged Coulombic interactions. This paper presents accurate approximations (effective long-range interaction and resulting hybrid methods) and multiple-program parallelization strategies for the efficient calculation of electrostatic interactions in reactive molecular simulations. PMID:25100924

Soft X-ray spectroscopy of transition metal compounds: a theoretical perspective

NASA Astrophysics Data System (ADS)

Bokarev, S. I.; Hilal, R.; Aziz, S. G.; Kühn, O.

2017-01-01

To date, X-ray spectroscopy has become a routine tool that can reveal highly local and element-specific information on the electronic structure of atoms in complex environments. Here, we report on the development of an efficient and versatile theoretical methodology for the treatment of soft X-ray spectra of transition metal compounds based on the multi-configurational self-consistent field electronic structure theory. A special focus is put on the L-edge photon-in/photon-out and photon-in/electron-out processes, i.e. X-ray absorption, resonant inelastic scattering, partial fluorescence yield, and photoelectron spectroscopy, all treated on the same theoretical footing. The investigated systems range from small prototypical coordination compounds and catalysts to aggregates of biomolecules.

On the Angular Dependence of the Vicinal Fluorine-Fluorine Coupling Constant in 1,2-Difluoroethane:  Deviation from a Karplus-like Shape.

PubMed

Provasi, Patricio F; Sauer, Stephan P A

2006-07-01

The angular dependence of the vicinal fluorine-fluorine coupling constant, (3)JFF, for 1,2-difluoroethane has been investigated with several polarization propagator methods. (3)JFF and its four Ramsey contributions were calculated using the random phase approximation (RPA), its multiconfigurational generalization, and both second-order polarization propagator approximations (SOPPA and SOPPA(CCSD)), using locally dense basis sets. The geometries were optimized for each dihedral angle at the level of density functional theory using the B3LYP functional and fourth-order Møller-Plesset perturbation theory. The resulting coupling constant curves were fitted to a cosine series with 8 coefficients. Our results are compared with those obtained previously and values estimated from experiment. It is found that the inclusion of electron correlation in the calculation of (3)JFF reduces the absolute values. This is mainly due to changes in the FC contribution, which for dihedral angles around the trans conformation even changes its sign. This sign change is responsible for the breakdown of the Karplus-like curve.

Polarization transfer in x-ray transitions due to photoionization in highly charged copper-like ions

NASA Astrophysics Data System (ADS)

Ma, Kun; Chen, Zhan-Bin; Xie, Lu-You; Dong, Chen-Zhong

2018-02-01

Using the density matrix theory and the multi-configuration Dirac-Fock method, the 3{d}3/2 subshell photoionization of highly charged ions is studied, together with their subsequent radiative decay. The effects of polarization transfer on the linear polarization and angular distribution of the 3{d}94{s}2{}2{D}3/2\\to 3{d}104p{}2{P}1/2 characteristic line photoemission for selected Cu-like Zn+, Ba27+, {{{W}}}45+, and {{{U}}}63+ ions are investigated. Our results show that the polarization transfer, arising from the originally polarized incident light, may lead to a considerable change in the alignment parameters and the polarization properties of the radiation, the character of which is highly sensitive to the initial photon polarization, yet virtually independent of the photon energy. These characteristics are very similar to those of the electron bremsstrahlung process reported by Märtin et al (2012 Phys. Rev. Lett. 108 264801). The present results are compared with available experimental results and show a good quantitative agreement.

Quantum dynamics of hydrogen atoms on graphene. I. System-bath modeling.

PubMed

Bonfanti, Matteo; Jackson, Bret; Hughes, Keith H; Burghardt, Irene; Martinazzo, Rocco

2015-09-28

An accurate system-bath model to investigate the quantum dynamics of hydrogen atoms chemisorbed on graphene is presented. The system comprises a hydrogen atom and the carbon atom from graphene that forms the covalent bond, and it is described by a previously developed 4D potential energy surface based on density functional theory ab initio data. The bath describes the rest of the carbon lattice and is obtained from an empirical force field through inversion of a classical equilibrium correlation function describing the hydrogen motion. By construction, model building easily accommodates improvements coming from the use of higher level electronic structure theory for the system. Further, it is well suited to a determination of the system-environment coupling by means of ab initio molecular dynamics. This paper details the system-bath modeling and shows its application to the quantum dynamics of vibrational relaxation of a chemisorbed hydrogen atom, which is here investigated at T = 0 K with the help of the multi-configuration time-dependent Hartree method. Paper II deals with the sticking dynamics.

Quantum dynamics of hydrogen atoms on graphene. I. System-bath modeling

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

Bonfanti, Matteo, E-mail: matteo.bonfanti@unimi.it; Jackson, Bret; Hughes, Keith H.

2015-09-28

An accurate system-bath model to investigate the quantum dynamics of hydrogen atoms chemisorbed on graphene is presented. The system comprises a hydrogen atom and the carbon atom from graphene that forms the covalent bond, and it is described by a previously developed 4D potential energy surface based on density functional theory ab initio data. The bath describes the rest of the carbon lattice and is obtained from an empirical force field through inversion of a classical equilibrium correlation function describing the hydrogen motion. By construction, model building easily accommodates improvements coming from the use of higher level electronic structure theorymore » for the system. Further, it is well suited to a determination of the system-environment coupling by means of ab initio molecular dynamics. This paper details the system-bath modeling and shows its application to the quantum dynamics of vibrational relaxation of a chemisorbed hydrogen atom, which is here investigated at T = 0 K with the help of the multi-configuration time-dependent Hartree method. Paper II deals with the sticking dynamics.« less

Towards an automated and efficient calculation of resonating vibrational states based on state-averaged multiconfigurational approaches

NASA Astrophysics Data System (ADS)

Meier, Patrick; Oschetzki, Dominik; Pfeiffer, Florian; Rauhut, Guntram

2015-12-01

Resonating vibrational states cannot consistently be described by single-reference vibrational self-consistent field methods but request the use of multiconfigurational approaches. Strategies are presented to accelerate vibrational multiconfiguration self-consistent field theory and subsequent multireference configuration interaction calculations in order to allow for routine calculations at this enhanced level of theory. State-averaged vibrational complete active space self-consistent field calculations using mode-specific and state-tailored active spaces were found to be very fast and superior to state-specific calculations or calculations with a uniform active space. Benchmark calculations are presented for trans-diazene and bromoform, which show strong resonances in their vibrational spectra.

Towards an automated and efficient calculation of resonating vibrational states based on state-averaged multiconfigurational approaches

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

Meier, Patrick; Oschetzki, Dominik; Pfeiffer, Florian

Resonating vibrational states cannot consistently be described by single-reference vibrational self-consistent field methods but request the use of multiconfigurational approaches. Strategies are presented to accelerate vibrational multiconfiguration self-consistent field theory and subsequent multireference configuration interaction calculations in order to allow for routine calculations at this enhanced level of theory. State-averaged vibrational complete active space self-consistent field calculations using mode-specific and state-tailored active spaces were found to be very fast and superior to state-specific calculations or calculations with a uniform active space. Benchmark calculations are presented for trans-diazene and bromoform, which show strong resonances in their vibrational spectra.

Electron Dynamics in Finite Quantum Systems

NASA Astrophysics Data System (ADS)

McDonald, Christopher R.

The multiconfiguration time-dependent Hartree-Fock (MCTDHF) and multiconfiguration time-dependent Hartree (MCTDH) methods are employed to investigate nonperturbative multielectron dynamics in finite quantum systems. MCTDHF is a powerful tool that allows for the investigation of multielectron dynamics in strongly perturbed quantum systems. We have developed an MCTDHF code that is capable of treating problems involving three dimensional (3D) atoms and molecules exposed to strong laser fields. This code will allow for the theoretical treatment of multielectron phenomena in attosecond science that were previously inaccessible. These problems include complex ionization processes in pump-probe experiments on noble gas atoms, the nonlinear effects that have been observed in Ne atoms in the presence of an x-ray free-electron laser (XFEL) and the molecular rearrangement of cations after ionization. An implementation of MCTDH that is optimized for two electrons, each moving in two dimensions (2D), is also presented. This implementation of MCTDH allows for the efficient treatment of 2D spin-free systems involving two electrons; however, it does not scale well to 3D or to systems containing more that two electrons. Both MCTDHF and MCTDH were used to treat 2D problems in nanophysics and attosecond science. MCTDHF is used to investigate plasmon dynamics and the quantum breathing mode for several electrons in finite lateral quantum dots. MCTDHF is also used to study the effects of manipulating the potential of a double lateral quantum dot containing two electrons; applications to quantum computing are discussed. MCTDH is used to examine a diatomic model molecular system exposed to a strong laser field; nonsequential double ionization and high harmonic generation are studied and new processes identified and explained. An implementation of MCTDHF is developed for nonuniform tensor product grids; this will allow for the full 3D implementation of MCTDHF and will provide a means to investigate a wide variety of problems that cannot be currently treated by any other method. Finally, the time it takes for an electron to tunnel from a bound state is investigated; a definition of the tunnel time is established and the Keldysh time is connected to the wavefunction dynamics.

Lifetimes of 3s3p2 J=12,52 levels in Au66+ and Br22+

NASA Astrophysics Data System (ADS)

Beck, Donald R.; Norquist, Peggy L.

2000-04-01

Relativistic configuration-interaction length and velocity lifetimes have been obtained for 3s3p2 J=1/2, 5/2 levels in Au66+ and Br22+. Results from the two gauges agree well, and we have moderately improved earlier multiconfigurational Dirac-Fock results, as compared to experiment. However, there remains a discrepancy for the Au66+ J=5/2 lifetime, which may be due to satellite spectra associated with 5g and other spectator electrons.

Continuous opacity from Ne^-

NASA Astrophysics Data System (ADS)

John, T. L.

1996-04-01

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

Application of the R-matrix method to photoionization of molecules.

PubMed

Tashiro, Motomichi

2010-04-07

The R-matrix method has been used for theoretical calculation of electron collision with atoms and molecules for long years. The method was also formulated to treat photoionization process, however, its application has been mostly limited to photoionization of atoms. In this work, we implement the R-matrix method to treat molecular photoionization problem based on the UK R-matrix codes. This method can be used for diatomic as well as polyatomic molecules, with multiconfigurational description for electronic states of both target neutral molecule and product molecular ion. Test calculations were performed for valence electron photoionization of nitrogen (N(2)) as well as nitric oxide (NO) molecules. Calculated photoionization cross sections and asymmetry parameters agree reasonably well with the available experimental results, suggesting usefulness of the method for molecular photoionization.

A project based on multi-configuration Dirac-Fock calculations for plasma spectroscopy

NASA Astrophysics Data System (ADS)

Comet, M.; Pain, J.-C.; Gilleron, F.; Piron, R.

2017-09-01

We present a project dedicated to hot plasma spectroscopy based on a Multi-Configuration Dirac-Fock (MCDF) code, initially developed by J. Bruneau. The code is briefly described and the use of the transition state method for plasma spectroscopy is detailed. Then an opacity code for local-thermodynamic-equilibrium plasmas using MCDF data, named OPAMCDF, is presented. Transition arrays for which the number of lines is too large to be handled in a Detailed Line Accounting (DLA) calculation can be modeled within the Partially Resolved Transition Array method or using the Unresolved Transition Arrays formalism in jj-coupling. An improvement of the original Partially Resolved Transition Array method is presented which gives a better agreement with DLA computations. Comparisons with some absorption and emission experimental spectra are shown. Finally, the capability of the MCDF code to compute atomic data required for collisional-radiative modeling of plasma at non local thermodynamic equilibrium is illustrated. In addition to photoexcitation, this code can be used to calculate photoionization, electron impact excitation and ionization cross-sections as well as autoionization rates in the Distorted-Wave or Close Coupling approximations. Comparisons with cross-sections and rates available in the literature are discussed.

Improving the distinguishable cluster results: spin-component scaling

NASA Astrophysics Data System (ADS)

Kats, Daniel

2018-06-01

The spin-component scaling is employed in the energy evaluation to improve the distinguishable cluster approach. SCS-DCSD reaction energies reproduce reference values with a root-mean-squared deviation well below 1 kcal/mol, the interaction energies are three to five times more accurate than DCSD, and molecular systems with a large amount of static electron correlation are still described reasonably well. SCS-DCSD represents a pragmatic approach to achieve chemical accuracy with a simple method without triples, which can also be applied to multi-configurational molecular systems.

MC-PDFT can calculate singlet-triplet splittings of organic diradicals

NASA Astrophysics Data System (ADS)

Stoneburner, Samuel J.; Truhlar, Donald G.; Gagliardi, Laura

2018-02-01

The singlet-triplet splittings of a set of diradical organic molecules are calculated using multiconfiguration pair-density functional theory (MC-PDFT), and the results are compared with those obtained by Kohn-Sham density functional theory (KS-DFT) and complete active space second-order perturbation theory (CASPT2) calculations. We found that MC-PDFT, even with small and systematically defined active spaces, is competitive in accuracy with CASPT2, and it yields results with greater accuracy and precision than Kohn-Sham DFT with the parent functional. MC-PDFT also avoids the challenges associated with spin contamination in KS-DFT. It is also shown that MC-PDFT is much less computationally expensive than CASPT2 when applied to larger active spaces, and this illustrates the promise of this method for larger diradical organic systems.

Energy–density functional plus quasiparticle–phonon model theory as a powerful tool for nuclear structure and astrophysics

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

Tsoneva, N., E-mail: Nadia.Tsoneva@theo.physik.uni-giessen.de; Lenske, H.

During the last decade, a theoretical method based on the energy–density functional theory and quasiparticle–phonon model, including up to three-phonon configurations was developed. The main advantages of themethod are that it incorporates a self-consistentmean-field and multi-configuration mixing which are found of crucial importance for systematic investigations of nuclear low-energy excitations, pygmy and giant resonances in an unified way. In particular, the theoretical approach has been proven to be very successful in predictions of new modes of excitations, namely pygmy quadrupole resonance which is also lately experimentally observed. Recently, our microscopically obtained dipole strength functions are implemented in predictions of nucleon-capturemore » reaction rates of astrophysical importance. A comparison to available experimental data is discussed.« less

Radiative one- and two-electron transitions into the empty K shell of He-like ions

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

Kadrekar, Riddhi; Natarajan, L.

2011-12-15

The branching ratios between the single and double electron radiative transitions to empty K shell in He-like ions with 2s2p configuration are evaluated for 15 ions with 4{<=}Z{<=}26 using fully relativistic multiconfiguration Dirac-Fock wavefunctions in the active space approximation. The effects of configuration interaction and Breit contributions on the transition parameters have been analyzed in detail. Though the influence of Breit interaction on the electric dipole allowed one-electron radiative transitions is negligible, it substantially changes the spin-forbidden rates and the two-electron one-photon transition probabilities. Also, while the single electron transition rates are gauge independent, the correlated double-electron probabilities are foundmore » to be gauge sensitive. The probable uncertainties in the computed transition rates have been evaluated by considering the line strengths and the differences between the calculated and experimental transition energies as accuracy indicators. The present results are compared with other available experimental and theoretical data.« less

Normal order and extended Wick theorem for a multiconfiguration reference wave function

NASA Astrophysics Data System (ADS)

Kutzelnigg, Werner; Mukherjee, Debashis

1997-07-01

A generalization of normal ordering and of Wick's theorem with respect to an arbitrary reference function Φ as some generalized "physical vacuum" is formulated in a different (but essentially equivalent) way than that suggested previously by one of the present authors. Guiding principles are that normal order operators with respect to any reference state must be expressible as linear combinations of those with respect to the genuine vacuum, that the vacuum expectation value of a normal order operator must vanish (with respect to the vacuum to which it is in normal order), and that the well-known formalism for a single Slater determinant as physical vacuum must be contained as a special case. The derivation is largely based on the concepts of "Quantum Chemistry in Fock space," which means that particle-number-conserving operators (excitation operators) play a central role. Nevertheless, the contraction rules in the frame of a generalized Wick theorem are derived, that hold for non-particle-number-conserving operators as well. The contraction rules are formulated and illustrated in terms of diagrams. The contractions involve the "residual n-particle density matrices" λ, which are the irreducible (non-factorizable) parts of the conventional n-particle density matrices γ, in the sense of a cumulant expansion for the density. A spinfree formulation is presented as well. The expression of the Hamiltonian in normal order with respect to a multiconfiguration reference function leads to a natural definition of a generalized Fock operator. MC-SCF-theory is easily worked out in this context. The paper concludes with a discussion of the excited configurations and the first-order interacting space, that underlies a perturbative coupled cluster type correction to the MCSCF function for an arbitrary reference function, and with general implications of the new formalism, that is related to "internally contracted multireference configuration interaction." The present generalization of normal ordering is not only valid for arbitrary reference functions, but also if the reference state is an ensemble state.

Production of the Q2 doubly excited states of the hydrogen molecule by electron impact in a single step

NASA Astrophysics Data System (ADS)

Santos, Leonardo O.; Rocha, Alexandre B.; Faria, Nelson Velho de Castro; Jalbert, Ginette

2017-03-01

We calculate the single step cross sections for excitation of Q 2 states of H2 and its subsequent dissociation. The cross section calculations were performed within the first Born approximation and the electronic wave functions were obtained via State-Averaged Multiconfigurational Self-Consistent Field followed by Configuration Interaction. We have assumed autoionization is the only important process competing with dissociation into neutral atoms. We have estimated its probability through a semi classical approach and compared with results of literature. Special attention was given to the Q 2 1Σg +(1) state which, as has been shown in a previous work, may dissociate into H(2 sσ) + H(2 sσ) fragments (some figures in this article are in colour only in the electronic version).

Bonding and structure of copper nitrenes.

PubMed

Cundari, Thomas R; Dinescu, Adriana; Kazi, Abul B

2008-11-03

Copper nitrenes are of interest as intermediates in the catalytic aziridination of olefins and the amination of C-H bonds. However, despite advances in the isolation and study of late-transition-metal multiply bonded complexes, a bona fide structurally characterized example of a terminal copper nitrene has, to our knowledge, not been reported. In anticipation of such a report, terminal copper nitrenes are studied from a computational perspective. The nitrene complexes studied here are of the form (beta-diketiminate)Cu(NPh). Density functional theory (DFT), complete active space self-consistent-field (CASSCF) electronic structure techniques, and hybrid quantum mechanical/molecular mechanical (QM/MM) methods are employed to study such species. While DFT methods indicate that a triplet (S = 1) is the ground state, CASSCF calculations indicate that a singlet (S = 0) is the ground state, with only a small energy gap between the singlet and triplet. Moreover, the ground-state (open-shell) singlet copper nitrene is found to be highly multiconfigurational (i.e., biradical) and to possess a bent geometry about the nitrene nitrogen, contrasting with the linear nitrene geometry of the triplet copper nitrenes. CASSCF calculations also reveal the existence of a closed-shell singlet state with some degree of multiple bonding character for the copper-nitrene bond.

Theoretical hyperfine structures of 19F i and 17O i

NASA Astrophysics Data System (ADS)

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

2018-03-01

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

Interpretation of the photoelectron spectra of FeS(2)(-) by a multiconfiguration computational approach.

PubMed

Clima, Sergiu; Hendrickx, Marc F A

2007-11-01

The ground states of FeS(2) and FeS(2)(-), and several low-lying excited electronic states of FeS(2) that are responsible for the FeS(2)(-) photoelectron spectrum, are calculated. At the B3LYP level an open, quasi-linear [SFeS](-) conformation is found as the most stable structure, which is confirmed at the ab initio CASPT2 computational level. Both the neutral and the anionic unsaturated complexes possess high-spin electronic ground states. For the first time a complete assignment of the photoelectron spectrum of FeS(2)(-) is proposed. The lowest energy band in this spectrum is ascribed to an electron detachment from the two highest-lying 3dpi antibonding orbitals (with respect to the iron-sulfur bonding) of iron. The next-lowest experimental band corresponds to an electron removal from nonbonding, nearly pure sulfur orbitals. The two highest bands in the spectra are assigned as electron detachments from pi and sigma bonding mainly sulfur orbitals.

MCDF calculations of Auger cascade processes

NASA Astrophysics Data System (ADS)

Beerwerth, Randolf; Fritzsche, Stephan

2017-10-01

We model the multiple ionization of near-neutral core-excited atoms where a cascade of Auger processes leads to the emission of several electrons. We utilize the multiconfiguration Dirac-Fock (MCDF) method to generate approximate wave functions for all fine-structure levels and to account for all decays between them. This approach allows to compute electron spectra, the population of final-states and ion yields, that are accessible in many experiments. Furthermore, our approach is based on the configuration interaction method. A careful treatment of correlation between electronic configurations enables one to model three-electron processes such as an Auger decay that is accompanied by an additional shake-up transition. Here, this model is applied to the triple ionization of atomic cadmium, where we show that the decay of inner-shell 4p holes to triply-charged final states is purely due to the shake-up transition of valence 5s electrons. Contribution to the Topical Issue "Atomic and Molecular Data and their Applications", edited by Gordon W.F. Drake, Jung-Sik Yoon, Daiji Kato, Grzegorz Karwasz.

Energy Levels, Lifetimes, and Transition Rates for P-like Ions from Cr X to Zn XVI from Large-scale Relativistic Multiconfiguration Calculations

NASA Astrophysics Data System (ADS)

Wang, K.; Jönsson, P.; Gaigalas, G.; Radžiūtė, L.; Rynkun, P.; Del Zanna, G.; Chen, C. Y.

2018-04-01

The fully relativistic multiconfiguration Dirac–Hartree–Fock method is used to compute excitation energies and lifetimes for the 143 lowest states of the 3{s}23{p}3, 3s3p 4, 3{s}23{p}23d, 3s3p 33d, 3p 5, 3{s}23p3{d}2 configurations in P-like ions from Cr X to Zn XVI. Multipole (E1, M1, E2, M2) transition rates, line strengths, oscillator strengths, and branching fractions among these states are also given. Valence–valence and core–valence electron correlation effects are systematically accounted for using large basis function expansions. Computed excitation energies are compared with the NIST ASD and CHIANTI compiled values and previous calculations. The mean average absolute difference, removing obvious outliers, between computed and observed energies for the 41 lowest identified levels in Fe XII, is only 0.057%, implying that the computed energies are accurate enough to aid identification of new emission lines from the Sun and other astrophysical sources. The amount of energy and transition data of high accuracy are significantly increased for several P-like ions of astrophysics interest, where experimental data are still very scarce.

Multilayer-MCTDH approach to the energy transfer dynamics in the LH2 antenna complex

NASA Astrophysics Data System (ADS)

Shibl, Mohamed F.; Schulze, Jan; Al-Marri, Mohammed J.; Kühn, Oliver

2017-09-01

The multilayer multiconfiguration time-dependent Hartree method is used to study the coupled exciton-vibrational dynamics in a high-dimensional nonameric model of the LH2 antenna complex of purple bacteria. The exciton-vibrational coupling is parametrized within the Huang-Rhys model according to phonon and intramolecular vibrational modes derived from an experimental bacteriochlorophyll spectral density. In contrast to reduced density matrix approaches, the Schrödinger equation is solved explicitly, giving access to the full wave function. This facilitates an unbiased analysis in terms of the coupled dynamics of excitonic and vibrational degrees of freedom. For the present system, we identify spectator modes for the B800 to B800 transfer and we find a non-additive effect of phonon and intramolecular vibrational modes on the B800 to B850 exciton transfer.

Multielectron spectroscopy: energy levels of K n+ and Rb n+ ions (n = 2, 3, 4)

NASA Astrophysics Data System (ADS)

Khalal, M. A.; Soronen, J.; Jänkälä, K.; Huttula, S.-M.; Huttula, M.; Bizau, J.-M.; Cubaynes, D.; Guilbaud, S.; Ito, K.; Andric, L.; Feng, J.; Lablanquie, P.; Palaudoux, J.; Penent, F.

2017-11-01

A magnetic bottle time-of-flight spectrometer has been used to perform spectroscopy of K n+ and Rb n+ states with ionization degrees n of 2, 3 and 4. Energy levels are directly measured by detecting in coincidence the n electrons that are emitted as a result of single photon absorption. Experimental results are compared with the energies from the NIST atomic database and ab initio multiconfiguration Dirac-Fock calculations. Previously unidentified 3p 4(3P)3d 1 4D energy levels of K2+ are assigned.

Theoretical Study of Tautomerization Reactions for the Ground and First Excited Electronic States of Adenine

NASA Technical Reports Server (NTRS)

Salter, Latasha M.; Chaban, Galina M.; Kwak, Dochan (Technical Monitor)

2002-01-01

Geometrical structures and energetic properties for different tautomers of adenine are calculated in this study, using multi-configurational wave functions. Both the ground and the lowest singlet excited state potential energy surfaces are studied. Four tautomeric forms are considered, and their energetic order is found to be different on the ground and the excited state potential energy surfaces. Minimum energy reaction paths are obtained for hydrogen atom transfer (tautomerization) reactions in the ground and the lowest excited electronic states. It is found that the barrier heights and the shapes of the reaction paths are different for the ground and the excited electronic states, suggesting that the probability of such tautomerization reaction is higher on the excited state potential energy surface. This tautomerization process should become possible in the presence of water or other polar solvent molecules and should play an important role in the photochemistry of adenine.

Normal Auger spectra of iodine in gas phase alkali iodide molecules

NASA Astrophysics Data System (ADS)

Hu, Zhengfa; Caló, Antonio; Kukk, Edwin; Aksela, Helena; Aksela, Seppo

2005-06-01

Molecular normal Auger electron spectra following the iodine 4d ionization in gas-phase alkali iodides were investigated both experimentally and theoretically. The Auger electron spectra for LiI, NaI and KI were recorded using electron impact, and for RbI by using photo-excitation. These Auger spectra were analyzed in detail and compared to the referenced normal Auger spectra of HI [L. Karlsson, S. Svensson, P. Baltzer, M. Carlsson-Göthe, M.P. Keane, A. Naves de Brito, N. Correia, B. Wannberg, J. Phys. B 22 (1989) 3001]. An energy shift toward higher kinetic energy and a narrowing in linewidth are observed in the Auger spectra series revealing the effect of the changing environment from covalently bonded HI to ionic alkali iodide compounds. The experimental results are also compared with the theoretical ab initio calculations and with the Auger spectra of I -, computed with the multiconfiguration Hartree-Fock (MCHF) method.

Assigning the Cerium Oxidation State for CH2CeF2 and OCeF2 Based on Multireference Wave Function Analysis.

PubMed

Mooßen, Oliver; Dolg, Michael

2016-06-09

The geometric and electronic structure of the recently experimentally studied molecules ZCeF2 (Z = CH2, O) was investigated by density functional theory (DFT) and wave function-based ab initio methods. Special attention was paid to the Ce-Z metal-ligand bonding, especially to the nature of the interaction between the Ce 4f and the Z 2p orbitals and the possible multiconfigurational character arising from it, as well as to the assignment of an oxidation state of Ce reflecting the electronic structure. Complete active space self-consistent field (CASSCF) calculations were performed, followed by orbital rotations in the active orbital space. The methylene compound CH2CeF2 has an open-shell singlet ground state, which is characterized by a two-configurational wave function in the basis of the strongly mixed natural CASSCF orbitals. The system can also be described in a very compact way by the dominant Ce 4f(1) C 2p(1) configuration, if nearly pure Ce 4f and C 2p orbitals are used. In the basis of these localized orbitals, the molecule is almost monoconfigurational and should be best described as a Ce(III) system. The singlet ground state of the oxygen OCeF2 complex is of closed-shell character when a monoconfigurational wave function with very strongly mixed Ce 4f and O 2p CASSCF natural orbitals is used for the description. The transformation to orbitals localized on the cerium and oxygen atoms leads to a multiconfigurational wave function and reveals characteristics of a mixed valent Ce(IV)/Ce(III) compound. Additionally, the interactions of the localized active orbitals were analyzed by evaluating the expectation values of the charge fluctuation operator and the local spin operator. The Ce 4f and C 2p orbital interaction of the CH2CeF2 compound is weakly covalent and resembles the interaction of the H 1s orbitals in a stretched hydrogen dimer. In contrast, the interaction of the localized active orbitals for OCeF2 shows ionic character. Calculated vibrational Ce-C and Ce-O stretching frequencies at the DFT, CASSCF, second-order Rayleigh-Schrödinger perturbation theory (RS2C), multireference configuration interaction (MRCI), as well as single, doubles, and perturbative triples coupled cluster (CCSD(T)) level are reported and compared to experimental infrared absorption data in a Ne and Ar matrix.

Entanglement entropy of electronic excitations.

PubMed

Plasser, Felix

2016-05-21

A new perspective into correlation effects in electronically excited states is provided through quantum information theory. The entanglement between the electron and hole quasiparticles is examined, and it is shown that the related entanglement entropy can be computed from the eigenvalue spectrum of the well-known natural transition orbital (NTO) decomposition. Non-vanishing entanglement is obtained whenever more than one NTO pair is involved, i.e., in the case of a multiconfigurational or collective excitation. An important implication is that in the case of entanglement it is not possible to gain a complete description of the state character from the orbitals alone, but more specific analysis methods are required to decode the mutual information between the electron and hole. Moreover, the newly introduced number of entangled states is an important property by itself giving information about excitonic structure. The utility of the formalism is illustrated in the cases of the excited states of two interacting ethylene molecules, the conjugated polymer para-phenylene vinylene, and the naphthalene molecule.

Photodissociation dynamics in the first absorption band of pyrrole. I. Molecular Hamiltonian and the Herzberg-Teller absorption spectrum for the A12(π σ* ) ←X˜ 1 A1(π π ) transition

NASA Astrophysics Data System (ADS)

Picconi, David; Grebenshchikov, Sergy Yu.

2018-03-01

This paper opens a series in which the photochemistry of the two lowest πσ* states of pyrrole and their interaction with each other and with the ground electronic state X ˜ are studied using ab initio quantum mechanics. New 24-dimensional potential energy surfaces for the photodissociation of the N-H bond and the formation of the pyrrolyl radical are calculated using the multiconfigurational perturbation theory (CASPT2) for the electronic states X ˜ (π π ) , 11A2(πσ*), and 11B1(πσ*) and locally diabatized. In this paper, the ab initio calculations are described and the photodissociation in the state 11A2(πσ*) is analyzed. The excitation 11 A2←X ˜ is mediated by the coordinate dependent transition dipole moment functions constructed using the Herzberg-Teller expansion. Nuclear dynamics, including 6, 11, and 15 active degrees of freedom, are studied using the multi-configurational time-dependent Hartree method. The focus is on the frequency resolved absorption spectrum as well as on the dissociation time scales and the resonance lifetimes. Calculations are compared with available experimental data. An approximate convolution method is developed and validated, with which absorption spectra can be calculated and assigned in terms of vibrational quantum numbers. The method represents the total absorption spectrum as a convolution of the diffuse spectrum of the detaching H-atom and the Franck-Condon spectrum of the heteroaromatic ring. Convolution calculation requires a minimal quantum chemical input and is a promising tool for studying the πσ* photodissociation in model biochromophores.

Time-dependent quantum chemistry of laser driven many-electron molecules

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

Nguyen-Dang, Thanh-Tung; Couture-Bienvenue, Étienne; Viau-Trudel, Jérémy

2014-12-28

A Time-Dependent Configuration Interaction approach using multiple Feshbach partitionings, corresponding to multiple ionization stages of a laser-driven molecule, has recently been proposed [T.-T. Nguyen-Dang and J. Viau-Trudel, J. Chem. Phys. 139, 244102 (2013)]. To complete this development toward a fully ab-initio method for the calculation of time-dependent electronic wavefunctions of an N-electron molecule, we describe how tools of multiconfiguration quantum chemistry such as the management of the configuration expansion space using Graphical Unitary Group Approach concepts can be profitably adapted to the new context, that of time-resolved electronic dynamics, as opposed to stationary electronic structure. The method is applied tomore » calculate the detailed, sub-cycle electronic dynamics of BeH{sub 2}, treated in a 3–21G bound-orbital basis augmented by a set of orthogonalized plane-waves representing continuum-type orbitals, including its ionization under an intense λ = 800 nm or λ = 80 nm continuous-wave laser field. The dynamics is strongly non-linear at the field-intensity considered (I ≃ 10{sup 15} W/cm{sup 2}), featuring important ionization of an inner-shell electron and strong post-ionization bound-electron dynamics.« less

Analytic model of a multi-electron atom

NASA Astrophysics Data System (ADS)

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

2017-12-01

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

Influence of Spin-Orbit Quenching on the Solvation of Indium in Helium Droplets

NASA Astrophysics Data System (ADS)

Meyer, Ralf; Pototschnig, Johann V.; Ernst, Wolfgang E.; Hauser, Andreas W.

2017-06-01

Recent experimental interest of the collaborating group of M. Koch on the dynamics of electronic excitations of indium in helium droplets triggered a series of computational studies on the group 13 elements Al, Ga and In and their indecisive behavior between wetting and non wetting when placed onto superfluid helium droplets. We employ a combination of multiconfigurational self consistent field calculations (MCSCF) and multireference configuration interaction (MRCI) to calculate the diatomic potentials. Particularly interesting is the case of indium with an Ancilotto parameter λ close to the threshold value of 1.9. As shown by Reho et al. the spin-orbit splitting of metal atoms solvated in helium droplets is subject to a quenching effect. This can drastically change the solvation behavior. In this work we extend the approach presented by Reho et al. to include distance dependent spin-orbit coupling. The resulting potential surfaces are used to calculate the solvation energy of the ground state and the first excited state with orbital-free helium density functional theory. F. Ancilotto, P. B. Lerner and M. W. Cole, Journal of Low Temperature Physics, 1995, 101, 1123-1146 J. H. Reho, U. Merker, M. R. Radcliff, K. K. Lehmann and G. Scoles, The Journal of Physical Chemistry A, 2000, 104, 3620-3626

DFT and ab initio study of the unimolecular decomposition of the lowest singlet and triplet states of nitromethane

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

Manaa, M.R.; Fried, L.E.

1998-11-26

The fully optimized potential energy curves for the unimolecular decomposition of the lowest singlet and triplet states of nitromethane through the C-NO{sub 2} bond dissociation pathway are calculated using various DFT and high-level ab initio electronic structure methods. The authors perform gradient corrected density functional theory (DFT) and multiconfiguration self-consistent field (MCSCF) to conclusively demonstrate that the triplet state of nitromethane is bound. The adiabatic curve of this state exhibits a 33 kcal/mol energy barrier as determined at the MCSCF level. DFT methods locate this barrier at a shorter C-N bond distance with 12--16 kcal/mol lower energy than does MCSCF.more » In addition to MCSCF and DFT, quadratic configuration interactions with single and double substitutions (QCISD) calculations are also performed for the singlet curve. The potential energy profiles of this state predicted by FT methods based on Becke`s 1988 exchange functional differ by as much as 17 kcal/mol from the predictions of MCSCF and QCISD in the vicinity of the equilibrium structure. The computational methods predict bond dissociation energies 5--9 kcal/mol lower than the experimental value. DFT techniques based on Becke`s 3-parameter exchange functional show the best overall agreement with the higher level methods.« less

[Mo2(CN)11]:5- A detailed description of ligand-field spectra and magnetic properties by first-principles calculations.

PubMed

Hendrickx, Marc F A; Clima, S; Chibotaru, L F; Ceulemans, A

2005-10-06

An ab initio multiconfigurational approach has been used to calculate the ligand-field spectrum and magnetic properties of the title cyano-bridged dinuclear molybdenum complex. The rather large magnetic coupling parameter J for a single cyano bridge, as derived experimentally for this complex by susceptibility measurements, is confirmed to a high degree of accuracy by our CASPT2 calculations. Its electronic structure is rationalized in terms of spin-spin coupling between the two constituent hexacyano-monomolybdate complexes. An in-depth analysis on the basis of Anderson's kinetic exchange theory provides a qualitative picture of the calculated CASSCF antiferromagnetic ground-state eigenvector in the Mo dimer. Dynamic electron correlations as incorporated into our first-principles calculations by means of the CASPT2 method are essential to obtain quantitative agreement between theory and experiment.

Multiconfigurational and DFT analyses of the electromeric formulation and UV-vis absorption spectra of the superoxide adduct of ferrous superoxide reductase.

PubMed

Attia, Amr A A; Cioloboc, Daniela; Lupan, Alexandru; Silaghi-Dumitrescu, Radu

2016-12-01

The putative initial adduct of ferrous superoxide reductase (SOR) with superoxide has been alternatively formulated as ferric-peroxo or ferrous-superoxo. The ~600-nm UV-vis absorption band proposed to be assigned to this adduct (either as sole intermediate in the SOR catalytic cycle, or as one of the two intermediates) has recently been interpreted as due to a ligand-to-metal charge transfer, involving thiolate and superoxide in a ferrous complex, contrary to an alternative assignment as a predominantly cysteine thiolate-to-ferric charge transfer in a ferric-peroxo electromer. In an attempt to clarify the electromeric formulation of this adduct, we report a computational study using a multiconfigurational complete active space self-consistent field (MC-CASSCF) wave function approach as well as modelling the UV-vis absorption spectra with time-dependent density functional theory (TD-DFT). The MC-CASSCF calculations disclose a weak interaction between iron and the dioxygenic ligand and a dominant configuration with an essentially ferrous-superoxo character. The computed UV-vis absorption spectra reveal a marked dependence on the choice of density functional - both in terms of location of bands and in terms of orbital contributors. For the main band in the visible region, besides the recently reported thiolate-to-superoxide charge transfer, a more salient, and less functional-dependent, feature is a thiolate-to-ferric iron charge transfer, consistent with a ferric-peroxo electromer. By contrast, the computed UV-vis spectra of a ferric-hydroperoxo SOR model match distinctly better (and with no qualitative dependence on the DFT methodology) the 600-nm band as due to a mainly thiolate-to-ferric character - supporting the assignment of the SOR "600-nm intermediate" as a S=5/2 ferric-hydroperoxo species. Copyright © 2016 Elsevier Inc. All rights reserved.

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

Plasser, Felix, E-mail: felix.plasser@univie.ac.at

A new perspective into correlation effects in electronically excited states is provided through quantum information theory. The entanglement between the electron and hole quasiparticles is examined, and it is shown that the related entanglement entropy can be computed from the eigenvalue spectrum of the well-known natural transition orbital (NTO) decomposition. Non-vanishing entanglement is obtained whenever more than one NTO pair is involved, i.e., in the case of a multiconfigurational or collective excitation. An important implication is that in the case of entanglement it is not possible to gain a complete description of the state character from the orbitals alone, butmore » more specific analysis methods are required to decode the mutual information between the electron and hole. Moreover, the newly introduced number of entangled states is an important property by itself giving information about excitonic structure. The utility of the formalism is illustrated in the cases of the excited states of two interacting ethylene molecules, the conjugated polymer para-phenylene vinylene, and the naphthalene molecule.« less

Fingerprints of electronic, spin and structural dynamics from resonant inelastic soft X-ray scattering in transient photo-chemical species

DOE PAGES

Norell, Jesper; Jay, Raphael M.; Hantschmann, Markus; ...

2018-02-20

Here, we describe how inversion symmetry separation of electronic state manifolds in resonant inelastic soft X-ray scattering (RIXS) can be applied to probe excited-state dynamics with compelling selectivity. In a case study of Fe L 3-edge RIXS in the ferricyanide complex Fe(CN) 6 3-, we demonstrate with multi-configurational restricted active space spectrum simulations how the information content of RIXS spectral fingerprints can be used to unambiguously separate species of different electronic configurations, spin multiplicities, and structures, with possible involvement in the decay dynamics of photo-excited ligand-to-metal charge-transfer. Specifically, we propose that this could be applied to confirm or reject themore » presence of a hitherto elusive transient Quartet species. Thus, RIXS offers a particular possibility to settle a recent controversy regarding the decay pathway, and we expect the technique to be similarly applicable in other model systems of photo-induced dynamics.« less

Fingerprints of electronic, spin and structural dynamics from resonant inelastic soft X-ray scattering in transient photo-chemical species

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

Norell, Jesper; Jay, Raphael M.; Hantschmann, Markus

Here, we describe how inversion symmetry separation of electronic state manifolds in resonant inelastic soft X-ray scattering (RIXS) can be applied to probe excited-state dynamics with compelling selectivity. In a case study of Fe L 3-edge RIXS in the ferricyanide complex Fe(CN) 6 3-, we demonstrate with multi-configurational restricted active space spectrum simulations how the information content of RIXS spectral fingerprints can be used to unambiguously separate species of different electronic configurations, spin multiplicities, and structures, with possible involvement in the decay dynamics of photo-excited ligand-to-metal charge-transfer. Specifically, we propose that this could be applied to confirm or reject themore » presence of a hitherto elusive transient Quartet species. Thus, RIXS offers a particular possibility to settle a recent controversy regarding the decay pathway, and we expect the technique to be similarly applicable in other model systems of photo-induced dynamics.« less

Pushing configuration-interaction to the limit: Towards massively parallel MCSCF calculations

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

Vogiatzis, Konstantinos D.; Ma, Dongxia; Olsen, Jeppe

A new large-scale parallel multiconfigurational self-consistent field (MCSCF) implementation in the open-source NWChem computational chemistry code is presented. The generalized active space approach is used to partition large configuration interaction (CI) vectors and generate a sufficient number of batches that can be distributed to the available cores. Massively parallel CI calculations with large active spaces can be performed. The new parallel MCSCF implementation is tested for the chromium trimer and for an active space of 20 electrons in 20 orbitals, which can now routinely be performed. Unprecedented CI calculations with an active space of 22 electrons in 22 orbitals formore » the pentacene systems were performed and a single CI iteration calculation with an active space of 24 electrons in 24 orbitals for the chromium tetramer was possible. In conclusion, the chromium tetramer corresponds to a CI expansion of one trillion Slater determinants (914 058 513 424) and is the largest conventional CI calculation attempted up to date.« less

Pushing configuration-interaction to the limit: Towards massively parallel MCSCF calculations

DOE PAGES

Vogiatzis, Konstantinos D.; Ma, Dongxia; Olsen, Jeppe; ...

2017-11-14

A new large-scale parallel multiconfigurational self-consistent field (MCSCF) implementation in the open-source NWChem computational chemistry code is presented. The generalized active space approach is used to partition large configuration interaction (CI) vectors and generate a sufficient number of batches that can be distributed to the available cores. Massively parallel CI calculations with large active spaces can be performed. The new parallel MCSCF implementation is tested for the chromium trimer and for an active space of 20 electrons in 20 orbitals, which can now routinely be performed. Unprecedented CI calculations with an active space of 22 electrons in 22 orbitals formore » the pentacene systems were performed and a single CI iteration calculation with an active space of 24 electrons in 24 orbitals for the chromium tetramer was possible. In conclusion, the chromium tetramer corresponds to a CI expansion of one trillion Slater determinants (914 058 513 424) and is the largest conventional CI calculation attempted up to date.« less

Pushing configuration-interaction to the limit: Towards massively parallel MCSCF calculations

NASA Astrophysics Data System (ADS)

Vogiatzis, Konstantinos D.; Ma, Dongxia; Olsen, Jeppe; Gagliardi, Laura; de Jong, Wibe A.

2017-11-01

A new large-scale parallel multiconfigurational self-consistent field (MCSCF) implementation in the open-source NWChem computational chemistry code is presented. The generalized active space approach is used to partition large configuration interaction (CI) vectors and generate a sufficient number of batches that can be distributed to the available cores. Massively parallel CI calculations with large active spaces can be performed. The new parallel MCSCF implementation is tested for the chromium trimer and for an active space of 20 electrons in 20 orbitals, which can now routinely be performed. Unprecedented CI calculations with an active space of 22 electrons in 22 orbitals for the pentacene systems were performed and a single CI iteration calculation with an active space of 24 electrons in 24 orbitals for the chromium tetramer was possible. The chromium tetramer corresponds to a CI expansion of one trillion Slater determinants (914 058 513 424) and is the largest conventional CI calculation attempted up to date.

The effect of sampling techniques used in the multiconfigurational Ehrenfest method

NASA Astrophysics Data System (ADS)

Symonds, C.; Kattirtzi, J. A.; Shalashilin, D. V.

2018-05-01

In this paper, we compare and contrast basis set sampling techniques recently developed for use in the ab initio multiple cloning method, a direct dynamics extension to the multiconfigurational Ehrenfest approach, used recently for the quantum simulation of ultrafast photochemistry. We demonstrate that simultaneous use of basis set cloning and basis function trains can produce results which are converged to the exact quantum result. To demonstrate this, we employ these sampling methods in simulations of quantum dynamics in the spin boson model with a broad range of parameters and compare the results to accurate benchmarks.

The effect of sampling techniques used in the multiconfigurational Ehrenfest method.

PubMed

Symonds, C; Kattirtzi, J A; Shalashilin, D V

2018-05-14

In this paper, we compare and contrast basis set sampling techniques recently developed for use in the ab initio multiple cloning method, a direct dynamics extension to the multiconfigurational Ehrenfest approach, used recently for the quantum simulation of ultrafast photochemistry. We demonstrate that simultaneous use of basis set cloning and basis function trains can produce results which are converged to the exact quantum result. To demonstrate this, we employ these sampling methods in simulations of quantum dynamics in the spin boson model with a broad range of parameters and compare the results to accurate benchmarks.

Theoretical Study of Decomposition Pathways for HArF and HKrF

NASA Technical Reports Server (NTRS)

Chaban, Galina M.; Lundell, Jan; Gerber, R. Benny; Kwak, Donchan (Technical Monitor)

2002-01-01

To provide theoretical insights into the stability and dynamics of the new rare gas compounds HArF and HKrF, reaction paths for decomposition processes HRgF to Rg + HF and HRgF to H + Rg + F (Rg = Ar, Kr) are calculated using ab initio electronic structure methods. The bending channels, HRgF to Rg + HF, are described by single-configurational MP2 and CCSD(T) electronic structure methods, while the linear decomposition paths, HRgF to H + Rg + F, require the use of multi-configurational wave functions that include dynamic correlation and are size extensive. HArF and HKrF molecules are found to be energetically stable with respect to atomic dissociation products (H + Rg + F) and separated by substantial energy barriers from Rg + HF products, which ensure their kinetic stability. The results are compatible with experimental data on these systems.

Dirac R -matrix calculations for the electron-impact excitation of neutral tungsten providing noninvasive diagnostics for magnetic confinement fusion

NASA Astrophysics Data System (ADS)

Smyth, R. T.; Ballance, C. P.; Ramsbottom, C. A.; Johnson, C. A.; Ennis, D. A.; Loch, S. D.

2018-05-01

Neutral tungsten is the primary candidate as a wall material in the divertor region of the International Thermonuclear Experimental Reactor (ITER). The efficient operation of ITER depends heavily on precise atomic physics calculations for the determination of reliable erosion diagnostics, helping to characterize the influx of tungsten impurities into the core plasma. The following paper presents detailed calculations of the atomic structure of neutral tungsten using the multiconfigurational Dirac-Fock method, drawing comparisons with experimental measurements where available, and includes a critical assessment of existing atomic structure data. We investigate the electron-impact excitation of neutral tungsten using the Dirac R -matrix method, and by employing collisional-radiative models, we benchmark our results with recent Compact Toroidal Hybrid measurements. The resulting comparisons highlight alternative diagnostic lines to the widely used 400.88-nm line.

Non-orthogonal internally contracted multi-configurational perturbation theory (NICPT): Dynamic electron correlation for large, compact active spaces

NASA Astrophysics Data System (ADS)

Kähler, Sven; Olsen, Jeppe

2017-11-01

A computational method is presented for systems that require high-level treatments of static and dynamic electron correlation but cannot be treated using conventional complete active space self-consistent field-based methods due to the required size of the active space. Our method introduces an efficient algorithm for perturbative dynamic correlation corrections for compact non-orthogonal MCSCF calculations. In the algorithm, biorthonormal expansions of orbitals and CI-wave functions are used to reduce the scaling of the performance determining step from quadratic to linear in the number of configurations. We describe a hierarchy of configuration spaces that can be chosen for the active space. Potential curves for the nitrogen molecule and the chromium dimer are compared for different configuration spaces. Already the most compact spaces yield qualitatively correct potentials that with increasing size of configuration spaces systematically approach complete active space results.

Electronic spectrum of the UO and UO(+) molecules.

PubMed

Tyagi, Rajni; Zhang, Zhiyong; Pitzer, Russell M

2014-12-18

Electronic theory calculations are applied to the study of the UO molecule and the UO(+) ion. Relativistic effective core potentials are used along with the accompanying valence spin-orbit operators. Polarized double-ς and triple-ς basis sets are used. Molecular orbitals are obtained from state-averaged multiconfiguration self-consistent field calculations and then used in multireference spin-orbit configuration interaction calculations with a number of millions of terms. The ground state of UO has open shells of 5f(3)7s(1), angular momentum Ω = 4, and a spin-orbit-induced avoided crossing near the equilibrium internuclear distance. Many UO excited states are studied with rotational constants, intensities, and experimental comparisons. The ground state of UO(+) is of 5f(3) nature with Ω = 9/2. Many UO(+) excited states are also studied. The open-shell nature of both UO and UO(+) leads to many low-lying excited states.

Surface hopping investigation of the relaxation dynamics in radical cations

DOE PAGES

Assmann, Mariana; Weinacht, Thomas; Matsika, Spiridoula

2016-01-19

Ionization processes can lead to the formation of radical cations with population in several ionic states. In this study, we examine the dynamics of three radical cations starting from an excited ionic state using trajectory surface hopping dynamics in combination with multiconfigurational electronic structure methods. The efficiency of relaxation to the ground state is examined in an effort to understand better whether fragmentation of cations is likely to occur directly on excited states or after relaxation to the ground state. The results on cyclohexadiene, hexatriene, and uracil indicate that relaxation to the ground ionic state is very fast in thesemore » systems, while fragmentation before relaxation is rare. Ultrafast relaxation is facilitated by the close proximity of electronic states and the presence of two- and three-state conical intersections. Furthermore, examining the properties of the systems in the Franck-Condon region can give some insight into the subsequent dynamics.« less

Control of concerted two bond versus single bond dissociation in CH(3)Co(CO)(4) via an intermediate state using pump-dump laser pulses.

PubMed

Ambrosek, David; González, Leticia

2007-10-07

Wavepacket propagations on ab initio multiconfigurational two-dimensional potential energy surfaces for CH(3)Co(CO)(4) indicate that after irradiation to the lowest first and second electronic excited states, concerted dissociation of CH(3) and the axial CO ligand takes place. We employ a pump-dump sequence of pulses with appropriate frequencies and time delays to achieve the selective breakage of a single bond by controlling the dissociation angle. The pump and dump pulse sequence exploits the unbound surface where dissociation occurs in a counterintuitive fashion; stretching of one bond in an intermediate state enhances the single dissociation of the other bond.

Ab initio MCHF structural calculations of Mg-like cerium

NASA Astrophysics Data System (ADS)

Wajid, Abdul; Jabeen, S.; Husain, Abid

2018-05-01

Energy levels and emission line wavelengths of high-Z materials are useful for impurity diagnostics in the next generation fusion devices. For this here we have calculated E1, M2 transitions, oscillator strengths, and transition probabilities for transitions among the terms belonging to the 2p63s2, 2p63s3p, 2p63p2 and 2p63s3d for the Magnesium like cerium (Ce XLVII) using the GRASP2K package based on the fully relativistic multi-configuration Dirac-Fock method. The electron correlation effects, Breit interaction and quantum electrodynamics effects to the atomic state wave functions and the corresponding energies have been taken into account.

Communication: Time-dependent optimized coupled-cluster method for multielectron dynamics

NASA Astrophysics Data System (ADS)

Sato, Takeshi; Pathak, Himadri; Orimo, Yuki; Ishikawa, Kenichi L.

2018-02-01

Time-dependent coupled-cluster method with time-varying orbital functions, called time-dependent optimized coupled-cluster (TD-OCC) method, is formulated for multielectron dynamics in an intense laser field. We have successfully derived the equations of motion for CC amplitudes and orthonormal orbital functions based on the real action functional, and implemented the method including double excitations (TD-OCCD) and double and triple excitations (TD-OCCDT) within the optimized active orbitals. The present method is size extensive and gauge invariant, a polynomial cost-scaling alternative to the time-dependent multiconfiguration self-consistent-field method. The first application of the TD-OCC method of intense-laser driven correlated electron dynamics in Ar atom is reported.

Communication: Time-dependent optimized coupled-cluster method for multielectron dynamics.

PubMed

Sato, Takeshi; Pathak, Himadri; Orimo, Yuki; Ishikawa, Kenichi L

2018-02-07

Time-dependent coupled-cluster method with time-varying orbital functions, called time-dependent optimized coupled-cluster (TD-OCC) method, is formulated for multielectron dynamics in an intense laser field. We have successfully derived the equations of motion for CC amplitudes and orthonormal orbital functions based on the real action functional, and implemented the method including double excitations (TD-OCCD) and double and triple excitations (TD-OCCDT) within the optimized active orbitals. The present method is size extensive and gauge invariant, a polynomial cost-scaling alternative to the time-dependent multiconfiguration self-consistent-field method. The first application of the TD-OCC method of intense-laser driven correlated electron dynamics in Ar atom is reported.

Adaptive multiconfigurational wave functions.

PubMed

Evangelista, Francesco A

2014-03-28

A method is suggested to build simple multiconfigurational wave functions specified uniquely by an energy cutoff Λ. These are constructed from a model space containing determinants with energy relative to that of the most stable determinant no greater than Λ. The resulting Λ-CI wave function is adaptive, being able to represent both single-reference and multireference electronic states. We also consider a more compact wave function parameterization (Λ+SD-CI), which is based on a small Λ-CI reference and adds a selection of all the singly and doubly excited determinants generated from it. We report two heuristic algorithms to build Λ-CI wave functions. The first is based on an approximate prescreening of the full configuration interaction space, while the second performs a breadth-first search coupled with pruning. The Λ-CI and Λ+SD-CI approaches are used to compute the dissociation curve of N2 and the potential energy curves for the first three singlet states of C2. Special attention is paid to the issue of energy discontinuities caused by changes in the size of the Λ-CI wave function along the potential energy curve. This problem is shown to be solvable by smoothing the matrix elements of the Hamiltonian. Our last example, involving the Cu2O2(2+) core, illustrates an alternative use of the Λ-CI method: as a tool to both estimate the multireference character of a wave function and to create a compact model space to be used in subsequent high-level multireference coupled cluster computations.

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

NASA Astrophysics Data System (ADS)

Ding, Feizhi

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

Multiconfiguration resonating-group theory of the seven-nucleon system with realistic cluster wave functions

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

Fujiwara, Y.; Tang, Y.C.

1985-02-01

The properties of the seven-nucleon system are examined with a multiconfiguration and multi- channel resonating-group calculation. The cluster internal functions employed explain the charge-form-factor data over a wide range of q/sup 2/ and satisfy the variational stability condition quite well. The model space used is spanned by /sup 3/H+..cap alpha.., n+ /sup 6/Li, n+ /sup 6/Li(, and d+ /sup 5/He cluster configurations. The result shows that the specific distortion of the /sup 3/H+..cap alpha.. system is quite significant. With our multiconfiguration calculation, the ground-state energy is improved by more than 1 MeV. The calculated level spectrum agrees well with themore » level spectrum empirically determined. The energy positions of both natural-parity and unnatural-parity levels are reasonably explained. In addition, we find that, because of centrifugal-barrier effects, the aligned configuration generally makes the most sig- nificant contribution. The characteristics of nucleon-exchange terms are also briefly examined. Here it is found that, at sufficiently high energies where sharp resonance levels do not exist, the essential properties of these terms can already be learned by performing relatively simple single-configuration calculations.« less

Single molecule conductivity: the role of junction-orbital degeneracy in the artificially high currents predicted by ab initio approaches.

PubMed

Solomon, Gemma C; Reimers, Jeffrey R; Hush, Noel S

2004-10-08

A priori evaluations, using Hartree-Fock self-consistent-field (SCF) theory or density-functional theory (DFT), of the current passing between two electrodes through a single bridging molecule result in predicted conductivities that may be up to one to two orders of magnitude larger than observed ones. We demonstrate that this is, in part, often due to the improper application of the computational methods. Conductivity is shown to arise from tunneling between junction states of the electrodes through the molecule; these states are inherently either quasi two-fold or four-fold degenerate and always comprise the (highest occupied molecular orbital) HOMO band at the Fermi energy of the system. Frequently, in previous cluster based molecular conduction calculations, closed-shell SCF or Kohn-Sham DFT methods have been applied to systems that we demonstrate to be intrinsically open shell in nature. Such calculations are shown to induce artificial HOMO-LUMO (LUMO-lowest unoccupied molecular orbital) band splittings that Landauer-based formalisms for steady-state conduction interpret as arising from extremely rapid through-molecule tunneling at the Fermi energy, hence, overestimating the low-voltage conductivity. It is demonstrated that these shortcomings can be eliminated, dramatically reducing calculated current magnitudes, through the alternate use of electronic-structure calculations based on the spin-restricted open-shell formalism and related multiconfigurational SCF of DFT approaches. Further, we demonstrate that most anomalies arising in DFT implementations arise through the use of hybrid density functionals such as B3LYP. While the enhanced band-gap properties of these functionals have made them the defacto standard in molecular conductivity calculations, we demonstrate that it also makes them particularly susceptible to open-shell anomalies.

Multiconfiguration Self-Consistent Field Study on Formonitrile Imine and N-Substituted Nitrile Imines HCN2-R: Energy Component Analysis of the Pseudo-Jahn-Teller Effect.

PubMed

Toyota, Azumao; Muramatsu, Takashi; Koseki, Shiro

2017-03-23

Stable geometrical structures for formonitrile imine (1) and N-substituted nitrile imines HCN 2 -R (R = Li, BeH, BH 2 , CH 3 , CN, CCH, C 6 H 5 , NH 2 , OH, and F) (2-11) were examined by using the multiconfiguration self-consistent-field (MCSCF) method followed by second-order configuration interaction (SOCI) calculations and second-order multiconfiguration quasi-degenerate perturbation theory (MCQDPT2) calculations, together with the aug-cc-pVTZ basis sets. The results show that 1 suffers a pseudo-Jahn-Teller (JT) distortion from a linear C ∞v structure to a C 1 structure via a planar bent C s structure. Each of the others is found to undergo pseudo-JT distortion from a symmetrical structure to a planar bent C s structure for 2, 3, and 7 and to a C 1 structure for 4, 5, 6, 8, 9, 10, and 11. At the stationary structures of 1-11, the structural characteristics were briefly discussed in terms of allenic and propargylic. To elucidate the nature of pseudo-JT distortions, energy component analyses were carried out at the MCSCF+SOCI level of theory at all of the stationary structures for the relevant molecules. In most of the molecules examined, pseudo-JT stabilizations were classified into two groups, one in which the stability arises from a lowering of the energy of the attractive term V en and the other in which the stability results from a lowering of the energy of the repulsive terms V nn and V ee . In addition to the above two groups, it was also found that the following three groups are responsible for the pseudo-JT stabilizations in a certain stage of the structural changes. Namely, one is a lowering of the energy of the term V ee observed in 6, another is a lowering of the energy of the terms V ee and V en observed in 9-11, and the other is a lowering of the energy of the terms V en and V nn observed in 10. These energetic behaviors were accounted in terms of an elongation or a contraction of the molecular skeleton, a migration of electrons from one part of the molecule to other parts, and the combined effects arising from these two factors.

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

Tang, Zhoufei; Ouyang, Xiaolong; Gong, Zhihao

An extended hierarchy equation of motion (HEOM) is proposed and applied to study the dynamics of the spin-boson model. In this approach, a complete set of orthonormal functions are used to expand an arbitrary bath correlation function. As a result, a complete dynamic basis set is constructed by including the system reduced density matrix and auxiliary fields composed of these expansion functions, where the extended HEOM is derived for the time derivative of each element. The reliability of the extended HEOM is demonstrated by comparison with the stochastic Hamiltonian approach under room-temperature classical ohmic and sub-ohmic noises and the multilayermore » multiconfiguration time-dependent Hartree theory under zero-temperature quantum ohmic noise. Upon increasing the order in the hierarchical expansion, the result obtained from the extended HOEM systematically converges to the numerically exact answer.« less

Electronic structures and geometries of the XF{sub 3} (X = Cl, Br, I, At) fluorides

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

Sergentu, Dumitru-Claudiu; CEISAM, UMR CNRS 6230, Université de Nantes, 2 Rue de la Houssinière, BP 92208, 44322 Nantes Cedex 3; Amaouch, Mohamed

The potential energy surfaces of the group 17 XF{sub 3} (X = Cl, Br, I, At) fluorides have been investigated for the first time with multiconfigurational wave function theory approaches. In agreement with experiment, bent T-shaped C{sub 2v} structures are computed for ClF{sub 3}, BrF{sub 3}, and IF{sub 3}, while we predict that an average D{sub 3h} structure would be experimentally observed for AtF{sub 3}. Electron correlation and scalar relativistic effects strongly reduce the energy difference between the D{sub 3h} geometry and the C{sub 2v} one, along the XF{sub 3} series, and in the X = At case, spin-orbit couplingmore » also slightly reduces this energy difference. AtF{sub 3} is a borderline system where the D{sub 3h} structure becomes a minimum, i.e., the pseudo-Jahn-Teller effect is inhibited since electron correlation and scalar-relativistic effects create small energy barriers leading to the global C{sub 2v} minima, although both types of effects interfere.« less

Candidates for direct laser cooling of diatomic molecules with the simplest 1Σ -1Σ electronic system

NASA Astrophysics Data System (ADS)

Li, Chuanliang; Li, Yachao; Ji, Zhonghua; Qiu, Xuanbing; Lai, Yunzhong; Wei, Jilin; Zhao, Yanting; Deng, Lunhua; Chen, Yangqin; Liu, Jinjun

2018-06-01

We propose to utilize the 1Σ-1Σ electronic transition system for direct laser cooling of heteronuclear diatomic molecules. AgH, as well as its deuterium isotopolog AgD, is used as an example to illustrate the cooling schemes. Potential-energy curves and relevant molecular parameters of both AgH and AgD, including the spin-orbit constants and the electronic transition dipole moments, are determined in internally contracted multiconfiguration-reference configuration interaction calculations. The highly diagonal Franck-Condon matrices of the A 1Σ+-X 1Σ+ transitions predicted by the calculations suggest the existence of quasi-closed-cycle transitions, which renders these molecules suitable for direct laser cooling. By solving rate equations numerically, we demonstrated that both AgH and AgD molecules can be cooled from 25 K to 2 mK temperature in approximately 20 ms. Our investigation elucidates and supports the hypothesis that molecules in the simplest 1Σ-1Σ system can serve as favorable candidates for direct laser cooling.

Dipole moments and transition probabilities of the a 3Sigma(+)g - b 3Sigma(+)u system of molecular hydrogen

NASA Technical Reports Server (NTRS)

Guberman, S.; Dalgarno, A.; Posen, A.; Kwok, T. L.

1986-01-01

Multiconfiguration variational calculations of the electronic wave functions of the a 3Sigma(+)g and b 3Sigma(+)u states of molecular hydrogen are presented, and the electric dipole transition moment between them (of interest in connection with stellar atmospheres and the UV spectrum of the Jovian planets) is obtained. The dipole moment is used to calculate the probabilities of radiative transitions from the discrete vibrational levels of the a 3Sigma(+)g state to the vibrational continuum of the repulsive b 3Sigma(+)u state as functions of the wavelength of the emitted photons. The total transition probabilities and radiative lifetimes of the levels v prime = 0-20 are presented.

Adaptive/learning control of large space structures - System identification techniques. [for multi-configuration flexible spacecraft

NASA Technical Reports Server (NTRS)

Thau, F. E.; Montgomery, R. C.

1980-01-01

Techniques developed for the control of aircraft under changing operating conditions are used to develop a learning control system structure for a multi-configuration, flexible space vehicle. A configuration identification subsystem that is to be used with a learning algorithm and a memory and control process subsystem is developed. Adaptive gain adjustments can be achieved by this learning approach without prestoring of large blocks of parameter data and without dither signal inputs which will be suppressed during operations for which they are not compatible. The Space Shuttle Solar Electric Propulsion (SEP) experiment is used as a sample problem for the testing of adaptive/learning control system algorithms.

Membrane Specifications for Multi-Configuration Membrane Distillation Model

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

Villa, Daniel; Vanneste, Johan; Cath, Tzahi

The data includes the membrane properties and specifications used for multi-configuration membrane distillation desalination. In this study, membranes from CLARCOR, 3M, and Aquastill are tested in counter-current, co-current and air-gap configurations at Colorado School of Mines (CSM), Advanced Water technology Center ( Aqwatech) laboratories. In the data sheets: The "theoretical" worksheet, contains steady-state values of the experimental runs and also provides several calculated values. The "Specifications" worksheet contains the inputs to the experiment. The "Data" spreadsheet contains the entire set of data and the rest of the sheets "20-40", "20-45", ...etc., contain individual portions of the data with variation ofmore » feed temperatures.« less

Application of relativistic distorted-wave method to electron-impact excitation of highly charged Fe XXIV ion embedded in weakly coupled plasmas

NASA Astrophysics Data System (ADS)

Chen, Zhanbin

2018-05-01

The process of excitation of highly charged Fe XXIV ion embedded in weakly coupled plasmas by electron impact is studied, together with the subsequent radiative decay. For the target structure, the calculation is performed using the multiconfiguration Dirac-Hartree-Fock method incorporating the Debye-Hückel potential for the electron-nucleus interaction. Fine-structure levels of the 1s22p and 1s2s2p configurations and the transition properties among these levels are presented over a wide range of screening parameters. For the collision dynamics, the distorted-wave method in the relativistic frame is adopted to include the effect of plasma background, in which the interparticle interactions in the system are described by screened interactions of the Debye-Hückel type. The continuum wave function of the projectile electron is obtained by solving the modified Dirac equations. The influence of plasma strength on the cross section, the linear polarization, and the angular distribution of x-ray photon emission are investigated in detail. Comparison of the present results with experimental data and other theoretical predictions, when available, is made.

Full-dimensional ground- and excited-state potential energy surfaces and state couplings for photodissociation of thioanisole

NASA Astrophysics Data System (ADS)

Li, Shaohong L.; Truhlar, Donald G.

2017-02-01

Analytic potential energy surfaces (PESs) and state couplings of the ground and two lowest singlet excited states of thioanisole (C6H5SCH3) are constructed in a diabatic representation based on electronic structure calculations including dynamic correlation. They cover all 42 internal degrees of freedom and a wide range of geometries including the Franck-Condon region and the reaction valley along the breaking S-CH3 bond with the full ranges of the torsion angles. The parameters in the PESs and couplings are fitted to the results of smooth diabatic electronic structure calculations including dynamic electron correlation by the extended multi-configurational quasi-degenerate perturbation theory method for the adiabatic state energies followed by diabatization by the fourfold way. The fit is accomplished by the anchor points reactive potential method with two reactive coordinates and 40 nonreactive degrees of freedom, where the anchor-point force fields are obtained with a locally modified version of the QuickFF package. The PESs and couplings are suitable for study of the topography of the trilayer potential energy landscape and for electronically nonadiabatic molecular dynamics simulations of the photodissociation of the S-CH3 bond.

Evaluating the electronic structure of formal Ln II ions in Ln II(C 5H 4SiMe 3) 3 1– using XANES spectroscopy and DFT calculations

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

Fieser, Megan E.; Ferrier, Maryline Ghislaine; Su, Jing

Here, the isolation of [K(2.2.2-cryptand)][Ln(C 5H 4SiMe 3) 3], formally containing LnII, for all lanthanides (excluding Pm) was surprising given that +2 oxidation states are typically regarded as inaccessible for most 4f-elements. Herein, X-ray absorption near-edge spectroscopy (XANES), ground-state density functional theory (DFT), and transition dipole moment calculations are used to investigate the possibility that Ln(C 5H 4SiMe 3) 3 1– (Ln = Pr, Nd, Sm, Gd, Tb, Dy, Y, Ho, Er, Tm, Yb and Lu) compounds represented molecular Ln II complexes. Results from the ground-state DFT calculations were supported by additional calculations that utilized complete-active-space multi-configuration approach with second-ordermore » perturbation theoretical correction (CASPT2). Through comparisons with standards, Ln(C 5H 4SiMe 3) 3 1– (Ln = Sm, Tm, Yb, Lu, Y) are determined to contain 4f 6 5d 0 (Sm II), 4f 13 5d 0 (Tm II), 4f 14 5d 0 (Yb II), 4f 14 5d 1 (Lu II), and 4d 1 (Y II) electronic configurations. Additionally, our results suggest that Ln(C 5H 4SiMe 3) 3 1– (Ln = Pr, Nd, Gd, Tb, Dy, Ho, and Er) also contain Ln II ions, but with 4f n 5d 1 configurations (not 4f n +1 5d 0). In these 4f n 5d 1 complexes, the C 3h-symmetric ligand environment provides a highly shielded 5d-orbital of a' symmetry that made the 4f n 5d 1 electronic configurations lower in energy than the more typical 4f n+1 5d 0 configuration.« less

Evaluating the electronic structure of formal Ln II ions in Ln II(C 5H 4SiMe 3) 3 1– using XANES spectroscopy and DFT calculations

DOE PAGES

Fieser, Megan E.; Ferrier, Maryline Ghislaine; Su, Jing; ...

2017-06-30

Here, the isolation of [K(2.2.2-cryptand)][Ln(C 5H 4SiMe 3) 3], formally containing LnII, for all lanthanides (excluding Pm) was surprising given that +2 oxidation states are typically regarded as inaccessible for most 4f-elements. Herein, X-ray absorption near-edge spectroscopy (XANES), ground-state density functional theory (DFT), and transition dipole moment calculations are used to investigate the possibility that Ln(C 5H 4SiMe 3) 3 1– (Ln = Pr, Nd, Sm, Gd, Tb, Dy, Y, Ho, Er, Tm, Yb and Lu) compounds represented molecular Ln II complexes. Results from the ground-state DFT calculations were supported by additional calculations that utilized complete-active-space multi-configuration approach with second-ordermore » perturbation theoretical correction (CASPT2). Through comparisons with standards, Ln(C 5H 4SiMe 3) 3 1– (Ln = Sm, Tm, Yb, Lu, Y) are determined to contain 4f 6 5d 0 (Sm II), 4f 13 5d 0 (Tm II), 4f 14 5d 0 (Yb II), 4f 14 5d 1 (Lu II), and 4d 1 (Y II) electronic configurations. Additionally, our results suggest that Ln(C 5H 4SiMe 3) 3 1– (Ln = Pr, Nd, Gd, Tb, Dy, Ho, and Er) also contain Ln II ions, but with 4f n 5d 1 configurations (not 4f n +1 5d 0). In these 4f n 5d 1 complexes, the C 3h-symmetric ligand environment provides a highly shielded 5d-orbital of a' symmetry that made the 4f n 5d 1 electronic configurations lower in energy than the more typical 4f n+1 5d 0 configuration.« less

Adaptive multiconfigurational wave functions

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

Evangelista, Francesco A., E-mail: francesco.evangelista@emory.edu

2014-03-28

A method is suggested to build simple multiconfigurational wave functions specified uniquely by an energy cutoff Λ. These are constructed from a model space containing determinants with energy relative to that of the most stable determinant no greater than Λ. The resulting Λ-CI wave function is adaptive, being able to represent both single-reference and multireference electronic states. We also consider a more compact wave function parameterization (Λ+SD-CI), which is based on a small Λ-CI reference and adds a selection of all the singly and doubly excited determinants generated from it. We report two heuristic algorithms to build Λ-CI wave functions.more » The first is based on an approximate prescreening of the full configuration interaction space, while the second performs a breadth-first search coupled with pruning. The Λ-CI and Λ+SD-CI approaches are used to compute the dissociation curve of N{sub 2} and the potential energy curves for the first three singlet states of C{sub 2}. Special attention is paid to the issue of energy discontinuities caused by changes in the size of the Λ-CI wave function along the potential energy curve. This problem is shown to be solvable by smoothing the matrix elements of the Hamiltonian. Our last example, involving the Cu{sub 2}O{sub 2}{sup 2+} core, illustrates an alternative use of the Λ-CI method: as a tool to both estimate the multireference character of a wave function and to create a compact model space to be used in subsequent high-level multireference coupled cluster computations.« less

Angular Distribution and Linear Polarization of X-ray Radiation Resulting from Electron Impact Excitation of Highly Charged Ions in Debye Plasmas

NASA Astrophysics Data System (ADS)

Chen, Zhanbin

2018-05-01

Plasma-screening effects on the 1s _{1/2} → 2l (l = s , p ) and 1s _{1/2} → 3d _{3/2} electron-impact excitation of highly charged ions are investigated, together with their subsequent radiative decay. The analysis is performed based on the multi-configuration Dirac-Fock method and the fully relativistic distorted-wave method incorporating the Debye-Hückel potential. To explore the nature of the effects, calculations are carried out based on detailed analyses of the integrated total and magnetic sublevel cross sections, the alignment parameters, the linear polarizations, and the angular distribution of the X-ray photoemission, as well as on corresponding data calculated in various Debye lengths/environments, taking the 2p _{3/2}→ 1s _{1/2} and 3d _{3/2}→ 1s _{1/2} characteristic lines of H-like Fe^{25+} ion as an example. The present results are compared with experimental data and other theoretical predictions where available.

Multi-reference approach to the calculation of photoelectron spectra including spin-orbit coupling.

PubMed

Grell, Gilbert; Bokarev, Sergey I; Winter, Bernd; Seidel, Robert; Aziz, Emad F; Aziz, Saadullah G; Kühn, Oliver

2015-08-21

X-ray photoelectron spectra provide a wealth of information on the electronic structure. The extraction of molecular details requires adequate theoretical methods, which in case of transition metal complexes has to account for effects due to the multi-configurational and spin-mixed nature of the many-electron wave function. Here, the restricted active space self-consistent field method including spin-orbit coupling is used to cope with this challenge and to calculate valence- and core-level photoelectron spectra. The intensities are estimated within the frameworks of the Dyson orbital formalism and the sudden approximation. Thereby, we utilize an efficient computational algorithm that is based on a biorthonormal basis transformation. The approach is applied to the valence photoionization of the gas phase water molecule and to the core ionization spectrum of the [Fe(H2O)6](2+) complex. The results show good agreement with the experimental data obtained in this work, whereas the sudden approximation demonstrates distinct deviations from experiments.

KLL dielectronic recombination resonant strengths of He-like up to O-like xenon ions

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

Yao, K.; Geng, Z.; Xiao, J.

2010-02-15

In this work, the KLL dielectronic recombination (DR) resonant strengths of He- through to O-like Xe ions were studied, both through experiment and calculation. The experiments were done using a fast electron beam-energy scanning technique at the Shanghai electron beam ion trap. The calculations were done by using the flexible atomic code (FAC), in which the relativistic configuration interaction (RCI) method was employed. For the total resonant strengths, the present experimental and theoretical results for He-, Be-, B-, C-, N-, and O-like Xe ions agree within experimental uncertainties (about 9%). But the experimental result for Li-like Xe is 14% highermore » than the calculation. The present FAC calculations of the total DR strengths were compared with the available previous calculations, using RCI or multiconfiguration Dirac-Fock (MCDF) methods, and the agreement was very good. In this work, some intermediate-state resolved KLL DR strengths were also obtained and compared with theoretical results, and more discrepancies were revealed.« less

MCTDH on-the-fly: Efficient grid-based quantum dynamics without pre-computed potential energy surfaces

NASA Astrophysics Data System (ADS)

Richings, Gareth W.; Habershon, Scott

2018-04-01

We present significant algorithmic improvements to a recently proposed direct quantum dynamics method, based upon combining well established grid-based quantum dynamics approaches and expansions of the potential energy operator in terms of a weighted sum of Gaussian functions. Specifically, using a sum of low-dimensional Gaussian functions to represent the potential energy surface (PES), combined with a secondary fitting of the PES using singular value decomposition, we show how standard grid-based quantum dynamics methods can be dramatically accelerated without loss of accuracy. This is demonstrated by on-the-fly simulations (using both standard grid-based methods and multi-configuration time-dependent Hartree) of both proton transfer on the electronic ground state of salicylaldimine and the non-adiabatic dynamics of pyrazine.

A surface hopping algorithm for nonadiabatic minimum energy path calculations.

PubMed

Schapiro, Igor; Roca-Sanjuán, Daniel; Lindh, Roland; Olivucci, Massimo

2015-02-15

The article introduces a robust algorithm for the computation of minimum energy paths transiting along regions of near-to or degeneracy of adiabatic states. The method facilitates studies of excited state reactivity involving weakly avoided crossings and conical intersections. Based on the analysis of the change in the multiconfigurational wave function the algorithm takes the decision whether the optimization should continue following the same electronic state or switch to a different state. This algorithm helps to overcome convergence difficulties near degeneracies. The implementation in the MOLCAS quantum chemistry package is discussed. To demonstrate the utility of the proposed procedure four examples of application are provided: thymine, asulam, 1,2-dioxetane, and a three-double-bond model of the 11-cis-retinal protonated Schiff base. © 2015 Wiley Periodicals, Inc.

Cotton-Mouton effect and shielding polarizabilities of ethylene: An MCSCF study

NASA Astrophysics Data System (ADS)

Coriani, Sonia; Rizzo, Antonio; Ruud, Kenneth; Helgaker, Trygve

1997-03-01

The static hypermagnetizabilities and nuclear shielding polarizabilities of the carbon and hydrogen atoms of ethylene have been computed using multiconfigurational linear-response theory and a finite-field method, in a mixed analytical-numerical approach. Extended sets of magnetic-field-dependent basis functions have been employed in large MCSCF calculations, involving active spaces giving rise to a few million configurations in the finite-field perturbed symmetry. The convergence of the observables with respect to the extension of the basis set as well as the effect of electron correlation have been investigated. Whereas for the shielding polarizabilities we can compare with other published SCF results, the ab initio estimates for the static hypermagnetizabilities and the observable to which they are related - the Cotton-Mouton constant, - are presented for the first time.

Embedded correlated wavefunction schemes: theory and applications.

PubMed

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

2014-09-16

Conspectus Ab initio modeling of matter has become a pillar of chemical research: with ever-increasing computational power, simulations can be used to accurately predict, for example, chemical reaction rates, electronic and mechanical properties of materials, and dynamical properties of liquids. Many competing quantum mechanical methods have been developed over the years that vary in computational cost, accuracy, and scalability: density functional theory (DFT), the workhorse of solid-state electronic structure calculations, features a good compromise between accuracy and speed. However, approximate exchange-correlation functionals limit DFT's ability to treat certain phenomena or states of matter, such as charge-transfer processes or strongly correlated materials. Furthermore, conventional DFT is purely a ground-state theory: electronic excitations are beyond its scope. Excitations in molecules are routinely calculated using time-dependent DFT linear response; however applications to condensed matter are still limited. By contrast, many-electron wavefunction methods aim for a very accurate treatment of electronic exchange and correlation. Unfortunately, the associated computational cost renders treatment of more than a handful of heavy atoms challenging. On the other side of the accuracy spectrum, parametrized approaches like tight-binding can treat millions of atoms. In view of the different (dis-)advantages of each method, the simulation of complex systems seems to force a compromise: one is limited to the most accurate method that can still handle the problem size. For many interesting problems, however, compromise proves insufficient. A possible solution is to break up the system into manageable subsystems that may be treated by different computational methods. The interaction between subsystems may be handled by an embedding formalism. In this Account, we review embedded correlated wavefunction (CW) approaches and some applications. We first discuss our density functional embedding theory, which is formally exact. We show how to determine the embedding potential, which replaces the interaction between subsystems, at the DFT level. CW calculations are performed using a fixed embedding potential, that is, a non-self-consistent embedding scheme. We demonstrate this embedding theory for two challenging electron transfer phenomena: (1) initial oxidation of an aluminum surface and (2) hot-electron-mediated dissociation of hydrogen molecules on a gold surface. In both cases, the interaction between gas molecules and metal surfaces were treated by sophisticated CW techniques, with the remainder of the extended metal surface being treated by DFT. Our embedding approach overcomes the limitations of conventional Kohn-Sham DFT in describing charge transfer, multiconfigurational character, and excited states. From these embedding simulations, we gained important insights into fundamental processes that are crucial aspects of fuel cell catalysis (i.e., O2 reduction at metal surfaces) and plasmon-mediated photocatalysis by metal nanoparticles. Moreover, our findings agree very well with experimental observations, while offering new views into the chemistry. We finally discuss our recently formulated potential-functional embedding theory that provides a seamless, first-principles way to include back-action onto the environment from the embedded region.

On the nature of actinide- and lanthanide-metal bonds in heterobimetallic compounds

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

Vlaisavljevich, Bess; Miró, Pere; Cramer, Christopher J.

2011-06-28

Eleven experimentally characterized complexes containing heterobimetallic bonds between elements of the f-block and other elements were examined by quantum chemical methods: [(η⁵-C₅H₅)₂(THF)LuRu(η⁵-C₅H₅) (CO)₂], [(η⁵-C₅Me₅)₂(I)ThRu(η⁵-C₅H₅) (CO)₂], [(η⁵-C₅H₅)₂YRe(η⁵-C₅H₅)₂], [{N(CH₂CH₂NSiMe₃)₃}URe(η⁵-C₅H₅)₂], [Y{Ga(NArCh)₂}{C(PPh₂NSiH₃)₂}(CH₃OCH₃)₂], [{N(CH₂CH₂NSiMe₃)₃}U{Ga(NArCH)₂}(THF)], [(η⁵-C₅H₅)₃UGa(η⁵-C₅Me₅)], [Yb(η⁵-C₅H₅){Si(SiMe₃)₃(THF)₂}], [(η⁵-C₅H₅)₃U(SnPh₃)], [(η⁵-C₅H₅)₃U(SiPh₃)], and (Ph[Me]N)₃USi(SiMe₃)₃. Geometries in good agreement with experiment were obtained at the density functional level of theory. The multiconfigurational complete active space self-consistent field method (CASSCF) and subsequent corrections with second order perturbation theory (CASPT2) were applied to further understand the electronic structure of the lanthanide/actinide–metal (or metal–metalloid) bonds. Fragment calculations and energy-decomposition analyses were also performed and indicate that charge transfer occurs from one supported metalmore » fragment to the other, while the bonding itself is always dominated by ionic character.« less

Theoretical study of the hyperfine-interaction constants and the isotope-shift factors for the 3 s21S0-3 s 3 p 3,1P1o transitions in Al+

NASA Astrophysics Data System (ADS)

Zhang, Tingxian; Xie, Luyou; Li, Jiguang; Lu, Zehuang

2017-07-01

We calculated the magnetic dipole and the electric quadrupole hyperfine interaction constants of 3 s 3 p 3,1P1o states and the isotope shift, including mass and field shift, factors for transitions from these two states to the ground state 3 s 2 1S0 in Al+ ions using the multiconfiguration Dirac-Hartree-Fock method. The effects of the electron correlations and the Breit interaction on these physical quantities were investigated in detail based on the active space approach. It is found that the core-core and the higher order correlations are considerable for evaluating the uncertainties of the atomic parameters concerned. The uncertainties of the hyperfine interaction constants in this work are less than 1.6%. Although the isotope shift factors are highly sensitive to the electron correlations, reasonable uncertainties were obtained by exploring the effects of the electron correlations. Moreover, we found that the relativistic nuclear recoil corrections to the mass shift factors are very small and insensitive to the electron correlations for Al+. These atomic parameters present in this work are valuable for extracting the nuclear electric quadrupole moments and the mean-square charge radii of Al isotopes.

Effective Collision Strengths for Fine-structure Transitions in Si VII

NASA Astrophysics Data System (ADS)

Sossah, A. M.; Tayal, S. S.

2014-05-01

The effective collision strengths for electron-impact excitation of fine-structure transitions in Si VII are calculated as a function of electron temperature in the range 5000-2,000,000 K. The B-spline Breit-Pauli R-matrix method has been used to calculate collision strengths by electron impact. The target wave functions have been obtained using the multi-configuration Hartree-Fock method with term-dependent non-orthogonal orbitals. The 92 fine-structure levels belonging to the 46 LS states of 2s 22p 4, 2s2p 5, 2p 6, 2s 22p 33s, 2s 22p 33p, 2s 22p 33d, and 2s2p 43s configurations are included in our calculations of oscillator strengths and collision strengths. There are 4186 possible fine-structure allowed and forbidden transitions among the 92 levels. The present excitation energies, oscillator strengths, and collision strengths have been compared with previous theoretical results and available experimental data. Generally, a good agreement is found with the 6 LS-state close-coupling approximation results of Butler & Zeippen and the 44 LS-state distorted wave calculation of Bhatia & Landi.

The time-resolved photoelectron spectrum of toluene using a perturbation theory approach

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

Richings, Gareth W.; Worth, Graham A., E-mail: g.a.worth@bham.ac.uk

A theoretical study of the intra-molecular vibrational-energy redistribution of toluene using time-resolved photo-electron spectra calculated using nuclear quantum dynamics and a simple, two-mode model is presented. Calculations have been carried out using the multi-configuration time-dependent Hartree method, using three levels of approximation for the calculation of the spectra. The first is a full quantum dynamics simulation with a discretisation of the continuum wavefunction of the ejected electron, whilst the second uses first-order perturbation theory to calculate the wavefunction of the ion. Both methods rely on the explicit inclusion of both the pump and probe laser pulses. The third method includesmore » only the pump pulse and generates the photo-electron spectrum by projection of the pumped wavepacket onto the ion potential energy surface, followed by evaluation of the Fourier transform of the autocorrelation function of the subsequently propagated wavepacket. The calculations performed have been used to study the periodic population flow between the 6a and 10b16b modes in the S{sub 1} excited state, and compared to recent experimental data. We obtain results in excellent agreement with the experiment and note the efficiency of the perturbation method.« less

Effect of Electronic Excitation on Hydrogen Atom Transfer (Tautomerization) Reactions for the DNA Base Adenine

NASA Technical Reports Server (NTRS)

Chaban, Galina M.; Salter, Latasha M.; Kwak, Dochan (Technical Monitor)

2002-01-01

Geometrical structures and energetic properties for four different tautomers of adenine are calculated in this study, using multi-configurational wave functions. Both the ground and the lowest single excited state potential energy surface are studied. The energetic order of the tautomers on the ground state potential surface is 9H less than 7H less than 3H less than 1H, while on the excited state surface this order is found to be different: 3H less than 1H less than 9H less than 7H. Minimum energy reaction paths are obtained for hydrogen atom transfer (9 yields 3 tautomerization) reactions in the ground and the lowest excited electronic state. It is found that the barrier heights and the shapes of the reaction paths are different for the ground and the excited electronic state, suggesting that the probability of such tautomerization reaction is higher on the excited state potential energy surface. The barrier for this reaction in the excited state may become very low in the presence of water or other polar solvent molecules, and therefore such tautomerization reaction may play an important role in the solution phase photochemistry of adenine.

Accurate study on the properties of spectral lines for Br-like W39+

NASA Astrophysics Data System (ADS)

Guo, X. L.; Li, M. C.; Si, R.; He, X. D.; Wang, K.; Dai, Z. T.; Liu, Y. M.; Zhang, H. J.; Chen, C. Y.

2018-01-01

As a primary candidate in tokamak plasmas, the spectroscopic parameters of tungsten ions have been studied extensively over the past decade. In this paper, we perform calculations of excitation energies, lifetimes, wavelengths and transition rates for all levels of the 4{s}24{p}5, 4{s}24{p}44d, and 4s4{p}6 configurations of {{{W}}}39+ by using the multiconfiguration Dirac-Hartree-Fock (MCDHF) method, and also the relativistic many-body perturbation theory (RMBPT) method. Detailed convergence studies on excitation energy from electron-correlation effects and relativistic effects are presented. It is necessary to include the core-valence correlation from deep lying subshells, e.g. 3d and 3p, to produce reliable atomic parameters. Results are compared with available theoretical and experimental work, and the accuracy of the results is confirmed.

Relativistic Atomic Data for Lines in Ge-Like Sm and Eu Ions

NASA Astrophysics Data System (ADS)

Nagy, O.; El Sayed, Fatma

2012-11-01

Energies, wavelengths, transition probabilities, and oscillator strengths have been calculated for the 4s24p2 - 4s4p3, 4s24p2 - 4s24p4d and 4s4p3 - 4p4 allowed transitions in heavy Ge-like Sm and Eu ions. The fully relativistic Multiconfiguration Dirac-Fock (MCDF) method taking into account both the correlations within the n = 4 complex and the quantum electrodynamic (QED) effects have been used in the calculations. MCDFGME code is used to calculate electron impact excitation cross sections for the 4s24p2 - 4s4p3, and 4s24p2 - 4s24p4d transitions with plane-wave Born approximation. The results of SmXXXI and Eu XXXII are compared with HFR method results.

A quantum dynamics study of the benzopyran ring opening guided by laser pulses

NASA Astrophysics Data System (ADS)

Saab, Mohamad; Doriol, Loïc Joubert; Lasorne, Benjamin; Guérin, Stéphane; Gatti, Fabien

2014-10-01

The ring-opening photoisomerization of benzopyran, which occurs via a photochemical route involving a conical intersection, has been studied with quantum dynamics calculations using the multi-configuration time-dependent Hartree method (MCTDH). We introduce a mechanistic strategy to control the conversion of benzopyran to merocyanine with laser pulses. We use a six-dimensional model developed in a previous work for the potential energy surfaces (PES) based on an extension of the vibronic-coupling Hamiltonian model (diabatization method by ansatz), which depends on the most active degrees of freedom. The main objective of these quantum dynamics simulations is to provide a set of strategies that could help experimentalists to control the photoreactivity vs. photostability ratio (selectivity). In this work we present: (i) a pump-dump technique used to control the photostability, (ii) a two-step strategy to enhance the reactivity of the system: first, a pure vibrational excitation in the electronic ground state that prepares the system and, second, an ultraviolet excitation that brings the system to the first adiabatic electronic state; (iii) finally the effect of a non-resonant pulse (Stark effect) on the dynamics.

Dielectronic recombination data for dynamic finite-density plasmas. XV. The silicon isoelectronic sequence

NASA Astrophysics Data System (ADS)

Kaur, Jagjit; Gorczyca, T. W.; Badnell, N. R.

2018-02-01

Context. We aim to present a comprehensive theoretical investigation of dielectronic recombination (DR) of the silicon-like isoelectronic sequence and provide DR and radiative recombination (RR) data that can be used within a generalized collisional-radiative modelling framework. Aims: Total and final-state level-resolved DR and RR rate coefficients for the ground and metastable initial levels of 16 ions between P+ and Zn16+ are determined. Methods: We carried out multi-configurational Breit-Pauli DR calculations for silicon-like ions in the independent processes, isolated resonance, distorted wave approximation. Both Δnc = 0 and Δnc = 1 core excitations are included using LS and intermediate coupling schemes. Results: Results are presented for a selected number of ions and compared to all other existing theoretical and experimental data. The total dielectronic and radiative recombination rate coefficients for the ground state are presented in tabulated form for easy implementation into spectral modelling codes. These data can also be accessed from the Atomic Data and Analysis Structure (ADAS) OPEN-ADAS database. This work is a part of an assembly of a dielectronic recombination database for the modelling of dynamic finite-density plasmas.

On regularizing the MCTDH equations of motion

NASA Astrophysics Data System (ADS)

Meyer, Hans-Dieter; Wang, Haobin

2018-03-01

The Multiconfiguration Time-Dependent Hartree (MCTDH) approach leads to equations of motion (EOM) which become singular when there are unoccupied so-called single-particle functions (SPFs). Starting from a Hartree product, all SPFs, except the first one, are unoccupied initially. To solve the MCTDH-EOMs numerically, one therefore has to remove the singularity by a regularization procedure. Usually the inverse of a density matrix is regularized. Here we argue and show that regularizing the coefficient tensor, which in turn regularizes the density matrix as well, leads to an improved performance of the EOMs. The initially unoccupied SPFs are rotated faster into their "correct direction" in Hilbert space and the final results are less sensitive to the choice of the value of the regularization parameter. For a particular example (a spin-boson system studied with a transformed Hamiltonian), we could even show that only with the new regularization scheme could one obtain correct results. Finally, in Appendix A, a new integration scheme for the MCTDH-EOMs developed by Lubich and co-workers is discussed. It is argued that this scheme does not solve the problem of the unoccupied natural orbitals because this scheme ignores the latter and does not propagate them at all.

Charge Radii of Neutron Deficient Fe,5352 Produced by Projectile Fragmentation

NASA Astrophysics Data System (ADS)

Minamisono, K.; Rossi, D. M.; Beerwerth, R.; Fritzsche, S.; Garand, D.; Klose, A.; Liu, Y.; Maaß, B.; Mantica, P. F.; Miller, A. J.; Müller, P.; Nazarewicz, W.; Nörtershäuser, W.; Olsen, E.; Pearson, M. R.; Reinhard, P.-G.; Saperstein, E. E.; Sumithrarachchi, C.; Tolokonnikov, S. V.

2016-12-01

Bunched-beam collinear laser spectroscopy is performed on neutron deficient Fe,5352 prepared through in-flight separation followed by a gas stopping. This novel scheme is a major step to reach nuclides far from the stability line in laser spectroscopy. Differential mean-square charge radii δ ⟨r2⟩ of Fe,5352 are determined relative to stable 56Fe as δ ⟨r2⟩56 ,52=-0.034 (13 ) fm2 and δ ⟨r2⟩56 ,53=-0.218 (13 ) fm2 , respectively, from the isotope shift of atomic hyperfine structures. The multiconfiguration Dirac-Fock method is used to calculate atomic factors to deduce δ ⟨r2⟩. The values of δ ⟨r2⟩ exhibit a minimum at the N =28 neutron shell closure. The nuclear density functional theory with Fayans and Skyrme energy density functionals is used to interpret the data. The trend of δ ⟨r2⟩ along the Fe isotopic chain results from an interplay between single-particle shell structure, pairing, and polarization effects and provides important data for understanding the intricate trend in the δ ⟨r2⟩ of closed-shell Ca isotopes.

AUSTRALIA TELESCOPE COMPACT ARRAY RADIO CONTINUUM 1384 AND 2368 MHz OBSERVATIONS OF SAGITTARIUS B

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

Jones, David I.; Protheroe, Raymond J.; Crocker, Roland M.

2011-03-15

We present images of the Sagittarius (Sgr) B giant molecular cloud at 1384 and 2368 MHz obtained using new, multi-configuration Australia Telescope Compact Array observations. We have combined these observations with archival single-dish observations yielding images at resolutions of 47'' x 14'' and 27'' x 8'' at 1384 and 2368 MHz, respectively. These observations were motivated by our theoretical work indicating the possibility that synchrotron emission from secondary electrons and positrons created in hadronic cosmic ray (CR) collisions with the ambient matter of the Sgr B2 cloud could provide a detectable (and possibly linearly polarized) non-thermal radio signal. We findmore » that the only detectable non-thermal emission from the Sgr B region is from a strong source to the south of Sgr B2, which we label Sgr B2 Southern Complex (SC). We find Sgr B2(SC) integrated flux densities of 1.2 {+-} 0.2 Jy at 1384 MHz and 0.7 {+-} 0.1 Jy at 2368 MHz for a source of FWHM size at 1384 MHz of {approx}54''. Despite its non-thermal nature, the synchrotron emission from this source is unlikely to be dominated due to secondary electrons and positrons. Failing to find clear evidence of non-thermal emission due to secondary electrons and positrons, we use polarization data to place 5{sigma} upper limits on the level of polarized intensity from the Sgr B2 cloud of 3.5 and 3 mJybeam{sup -1} at 1384 and 2368 MHz, respectively. We also use the angular distribution of the total intensity of archival 330 MHz Very Large Array and the total intensity and polarized emission of our new 1384 and 2368 MHz data to constrain the diffusion coefficient for transport of the parent hadronic CRs into the dense core of Sgr B2 to be no larger than about 1% of that in the Galactic disk. Finally, we have also used the data to perform a spectral and morphological study of the features of the Sgr B cloud and compare and contrast these to previous studies.« less

Quantum Tunneling in Testosterone 6β-Hydroxylation by Cytochrome P450: Reaction Dynamics Calculations Employing Multiconfiguration Molecular-Mechanical Potential Energy Surfaces

NASA Astrophysics Data System (ADS)

Zhang, Yan; Lin, Hai

2009-05-01

Testosterone hydroxylation is a prototypical reaction of human cytochrome P450 3A4, which metabolizes about 50% of oral drugs on the market. Reaction dynamics calculations were carried out for the testosterone 6β-hydrogen abstraction and the 6β-d1-testosterone 6β-duterium abstraction employing a model that consists of the substrate and the active oxidant compound I. The calculations were performed at the level of canonical variational transition state theory with multidimensional tunneling and were based on a semiglobal full-dimensional potential energy surface generated by the multiconfiguration molecular mechanics technique. The tunneling coefficients were found to be around 3, indicating substantial contributions by quantum tunneling. However, the tunneling made only modest contributions to the kinetic isotope effects. The kinetic isotope effects were computed to be about 2 in the doublet spin state and about 5 in the quartet spin state.

MCSCF wave functions for excited states of polar molecules - Application to BeO. [Multi-Configuration Self-Consistent Field

NASA Technical Reports Server (NTRS)

Bauschlicher, C. W., Jr.; Yarkony, D. R.

1980-01-01

A previously reported multi-configuration self-consistent field (MCSCF) algorithm based on the generalized Brillouin theorem is extended in order to treat the excited states of polar molecules. In particular, the algorithm takes into account the proper treatment of nonorthogonality in the space of single excitations and invokes, when necessary, a constrained optimization procedure to prevent the variational collapse of excited states. In addition, a configuration selection scheme (suitable for use in conjunction with extended configuration interaction methods) is proposed for the MCSCF procedure. The algorithm is used to study the low-lying singlet states of BeO, a system which has not previously been studied using an MCSCF procedure. MCSCF wave functions are obtained for three 1 Sigma + and two 1 Pi states. The 1 Sigma + results are juxtaposed with comparable results for MgO in order to assess the generality of the description presented here.

Valence-electron configuration of Fe, Cr, and Ni in binary and ternary alloys from Kβ -to- Kα x-ray intensity ratios

NASA Astrophysics Data System (ADS)

Han, I.; Demir, L.

2009-11-01

Kβ -to- Kα x-ray intensity ratios of Fe, Cr, and Ni have been measured in pure metals and in alloys of FexNi1-x ( x=0.8 , 0.7, 0.6, 0.5, 0.4, 0.3, and 0.2), NixCr1-x ( x=0.8 , 0.6, 0.5, 0.4, and 0.2), FexCr1-x ( x=0.9 , 0.7, and 0.5), and FexCryNi1-(x+y) ( x=0.7-y=0.1 , x=0.5-y=0.2 , x=0.4-y=0.3 , x=0.3-y=0.3 , x=0.2-y=0.2 , and x=0.1-y=0.2 ) following excitation by 22.69 keV x rays from a 10 mCi C109d radioactive point source. The valence-electron configurations of these metals were determined by corporation of measured Kβ -to- Kα x-ray intensity ratios with the results of multiconfiguration Dirac-Fock calculation for various valence-electron configurations. Valence-electron configurations of 3d transition metals in alloys indicate significant differences with respect to the pure metals. Our analysis indicates that these differences arise from delocalization and/or charge transfer phenomena in alloys. Namely, the observed change of the valence-electron configurations of metals in alloys can be explained with the transfer of 3d electrons from one element to the other element and/or the rearrangement of electrons between 3d and 4s,4p states of individual metal atoms.

Electronic Structure of the [Cu 3 (μ-O) 3] 2+ Cluster in Mordenite Zeolite and Its Effects on the Methane to Methanol Oxidation

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

Vogiatzis, Konstantinos D.; Li, Guanna; Hensen, Emiel J. M.

Identifying Cu-exchanged zeolites able to activate C–H bonds and selectively convert methane to methanol is a challenge in the field of biomimetic heterogeneous catalysis. Recent experiments point to the importance of trinuclear [Cu 3(μ-O) 3] 2+ complexes inside the micropores of mordenite (MOR) zeolite for selective oxo-functionalization of methane. The electronic structures of these species, namely, the oxidation state of Cu ions and the reactive character of the oxygen centers, are not yet fully understood. In this study, we performed a detailed analysis of the electronic structure of the [Cu 3(μ-O) 3] 2+ site using multiconfigurational wave-function-based methods and densitymore » functional theory. The calculations reveal that all Cu sites in the cluster are predominantly present in the Cu(II) formal oxidation state with a minor contribution from Cu(III), whereas two out of three oxygen anions possess a radical character. These electronic properties, along with the high accessibility of the out-of-plane oxygen center, make this oxygen the preferred site for the homolytic C–H activation of methane by [Cu 3(μ-O) 3] 2+. These new insights aid in the construction of a theoretical framework for the design of novel catalysts for oxyfunctionalization of natural gas and suggest further spectroscopic examination.« less

Electronic Structure of the [Cu 3 (μ-O) 3] 2+ Cluster in Mordenite Zeolite and Its Effects on the Methane to Methanol Oxidation

DOE PAGES

Vogiatzis, Konstantinos D.; Li, Guanna; Hensen, Emiel J. M.; ...

2017-09-28

Identifying Cu-exchanged zeolites able to activate C–H bonds and selectively convert methane to methanol is a challenge in the field of biomimetic heterogeneous catalysis. Recent experiments point to the importance of trinuclear [Cu 3(μ-O) 3] 2+ complexes inside the micropores of mordenite (MOR) zeolite for selective oxo-functionalization of methane. The electronic structures of these species, namely, the oxidation state of Cu ions and the reactive character of the oxygen centers, are not yet fully understood. In this study, we performed a detailed analysis of the electronic structure of the [Cu 3(μ-O) 3] 2+ site using multiconfigurational wave-function-based methods and densitymore » functional theory. The calculations reveal that all Cu sites in the cluster are predominantly present in the Cu(II) formal oxidation state with a minor contribution from Cu(III), whereas two out of three oxygen anions possess a radical character. These electronic properties, along with the high accessibility of the out-of-plane oxygen center, make this oxygen the preferred site for the homolytic C–H activation of methane by [Cu 3(μ-O) 3] 2+. These new insights aid in the construction of a theoretical framework for the design of novel catalysts for oxyfunctionalization of natural gas and suggest further spectroscopic examination.« less

Investigation of the RbCa molecule: Experiment and theory.

PubMed

Pototschnig, Johann V; Krois, Günter; Lackner, Florian; Ernst, Wolfgang E

2015-04-01

We present a thorough theoretical and experimental study of the electronic structure of RbCa. The mixed alkali-alkaline earth molecule RbCa was formed on superfluid helium nanodroplets. Excited states of the molecule in the range of 13 000-23 000 cm -1 were recorded by resonance enhanced multi-photon ionization time-of-flight spectroscopy. The experiment is accompanied by high level ab initio calculations of ground and excited state properties, utilizing a multireference configuration interaction method based on multiconfigurational self consistent field calculations. With this approach the potential energy curves and permanent electric dipole moments of 24 electronic states were calculated. In addition we computed the transition dipole moments for transitions from the ground into excited states. The combination of experiment and theory allowed the assignment of features in the recorded spectrum to the excited [Formula: see text], [Formula: see text], [Formula: see text], [Formula: see text], [Formula: see text], [Formula: see text], [Formula: see text], and [Formula: see text] states, where the experiment allowed to benchmark the calculation. This is the first experimental work giving insight into the previously unknown RbCa molecule, which offers great prospects in ultracold molecular physics due to its magnetic and electronic dipole moment in the [Formula: see text] ground state.

Basis set construction for molecular electronic structure theory: natural orbital and Gauss-Slater basis for smooth pseudopotentials.

PubMed

Petruzielo, F R; Toulouse, Julien; Umrigar, C J

2011-02-14

A simple yet general method for constructing basis sets for molecular electronic structure calculations is presented. These basis sets consist of atomic natural orbitals from a multiconfigurational self-consistent field calculation supplemented with primitive functions, chosen such that the asymptotics are appropriate for the potential of the system. Primitives are optimized for the homonuclear diatomic molecule to produce a balanced basis set. Two general features that facilitate this basis construction are demonstrated. First, weak coupling exists between the optimal exponents of primitives with different angular momenta. Second, the optimal primitive exponents for a chosen system depend weakly on the particular level of theory employed for optimization. The explicit case considered here is a basis set appropriate for the Burkatzki-Filippi-Dolg pseudopotentials. Since these pseudopotentials are finite at nuclei and have a Coulomb tail, the recently proposed Gauss-Slater functions are the appropriate primitives. Double- and triple-zeta bases are developed for elements hydrogen through argon. These new bases offer significant gains over the corresponding Burkatzki-Filippi-Dolg bases at various levels of theory. Using a Gaussian expansion of the basis functions, these bases can be employed in any electronic structure method. Quantum Monte Carlo provides an added benefit: expansions are unnecessary since the integrals are evaluated numerically.

Electronic structure of graphene nanoribbons doped with nitrogen atoms: a theoretical insight.

PubMed

Torres, A E; Fomine, S

2015-04-28

The electronic structure of graphene nanoribbons doped with a graphitic type of nitrogen atoms has been studied using B3LYP, B2PLYP and CAS methods. In all but one case the restricted B3LYP solutions were unstable and the CAS calculations provided evidence for the multiconfigurational nature of the ground state with contributions from two dominant configurations. The relative stability of the doped nanoribbons depends mostly on the mutual position of the dopant atoms and notably less on the position of nitrogen atoms within the nanoribbon. N-graphitic doping affects cationic states much more than anionic ones due the participation of the nitrogen atoms in the stabilization of the positive charge, resulting in a drop in ionization energies (IPs) for N-graphitic doped systems. Nitrogen atoms do not participate in the negative charge stabilization of anionic species and, therefore, the doping does not affect the electron affinities (EAs). The unrestricted B3LYP method is the method of choice for the calculation of IPs and EAs. Restricted B3LYP and B2PLYP produces unreliable results for both IPs and EAs while CAS strongly underestimates the electron affinities. This is also true for the reorganization energies where restricted B3LYP produces qualitatively incorrect results. Doping changes the reorganization energy of the nanoribbons; the hole reorganization energy is generally higher than the corresponding electron reorganization energy due to the participation of nitrogen atoms in the stabilization of the positive charge.

Dissociative Ionization and Product Distributions of Benzene and Pyridine by Electron Impact

NASA Technical Reports Server (NTRS)

Dateo, Christopher E.; Huo, Winifred M.; Fletcher, Graham D.

2003-01-01

We report a theoretical study of the dissociative ionization (DI) and product distributions of benzene (C6H6) and pyridine (C5H5N) from their low-lying ionization channels. Our approach makes use of the fact that electronic motion is much faster than nuclear motion allowing DI to be treated as a two-step process. The first step is the electron-impact ionization resulting in an ion with the same nuclear geometry as the neutral molecule. In the second step, the nuclei relax from the initial geometry and undergo unimolecular dissociation. For the ionization process we use the improved binary-encounter dipole (iBED) model [W.M. Huo, Phys. Rev. A64,042719-I (2001)]. For the unimolecular dissociation, we use multiconfigurational self-consistent field (MCSCF) methods to determine the steepest descent pathways to the possible product channels. More accurate methods are then used to obtain better energetics of the paths which are used to determine unimolecular dissociation probabilities and product distributions. Our analysis of the dissociation products and the thresholds of their productions for benzene are compared with the recent dissociative photoionization meausurements of benzene by Feng et al. [R. Feng, G. Cooper, C.E. Brion, J. Electron Spectrosc. Relat. Phenom. 123,211 (2002)] and the dissociative photoionization measurements of pyridine by Tixier et al. [S. Tixier, G. Cooper, R. Feng, C.E. Brion, J. Electron Spectrosc. Relat. Phenom. 123,185 (2002)] using dipole (e,e+ion) coincidence spectroscopy.

A new Gaussian MCTDH program: Implementation and validation on the levels of the water and glycine molecules

NASA Astrophysics Data System (ADS)

Skouteris, D.; Barone, V.

2014-06-01

We report the main features of a new general implementation of the Gaussian Multi-Configuration Time-Dependent Hartree model. The code allows effective computations of time-dependent phenomena, including calculation of vibronic spectra (in one or more electronic states), relative state populations, etc. Moreover, by expressing the Dirac-Frenkel variational principle in terms of an effective Hamiltonian, we are able to provide a new reliable estimate of the representation error. After validating the code on simple one-dimensional systems, we analyze the harmonic and anharmonic vibrational spectra of water and glycine showing that reliable and converged energy levels can be obtained with reasonable computing resources. The data obtained on water and glycine are compared with results of previous calculations using the vibrational second-order perturbation theory method. Additional features and perspectives are also shortly discussed.

Benchmarking Atomic Data for Astrophysics: Be-like Ions between B II and Ne VII

NASA Astrophysics Data System (ADS)

Wang, Kai; Chen, Zhan Bin; Zhang, Chun Yu; Si, Ran; Jönsson, Per; Hartman, Henrik; Gu, Ming Feng; Chen, Chong Yang; Yan, Jun

2018-02-01

Large-scale self-consistent multiconfiguration Dirac–Hartree–Fock and relativistic configuration interaction calculations are reported for the n≤slant 6 levels in Be-like ions from B II to Ne VII. Effects from electron correlation are taken into account by means of large expansions in terms of a basis of configuration state functions, and a complete and accurate data set of excitation energies; lifetimes; wavelengths; electric dipole, magnetic dipole, electric quadrupole, and magnetic quadrupole line strengths; transition rates; and oscillator strengths for these levels is provided for each ion. Comparisons are made with available experimental and theoretical results. The uncertainty of excitation energies is assessed to be 0.01% on average, which makes it possible to find and rule out misidentifications and aid new line identifications involving high-lying levels in astrophysical spectra. The complete data set is also useful for modeling and diagnosing astrophysical plasmas.

Fine- and hyperfine structure investigations of the even-parity configuration system of the atomic holmium

NASA Astrophysics Data System (ADS)

Stefanska, D.; Ruczkowski, J.; Elantkowska, M.; Furmann, B.

2018-04-01

In this work new experimental results concerning the hyperfine structure (hfs) for the even-parity level system of the holmium atom (Ho I) were obtained; additionally, hfs data obtained recently as a by-product in investigations of the odd-parity level system were summarized. In the present work the values of the magnetic dipole and the electric quadrupole hfs constants A and B were determined for 24 even-parity levels, for 14 of them for the first time. On the basis of these results, as well as on available literature data, a parametric study of the fine structure and the hyperfine structure for the even-parity configurations of atomic holmium was performed. A multi-configuration fit of 7 configurations was carried out, taking into account second-order of the perturbation theory. For unknown electronic levels predicted values of the level energies and hfs constants are given, which can facilitate further experimental investigations.

Cerocene Revisited: The Electronic Structure of and Interconversion Between Ce2(C8H8)3 and Ce(C8H8)2

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

Walter, Marc D.; Booth, Corwin H.; Lukens, Wayne W.

2009-02-02

New synthetic procedures for the preparation of Ce(cot)2, cerocene, from [Li(thf)4][Ce(cot)2], and Ce2(cot)3 in high yield and purity are reported. Heating solid Ce(cot)2 yields Ce2(cot)3 and COT while heating Ce2(cot)3 with an excess of COT in C6D6 to 65oC over four months yields Ce(cot)2. The solid state magnetic susceptibility of these three organocerium compounds shows that Ce(cot)2 behaves as a TIP (temperature independent paramagnet) over the temperature range of 5-300 K, while that of Ce2(cot)3 shows that the spin carriers are antiferromagnetically coupled below 10 K; above 10 K, the individual spins are uncorrelated, and [Ce(cot)2]- behaves as an isolatedmore » f1 paramagnet. The EPR at 1.5K for Ce2(cot)3 and [Ce(cot)2]- have ground state of MJ= +- 1/2. The LIII edge XANES of Ce(cot)2 (Booth, C.H.; Walter, M.D.; Daniel, M.; Lukens, W.W., Andersen, R.A., Phys. Rev. Lett. 2005, 95, 267202) and 2Ce2(cot)3 over 30-500 K are reported; the Ce(cot)2 XANES spectra show Ce(III) and Ce(IV) signatures up to a temperature of approximately 500 K, whereupon the Ce(IV) signature disappears, consistent with the thermal behavior observed in the melting experiment. The EXAFS of Ce(cot)2 and Ce2(cot)3 are reported at 30 K; the agreement between the molecular parameters for Ce(cot)2 derived from EXAFS and single crystal X-ray diffraction data are excellent. In the case of Ce2(cot)3 no X-ray diffraction data are known to exist, but the EXAFS are consistent with a"triple-decker" sandwich structure. A molecular rationalization is presented for the electronic structure of cerocene having a multiconfiguration ground state that is an admixture of the two configurations Ce(III, 4f1)(cot1.5-)2 and Ce(IV, 4f0)(cot2-)2; the multiconfigurational ground state has profound effects on the magnetic properties and on the nature of the chemical bond in cerocene and, perhaps, other molecules.« less

Combining two-body density functionals with multiconfigurational wavefunctions: diatomic molecules

NASA Astrophysics Data System (ADS)

McDouall, Joseph J. W.

The MCSCF method provides a correct zero-order wavefunction for all regions of molecular potential energy surfaces. To obtain quantitative accuracy a proper treatment of the dynamic correlation problem must be implemented. Traditionally this has been achieved through multireference variants of perturbation theory, configuration interaction and coupled cluster theory. The computational cost of such techniques makes them prohibitive for all but the smallest molecular problems. Reported here is an investigation into the efficacy of two-body density functionals in providing the dynamic correlation energy for MCSCF reference states. Tests were made on the two-body density functionals of Colle and Salvetti (CS), Moscardó and San-Fabián (MSF), and Moscardó and Pérez-Jiménez (MPJ5) in predicting the equilibrium bond lengths, harmonic frequencies and dissociation energies of fifteen diatomic molecules (3B2, 3BN, 2BS, 1C2, 2CN, 1CO, 1F2, 1FCl, 1N2, 3NCl, 3O2, 1PN, 3Si2, 3SiO, 3SO) using full valence-shell CASSCF reference wavefunctions. Also studied were modifications of these functionals recently suggested by Miehlich, Stoll and Savin (MSS) and Gräfenstein and Cremer (GC). The results obtained show accuracy comparable with and typically superior to the popular Kohn-Sham BLYP and B3LYP methods. However, the latter methods are not applicable in all regions of a potential energy surface, and even predict incorrect ground states for some systems. The use of two-body density functionals with MCSCF reference states does not share this shortcoming.

A full-dimensional multilayer multiconfiguration time-dependent Hartree study on the ultraviolet absorption spectrum of formaldehyde oxide

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

Meng, Qingyong, E-mail: mengqingyong@dicp.ac.cn; Meyer, Hans-Dieter, E-mail: hans-dieter.meyer@pci.uni-heidelberg.de

2014-09-28

Employing the multilayer multiconfiguration time-dependent Hartree (ML-MCTDH) method in conjunction with the multistate multimode vibronic coupling Hamiltonian (MMVCH) model, we perform a full dimensional (9D) quantum dynamical study on the simplest Criegee intermediate, formaldehyde oxide, in five lower-lying singlet electronic states. The ultraviolet (UV) spectrum is then simulated by a Fourier transform of the auto-correlation function. The MMVCH model is built based on extensive MRCI(8e,8o)/aug-cc-pVTZ calculations. To ensure a fast convergence of the final calculations, a large number of ML-MCTDH test calculations is performed to find an appropriate multilayer separations (ML-trees) of the ML-MCTDH nuclear wave functions, and the dynamicalmore » calculations are carefully checked to ensure that the calculations are well converged. To compare the computational efficiency, standard MCTDH simulations using the same Hamiltonian are also performed. A comparison of the MCTDH and ML-MCTDH calculations shows that even for the present not-too-large system (9D here) the ML-MCTDH calculations can save a considerable amount of computational resources while producing identical spectra as the MCTDH calculations. Furthermore, the present theoretical B{sup ~} {sup 1}A{sup ′}←X{sup ~} {sup 1}A{sup ′} UV spectral band and the corresponding experimental measurements [J. M. Beames, F. Liu, L. Lu, and M. I. Lester, J. Am. Chem. Soc. 134, 20045–20048 (2012); L. Sheps, J. Phys. Chem. Lett. 4, 4201–4205 (2013); W.-L. Ting, Y.-H. Chen, W. Chao, M. C. Smith, and J. J.-M. Lin, Phys. Chem. Chem. Phys. 16, 10438–10443 (2014)] are discussed. To the best of our knowledge, this is the first theoretical UV spectrum simulated for this molecule including nuclear motion beyond an adiabatic harmonic approximation.« less

Prediction of Rate Constant for Supramolecular Systems with Multiconfigurations.

PubMed

Guo, Tao; Li, Haiyan; Wu, Li; Guo, Zhen; Yin, Xianzhen; Wang, Caifen; Sun, Lixin; Shao, Qun; Gu, Jingkai; York, Peter; Zhang, Jiwen

2016-02-25

The control of supramolecular systems requires a thorough understanding of their dynamics, especially on a molecular level. It is extremely difficult to determine the thermokinetic parameters of supramolecular systems, such as drug-cyclodextrin complexes with fast association/dissociation processes by experimental techniques. In this paper, molecular modeling combined with novel mathematical relationships integrating the thermodynamic/thermokinetic parameters of a series of isomeric multiconfigurations to predict the overall parameters in a range of pH values have been employed to study supramolecular dynamics at the molecular level. A suitable form of Eyring's equation was derived and a two-stage model was introduced. The new approach enabled accurate prediction of the apparent dissociation/association (k(off)/k(on)) and unbinding/binding (k-r/kr) rate constants of the ubiquitous multiconfiguration complexes of the supramolecular system. The pyronine Y (PY) was used as a model system for the validation of the presented method. Interestingly, the predicted k(off) value ((40 ± 1) × 10(5) s(-1), 298 K) of PY is largely in agreement with that previously determined by fluorescence correlation spectroscopy ((5 ± 3) × 10(5) s(-1), 298 K). Moreover, the k(off)/k(on) and k-r/kr for flurbiprofen-β-cylcodextrin and ibuprofen-β-cyclodextrin systems were also predicted and suggested that the association processes are diffusion-controlled. The methodology is considered to be especially useful in the design and selection of excipients for a supramolecular system with preferred association and dissociation rate constants and understanding their mechanisms. It is believed that this new approach could be applicable to a wide range of ligand-receptor supramolecular systems and will surely help in understanding their complex mechanism.

Excited electronic states of the methyl radical. Ab initio molecular orbital study of geometries, excitation energies and vibronic spectra

NASA Astrophysics Data System (ADS)

Mebel, Alexander M.; Lin, Sheng-Hsien

1997-03-01

The geometries, vibrational frequencies and vertical and adiabatic excitation energies of the excited valence and Rydberg 3s, 3p, 3d, and 4s electronic states of CH 3 have been studied using ab initio molecular orbital multiconfigurational SCF (CASSCF), internally contracted multireference configuration interaction (MRCI) and equation-of-motion coupled cluster (EOM-CCSD) methods. The vibronic spectra are determined through the calculation of Franck-Condon factors. Close agreement between theory and experiment has been found for the excitation energies, vibrational frequencies and vibronic spectra. The adiabatic excitation energies of the Rydberg 3s B˜ 2A' 1 and 3p 2 2A″ 2 states are calculated to be 46435 and 60065 cm -1 compared to the experimental values of 46300 and 59972 cm -1, respectively. The valence 2A″ excited state of CH 3 has been found to have a pyramidal geometry within C s symmetry and to be adiabatically by 97 kcal/mol higher in energy than the ground state. The 2A″ state is predicted to be stable by 9 and 13 kcal/mol with respect to H 2 and H elimination.

Electron-ion collision spectroscopy: Lithium-like xenon ions

NASA Astrophysics Data System (ADS)

Bernhardt, D.; Brandau, C.; Harman, Z.; Kozhuharov, C.; Böhm, S.; Bosch, F.; Fritzsche, S.; Jacobi, J.; Kieslich, S.; Knopp, H.; Nolden, F.; Shi, W.; Stachura, Z.; Steck, M.; Stöhlker, Th.; Schippers, S.; Müller, A.

2015-01-01

The resonant process of dielectronic recombination (DR) has been applied as a spectroscopic tool to investigate intra-L -shell excitations 2 s -2 pj in Li-like 136Xe51+ . The experiments were carried out at the electron cooler of the Experimental Storage Ring of the GSI-Helmholtzzentrum für Schwerionenforschung, Darmstadt, Germany. The observed center-of-mass energy range (0-505 eV) covers all resonances associated with the 2 s +e-→(2p1/2n lj) J and (2p3/2n lj) J DR processes. Energies and strengths of isolated 2 p1 /2n and 2 p3 /2n DR-resonance groups were obtained for principal quantum numbers n up to 43 and 36, respectively. The 2 s -2 p1 /2 and 2 s -2 p3 /2 excitation energies were deduced to be 119.816(42) eV and 492.174(52) eV. The excitation energies are compared with previous measurements of other groups and with recent QED calculations. In addition, the experimental spectra and extracted resonance strengths are compared with multiconfiguration Dirac-Fock calculations. Measurements and theory are found to be in good agreement with each other.

Vicinal fluorine-fluorine coupling constants: Fourier analysis.

PubMed

San Fabián, J; Westra Hoekzema, A J A

2004-10-01

Stereochemical dependences of vicinal fluorine-fluorine nuclear magnetic resonance coupling constants (3JFF) have been studied with the multiconfigurational self-consistent field in the restricted active space approach, with the second-order polarization propagator approximation (SOPPA), and with density functional theory. The SOPPA results show the best overall agreement with experimental couplings. The relationship with the dihedral angle between the coupled fluorines has been studied by Fourier analysis, the result is very different from that of proton-proton couplings. The Fourier coefficients do not resemble those of a typical Karplus equation. The four nonrelativistic contributions to the coupling constants of 1,2-difluoroethane configurations have been studied separately showing that up to six Fourier coefficients are required to reproduce the calculated values satisfactorily. Comparison with Fourier coefficients for matching hydrogen fluoride dimer configurations suggests that the higher order Fourier coefficients (Cn> or =3) originate mainly from through-space Fermi contact interaction. The through-space interaction is the main reason 3JFF do not follow the Karplus equation. (c) 2004 American Institute of Physics

Vicinal fluorine-fluorine coupling constants: Fourier analysis

NASA Astrophysics Data System (ADS)

San Fabián, J.; Westra Hoekzema, A. J. A.

2004-10-01

Stereochemical dependences of vicinal fluorine-fluorine nuclear magnetic resonance coupling constants (3JFF) have been studied with the multiconfigurational self-consistent field in the restricted active space approach, with the second-order polarization propagator approximation (SOPPA), and with density functional theory. The SOPPA results show the best overall agreement with experimental couplings. The relationship with the dihedral angle between the coupled fluorines has been studied by Fourier analysis, the result is very different from that of proton-proton couplings. The Fourier coefficients do not resemble those of a typical Karplus equation. The four nonrelativistic contributions to the coupling constants of 1,2-difluoroethane configurations have been studied separately showing that up to six Fourier coefficients are required to reproduce the calculated values satisfactorily. Comparison with Fourier coefficients for matching hydrogen fluoride dimer configurations suggests that the higher order Fourier coefficients (Cn⩾3) originate mainly from through-space Fermi contact interaction. The through-space interaction is the main reason 3JFF do not follow the Karplus equation.

Enhanced reactivity in dioxirane C-H oxidations via strain release: a computational and experimental study.

PubMed

Zou, Lufeng; Paton, Robert S; Eschenmoser, Albert; Newhouse, Timothy R; Baran, Phil S; Houk, K N

2013-04-19

The site selectivities and stereoselectivities of C-H oxidations of substituted cyclohexanes and trans-decalins by dimethyldioxirane (DMDO) were investigated computationally with quantum mechanical density functional theory (DFT). The multiconfiguration CASPT2 method was employed on model systems to establish the preferred mechanism and transition state geometry. The reaction pathway involving a rebound step is established to account for the retention of stereochemistry. The oxidation of sclareolide with dioxirane reagents is reported, including the oxidation by the in situ generated tBu-TFDO, a new dioxirane that better discriminates between C-H bonds on the basis of steric effects. The release of 1,3-diaxial strain in the transition state contributes to the site selectivity and enhanced equatorial C-H bond reactivity for tertiary C-H bonds, a result of the lowering of distortion energy. In addition to this strain release factor, steric and inductive effects contribute to the rates of C-H oxidation by dioxiranes.

Designing a capacitated multi-configuration logistics network under disturbances and parameter uncertainty: a real-world case of a drug supply chain

NASA Astrophysics Data System (ADS)

Shishebori, Davood; Babadi, Abolghasem Yousefi

2018-03-01

This study investigates the reliable multi-configuration capacitated logistics network design problem (RMCLNDP) under system disturbances, which relates to locating facilities, establishing transportation links, and also allocating their limited capacities to the customers conducive to provide their demand on the minimum expected total cost (including locating costs, link constructing costs, and also expected costs in normal and disturbance conditions). In addition, two types of risks are considered; (I) uncertain environment, (II) system disturbances. A two-level mathematical model is proposed for formulating of the mentioned problem. Also, because of the uncertain parameters of the model, an efficacious possibilistic robust optimization approach is utilized. To evaluate the model, a drug supply chain design (SCN) is studied. Finally, an extensive sensitivity analysis was done on the critical parameters. The obtained results show that the efficiency of the proposed approach is suitable and is worthwhile for analyzing the real practical problems.

The multi-layer multi-configuration time-dependent Hartree method for bosons: theory, implementation, and applications.

PubMed

Cao, Lushuai; Krönke, Sven; Vendrell, Oriol; Schmelcher, Peter

2013-10-07

We develop the multi-layer multi-configuration time-dependent Hartree method for bosons (ML-MCTDHB), a variational numerically exact ab initio method for studying the quantum dynamics and stationary properties of general bosonic systems. ML-MCTDHB takes advantage of the permutation symmetry of identical bosons, which allows for investigations of the quantum dynamics from few to many-body systems. Moreover, the multi-layer feature enables ML-MCTDHB to describe mixed bosonic systems consisting of arbitrary many species. Multi-dimensional as well as mixed-dimensional systems can be accurately and efficiently simulated via the multi-layer expansion scheme. We provide a detailed account of the underlying theory and the corresponding implementation. We also demonstrate the superior performance by applying the method to the tunneling dynamics of bosonic ensembles in a one-dimensional double well potential, where a single-species bosonic ensemble of various correlation strengths and a weakly interacting two-species bosonic ensemble are considered.

Charge radii of neutron deficient Fe 52 , 53 produced by projectile fragmentation

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

Minamisono, K.; Rossi, D. M.; Beerwerth, R.

Bunched-beam collinear laser spectroscopy is performed on neutron deficient 52,53Fe prepared through in-flight separation followed by a gas stopping. This novel scheme is a major step to reach nuclides far from the stability line in laser spectroscopy. Differential mean-square charge radii δmore » $$\\langle$$r 2$$\\rangle$$ of 52,53Fe are determined relative to stable 56Fe as δ$$\\langle$$r2$$\\rangle$$ 56,52=$-$0.034(13) fm 2 and δ$$\\langle$$r 2$$\\rangle$$56,53=$-$0.218(13) fm 2, respectively, from the isotope shift of atomic hyperfine structures. The multiconfiguration Dirac-Fock method is used to calculate atomic factors to deduce δ$$\\langle$$r 2$$\\rangle$$. The values of δ$$\\langle$$r 2$$\\rangle$$ exhibit a minimum at the N=28 neutron shell closure. The nuclear density functional theory with Fayans and Skyrme energy density functionals is used to interpret the data. As a result, the trend of δ$$\\langle$$r 2$$\\rangle$$ along the Fe isotopic chain results from an interplay between single-particle shell structure, pairing, and polarization effects and provides important data for understanding the intricate trend in the δ$$\\langle$$r 2$$\\rangle$$ of closed-shell Ca isotopes« less

Biofuel combustion. Energetics and kinetics of hydrogen abstraction from carbon-1 in n-butanol by the hydroperoxyl radical calculated by coupled cluster and density functional theories and multistructural variational transition-state theory with multidimensional tunneling.

PubMed

Alecu, I M; Zheng, Jingjing; Papajak, Ewa; Yu, Tao; Truhlar, Donald G

2012-12-20

Multistructural canonical variational transition-state theory with small-curvature multidimensional tunneling (MS-CVT/SCT) is employed to calculate thermal rate constants for hydrogen-atom abstraction from carbon-1 of n-butanol by the hydroperoxyl radical over the temperature range 250-2000 K. The M08-SO hybrid meta-GGA density functional was validated against CCSD(T)-F12a explicitly correlated wave function calculations with the jul-cc-pVTZ basis set. It was then used to compute the properties of all stationary points and the energies and Hessians of a few nonstationary points along the reaction path, which were then used to generate a potential energy surface by the multiconfiguration Shepard interpolation (MCSI) method. The internal rotations in the transition state for this reaction (like those in the reactant alcohol) are strongly coupled to each other and generate multiple stable conformations, which make important contributions to the partition functions. It is shown that neglecting to account for the multiple-structure effects and torsional potential anharmonicity effects that arise from the torsional modes would lead to order-of-magnitude errors in the calculated rate constants at temperatures of interest in combustion.

Charge radii of neutron deficient Fe 52 , 53 produced by projectile fragmentation

DOE PAGES

Minamisono, K.; Rossi, D. M.; Beerwerth, R.; ...

2016-12-15

Bunched-beam collinear laser spectroscopy is performed on neutron deficient 52,53Fe prepared through in-flight separation followed by a gas stopping. This novel scheme is a major step to reach nuclides far from the stability line in laser spectroscopy. Differential mean-square charge radii δmore » $$\\langle$$r 2$$\\rangle$$ of 52,53Fe are determined relative to stable 56Fe as δ$$\\langle$$r2$$\\rangle$$ 56,52=$-$0.034(13) fm 2 and δ$$\\langle$$r 2$$\\rangle$$56,53=$-$0.218(13) fm 2, respectively, from the isotope shift of atomic hyperfine structures. The multiconfiguration Dirac-Fock method is used to calculate atomic factors to deduce δ$$\\langle$$r 2$$\\rangle$$. The values of δ$$\\langle$$r 2$$\\rangle$$ exhibit a minimum at the N=28 neutron shell closure. The nuclear density functional theory with Fayans and Skyrme energy density functionals is used to interpret the data. As a result, the trend of δ$$\\langle$$r 2$$\\rangle$$ along the Fe isotopic chain results from an interplay between single-particle shell structure, pairing, and polarization effects and provides important data for understanding the intricate trend in the δ$$\\langle$$r 2$$\\rangle$$ of closed-shell Ca isotopes« less

Dynamics of exciton transfer in coupled polymer chains.

PubMed

Zhang, Y L; Liu, X J; Sun, Z; An, Z

2013-05-07

The dynamics of singlet and triplet exciton transfer in coupled polymer chains are investigated within the Su-Schrieffer-Heeger+Pariser-Parr-Pople model including both electron-phonon (e-p) coupling and electron-electron (e-e) interactions, using a multi-configurational time-dependent Hartree-Fock dynamic method. In order to explain the processes involved, the effects of on-site and long-range e-e interactions on the locality of the singlet and triplet excitons are first investigated on an isolated chain. It is found that the locality of the singlet exciton decreases, while the locality of the triplet exciton increases with an increase in the on-site e-e interactions. On the other hand, an increase in the long-range e-e interaction results in a more localized singlet exciton and triplet exciton. In coupled polymer chains, we then quantitatively show the yields of singlet and triplet exciton transfer products under the same interchain coupling. It is found that the yield of singlet interchain excitons is much higher than that of triplet interchain excitons, that is to say, singlet exciton transfer is significantly easier than that for triplet excitons. This results from the fact that the singlet exciton is more delocalized than the triplet exciton. In addition, hopping of electrons with opposite spins between the coupled chains can facilitate the transfer of singlet excitons. The results are of great significance for understanding the photoelectric conversion process and developing high-power organic optoelectronic applications.

Impact of charge-transfer excitons in regioregular polythiophene on the charge separation at polythiophene-fullerene heterojunctions

NASA Astrophysics Data System (ADS)

Polkehn, M.; Tamura, H.; Burghardt, I.

2018-01-01

This study addresses the mechanism of ultrafast charge separation in regioregular oligothiophene-fullerene assemblies representative of poly-3-hexylthiophene (P3HT)-[6,6]-phenyl-C61 butyric acid methyl ester (PCBM) heterojunctions, with special emphasis on the inclusion of charge transfer excitons in the oligothiophene phase. The formation of polaronic inter-chain charge separated species in highly ordered oligothiophene has been demonstrated in recent experiments and could have a significant impact on the net charge transfer to the fullerene acceptor. The present approach combines a first-principles parametrized multi-site Hamiltonian, based on time-dependent density functional theory calculations, with accurate quantum dynamics simulations using the multi-layer multi-configuration time-dependent Hartree method. Quantum dynamical studies are carried out for up to 182 electronic states and 112 phonon modes. The present analysis follows up on our previous study of (Huix-Rotllant et al 2015 J. Phys. Chem. Lett. 6 1702) and significantly expands the scope of this analysis by including the dynamical role of charge transfer excitons. Our investigation highlights the pronounced mixing of photogenerated Frenkel excitons with charge transfer excitons in the oligothiophene domain, and the opening of new transfer channels due the creation of such charge-separated species. As a result, it turns out that the interfacial donor/acceptor charge transfer state can be largely circumvented due to the presence of charge transfer excitons. However, the latter states in turn act as a trap, such that the free carrier yield observed on ultrafast time scales is tangibly reduced. The present analysis underscores the complexity of the transfer pathways at P3HT-PCBM type junctions.

Exciton-vibrational coupling in the dynamics and spectroscopy of Frenkel excitons in molecular aggregates

NASA Astrophysics Data System (ADS)

Schröter, M.; Ivanov, S. D.; Schulze, J.; Polyutov, S. P.; Yan, Y.; Pullerits, T.; Kühn, O.

2015-03-01

The influence of exciton-vibrational coupling on the optical and transport properties of molecular aggregates is an old problem that gained renewed interest in recent years. On the experimental side, various nonlinear spectroscopic techniques gave insight into the dynamics of systems as complex as photosynthetic antennae. Striking evidence was gathered that in these protein-pigment complexes quantum coherence is operative even at room temperature conditions. Investigations were triggered to understand the role of vibrational degrees of freedom, beyond that of a heat bath characterized by thermal fluctuations. This development was paralleled by theory, where efficient methods emerged, which could provide the proper frame to perform non-Markovian and non-perturbative simulations of exciton-vibrational dynamics and spectroscopy. This review summarizes the state of affairs of the theory of exciton-vibrational interaction in molecular aggregates and photosynthetic antenna complexes. The focus is put on the discussion of basic effects of exciton-vibrational interaction from the stationary and dynamics points of view. Here, the molecular dimer plays a prominent role as it permits a systematic investigation of absorption and emission spectra by numerical diagonalization of the exciton-vibrational Hamiltonian in a truncated Hilbert space. An extension to larger aggregates, having many coupled nuclear degrees of freedom, becomes possible with the Multi-Layer Multi-Configuration Time-Dependent Hartree (ML-MCTDH) method for wave packet propagation. In fact it will be shown that this method allows one to approach the limit of almost continuous spectral densities, which is usually the realm of density matrix theory. Real system-bath situations are introduced for two models, which differ in the way strongly coupled nuclear coordinates are treated, as a part of the relevant system or the bath. A rather detailed exposition of the Hierarchy Equations Of Motion (HEOM) method will be given in terms of a stochastic decoupling ansatz. This method has become the standard in exciton-vibrational theory and illustrative examples will be presented as well as a comparison with ML-MCTDH. Applications will be shown for generic model systems as well as for small aggregates mimicking those formed by perylene bisimide dyes. Further, photosynthetic antenna complexes will be discussed, including spectral densities and the role of exciton-vibrational coupling in two-dimensional electronic spectroscopy.

Energy levels, lifetimes and radiative data of W LV

NASA Astrophysics Data System (ADS)

Ding, Xiao-bin; Sun, Rui; Koike, Fumihiro; Murakami, Izumi; Kato, Daiji; Sakaue, Hiroyuki A.; Nakamura, Nobuyuki; Dong, Chen-zhong

2018-01-01

Calculations of energy levels, radiative data and lifetimes are reported for tungsten Ca-like ion (W LV) by using multi-configuration Dirac-Fock (MCDF) method. The GRASP2K package is adopted to carry out a large-scale systematic computation with a restricted active space treatment; the Breit interaction and QED effects are included in subsequent relativistic configuration interaction calculations. The energies and lifetimes of the lowest 119 levels are listed; the main leading configuration of the levels is of the ground state configuration [Ne]3s23p63d2 and the first excited configuration [Ne]3s23p53d3. The wavelengths, radiative rates and oscillator strengths for relatively strong E1, E2, M1, and M2 transitions are listed. Comparisons with earlier experimental and theoretical values are made. The average relative deviations of energy levels from the NIST results and E1 transition wavelengths from the EBIT experimental results have turned to be only 0.20% and 0.13%, respectively. The other present results are in reasonable agreement with available data. These agreements confirm the reliability and accuracy of the current results. The present datasets may help us with the investigation of the electron-electron correlation effects in complex multi-electron highly charged heavy ions and of the diagnosis of tungsten impurity plasmas in fusion science.

Modelling Time-Resolved Two-Dimensional Electronic Spectroscopy of the Primary Photoisomerization Event in Rhodopsin

PubMed Central

2015-01-01

Time-resolved two-dimensional (2D) electronic spectra (ES) tracking the evolution of the excited state manifolds of the retinal chromophore have been simulated along the photoisomerization pathway in bovine rhodopsin, using a state-of-the-art hybrid QM/MM approach based on multiconfigurational methods. Simulations of broadband 2D spectra provide a useful picture of the overall detectable 2D signals from the near-infrared (NIR) to the near-ultraviolet (UV). Evolution of the stimulated emission (SE) and excited state absorption (ESA) 2D signals indicates that the S1 → SN (with N ≥ 2) ESAs feature a substantial blue-shift only after bond inversion and partial rotation along the cis → trans isomerization angle, while the SE rapidly red-shifts during the photoinduced skeletal relaxation of the polyene chain. Different combinations of pulse frequencies are proposed in order to follow the evolution of specific ESA signals. These include a two-color 2DVis/NIR setup especially suited for tracking the evolution of the S1 → S2 transitions that can be used to discriminate between different photochemical mechanisms of retinal photoisomerization as a function of the environment. The reported results are consistent with the available time-resolved pump–probe experimental data, and may be used for the design of more elaborate transient 2D electronic spectroscopy techniques. PMID:24794143

Spin-vibronic quantum dynamics for ultrafast excited-state processes.

PubMed

Eng, Julien; Gourlaouen, Christophe; Gindensperger, Etienne; Daniel, Chantal

2015-03-17

Ultrafast intersystem crossing (ISC) processes coupled to nuclear relaxation and solvation dynamics play a central role in the photophysics and photochemistry of a wide range of transition metal complexes. These phenomena occurring within a few hundred femtoseconds are investigated experimentally by ultrafast picosecond and femtosecond transient absorption or luminescence spectroscopies, and optical laser pump-X-ray probe techniques using picosecond and femtosecond X-ray pulses. The interpretation of ultrafast structural changes, time-resolved spectra, quantum yields, and time scales of elementary processes or transient lifetimes needs robust theoretical tools combining state-of-the-art quantum chemistry and developments in quantum dynamics for solving the electronic and nuclear problems. Multimode molecular dynamics beyond the Born-Oppenheimer approximation has been successfully applied to many small polyatomic systems. Its application to large molecules containing a transition metal atom is still a challenge because of the nuclear dimensionality of the problem, the high density of electronic excited states, and the spin-orbit coupling effects. Rhenium(I) α-diimine carbonyl complexes, [Re(L)(CO)3(N,N)](n+) are thermally and photochemically robust and highly flexible synthetically. Structural variations of the N,N and L ligands affect the spectroscopy, the photophysics, and the photochemistry of these chromophores easily incorporated into a complex environment. Visible light absorption opens the route to a wide range of applications such as sensors, probes, or emissive labels for imaging biomolecules. Halide complexes [Re(X)(CO)3(bpy)] (X = Cl, Br, or I; bpy = 2,2'-bipyridine) exhibit complex electronic structure and large spin-orbit effects that do not correlate with the heavy atom effects. Indeed, the (1)MLCT → (3)MLCT intersystem crossing (ISC) kinetics is slower than in [Ru(bpy)3](2+) or [Fe(bpy)3](2+) despite the presence of a third-row transition metal. Counterintuitively, singlet excited-state lifetime increases on going from Cl (85 fs) to Br (128 fs) and to I (152 fs). Moreover, correlation between the Re-X stretching mode and the rate of ISC is observed. In this Account, we emphasize on the role of spin-vibronic coupling on the mechanism of ultrafast ISC put in evidence in [Re(Br)(CO)3(bpy)]. For this purpose, we have developed a model Hamiltonian for solving an 11 electronic excited states multimode problem including vibronic and SO coupling within the linear vibronic coupling (LVC) approximation and the assumption of harmonic potentials. The presence of a central metal atom coupled to rigid ligands, such as α-diimine, ensures nuclear motion of small amplitudes and a priori justifies the use of the LVC model. The simulation of the ultrafast dynamics by wavepacket propagations using the multiconfiguration time-dependent Hartree (MCTDH) method is based on density functional theory (DFT), and its time-dependent extension to excited states (TD-DFT) electronic structure data. We believe that the interplay between time-resolved experiments and these pioneering simulations covering the first picoseconds and including spin-vibronic coupling will promote a number of quantum dynamical studies that will contribute to a better understanding of ultrafast processes in a wide range of organic and inorganic chromophores easily incorporated in biosystems or supramolecular devices for specific functions.

Implementation of polyatomic MCTDHF capability

NASA Astrophysics Data System (ADS)

Haxton, Daniel; Jones, Jeremiah; Rescigno, Thomas; McCurdy, C. William; Ibrahim, Khaled; Williams, Sam; Vecharynski, Eugene; Rouet, Francois-Henry; Li, Xiaoye; Yang, Chao

2015-05-01

The implementation of the Multiconfiguration Time-Dependent Hartree-Fock method for poly- atomic molecules using a cartesian product grid of sinc basis functions will be discussed. The focus will be on two key components of the method: first, the use of a resolution-of-the-identity approximation; sec- ond, the use of established techniques for triple Toeplitz matrix algebra using fast Fourier transform over distributed memory architectures (MPI 3D FFT). The scaling of two-electron matrix element transformations is converted from O(N4) to O(N log N) by including these components. Here N = n3, with n the number of points on a side. We test the prelim- inary implementation by calculating absorption spectra of small hydro- carbons, using approximately 16-512 points on a side. This work is supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under the Early Career program, and by the offices of BES and Advanced Scientific Computing Research, under the SciDAC program.

Archaea S-layer nanotube from a "black smoker" in complex with cyclo-octasulfur (S8 ) rings.

PubMed

McDougall, Matthew; Francisco, Olga; Harder-Viddal, Candice; Roshko, Roy; Meier, Markus; Stetefeld, Jörg

2017-12-01

Elemental sulfur exists primarily as an S80 ring and serves as terminal electron acceptor for a variety of sulfur-fermenting bacteria. Hyperthermophilic archaea from black smoker vents are an exciting research tool to advance our knowledge of sulfur respiration under extreme conditions. Here, we use a hybrid method approach to demonstrate that the proteinaceous cavities of the S-layer nanotube of the hyperthermophilic archaeon Staphylothermus marinus act as a storage reservoir for cyclo-octasulfur S8. Fully atomistic molecular dynamics (MD) simulations were performed and the method of multiconfigurational thermodynamic integration was employed to compute the absolute free energy for transferring a ring of elemental sulfur S8 from an aqueous bath into the largest hydrophobic cavity of a fragment of archaeal tetrabrachion. Comparisons with earlier MD studies of the free energy of hydration as a function of water occupancy in the same cavity of archaeal tetrabrachion show that the sulfur ring is energetically favored over water. © 2017 Wiley Periodicals, Inc.

ELSEPA—Dirac partial-wave calculation of elastic scattering of electrons and positrons by atoms, positive ions and molecules

NASA Astrophysics Data System (ADS)

Salvat, Francesc; Jablonski, Aleksander; Powell, Cedric J.

2005-01-01

The FORTRAN 77 code system ELSEPA for the calculation of elastic scattering of electrons and positrons by atoms, positive ions and molecules is presented. These codes perform relativistic (Dirac) partial-wave calculations for scattering by a local central interaction potential V(r). For atoms and ions, the static-field approximation is adopted, with the potential set equal to the electrostatic interaction energy between the projectile and the target, plus an approximate local exchange interaction when the projectile is an electron. For projectiles with kinetic energies up to 10 keV, the potential may optionally include a semiempirical correlation-polarization potential to describe the effect of the target charge polarizability. Also, for projectiles with energies less than 1 MeV, an imaginary absorptive potential can be introduced to account for the depletion of the projectile wave function caused by open inelastic channels. Molecular cross sections are calculated by means of a single-scattering independent-atom approximation in which the electron density of a bound atom is approximated by that of the free neutral atom. Elastic scattering by individual atoms in solids is described by means of a muffin-tin model potential. Partial-wave calculations are feasible on modest personal computers for energies up to about 5 MeV. The ELSEPA code also implements approximate factorization methods that allow the fast calculation of elastic cross sections for much higher energies. The interaction model adopted in the calculations is defined by the user by combining the different options offered by the code. The nuclear charge distribution can be selected among four analytical models (point nucleus, uniformly charged sphere, Fermi's distribution and Helm's uniform-uniform distribution). The atomic electron density is handled in numerical form. The distribution package includes data files with electronic densities of neutral atoms of the elements hydrogen to lawrencium ( Z=1-103) obtained from multiconfiguration Dirac-Fock self-consistent calculations. For comparison purposes, three simple analytical approximations to the electron density of neutral atoms (corresponding to the Thomas-Fermi, the Thomas-Fermi-Dirac and the Dirac-Hartree-Fock-Slater models) are also included. For calculations of elastic scattering by ions, the electron density should be provided by the user. The exchange potential for electron scattering can be selected among three different analytical approximations (Thomas-Fermi, Furness-McCarthy, Riley-Truhlar). The offered options for the correlation-polarization potential are based on the empirical Buckingham potential. The imaginary absorption potential is calculated from the local-density approximation proposed by Salvat [Phys. Rev. A 68 (2003) 012708]. Program summaryTitle of program:ELSEPA Catalogue identifier: ADUS Program summary URL:http://cpc.cs.qub.ac.uk/cpc/summaries/ADUS Program obtainable from: CPC Program Library, Queen's University of Belfast, N. Ireland License provisions: none Computer for which the program is designed and others in which it is operable: Any computer with a FORTRAN 77 compiler Operating systems under which the program has been tested: Windows XP, Windows 2000, Debian GNU/Linux 3.0r0 (sarge) Compilers:Compaq Visual Fortran v6.5 (Windows); GNU FORTRAN, g77 (Windows and Linux) Programming language used: FORTRAN 77 No. of bits in a word: 32 Memory required to execute with typical data: 0.6 Mb No. of lines in distributed program, including test data, etc.:135 489 No. of bytes in distributed program, including test data, etc.: 1 280 006 Distribution format: tar.gz Keywords: Dirac partial-wave analysis, electron elastic scattering, positron elastic scattering, differential cross sections, momentum transfer cross sections, transport cross sections, scattering amplitudes, spin polarization, scattering by complex potentials, high-energy atomic screening functions Nature of the physical problem: The code calculates differential cross sections, total cross sections and transport cross sections for single elastic scattering of electrons and positrons by neutral atoms, positive ions and randomly oriented molecules. For projectiles with kinetic energies less than about 5 MeV, the programs can also compute scattering amplitudes and spin polarization functions. Method of solution: The effective interaction between the projectile and a target atom is represented by a local central potential that can optionally include an imaginary (absorptive) part to account approximately for the coupling with inelastic channels. For projectiles with kinetic energy less that about 5 MeV, the code performs a conventional relativistic Dirac partial-wave analysis. For higher kinetic energies, where the convergence of the partial-wave series is too slow, approximate factorization methods are used. Restrictions on the complexity of the program: The calculations are based on the static-field approximation. The optional correlation-polarization and inelastic absorption corrections are obtained from approximate, semiempirical models. Calculations for molecules are based on a single-scattering independent-atom approximation. To ensure accuracy of the results for scattering by ions, the electron density of the ion must be supplied by the user. Typical running time: on a 2.8 GHz Pentium 4, the calculation of elastic scattering by atoms and ions takes between a few seconds and about two minutes, depending on the atomic number of the target, the adopted potential model and the kinetic energy of the projectile. Unusual features of the program: The program calculates elastic cross sections for electrons and positrons with kinetic energies in a wide range, from a few tens of eV up to about 1 GeV. Calculations can be performed for neutral atoms of all elements, from hydrogen to lawrencium ( Z=1-103), ions and simple molecules. Commercial products are identified to specify the calculational procedures. Such identification does not imply recommendation or endorsement by the National Institute of Standards and Technology, the University of Barcelona or the Polish Academy of Sciences, nor does it imply that the products are necessarily the best available for the purpose.

Wavepacket dynamics and the multi-configurational time-dependent Hartree approach

NASA Astrophysics Data System (ADS)

Manthe, Uwe

2017-06-01

Multi-configurational time-dependent Hartree (MCTDH) based approaches are efficient, accurate, and versatile methods for high-dimensional quantum dynamics simulations. Applications range from detailed investigations of polyatomic reaction processes in the gas phase to high-dimensional simulations studying the dynamics of condensed phase systems described by typical solid state physics model Hamiltonians. The present article presents an overview of the different areas of application and provides a comprehensive review of the underlying theory. The concepts and guiding ideas underlying the MCTDH approach and its multi-mode and multi-layer extensions are discussed in detail. The general structure of the equations of motion is highlighted. The representation of the Hamiltonian and the correlated discrete variable representation (CDVR), which provides an efficient multi-dimensional quadrature in MCTDH calculations, are discussed. Methods which facilitate the calculation of eigenstates, the evaluation of correlation functions, and the efficient representation of thermal ensembles in MCTDH calculations are described. Different schemes for the treatment of indistinguishable particles in MCTDH calculations and recent developments towards a unified multi-layer MCTDH theory for systems including bosons and fermions are discussed.

Full-dimensional treatment of short-time vibronic dynamics in a molecular high-order-harmonic-generation process in methane

NASA Astrophysics Data System (ADS)

Patchkovskii, Serguei; Schuurman, Michael S.

2017-11-01

We present derivation and implementation of the multiconfigurational strong-field approximation with Gaussian nuclear wave packets (MC-SFA-GWP)—a version of the molecular strong-field approximation which treats all electronic and nuclear degrees of freedom, including their correlations, quantum mechanically. The technique allows realistic simulation of high-order-harmonic emission in polyatomic molecules without invoking reduced-dimensionality models for the nuclear motion or the electronic structure. We use MC-SFA-GWP to model isotope effects in high-order-harmonic-generation (HHG) spectroscopy of methane. The HHG emission in this molecule transiently involves the strongly vibronically coupled F22 electronic state of the CH4+ cation. We show that the isotopic HHG ratio in methane contains signatures of (a) field-free vibronic dynamics at the conical intersection (CI); (b) resonant features in the recombination cross sections; (c) laser-driven bound-state dynamics; as well as (d) the well-known short-time Gaussian decay of the emission. We assign the intrinsic vibronic feature (a) to a relatively long-lived (≥4 fs) vibronic wave packet of the singly excited ν4 (t2) and ν2 (e ) vibrational modes, strongly coupled to the components of the F22 electronic state. We demonstrate that these physical effects differ in their dependence on the wavelength, intensity, and duration of the driving pulse, allowing them to be disentangled. We thus show that HHG spectroscopy provides a versatile tool for exploring both conical intersections and resonant features in photorecombination matrix elements in the regime not easily accessible with other techniques.

Statistical density modification using local pattern matching

DOEpatents

Terwilliger, Thomas C.

2007-01-23

A computer implemented method modifies an experimental electron density map. A set of selected known experimental and model electron density maps is provided and standard templates of electron density are created from the selected experimental and model electron density maps by clustering and averaging values of electron density in a spherical region about each point in a grid that defines each selected known experimental and model electron density maps. Histograms are also created from the selected experimental and model electron density maps that relate the value of electron density at the center of each of the spherical regions to a correlation coefficient of a density surrounding each corresponding grid point in each one of the standard templates. The standard templates and the histograms are applied to grid points on the experimental electron density map to form new estimates of electron density at each grid point in the experimental electron density map.

Chemical Bonding: The Orthogonal Valence-Bond View

PubMed Central

Sax, Alexander F.

2015-01-01

Chemical bonding is the stabilization of a molecular system by charge- and spin-reorganization processes in chemical reactions. These processes are said to be local, because the number of atoms involved is very small. With multi-configurational self-consistent field (MCSCF) wave functions, these processes can be calculated, but the local information is hidden by the delocalized molecular orbitals (MO) used to construct the wave functions. The transformation of such wave functions into valence bond (VB) wave functions, which are based on localized orbitals, reveals the hidden information; this transformation is called a VB reading of MCSCF wave functions. The two-electron VB wave functions describing the Lewis electron pair that connects two atoms are frequently called covalent or neutral, suggesting that these wave functions describe an electronic situation where two electrons are never located at the same atom; such electronic situations and the wave functions describing them are called ionic. When the distance between two atoms decreases, however, every covalent VB wave function composed of non-orthogonal atomic orbitals changes its character from neutral to ionic. However, this change in the character of conventional VB wave functions is hidden by its mathematical form. Orthogonal VB wave functions composed of orthonormalized orbitals never change their character. When localized fragment orbitals are used instead of atomic orbitals, one can decide which local information is revealed and which remains hidden. In this paper, we analyze four chemical reactions by transforming the MCSCF wave functions into orthogonal VB wave functions; we show how the reactions are influenced by changing the atoms involved or by changing their local symmetry. Using orthogonal instead of non-orthogonal orbitals is not just a technical issue; it also changes the interpretation, revealing the properties of wave functions that remain otherwise undetected. PMID:25906476

Coupled potential energy surface for the F(2P)+CH4→HF+CH3 entrance channel and quantum dynamics of the CH4·F- photodetachment.

PubMed

Westermann, Till; Eisfeld, Wolfgang; Manthe, Uwe

2013-07-07

An approach to construct vibronically and spin-orbit coupled diabatic potential energy surfaces (PESs) which describe all three relevant electronic states in the entrance channels of the X(P) + CH4 →HX + CH3 reactions (with X=F((2)P), Cl((2)P), or O((3)P)) is introduced. The diabatization relies on the permutational symmetry present in the methane molecule and results in diabatic states which transform as the three p orbitals of the X atom. Spin-orbit coupling is easily and accurately included using the atomic spin-orbit coupling matrix of the isolated X atom. The method is applied to the F + CH4 system obtaining an accurate PES for the entrance channel based on ab initio multi-reference configuration interaction (MRCI) calculations. Comparing the resulting PESs with spin-orbit MRCI calculations, excellent agreement is found for the excited electronic states at all relevant geometries. The photodetachment spectrum of CH4·F(-) is investigated via full-dimensional (12D) quantum dynamics calculations on the coupled PESs using the multi-layer multi-configurational time-dependent Hartree approach. Extending previous work [J. Palma and U. Manthe, J. Chem. Phys. 137, 044306 (2012)], which was restricted to the dynamics on a single adiabatic PES, the contributions of the electronically excited states to the photodetachment spectrum are calculated and compared to experiment. Considering different experimental setups, good agreement between experiment and theory is found. Addressing questions raised in the previous work, the present dynamical calculations show that the main contribution to the second peak in the photodetachment spectrum results from electron detachment into the electronically excited states of the CH4F complex.

Computational Study of Electron-Molecule Collisions Related to Low-Temperature Plasmas.

NASA Astrophysics Data System (ADS)

Huo, Winifred M.

1997-10-01

Computational study of electron-molecule collisions not only complements experimental measurements, but can also be used to investigate processes not readily accessible experimentally. A number of ab initio computational methods are available for this type of calculations. Here we describe a recently developed technique, the finite element Z-matrix method. Analogous to the R-matrix method, it partitions the space into regions and employs real matrix elements. However, unlike the implementation of the R-matrix method commonly used in atomic and molecular physics,(C. J. Gillan, J. Tennyson, and P. G. Burke, Chapter 10 in Computational Methods for Electron-Molecule Collisions), W. M. Huo and F. A. Gianturco, Editors, Plenum, New York (1995), p. 239. the Z-matrix method is fully variational.(D. Brown and J. C. Light, J. Chem. Phys. 101), 3723 (1994). In the present implementation, a mixed basis of finite elements and Gaussians is used to represent the continuum electron, thus offering full flexibility without imposing fixed boundary conditions. Numerical examples include the electron-impact dissociation of N2 via the metastable A^3Σ_u^+ state, a process which may be important in the lower thermosphere, and the dissociation of the CF radical, a process of interest to plasma etching. To understand the dissociation pathways, large scale quantum chemical calculations have been carried out for all target states which dissociate to the lowest five limits in the case of N_2, and to the lowest two limits in the case of CF. For N_2, the structural calculations clearly show the preference for predissociation if the initial state is the ground X^1Σ_g^+ state, but direct dissociation appears to be preferable if the initial state is the A^3Σ_u^+ state. Multi-configuration SCF target functions are used in the collisional calculation,

Electron Impact Exciation of Fe IX

NASA Astrophysics Data System (ADS)

Tayal, Swaraj; Zatsarinny, Oleg

2015-05-01

Transition probabilities and electron impact excitation collision strengths and rates for astrophysically important extreme ultraviolet lines of Fe IX are calculated. The 322 fine-structure levels of the 3s2 3p6 , 3s2 3p5 3 d , 3 s 3p6 3 d , 3s2 3p5 4 s , and 3s2 3p4 3d2 configurations are included in our calculations. The collision strengths have been calculated using the B-spline Breit-Pauli R-matrix method for all fine-structure transitions among the 322 levels. The mass, Darwin, and spin-orbit relativistic effects are included in the Breit-Pauli Hamiltonian in the scattering calculation. The one-body and two-body relativistic operators are included in the multi-configuration Hartree-Fock calculations of transition probabilities. Several sets of non-orthogonal spectroscopic and correlation radial orbitals are used to obtain accurate description of Fe IX levels and to represent the scattering functions. The calculated excitation energies are in very good agreement with experiment and represents an improvement over the previous calculations. The present collision strengths show reasonable agreement with the previously available R-matrix and distorted-wave calculations. This research is supported by NASA grant from the Solar and Heliophysics Program.

Automated Construction of Molecular Active Spaces from Atomic Valence Orbitals.

PubMed

Sayfutyarova, Elvira R; Sun, Qiming; Chan, Garnet Kin-Lic; Knizia, Gerald

2017-09-12

We introduce the atomic valence active space (AVAS), a simple and well-defined automated technique for constructing active orbital spaces for use in multiconfiguration and multireference (MR) electronic structure calculations. Concretely, the technique constructs active molecular orbitals capable of describing all relevant electronic configurations emerging from a targeted set of atomic valence orbitals (e.g., the metal d orbitals in a coordination complex). This is achieved via a linear transformation of the occupied and unoccupied orbital spaces from an easily obtainable single-reference wave function (such as from a Hartree-Fock or Kohn-Sham calculations) based on projectors to targeted atomic valence orbitals. We discuss the premises, theory, and implementation of the idea, and several of its variations are tested. To investigate the performance and accuracy, we calculate the excitation energies for various transition-metal complexes in typical application scenarios. Additionally, we follow the homolytic bond breaking process of a Fenton reaction along its reaction coordinate. While the described AVAS technique is not a universal solution to the active space problem, its premises are fulfilled in many application scenarios of transition-metal chemistry and bond dissociation processes. In these cases the technique makes MR calculations easier to execute, easier to reproduce by any user, and simplifies the determination of the appropriate size of the active space required for accurate results.

High-resolution tungsten spectroscopy relevant to the diagnostic of high-temperature tokamak plasmas

NASA Astrophysics Data System (ADS)

Rzadkiewicz, J.; Yang, Y.; Kozioł, K.; O'Mullane, M. G.; Patel, A.; Xiao, J.; Yao, K.; Shen, Y.; Lu, D.; Hutton, R.; Zou, Y.; JET Contributors

2018-05-01

The x-ray transitions in Cu- and Ni-like tungsten ions in the 5.19-5.26 Å wavelength range that are relevant as a high-temperature tokamak diagnostic, in particular for JET in the ITER-like wall configuration, have been studied. Tungsten spectra were measured at the upgraded Shanghai- Electron Beam Ion Trap operated with electron-beam energies from 3.16 to 4.55 keV. High-resolution measurements were performed by means of a flat Si 111 crystal spectrometer equipped by a CCD camera. The experimental wavelengths were determined with an accuracy of 0.3-0.4 mÅ. The wavelength of the ground-state transition in Cu-like tungsten from the 3 p53 d104 s 4 d [ (3/2 ,(1/2,5/2 ) 2] 1 /2 level was measured. All measured wavelengths were compared with those measured from JET ITER-like wall plasmas and with other experiments and various theoretical predictions including cowan, relac, multiconfigurational Dirac-Fock (MCDF), and fac calculations. To obtain a higher accuracy from theoretical predictions, the MCDF calculations were extended by taking into account correlation effects (configuration-interaction approach). It was found that such an extension brings the calculations closer to the experimental values in comparison with other calculations.

Potential energy surfaces of LaH + and LaH + 2

NASA Astrophysics Data System (ADS)

Das, Kalyan K.; Balasubramanian, K.

1991-03-01

Using the complete active space multiconfiguration self-consistent field (CAS-MCSCF) followed by full second-order configuration interaction (SOCI) calculations, 16 electronic states of LaH+ and 8 electronic states of LaH+2 are investigated. The potential energy surface of these electronic states of LaH+2 and LaH+ are computed. These calculations show that the 3F(5d2) ground state of La+ ion forms a weak complex with H2. The La+(1D) excited state inserts into H2 with a small barrier (<8 kcal/mol) to form the 1A1 ground state of LaH+2 (re=2.057 Å, θe=106°). At the SOCI level of theory LaH+2 is found to be 11 kcal/mol more stable than La+(3F)+H2. Our calculations explain the experimental observations on La++H2→LaH++H reaction. The adiabatic ionization potential (IP) of LaH2 and LaH are calculated as 5.23 and 5.33 eV, respectively. The ground state of LaH+ was found to be a 2Δ state. We compute De(LaH+) and De(HLa-H+) as 2.54 eV in excellent agreement with the experimental De(LaH+)=2.57 eV measured by Armentrout and co-workers. The spin-orbit effects of LaH+ were also studied using the relativistic configuration interaction (RCI) method.

Accurate bond energies of hydrocarbons from complete basis set extrapolated multi-reference singles and doubles configuration interaction.

PubMed

Oyeyemi, Victor B; Pavone, Michele; Carter, Emily A

2011-12-09

Quantum chemistry has become one of the most reliable tools for characterizing the thermochemical underpinnings of reactions, such as bond dissociation energies (BDEs). The accurate prediction of these particular properties (BDEs) are challenging for ab initio methods based on perturbative corrections or coupled cluster expansions of the single-determinant Hartree-Fock wave function: the processes of bond breaking and forming are inherently multi-configurational and require an accurate description of non-dynamical electron correlation. To this end, we present a systematic ab initio approach for computing BDEs that is based on three components: 1) multi-reference single and double excitation configuration interaction (MRSDCI) for the electronic energies; 2) a two-parameter scheme for extrapolating MRSDCI energies to the complete basis set limit; and 3) DFT-B3LYP calculations of minimum-energy structures and vibrational frequencies to account for zero point energy and thermal corrections. We validated our methodology against a set of reliable experimental BDE values of CC and CH bonds of hydrocarbons. The goal of chemical accuracy is achieved, on average, without applying any empirical corrections to the MRSDCI electronic energies. We then use this composite scheme to make predictions of BDEs in a large number of hydrocarbon molecules for which there are no experimental data, so as to provide needed thermochemical estimates for fuel molecules. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Neon in ultrashort and intense x-rays from free electron lasers

NASA Astrophysics Data System (ADS)

Buth, Christian; Beerwerth, Randolf; Obaid, Razib; Berrah, Nora; Cederbaum, Lorenz S.; Fritzsche, Stephan

2018-03-01

We theoretically examine neon atoms in ultrashort and intense x-rays from free electron lasers and compare our results with data from experiments conducted at the Linac Coherent Light Source. For this purpose, we treat in detail the electronic structure in all possible nonrelativistic cationic configurations using a relativistic multiconfiguration approach. The interaction with the x-rays is described in rate-equation approximation. To understand the mechanisms of the interaction, a path analysis is devised which allows us to investigate what sequences of photoionization and decay processes lead to a specific configuration and with what probability. Thereby, we uncover a connection to the mathematics of graph theory and formal languages. In detail, we study the ion yields and find that plain rate equations do not provide a satisfactory description. We need to extend the rate equations for neon to incorporate double Auger decay of a K-shell vacancy and photoionization shake off for neutral neon. Shake off is included for valence and core ionization; the former has hitherto been overlooked but has important consequences for the ion yields from an x-ray energy below the core ionization threshold. Furthermore, we predict the photon yields from XUV and x-ray fluorescence these allow one insights into the configurations populated by the interaction with the x-rays. Finally, we discover that inaccuracies in those Auger decay widths employed in previous studies have only a minor influence on ion and photon yields.

Reaction of H2 with O2 in Excited Electronic States: Reaction Pathways and Rate Constants.

PubMed

Pelevkin, Alexey V; Loukhovitski, Boris I; Sharipov, Alexander S

2017-12-21

Comprehensive quantum chemical analysis with the use of the multireference state-averaged complete active space self-consistent field approach was carried out to study the reactions of H 2 with O 2 in a 1 Δ g , b 1 Σ g + , c 1 Σ u - , and A' 3 Δ u electronically excited states. The energetically favorable reaction pathways and possible intersystem crossings have been revealed. The energy barriers were refined employing the extended multiconfiguration quasi-degenerate second-order perturbation theory. It has been shown that the interaction of O 2 (a 1 Δ g ) and O 2 (A' 3 Δ u ) with H 2 occurs through the H-abstraction process with relatively low activation barriers that resulted in the formation of the HO 2 molecule in A″ and A' electronic states, respectively. Meanwhile, molecular oxygen in singlet sigma states (b 1 Σ g + and c 1 Σ u - ) was proved to be nonreactive with respect to the molecular hydrogen. Appropriate rate constants for revealed reaction and quenching channels have been estimated using variational transition-state theory including corrections for the tunneling effect, possible nonadiabatic transitions, and anharmonicity of vibrations for transition states and reactants. It was demonstrated that the calculated reaction rate constant for the H 2 + O 2 (a 1 Δ g ) process is in reasonable agreement with known experimental data. The Arrhenius approximations for these processes have been proposed for the temperature range T = 300-3000 K.

Modeling the absorption spectrum of the permanganate ion in vacuum and in aqueous solution

NASA Astrophysics Data System (ADS)

Olsen, Jógvan Magnus Haugaard; Hedegård, Erik Donovan

The absorption spectrum of the MnO$_{4}$$^{-}$ ion has been a test-bed for quantum-chemical methods over the last decades. Its correct description requires highly-correlated multiconfigurational methods, which are incompatible with the inclusion of finite-temperature and solvent effects due to their high computational demands. Therefore, implicit solvent models are usually employed. Here we show that implicit solvent models are not sufficiently accurate to model the solvent shift of MnO$_{4}$$^{-}$, and we analyze the origins of their failure. We obtain the correct solvent shift for MnO$_{4}$$^{-}$ in aqueous solution by employing the polarizable embedding (PE) model combined with a range-separated complete active space short-range density functional theory method (CAS-srDFT). Finite-temperature effects are taken into account by averaging over structures obtained from ab initio molecular dynamics simulations. The explicit treatment of finite-temperature and solvent effects facilitates the interpretation of the bands in the low-energy region of the MnO$_{4}$$^{-}$ absorption spectrum, whose assignment has been elusive.

Performance of quantum Monte Carlo for calculating molecular bond lengths

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

Cleland, Deidre M., E-mail: deidre.cleland@csiro.au; Per, Manolo C., E-mail: manolo.per@csiro.au

2016-03-28

This work investigates the accuracy of real-space quantum Monte Carlo (QMC) methods for calculating molecular geometries. We present the equilibrium bond lengths of a test set of 30 diatomic molecules calculated using variational Monte Carlo (VMC) and diffusion Monte Carlo (DMC) methods. The effect of different trial wavefunctions is investigated using single determinants constructed from Hartree-Fock (HF) and Density Functional Theory (DFT) orbitals with LDA, PBE, and B3LYP functionals, as well as small multi-configurational self-consistent field (MCSCF) multi-determinant expansions. When compared to experimental geometries, all DMC methods exhibit smaller mean-absolute deviations (MADs) than those given by HF, DFT, and MCSCF.more » The most accurate MAD of 3 ± 2 × 10{sup −3} Å is achieved using DMC with a small multi-determinant expansion. However, the more computationally efficient multi-determinant VMC method has a similar MAD of only 4.0 ± 0.9 × 10{sup −3} Å, suggesting that QMC forces calculated from the relatively simple VMC algorithm may often be sufficient for accurate molecular geometries.« less

Radiative lifetimes and transition probabilities for electric-dipole delta n equals zero transitions in highly stripped sulfur ions

NASA Technical Reports Server (NTRS)

Pegg, D. J.; Elston, S. B.; Griffin, P. M.; Forester, J. P.; Thoe, R. S.; Peterson, R. S.; Sellin, I. A.; Hayden, H. C.

1976-01-01

The beam-foil time-of-flight method has been used to investigate radiative lifetimes and transition rates involving allowed intrashell transitions within the L shell of highly ionized sulfur. The results for these transitions, which can be particularly correlation-sensitive, are compared with current calculations based upon multiconfigurational models.

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

NASA Astrophysics Data System (ADS)

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

2017-01-01

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

Transition energy and potential energy curves for ionized inner-shell states of CO, O2 and N 2 calculated by several inner-shell multiconfigurational approaches.

PubMed

Moura, Carlos E V de; Oliveira, Ricardo R; Rocha, Alexandre B

2013-05-01

Potential energy curves and inner-shell ionization energies of carbon monoxide, oxygen and nitrogen molecules were calculated using several forms of the inner-shell multiconfigurational self-consistent field (IS-MCSCF) method-a recently proposed protocol to obtain specifically converged inner-shell states at this level. The particular forms of the IS-MCSCF method designated IS-GVB-PP, IS-FVBL and IS-CASSCF stand for perfect pairing generalized valence bond, full valence bond-like MCSCF and complete active space self consistent field, respectively. A comparison of these different versions of the IS-MCSCF method was carried out for the first time. The results indicate that inner-shell states are described accurately even for the simplest version of the method (IS-GVB-PP). Dynamic correlation was recovered by multireference configuration interaction or multireference perturbation theory. For molecules not having equivalent atoms, all methods led to comparable and accurate transition energies. For molecules with equivalent atoms, the most accurate results were obtained by multireference perturbation theory. Scalar relativistic effects were accounted for using the Douglas-Kroll-Hess Hamiltonian.

An explanation of the very low fluorescence and phosphorescence in pyridine: a CASSCF/CASMP2 study

NASA Astrophysics Data System (ADS)

Varras, Panayiotis C.; Gritzapis, Panagiotis S.; Fylaktakidou, Konstantina C.

2018-01-01

In this work, we applied the multiconfigurational complete active space self-consistent field method and the multiconfigurational second-order perturbation theory CASMP2 to study the fundamental excited states of pyridine and its possible photophysical and photochemical transformations. Our calculations, which are in agreement with the experimental results corresponding to excitations around the 0-0 transition, showed that the very low experimentally observed fluorescence of pyridine is due to the presence of two almost isoenergetic crossings, one of triple character, S1/T1/S0 and the other of S1/S0 character. Both crossings are below the minimum of S1(nπ*) and have a common transition state (S1(TS)) with a very low energy barrier (1.85 kcal/mol or 0.08 eV at the CASMP2 level of theory) separating them. A third triple crossing of the type S1/T1/S0 lying lower with respect to the other two elucidates the observed T1→S0 radiationless transition. This explains not only pyridine's very low fluorescence and phosphorescence but also its almost negligible photochemistry, showing that photophysics is the prevalent process in this molecule.

Molecular and electronic structure of Re 2Br 4(PMe 3) 4

DOE PAGES

Johnstone, Erik V.; Poineau, Frederic; Todorova, Tanya K.; ...

2016-07-07

The dinuclear rhenium(II) complex Re 2Br 4(PMe 3) 4 was prepared from the reduction of [Re 2Br 8] 2– with ( n-Bu 4N)BH 4 in the presence of PMe 3 in propanol. The complex was characterized by single-crystal X-ray diffraction (SCXRD) and UV–visible spectroscopy. It crystallizes in the monoclinic C2/c space group and is isostructural with its molybdenum and technetium analogues. The Re–Re distance (2.2521(3) Å) is slightly longer than the one in Re 2Cl 4(PMe 3) 4 (2.247(1) Å). The molecular and electronic structure of Re 2X 4(PMe 3) 4 (X = Cl, Br) were studied by multiconfigurational quantummore » chemical methods. The computed ground-state geometry is in excellent agreement with the experimental structure determined by SCXRD. The calculated total bond order (2.75) is consistent with the presence of an electron-rich triple bond and is similar to the one found for Re 2Cl 4(PMe 3) 4. The electronic absorption spectrum of Re 2Br 4(PMe 3) 4 was recorded in benzene and shows a series of low-intensity bands in the range 10 000–26 000 cm –1. The absorption bands were assigned based on calculations of the excitation energies with the multireference wave functions followed by second-order perturbation theory using the CASSCF/CASPT2 method. As a result, calculations predict that the lowest energy band corresponds to the δ* → σ* transition, while the next higher energy bands were attributed to the δ* → π*, δ → σ*, and δ → π* transitions.« less

Multicomponent density functional theory embedding formulation.

PubMed

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

2016-07-28

Multicomponent density functional theory (DFT) methods have been developed to treat two types of particles, such as electrons and nuclei, quantum mechanically at the same level. In the nuclear-electronic orbital (NEO) approach, all electrons and select nuclei, typically key protons, are treated quantum mechanically. For multicomponent DFT methods developed within the NEO framework, electron-proton correlation functionals based on explicitly correlated wavefunctions have been designed and used in conjunction with well-established electronic exchange-correlation functionals. Herein a general theory for multicomponent embedded DFT is developed to enable the accurate treatment of larger systems. In the general theory, the total electronic density is separated into two subsystem densities, denoted as regular and special, and different electron-proton correlation functionals are used for these two electronic densities. In the specific implementation, the special electron density is defined in terms of spatially localized Kohn-Sham electronic orbitals, and electron-proton correlation is included only for the special electron density. The electron-proton correlation functional depends on only the special electron density and the proton density, whereas the electronic exchange-correlation functional depends on the total electronic density. This scheme includes the essential electron-proton correlation, which is a relatively local effect, as well as the electronic exchange-correlation for the entire system. This multicomponent DFT-in-DFT embedding theory is applied to the HCN and FHF(-) molecules in conjunction with two different electron-proton correlation functionals and three different electronic exchange-correlation functionals. The results illustrate that this approach provides qualitatively accurate nuclear densities in a computationally tractable manner. The general theory is also easily extended to other types of partitioning schemes for multicomponent systems.

Multicomponent density functional theory embedding formulation

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

Culpitt, Tanner; Brorsen, Kurt R.; Pak, Michael V.

Multicomponent density functional theory (DFT) methods have been developed to treat two types of particles, such as electrons and nuclei, quantum mechanically at the same level. In the nuclear-electronic orbital (NEO) approach, all electrons and select nuclei, typically key protons, are treated quantum mechanically. For multicomponent DFT methods developed within the NEO framework, electron-proton correlation functionals based on explicitly correlated wavefunctions have been designed and used in conjunction with well-established electronic exchange-correlation functionals. Herein a general theory for multicomponent embedded DFT is developed to enable the accurate treatment of larger systems. In the general theory, the total electronic density ismore » separated into two subsystem densities, denoted as regular and special, and different electron-proton correlation functionals are used for these two electronic densities. In the specific implementation, the special electron density is defined in terms of spatially localized Kohn-Sham electronic orbitals, and electron-proton correlation is included only for the special electron density. The electron-proton correlation functional depends on only the special electron density and the proton density, whereas the electronic exchange-correlation functional depends on the total electronic density. This scheme includes the essential electron-proton correlation, which is a relatively local effect, as well as the electronic exchange-correlation for the entire system. This multicomponent DFT-in-DFT embedding theory is applied to the HCN and FHF{sup −} molecules in conjunction with two different electron-proton correlation functionals and three different electronic exchange-correlation functionals. The results illustrate that this approach provides qualitatively accurate nuclear densities in a computationally tractable manner. The general theory is also easily extended to other types of partitioning schemes for multicomponent systems.« less

Normal and abnormal evolution of argon metastable density in high-density plasmas

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

Seo, B. H.; Kim, J. H., E-mail: jhkim86@kriss.re.kr; You, S. J., E-mail: sjyou@cnu.ac.kr

2015-05-15

A controversial problem on the evolution of Ar metastable density as a function of electron density (increasing trend versus decreasing trend) was resolved by discovering the anomalous evolution of the argon metastable density with increasing electron density (discharge power), including both trends of the metastable density [Daltrini et al., Appl. Phys. Lett. 92, 061504 (2008)]. Later, by virtue of an adequate physical explanation based on a simple global model, both evolutions of the metastable density were comprehensively understood as part of the abnormal evolution occurring at low- and high-density regimes, respectively, and thus the physics behind the metastable evolution hasmore » seemed to be clearly disclosed. In this study, however, a remarkable result for the metastable density behavior with increasing electron density was observed: even in the same electron density regime, there are both normal and abnormal evolutions of metastable-state density with electron density depending on the measurement position: The metastable density increases with increasing electron density at a position far from the inductively coupled plasma antenna but decreases at a position close to the antenna. The effect of electron temperature, which is spatially nonuniform in the plasma, on the electron population and depopulation processes of Argon metastable atoms with increasing electron density is a clue to understanding the results. The calculated results of the global model, including multistep ionization for the argon metastable state and measured electron temperature, are in a good agreement with the experimental results.« less

Energy levels, lifetimes, and transition rates for the selenium isoelectronic sequence Pd XIII-Te XIX, Xe XXI-Nd XXVII, W XLI

NASA Astrophysics Data System (ADS)

Wang, K.; Yang, X.; Chen, Z. B.; Si, R.; Chen, C. Y.; Yan, J.; Zhao, X. H.; Dang, W.

2017-09-01

Energy levels, wavelengths, lifetimes, oscillator strengths, and electric dipole (E1), magnetic dipole (M1), electric quadrupole (E2), magnetic quadrupole (M2) transition rates among the 46 fine structure levels belonging to the ([ Ar ] 3d10) 4s2 4p4, ([ Ar ] 3d10) 4s2 4p3 4 d, and ([ Ar ] 3d10) 4 s 4p5 configurations for the selenium isoelectronic sequence Pd XIII-Te XIX, Xe XXI-Nd XXVII, W XLI are reported. These data are determined in the multi-configuration Dirac-Fock (MCDF) approach, in which relativistic effects, main electron correlations within the n = 7 complex, Breit interaction (BI), and quantum electrodynamic (QED) corrections are included. The many-body perturbation theory (MBPT) method is also employed as an independent calculation to confirm the present accuracy, taking W XLI as an example. Comparisons and analysis are made between the present results and available experimental and theoretical ones, and good agreements are obtained. These accurate data are expected to be useful in nuclear fusion research and astrophysical applications.

Correlation, Breit and Quantum Electrodynamics effects on energy level and transition properties of W54+ ion

NASA Astrophysics Data System (ADS)

Ding, Xiaobin; Sun, Rui; Koike, Fumihiro; Kato, Daiji; Murakami, Izumi; Sakaue, Hiroyuki A.; Dong, Chenzhong

2017-03-01

The electron correlation effects and Breit interaction as well as Quantum Electro-Dynamics (QED) effects were expected to have important contribution to the energy level and transition properties of heavy highly charged ions. The ground states [Ne]3s23p63d2 and first excited states [Ne]3s23p53d3 of W54+ ion have been studied by using Multi-Configuration Dirac-Fock method with the implementation of Grasp2K package. A restricted active space method was employed to investigate the correlation contribution from different models. The Breit interaction and QED effects were taken into account in the relativistic configuration interaction calculation with the converged wavefunction. It is found that the correlation contribution from 3s and 3p orbital have important contribution to the energy level, transition wavelength and probability of the ground and the first excited state of W54+ ion. Contribution to the Topical Issue "Atomic and Molecular Data and their Applications", edited by Gordon W.F. Drake, Jung-Sik Yoon, Daiji Kato, Grzegorz Karwasz.

Influence of dense plasma on the energy levels and transition properties in highly charged ions

NASA Astrophysics Data System (ADS)

Chen, Zhan-Bin; Hu, Hong-Wei; Ma, Kun; Liu, Xiao-Bin; Guo, Xue-Ling; Li, Shuang; Zhu, Bo-Hong; Huang, Lian; Wang, Kai

2018-03-01

The studies of the influence of plasma environments on the level structures and transition properties for highly charged ions are presented. For the relativistic treatment, we implemented the multiconfiguration Dirac-Fock method incorporating the ion sphere (IS) model potential, in which the plasma screening is taken into account as a modified interaction potential between the electron and the nucleus. For the nonrelativistic treatment, analytical solutions of the Schrödinger equation with two types of the IS screened potential are proposed. The Ritz variation method is used with hydrogenic wave function as a trial wave function that contains two unknown variational parameters. Bound energies are derived from an energy equation, and the variational parameters are obtained from the minimisation condition of the expectation value of the energy. Numerical results for hydrogen-like ions in dense plasmas are presented as examples. A detailed analysis of the influence of relativistic effects on the energy levels and transition properties is also reported. Our results are compared with available results in the literature showing a good quantitative agreement.

Ultrafast exciton migration in an HJ-aggregate: Potential surfaces and quantum dynamics

NASA Astrophysics Data System (ADS)

Binder, Robert; Polkehn, Matthias; Ma, Tianji; Burghardt, Irene

2017-01-01

Quantum dynamical and electronic structure calculations are combined to investigate the mechanism of exciton migration in an oligothiophene HJ aggregate, i.e., a combination of oligomer chains (J-type aggregates) and stacked aggregates of such chains (H-type aggregates). To this end, a Frenkel exciton model is parametrized by a recently introduced procedure [Binder et al., J. Chem. Phys. 141, 014101 (2014)] which uses oligomer excited-state calculations to perform an exact, point-wise mapping of coupled potential energy surfaces to an effective Frenkel model. Based upon this parametrization, the Multi-Layer Multi-Configuration Time-Dependent Hartree (ML-MCTDH) method is employed to investigate ultrafast dynamics of exciton transfer in a small, asymmetric HJ aggregate model composed of 30 sites and 30 active modes. For a partially delocalized initial condition, it is shown that a torsional defect confines the trapped initial exciton, and planarization induces an ultrafast resonant transition between an HJ-aggregated segment and a covalently bound "dangling chain" end. This model is a minimal realization of experimentally investigated mixed systems exhibiting ultrafast exciton transfer between aggregated, highly planarized chains and neighboring disordered segments.

Theoretical investigation of the He4Br2 conformers.

PubMed

Valdés, Álvaro; Prosmiti, Rita; Villarreal, Pablo; Delgado-Barrio, Gerardo

2012-07-05

Full dimensional quantum dynamics calculations of the three lowest isomers of the He(4)Br(2) van der Waals molecule in its ground electronic state are reported. The calculations are performed using the multiconfiguration time-dependent Hartree (MCTDH) method and a realistic potential form that includes the sum of three body ab initio coupled-cluster single double triple [CCSD(T)] He-Br(2) interactions plus the He-He and Br-Br interactions. This potential exhibits several multiple minima, with the three lowest ones lying very close in energy, just within 2 cm(-1). Such small differences are also found in the calculated binding energies of the three most stable conformers, indicating the floppiness of the system and, thus, the need of accurate potential forms and quantum full dynamics methods to treat this kind of complexes. The 12 dimensional results reported in this work present benchmark data and, thus, can serve to evaluate approximate methods aiming to describe higher order rare gas-dihalogen (N > 4) complexes. A comparison with previous studies using different potential forms and approaches to the energetics for the He(4)Br(2) cluster is also presented.

Excited state non-adiabatic dynamics of pyrrole: A time-resolved photoelectron spectroscopy and quantum dynamics study

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

Wu, Guorong; State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, Liaoning 116023; Synergetic Innovation Center of Quantum Information and Quantum Physics, University of Science and Technology of China, Hefei, Anhui 230026

The dynamics of pyrrole excited at wavelengths in the range 242-217 nm are studied using a combination of time-resolved photoelectron spectroscopy and wavepacket propagations performed using the multi-configurational time-dependent Hartree method. Excitation close to the origin of pyrrole’s electronic spectrum, at 242 and 236 nm, is found to result in an ultrafast decay of the system from the ionization window on a single timescale of less than 20 fs. This behaviour is explained fully by assuming the system to be excited to the A{sub 2}(πσ{sup ∗}) state, in accord with previous experimental and theoretical studies. Excitation at shorter wavelengths hasmore » previously been assumed to result predominantly in population of the bright A{sub 1}(ππ{sup ∗}) and B{sub 2}(ππ{sup ∗}) states. We here present time-resolved photoelectron spectra at a pump wavelength of 217 nm alongside detailed quantum dynamics calculations that, together with a recent reinterpretation of pyrrole’s electronic spectrum [S. P. Neville and G. A. Worth, J. Chem. Phys. 140, 034317 (2014)], suggest that population of the B{sub 1}(πσ{sup ∗}) state (hitherto assumed to be optically dark) may occur directly when pyrrole is excited at energies in the near UV part of its electronic spectrum. The B{sub 1}(πσ{sup ∗}) state is found to decay on a timescale of less than 20 fs by both N-H dissociation and internal conversion to the A{sub 2}(πσ{sup ∗}) state.« less

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

Johnstone, Erik V.; Poineau, Frederic; Todorova, Tanya K.

The dinuclear rhenium(II) complex Re 2Br 4(PMe 3) 4 was prepared from the reduction of [Re 2Br 8] 2– with ( n-Bu 4N)BH 4 in the presence of PMe 3 in propanol. The complex was characterized by single-crystal X-ray diffraction (SCXRD) and UV–visible spectroscopy. It crystallizes in the monoclinic C2/c space group and is isostructural with its molybdenum and technetium analogues. The Re–Re distance (2.2521(3) Å) is slightly longer than the one in Re 2Cl 4(PMe 3) 4 (2.247(1) Å). The molecular and electronic structure of Re 2X 4(PMe 3) 4 (X = Cl, Br) were studied by multiconfigurational quantummore » chemical methods. The computed ground-state geometry is in excellent agreement with the experimental structure determined by SCXRD. The calculated total bond order (2.75) is consistent with the presence of an electron-rich triple bond and is similar to the one found for Re 2Cl 4(PMe 3) 4. The electronic absorption spectrum of Re 2Br 4(PMe 3) 4 was recorded in benzene and shows a series of low-intensity bands in the range 10 000–26 000 cm –1. The absorption bands were assigned based on calculations of the excitation energies with the multireference wave functions followed by second-order perturbation theory using the CASSCF/CASPT2 method. As a result, calculations predict that the lowest energy band corresponds to the δ* → σ* transition, while the next higher energy bands were attributed to the δ* → π*, δ → σ*, and δ → π* transitions.« less

Relativistic R -matrix calculations for the electron-impact excitation of neutral molybdenum

NASA Astrophysics Data System (ADS)

Smyth, R. T.; Johnson, C. A.; Ennis, D. A.; Loch, S. D.; Ramsbottom, C. A.; Ballance, C. P.

2017-10-01

A recent PISCES-B Mod experiment [Nishijima et al., J. Phys. B 43, 225701 (2010), 10.1088/0953-4075/43/22/225701] has revealed up to a factor of 5 discrepancy between measurement and the two existing theoretical models [Badnell et al., J. Phys. B 29, 3683 (1996), 10.1088/0953-4075/29/16/014; Bartschat et al., J. Phys. B 35, 2899 (2002), 10.1088/0953-4075/35/13/305], providing important diagnostics for Mo i. In the following paper we address this issue by employing a relativistic atomic structure and R -matrix scattering calculations to improve upon the available models for future applications and benchmark results against a recent Compact Toroidal Hybrid experiment [Hartwell et al., Fusion Sci. Technol. 72, 76 (2017), 10.1080/15361055.2017.1291046]. We determine the atomic structure of Mo i using grasp0, which implements the multiconfigurational Dirac-Fock method. Fine structure energies and radiative transition rates are presented and compared to existing experimental and theoretical values. The electron-impact excitation of Mo i is investigated using the relativistic R -matrix method and the parallel versions of the Dirac atomic R -matrix codes. Electron-impact excitation cross sections are presented and compared to the few available theoretical cross sections. Throughout, our emphasis is on improving the results for the z 1,2,3o5P →a S52,z 2,3,4o7P → a S73 and y 2,3,4o7P → a S73 electric dipole transitions of particular relevance for diagnostic work.

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

Bhattacharyya, Swarnendu, E-mail: swarnendu.bhattacharyya@ch.tum.de; Domcke, Wolfgang, E-mail: wolfgang.domcke@ch.tum.de; Dai, Zuyang

A diabatic three-sheeted six-dimensional potential-energy surface has been constructed for the ground state and the lowest excited state of the PH{sub 3}{sup +} cation. Coupling terms of Jahn-Teller and pseudo-Jahn-Teller origin up to eighth order had to be included to describe the pronounced anharmonicity of the surface due to multiple conical intersections. The parameters of the diabatic Hamiltonian have been optimized by fitting the eigenvalues of the potential-energy matrix to ab initio data calculated at the CASSCF/MRCI level employing the correlation-consistent triple-ζ basis. The theoretical photoelectron spectrum of phosphine and the non-adiabatic nuclear dynamics of the phosphine cation have beenmore » computed by propagating nuclear wave packets with the multiconfiguration time-dependent Hartree method. The theoretical photoelectron bands obtained by Fourier transformation of the autocorrelation function agree well with the experimental results. It is shown that the ultrafast non-radiative decay dynamics of the first excited state of PH{sub 3}{sup +} is dominated by the exceptionally strong Jahn-Teller coupling of the asymmetric bending vibrational mode together with a hyperline of conical intersections with the electronic ground state induced by the umbrella mode. Time-dependent population probabilities have been computed for the three adiabatic electronic states. The non-adiabatic Jahn-Teller dynamics within the excited state takes place within ≈5 fs. Almost 80% of the excited-state population decay to the ground state within about 10 fs. The wave packets become highly complex and delocalized after 20 fs and no further significant transfer of electronic population seems to occur up to 100 fs propagation time.« less

Many-body quantum dynamics in the decay of bent dark solitons of Bose-Einstein condensates

NASA Astrophysics Data System (ADS)

Katsimiga, G. C.; Mistakidis, S. I.; Koutentakis, G. M.; Kevrekidis, P. G.; Schmelcher, P.

2017-12-01

The beyond mean-field (MF) dynamics of a bent dark soliton (BDS) embedded in a two-dimensional repulsively interacting Bose-Einstein condensate is explored. We examine the case of a single BDS comparing the MF dynamics to a correlated approach, the multi-configuration time-dependent Hartree method for bosons. Dynamical snaking of this bent structure is observed, signaling the onset of fragmentation which becomes significant during the vortex nucleation. In contrast to the MF approximation ‘filling’ of the vortex core is observed, leading in turn to the formation of filled-core vortices, instead of the MF vortex-antivortex pairs. The resulting smearing effect in the density is a rather generic feature, occurring when solitonic structures are exposed to quantum fluctuations. Here, we show that this filling owes its existence to the dynamical building of an antidark structure developed in the next-to-leading order orbital. We further demonstrate that the aforementioned beyond MF dynamics can be experimentally detected using the variance of single shot measurements. Additionally, a variety of excitations including vortices, oblique dark solitons, and open ring dark soliton-like structures building upon higher-lying orbitals is observed. We demonstrate that signatures of the higher-lying orbital excitations emerge in the total density, and can be clearly captured by inspecting the one-body coherence. In the latter context, the localization of one-body correlations exposes the existence of the multi-orbital vortex-antidark structure.

A minimal multiconfigurational technique.

PubMed

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

1986-04-01

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

Electron temperatures within magnetic clouds between 2 and 4 AU: Voyager 2 observations

NASA Astrophysics Data System (ADS)

Sittler, E. C.; Burlaga, L. F.

1998-08-01

We have performed an analysis of Voyager 2 plasma electron observations within magnetic clouds between 2 and 4 AU identified by Burlaga and Behannon [1982]. The analysis has been confined to three of the magnetic clouds identified by Burlaga and Behannon that had high-quality data. The general properties of the plasma electrons within a magnetic cloud are that (1) the moment electron temperature anticorrelates with the electron density within the cloud, (2) the ratio Te/Tp tends to be >1, and (3) on average, Te/Tp~7.0. All three results are consistent with previous electron observations within magnetic clouds. Detailed analyses of the core and halo populations within the magnetic clouds show no evidence of either an anticorrelation between the core temperature TC and the electron density Ne or an anticorrelation between the halo temperature TH and the electron density. Within the magnetic clouds the halo component can contribute more than 50% of the electron pressure. The anticorrelation of Te relative to Ne can be traced to the density of the halo component relative to the density of the core component. The core electrons dominate the electron density. When the density goes up, the halo electrons contribute less to the electron pressure, so we get a lower Te. When the electron density goes down, the halo electrons contribute more to the electron pressure, and Te goes up. We find a relation between the electron pressure and density of the form Pe=αNeγ with γ~0.5.

Lowest triplet (n, π*) electronic state of acrolein: Determination of structural parameters by cavity ringdown spectroscopy and quantum-chemical methods

NASA Astrophysics Data System (ADS)

Hlavacek, Nikolaus C.; McAnally, Michael O.; Drucker, Stephen

2013-02-01

The cavity ringdown absorption spectrum of acrolein (propenal, CH2=CH—CH=O) was recorded near 412 nm, under bulk-gas conditions at room temperature and in a free-jet expansion. The measured spectral region includes the 0^0_0 band of the T1(n, π*) ← S0 system. We analyzed the 0^0_0 rotational contour by using the STROTA computer program [R. H. Judge et al., J. Chem. Phys. 103, 5343 (1995)], 10.1063/1.470569, which incorporates an asymmetric rotor Hamiltonian for simulating and fitting singlet-triplet spectra. We used the program to fit T1(n, π*) inertial constants to the room-temperature contour. The determined values (cm-1), with 2σ confidence intervals, are A = 1.662 ± 0.003, B = 0.1485 ± 0.0006, C = 0.1363 ± 0.0004. Linewidth analysis of the jet-cooled spectrum yielded a value of 14 ± 2 ps for the lifetime of isolated acrolein molecules in the T1(n, π*), v = 0 state. We discuss the observed lifetime in the context of previous computational work on acrolein photochemistry. The spectroscopically derived inertial constants for the T1(n, π*) state were used to benchmark a variety of computational methods. One focus was on complete active space methods, such as complete active space self-consistent field (CASSCF) and second-order perturbation theory with a CASSCF reference function (CASPT2), which are applicable to excited states. We also examined the equation-of-motion coupled-cluster and time-dependent density function theory excited-state methods, and finally unrestricted ground-state techniques, including unrestricted density functional theory and unrestricted coupled-cluster theory with single and double and perturbative triple excitations. For each of the above methods, we or others [O. S. Bokareva et al., Int. J. Quantum Chem. 108, 2719 (2008)], 10.1002/qua.21803 used a triple zeta-quality basis set to optimize the T1(n, π*) geometry of acrolein. We find that the multiconfigurational methods provide the best agreement with fitted inertial constants, while the economical unrestricted Perdew-Burke-Ernzerhof exchange-correlation hybrid functional (UPBE0) technique performs nearly as well.

Ground and excited states of the [Fe(H2O)6]2+ and [Fe(H2O)6]3+ clusters: Insight into the electronic structure of the [Fe(H2O)6]2+ – [Fe(H2O)6]3+ complex

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

Miliordos, Evangelos; Xantheas, Sotiris S.

We report the ground and low lying electronically excited states of the [Fe(H2O)6]2+ and [Fe(H2O)6]3+ clusters using multi-configuration electronic structure theory. In particular, we have constructed the Potential Energy Curves (PECs) with respect to the iron-oxygen distance when removing all water ligands at the same time from the cluster minima and established their correlation to the long range dissociation channels. Due to the fact that both the second and third ionization potentials of iron are larger than the one for water, the ground state products asymptotically correlate with dissociation channels that are repulsive in nature at large separations as theymore » contain at least one H2O+ fragment and a positive metal center. The most stable equilibrium structures emanate – via intersections and/or avoided crossings – from the channels consisting of the lowest electronic states of Fe2+(5D; 3d6) or Fe3+(6S; 3d5) and six neutral water molecules. Upon hydration, the ground state of Fe2+(H2O)6 is a triply (5Tg) degenerate one with the doubly (5Eg) degenerate state lying slightly higher in energy. Similarly, Fe3+(H2O)6 has a ground state of 6Ag symmetry under Th symmetry. We furthermore examine a multitude of electronically excited states of many possible spin multiplicities, and report the optimized geometries for several selected states. The PECs for those cases are characterized by a high density of states. Focusing on the ground and the first few excited states of the [Fe(H2O)6]2+ and [Fe(H2O)6]3+ clusters, we studied their mutual interaction in the gas phase. We obtained the optimal geometries of the Fe2+(H2O)6 – Fe3+(H2O)6 gas phase complex for different Fe–Fe distances. For distances shorter than 6.0 Å, the water molecules in the respective first solvation shells located between the two metal centers were found to interact via weak hydrogen bonds. We examined a total of ten electronic states for this complex, including those corresponding to the electron transfer (ET) from the ferrous to the ferric ion. The ET process is discussed and a possible path via a quasi-symmetric transition state is suggested. This work was supported by the US Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences and Biosciences. Pacific Northwest National Laboratory (PNNL) is a multiprogram national laboratory operated for DOE by Battelle. This research used resources of the National Energy Research Scientific Computing Center, which is supported by the Office of Science of the U.S. Department of Energy under Contract No. DE-AC02-05CH11231.« less

Fingerprint-Based Structure Retrieval Using Electron Density

PubMed Central

Yin, Shuangye; Dokholyan, Nikolay V.

2010-01-01

We present a computational approach that can quickly search a large protein structural database to identify structures that fit a given electron density, such as determined by cryo-electron microscopy. We use geometric invariants (fingerprints) constructed using 3D Zernike moments to describe the electron density, and reduce the problem of fitting of the structure to the electron density to simple fingerprint comparison. Using this approach, we are able to screen the entire Protein Data Bank and identify structures that fit two experimental electron densities determined by cryo-electron microscopy. PMID:21287628

Fingerprint-based structure retrieval using electron density.

PubMed

Yin, Shuangye; Dokholyan, Nikolay V

2011-03-01

We present a computational approach that can quickly search a large protein structural database to identify structures that fit a given electron density, such as determined by cryo-electron microscopy. We use geometric invariants (fingerprints) constructed using 3D Zernike moments to describe the electron density, and reduce the problem of fitting of the structure to the electron density to simple fingerprint comparison. Using this approach, we are able to screen the entire Protein Data Bank and identify structures that fit two experimental electron densities determined by cryo-electron microscopy. Copyright © 2010 Wiley-Liss, Inc.

Stabilization of electron-scale turbulence by electron density gradient in national spherical torus experiment

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

Ruiz Ruiz, J.; White, A. E.; Ren, Y.

2015-12-15

Theory and experiments have shown that electron temperature gradient (ETG) turbulence on the electron gyro-scale, k{sub ⊥}ρ{sub e} ≲ 1, can be responsible for anomalous electron thermal transport in NSTX. Electron scale (high-k) turbulence is diagnosed in NSTX with a high-k microwave scattering system [D. R. Smith et al., Rev. Sci. Instrum. 79, 123501 (2008)]. Here we report on stabilization effects of the electron density gradient on electron-scale density fluctuations in a set of neutral beam injection heated H-mode plasmas. We found that the absence of high-k density fluctuations from measurements is correlated with large equilibrium density gradient, which ismore » shown to be consistent with linear stabilization of ETG modes due to the density gradient using the analytical ETG linear threshold in F. Jenko et al. [Phys. Plasmas 8, 4096 (2001)] and linear gyrokinetic simulations with GS2 [M. Kotschenreuther et al., Comput. Phys. Commun. 88, 128 (1995)]. We also found that the observed power of electron-scale turbulence (when it exists) is anti-correlated with the equilibrium density gradient, suggesting density gradient as a nonlinear stabilizing mechanism. Higher density gradients give rise to lower values of the plasma frame frequency, calculated based on the Doppler shift of the measured density fluctuations. Linear gyrokinetic simulations show that higher values of the electron density gradient reduce the value of the real frequency, in agreement with experimental observation. Nonlinear electron-scale gyrokinetic simulations show that high electron density gradient reduces electron heat flux and stiffness, and increases the ETG nonlinear threshold, consistent with experimental observations.« less

"Almost Darks": HI Mapping and Optical Analysis

NASA Astrophysics Data System (ADS)

Singer, Quinton; Ball, Catie; Cannon, John M.; Leisman, Luke; Haynes, Martha P.; Adams, Elizabeth A.; Bernal Neira, David; Giovanelli, Riccardo; Hallenbeck, Gregory L.; Janesh, William; Janowiecki, Steven; Jozsa, Gyula; Rhode, Katherine L.; Salzer, John Joseph

2017-01-01

We present VLA HI imaging of the "Almost Dark" galaxies AGC 227982, AGC 268363, and AGC 219533. Selected from the ALFALFA survey, "Almost Dark" galaxies have significant HI reservoirs but lack an obvious stellar counterpart in survey-depth ground-based optical imaging. These three HI-rich objects harbor some of the most extreme levels of suppressed star formation amongst the isolated sources in the ALFALFA catalog. Our new multi-configuration, high angular (~20") and spectral (1.7 km/s) resolution HI observations produce spatially resolved column density and velocity distribution moment maps. We compare these images to Sloan Digitized Sky Survey (SDSS) optical images. By localizing the HI gas, we identify previously unknown optical components (offset from the ALFALFA pointing center) for AGC 227982 and AGC 268363, and confirm the association with a very low surface brightness stellar counterpart for AGC 219533. Baryonic masses are derived from VLA flux integral values and ALFALFA distance estimates, giving answers consistent with those derived from ALFALFA fluxes. All three sources appear to have fairly regular HI morphologies and show evidence of ordered rotation.Support for this work was provided by NSF grant 1211683 to JMC at Macalester College.

Postperovskite phase equilibria in the MgSiO3-Al2O3 system.

PubMed

Tsuchiya, Jun; Tsuchiya, Taku

2008-12-09

We investigate high-P,T phase equilibria of the MgSiO(3)-Al(2)O(3) system by means of the density functional ab initio computation methods with multiconfiguration sampling. Being different from earlier studies based on the static substitution properties with no consideration of Rh(2)O(3)(II) phase, present calculations demonstrate that (i) dissolving Al(2)O(3) tends to decrease the postperovskite transition pressure of MgSiO(3) but the effect is not significant ( approximately -0.2 GPa/mol% Al(2)O(3)); (ii) Al(2)O(3) produces the narrow perovskite+postperovskite coexisting P,T area (approximately 1 GPa) for the pyrolitic concentration (x(Al2O3) approximately 6 mol%), which is sufficiently responsible to the deep-mantle D'' seismic discontinuity; (iii) the transition would be smeared (approximately 4 GPa) for the basaltic Al-rich composition (x(Al2O3) approximately 20 mol%), which is still seismically visible unless iron has significant effects; and last (iv) the perovskite structure spontaneously changes to the Rh(2)O(3)(II) with increasing the Al concentration involving small displacements of the Mg-site cations.

Postperovskite phase equilibria in the MgSiO3–Al2O3 system

PubMed Central

Tsuchiya, Jun; Tsuchiya, Taku

2008-01-01

We investigate high-P,T phase equilibria of the MgSiO3–Al2O3 system by means of the density functional ab initio computation methods with multiconfiguration sampling. Being different from earlier studies based on the static substitution properties with no consideration of Rh2O3(II) phase, present calculations demonstrate that (i) dissolving Al2O3 tends to decrease the postperovskite transition pressure of MgSiO3 but the effect is not significant (≈-0.2 GPa/mol% Al2O3); (ii) Al2O3 produces the narrow perovskite+postperovskite coexisting P,T area (≈1 GPa) for the pyrolitic concentration (xAl2O3 ≈6 mol%), which is sufficiently responsible to the deep-mantle D″ seismic discontinuity; (iii) the transition would be smeared (≈4 GPa) for the basaltic Al-rich composition (xAl2O3 ≈20 mol%), which is still seismically visible unless iron has significant effects; and last (iv) the perovskite structure spontaneously changes to the Rh2O3(II) with increasing the Al concentration involving small displacements of the Mg-site cations. PMID:19036928

Comparative electronic structure of a lanthanide and actinide diatomic oxide: Nd versus U

NASA Astrophysics Data System (ADS)

Krauss, M.; Stevens, W. J.

2003-01-01

Using a modified version of the Alchemy electronic structure code and relativistic pseudopotentials, the electronic structure of the ground and low lying excited states of UO, NdO, and NdO + have been calculated at the Hartree-Fock (HF) and multiconfiguration self-consistent field (MCSCF) levels of theory. Including results from an earlier study of UO + this provides the information for a comparative analysis of a lanthanide and an actinide diatomic oxide. UO and NdO are both described formally as M +2 O -2 and the cations as M +3 O -2 , but the HF and MCSCF calculations show that these systems are considerably less ionic due to large charge back-transfer in the πorbitals. The electronic states putatively arise from the ligand field (oxygen anion) perturbed f 4 , sf 3 , df 3 , sdf 2 , or s 2 f 2 states of M +2 and f 3 , sf 2 or df 2 states of M +3 . Molecular orbital results show a substantial stabilization of the sf 3 or s 2 f 2 configurations relative to the f 4 or df 3 configurations that are the even or odd parity ground states in the M +2 free ion. The compact f and d orbitals are more destabilized by the anion field than the diffuse s orbital. The ground states of the neutral species are dominated by orbitals arising from the M +2 sf 3 term, and all the potential energy curves arising from this configuration are similar, which allows an estimate of the vibrational frequencies for UO and NdO of 862 cm -1 and 836 cm -1 , respectively. For NdO + and UO + the excitation energies for the Ωstates were calculated with a valence configuration interaction method using ab initio effective spin-orbit operators to couple the molecular orbital configurations. The results for NdO + are very comparable with the results for UO + , and show the vibrational and electronic states to be interleaved.

Electronic energy density in chemical reaction systems

NASA Astrophysics Data System (ADS)

Tachibana, Akitomo

2001-08-01

The energy of chemical reaction is visualized in real space using the electronic energy density nE(r⃗) associated with the electron density n(r⃗). The electronic energy density nE(r⃗) is decomposed into the kinetic energy density nT(r⃗), the external potential energy density nV(r⃗), and the interelectron potential energy density nW(r⃗). Using the electronic energy density nE(r⃗) we can pick up any point in a chemical reaction system and find how the electronic energy E is assigned to the selected point. We can then integrate the electronic energy density nE(r⃗) in any region R surrounding the point and find out the regional electronic energy ER to the global E. The kinetic energy density nT(r⃗) is used to identify the intrinsic shape of the reactants, the electronic transition state, and the reaction products along the course of the chemical reaction coordinate. The intrinsic shape is identified with the electronic interface S that discriminates the region RD of the electronic drop from the region RA of the electronic atmosphere in the density distribution of the electron gas. If the R spans the whole space, then the integral gives the total E. The regional electronic energy ER in thermodynamic ensemble is realized in electrochemistry as the intrinsic Volta electric potential φR and the intrinsic Herring-Nichols work function ΦR. We have picked up first a hydrogen-like atom for which we have analytical exact expressions of the relativistic kinetic energy density nTM(r⃗) and its nonrelativistic version nT(r⃗). These expressions are valid for any excited bound states as well as the ground state. Second, we have selected the following five reaction systems and show the figures of the nT(r⃗) as well as the other energy densities along the intrinsic reaction coordinates: a protonation reaction to He, addition reactions of HF to C2H4 and C2H2, hydrogen abstraction reactions of NH3+ from HF and NH3. Valence electrons possess their unique delocalized drop region remote from those heavily localized drop regions adhered to core electrons. The kinetic energy density nT(r⃗) and the tension density τ⃗S(r⃗) can vividly demonstrate the formation of the chemical bond. Various basic chemical concepts in these chemical reaction systems have been clearly visualized in real three-dimensional space.

Molecular Quantum Mechanics: Analytic Gradients and Beyond - Program and Abstracts

DTIC Science & Technology

2007-06-03

Kutzelnigg (Bochum, Germany) Chair: Pekka Pyykko (Helsinki, Finland) Which Masses are Vibrating or Rotating in a Molecule? 15:40-16:15 O30...Krylov (Los Angeles, CA, U.S.A.) Multiconfigurational Quantum Chemistry for Actinide Containing Systems: From Isolated Molecules to Condensed...the genetic algorithm will be critically assessed. For B4n, the double rings are notably stable. The DFT calculations provide strong indications of

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

NASA Astrophysics Data System (ADS)

Singh, Narendra; Aggarwal, Sunny

2018-03-01

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

Using a pruned, nondirect product basis in conjunction with the multi-configuration time-dependent Hartree (MCTDH) method

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

Wodraszka, Robert, E-mail: Robert.Wodraszka@chem.queensu.ca; Carrington, Tucker, E-mail: Tucker.Carrington@queensu.ca

In this paper, we propose a pruned, nondirect product multi-configuration time dependent Hartree (MCTDH) method for solving the Schrödinger equation. MCTDH uses optimized 1D basis functions, called single particle functions, but the size of the standard direct product MCTDH basis scales exponentially with D, the number of coordinates. We compare the pruned approach to standard MCTDH calculations for basis sizes small enough that the latter are possible and demonstrate that pruning the basis reduces the CPU cost of computing vibrational energy levels of acetonitrile (D = 12) by more than two orders of magnitude. Using the pruned method, it ismore » possible to do calculations with larger bases, for which the cost of standard MCTDH calculations is prohibitive. Pruning the basis complicates the evaluation of matrix-vector products. In this paper, they are done term by term for a sum-of-products Hamiltonian. When no attempt is made to exploit the fact that matrices representing some of the factors of a term are identity matrices, one needs only to carefully constrain indices. In this paper, we develop new ideas that make it possible to further reduce the CPU time by exploiting identity matrices.« less

Non-null annular subaperture stitching interferometry for aspheric test

NASA Astrophysics Data System (ADS)

Zhang, Lei; Liu, Dong; Shi, Tu; Yang, Yongying; Chong, Shiyao; Miao, Liang; Huang, Wei; Shen, Yibing; Bai, Jian

2015-10-01

A non-null annular subaperture stitching interferometry (NASSI), combining the subaperture stitching idea and non-null test method, is proposed for steep aspheric testing. Compared with standard annular subaperture stitching interferometry (ASSI), a partial null lens (PNL) is employed as an alternative to the transmission sphere, to generate different aspherical wavefronts as the references. The coverage subaperture number would thus be reduced greatly for the better performance of aspherical wavefronts in matching the local slope of aspheric surfaces. Instead of various mathematical stitching algorithms, a simultaneous reverse optimizing reconstruction (SROR) method based on system modeling and ray tracing is proposed for full aperture figure error reconstruction. All the subaperture measurements are simulated simultaneously with a multi-configuration model in a ray-tracing program, including the interferometric system modeling and subaperture misalignments modeling. With the multi-configuration model, full aperture figure error would be extracted in form of Zernike polynomials from subapertures wavefront data by the SROR method. This method concurrently accomplishes subaperture retrace error and misalignment correction, requiring neither complex mathematical algorithms nor subaperture overlaps. A numerical simulation exhibits the comparison of the performance of the NASSI and standard ASSI, which demonstrates the high accuracy of the NASSI in testing steep aspheric. Experimental results of NASSI are shown to be in good agreement with that of Zygo® VerifireTM Asphere interferometer.

Shack-Hartmann Electron Densitometer (SHED): An Optical System for Diagnosing Free Electron Density in Laser-Produced Plasmas

DTIC Science & Technology

2016-11-01

a few nanoseconds. The challenge remains to diagnose plasmas via the free electron density in this short window of time and often in a small volume ...Free Electron Density in Laser-Produced Plasmas by Anthony R Valenzuela Approved for public release; distribution is...US Army Research Laboratory Shack-Hartmann Electron Densitometer (SHED): An Optical System for Diagnosing Free Electron Density in Laser

Electron dynamics in high energy density plasma bunch generation driven by intense picosecond laser pulse

NASA Astrophysics Data System (ADS)

Li, M.; Yuan, T.; Xu, Y. X.; Luo, S. N.

2018-05-01

When an intense picosecond laser pulse is loaded upon a dense plasma, a high energy density plasma bunch, including electron bunch and ion bunch, can be generated in the target. We simulate this process through one-dimensional particle-in-cell simulation and find that the electron bunch generation is mainly due to a local high energy density electron sphere originated in the plasma skin layer. Once generated the sphere rapidly expands to compress the surrounding electrons and induce high density electron layer, coupled with that, hot electrons are efficiently triggered in the local sphere and traveling in the whole target. Under the compressions of light pressure, forward-running and backward-running hot electrons, a high energy density electron bunch generates. The bunch energy density is as high as TJ/m3 order of magnitude in our conditions, which is significant in laser driven dynamic high pressure generation and may find applications in high energy density physics.

The topology of the Coulomb potential density. A comparison with the electron density, the virial energy density, and the Ehrenfest force density.

PubMed

Ferreira, Lizé-Mari; Eaby, Alan; Dillen, Jan

2017-12-15

The topology of the Coulomb potential density has been studied within the context of the theory of Atoms in Molecules and has been compared with the topologies of the electron density, the virial energy density and the Ehrenfest force density. The Coulomb potential density is found to be mainly structurally homeomorphic with the electron density. The Coulomb potential density reproduces the non-nuclear attractor which is observed experimentally in the molecular graph of the electron density of a Mg dimer, thus, for the first time ever providing an alternative and energetic foundation for the existence of this critical point. © 2017 Wiley Periodicals, Inc. © 2017 Wiley Periodicals, Inc.

Method for removing atomic-model bias in macromolecular crystallography

DOEpatents

Terwilliger, Thomas C [Santa Fe, NM

2006-08-01

Structure factor bias in an electron density map for an unknown crystallographic structure is minimized by using information in a first electron density map to elicit expected structure factor information. Observed structure factor amplitudes are combined with a starting set of crystallographic phases to form a first set of structure factors. A first electron density map is then derived and features of the first electron density map are identified to obtain expected distributions of electron density. Crystallographic phase probability distributions are established for possible crystallographic phases of reflection k, and the process is repeated as k is indexed through all of the plurality of reflections. An updated electron density map is derived from the crystallographic phase probability distributions for each one of the reflections. The entire process is then iterated to obtain a final set of crystallographic phases with minimum bias from known electron density maps.

Device and method for electron beam heating of a high density plasma

DOEpatents

Thode, Lester E.

1981-01-01

A device and method for relativistic electron beam heating of a high density plasma in a small localized region. A relativistic electron beam generator produces a high voltage electron beam which propagates along a vacuum drift tube and is modulated to initiate electron bunching within the beam. The beam is then directed through a low density gas chamber which provides isolation between the vacuum modulator and the relativistic electron beam target. The relativistic beam is then applied to a high density target plasma which typically comprises DT, DD, hydrogen boron or similar thermonuclear gas at a density of 10.sup.17 to 10.sup.20 electrons per cubic centimeter. The target plasma is ionized prior to application of the electron beam by means of a laser or other preionization source. Utilizing a relativistic electron beam with an individual particle energy exceeding 3 MeV, classical scattering by relativistic electrons passing through isolation foils is negligible. As a result, relativistic streaming instabilities are initiated within the high density target plasma causing the relativistic electron beam to efficiently deposit its energy into a small localized region within the high density plasma target.

Handling Density Conversion in TPS.

PubMed

Isobe, Tomonori; Mori, Yutaro; Takei, Hideyuki; Sato, Eisuke; Tadano, Kiichi; Kobayashi, Daisuke; Tomita, Tetsuya; Sakae, Takeji

2016-01-01

Conversion from CT value to density is essential to a radiation treatment planning system. Generally CT value is converted to the electron density in photon therapy. In the energy range of therapeutic photon, interactions between photons and materials are dominated with Compton scattering which the cross-section depends on the electron density. The dose distribution is obtained by calculating TERMA and kernel using electron density where TERMA is the energy transferred from primary photons and kernel is a volume considering spread electrons. Recently, a new method was introduced which uses the physical density. This method is expected to be faster and more accurate than that using the electron density. As for particle therapy, dose can be calculated with CT-to-stopping power conversion since the stopping power depends on the electron density. CT-to-stopping power conversion table is also called as CT-to-water-equivalent range and is an essential concept for the particle therapy.

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

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

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

2016-03-25

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

Energy levels and life times calculations of Mo XXXI

NASA Astrophysics Data System (ADS)

Wajid, Abdul; Jabeen, S.; Husain, Abid

2018-05-01

Fine-structure energy levels belonging to 2p63s2, 2p63s3p, 2p63p2 and 2p63p3d for Mo XXXI have been calculated using the multi-configuration Dirac-Fock method including Quantum electrodynamics (QED) corrections. Most of our calculations of energy levels show good agreement with experimental data available on NIST. Lifetimes for excited levels have also been calculated.

Excitation Mechanisms in Moderate-Energy Li+-He Collisions

NASA Astrophysics Data System (ADS)

Kita, Shigetomo; Itaya, Jun; Sawatari, Yugo; Tabata, Tadanobu; Hayashi, Takeo; Shimakura, Noriyuki; Koseki, Shiro

2018-02-01

Excitation mechanisms in Li+-He collisions were studied at laboratory collision energies of 350 ≤ Elab ≤ 2000 eV by measuring double differential cross sections (DCSs) σ(Θ)k over a wide range of center-of-mass scattering angles, 2.5 ≤ Θ ≤ 175°. At Elab ≥ 500 eV, two-electron (2e) excitations were observed as well as one-electron (1e) excitations. At the higher collision energies, excitation probabilities P(Θ)k for the 1e and 2e excitations have characteristic angular dependences, i.e., at Elab = 1500 and 2000 eV, P(Θ)1e for the 1e excitations has double maxima around Θ = 20 and 120° and P(Θ)2e for the 2e excitations has a broad maximum around Θ = 60°. As a first analysis of the experimental data, P(Θ)k, σ(Θ)k, and the integral cross sections Sk(Elab) were calculated by assuming excitations from the 11Σ state into the 11Π and 11Δ states through rotational couplings using the model potentials and couplings. As the next step, ab initio potential energies for the ground and excited states were calculated by a multiconfiguration self-consistent field (MCSCF) method, and then the electronic transitions among the seven states through the radial and rotational couplings were calculated using the theoretical potentials and couplings. Autoionizations from the 2e-excited He**(2s2 and 2p2) atoms were also simulated at Elab = 750-1500 eV and small laboratory angles of θ ≤ 25° by using the MCSCF potentials. The excitation mechanisms were reasonably well understood through these analyses.

Summary of initial results from the Magnetized Dusty Plasma Experiment (MDPX) device

NASA Astrophysics Data System (ADS)

Thomas, Edward

2015-11-01

Dusty (or complex) plasmas are four-component plasma systems consisting of electrons, ions, neutral atoms and charged, solid particulates. These particulates, i.e., the ``dust,'' become charged through interactions with the surrounding plasma particles and are therefore fully coupled to the background. The study of dusty plasmas began with astrophysical studies and has developed into a distinct area of plasma science with contributions to industrial, space, and fundamental plasma science. However, the vast majority of the laboratory studies are performed without the presence of a magnetic field. This is because, compared to the masses of the electrons and ions, the dust particles are significantly more massive and therefore the charge-to-mass ratio of the dust is very small. As a result, large (B > 1 T) magnetic fields are required to achieve conditions in which the dynamics of electrons, ions, and dust particles are dominated by the magnetic field. This presentation will provide a brief description of the design of the large bore (50 cm diameter x 158 cm long), multi-configuration, 4-Tesla class, superconducting magnet and integrated plasma chamber optimized for the study of dusty plasmas at high magnetic field - the MDPX device. The presentation will then focus on initial results of measurements made using MDPX - including observations of a new type of imposed ordered structures formed by the dust particles in a magnetized plasma, E x B driven flows of the particles, and observations of instabilities. This work is a collaboration of the author with Uwe Konopka (Auburn), Robert L. Merlino (Univ. of Iowa), Marlene Rosenberg (UCSD), and the MDPX team at Auburn University. Construction of the MDPX device was supported by the NSF-MRI program. Operations are supported by the NSF and DOE.

New Accurate Oscillator Strengths and Electron Excitation Collision Strengths for N I

NASA Astrophysics Data System (ADS)

Tayal, S. S.

2006-03-01

The nonorthogonal orbitals technique in a multiconfiguration Hartree-Fock approach is used to calculate oscillator strengths and transition probabilities of N I lines. The relativistic effects are allowed by means of Breit-Pauli operators. The length and velocity forms of oscillator strengths show good agreement for most transitions. The B-spline R-matrix with pseudostates approach has been used to calculate electron excitation collision strengths and rates. The nonorthogonal orbitals are used for an accurate description of both target wave functions and the R-matrix basis functions. The 24 spectroscopic bound and autoionizing states together with 15 pseudostates are included in the close-coupling expansion. The collision strengths for transitions between fine-structure levels are calculated by transforming the LS-coupled K-matrices to K-matrices in an intermediate coupling scheme. Thermally averaged collision strengths have been determined by integrating collision strengths over a Maxwellian distribution of electron energies over a temperature range suitable for the modeling of astrophysical plasmas. The oscillator strengths and thermally averaged collision strengths are presented for transitions between the fine-structure levels of the 2s22p3 4So, 2Do, 2Po, 2s2p4 4P, 2s22p23s 4P, and 2P terms and from these levels to the levels of the 2s22p23p 2So, 4Do, 4Po, 4So, 2Do, 2Po, 2s22p23s 2D, 2s22p24s 4P, 2P, 2s22p23d 2P, 4F, 2F, 4P, 4D, and 2D terms. Thermally averaged collision strengths are tabulated over a temperature range from 500 to 50,000 K.

X-Ray Sum Frequency Diffraction for Direct Imaging of Ultrafast Electron Dynamics

NASA Astrophysics Data System (ADS)

Rouxel, Jérémy R.; Kowalewski, Markus; Bennett, Kochise; Mukamel, Shaul

2018-06-01

X-ray diffraction from molecules in the ground state produces an image of their charge density, and time-resolved x-ray diffraction can thus monitor the motion of the nuclei. However, the density change of excited valence electrons upon optical excitation can barely be monitored with regular diffraction techniques due to the overwhelming background contribution of the core electrons. We present a nonlinear x-ray technique made possible by novel free electron laser sources, which provides a spatial electron density image of valence electron excitations. The technique, sum frequency generation carried out with a visible pump and a broadband x-ray diffraction pulse, yields snapshots of the transition charge densities, which represent the electron density variations upon optical excitation. The technique is illustrated by ab initio simulations of transition charge density imaging for the optically induced electronic dynamics in a donor or acceptor substituted stilbene.

Anomalous evolution of Ar metastable density with electron density in high density Ar discharge

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

Park, Min; Chang, Hong-Young; You, Shin-Jae

2011-10-15

Recently, an anomalous evolution of argon metastable density with plasma discharge power (electron density) was reported [A. M. Daltrini, S. A. Moshkalev, T. J. Morgan, R. B. Piejak, and W. G. Graham, Appl. Phys. Lett. 92, 061504 (2008)]. Although the importance of the metastable atom and its density has been reported in a lot of literature, however, a basic physics behind the anomalous evolution of metastable density has not been clearly understood yet. In this study, we investigated a simple global model to elucidate the underlying physics of the anomalous evolution of argon metastable density with the electron density. Onmore » the basis of the proposed simple model, we reproduced the anomalous evolution of the metastable density and disclosed the detailed physics for the anomalous result. Drastic changes of dominant mechanisms for the population and depopulation processes of Ar metastable atoms with electron density, which take place even in relatively low electron density regime, is the clue to understand the result.« less

MAVEN observations of dayside peak electron densities in the ionosphere of Mars

NASA Astrophysics Data System (ADS)

Vogt, Marissa F.; Withers, Paul; Fallows, Kathryn; Andersson, Laila; Girazian, Zachary; Mahaffy, Paul R.; Benna, Mehdi; Elrod, Meredith K.; Connerney, John E. P.; Espley, Jared R.; Eparvier, Frank G.; Jakosky, Bruce M.

2017-01-01

The peak electron density in the dayside Martian ionosphere is a valuable diagnostic of the state of the ionosphere. Its dependence on factors like the solar zenith angle, ionizing solar irradiance, neutral scale height, and electron temperature has been well studied. The Mars Atmosphere and Volatile EvolutioN spacecraft's September 2015 "deep dip" orbits, in which the orbital periapsis was lowered to 125 km, provided the first opportunity since Viking to sample in situ a complete dayside electron density profile including the main peak. Here we present peak electron density measurements from 37 deep dip orbits and describe conditions at the altitude of the main peak, including the electron temperature and composition of the ionosphere and neutral atmosphere. We find that the dependence of the peak electron density and the altitude of the main peak on solar zenith angle are well described by analytical photochemical theory. Additionally, we find that the electron temperatures at the main peak display a dependence on solar zenith angle that is consistent with the observed variability in the peak electron density. Several peak density measurements were made in regions of large crustal magnetic field, but there is no clear evidence that the crustal magnetic field strength influences the peak electron density, peak altitude, or electron temperature. Finally, we find that the fractional abundance of O2+ and CO2+ at the peak altitude is variable but that the two species together consistently represent 95% of the total ion density.

Configuration interaction singles natural orbitals: An orbital basis for an efficient and size intensive multireference description of electronic excited states

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

Shu, Yinan; Levine, Benjamin G., E-mail: levine@chemistry.msu.edu; Hohenstein, Edward G.

2015-01-14

Multireference quantum chemical methods, such as the complete active space self-consistent field (CASSCF) method, have long been the state of the art for computing regions of potential energy surfaces (PESs) where complex, multiconfigurational wavefunctions are required, such as near conical intersections. Herein, we present a computationally efficient alternative to the widely used CASSCF method based on a complete active space configuration interaction (CASCI) expansion built from the state-averaged natural orbitals of configuration interaction singles calculations (CISNOs). This CISNO-CASCI approach is shown to predict vertical excitation energies of molecules with closed-shell ground states similar to those predicted by state averaged (SA)-CASSCFmore » in many cases and to provide an excellent reference for a perturbative treatment of dynamic electron correlation. Absolute energies computed at the CISNO-CASCI level are found to be variationally superior, on average, to other CASCI methods. Unlike SA-CASSCF, CISNO-CASCI provides vertical excitation energies which are both size intensive and size consistent, thus suggesting that CISNO-CASCI would be preferable to SA-CASSCF for the study of systems with multiple excitable centers. The fact that SA-CASSCF and some other CASCI methods do not provide a size intensive/consistent description of excited states is attributed to changes in the orbitals that occur upon introduction of non-interacting subsystems. Finally, CISNO-CASCI is found to provide a suitable description of the PES surrounding a biradicaloid conical intersection in ethylene.« less

Ab initio study of dynamical E × e Jahn-Teller and spin-orbit coupling effects in the transition-metal trifluorides TiF3, CrF3, and NiF3

NASA Astrophysics Data System (ADS)

Mondal, Padmabati; Opalka, Daniel; Poluyanov, Leonid V.; Domcke, Wolfgang

2012-02-01

Multiconfiguration ab initio methods have been employed to study the effects of Jahn-Teller (JT) and spin-orbit (SO) coupling in the transition-metal trifluorides TiF3, CrF3, and NiF3, which possess spatially doubly degenerate excited states (ME) of even spin multiplicities (M = 2 or 4). The ground states of TiF3, CrF3, and NiF3 are nondegenerate and exhibit minima of D3h symmetry. Potential-energy surfaces of spatially degenerate excited states have been calculated using the state-averaged complete-active-space self-consistent-field method. SO coupling is described by the matrix elements of the Breit-Pauli operator. Linear and higher order JT coupling constants for the JT-active bending and stretching modes as well as SO-coupling constants have been determined. Vibronic spectra of JT-active excited electronic states have been calculated, using JT Hamiltonians for trigonal systems with inclusion of SO coupling. The effect of higher order (up to sixth order) JT couplings on the vibronic spectra has been investigated for selected electronic states and vibrational modes with particularly strong JT couplings. While the weak SO couplings in TiF3 and CrF3 are almost completely quenched by the strong JT couplings, the stronger SO coupling in NiF3 is only partially quenched by JT coupling.

Correlation between Na/K ratio and electron densities in blood samples of breast cancer patients.

PubMed

Topdağı, Ömer; Toker, Ozan; Bakırdere, Sezgin; Bursalıoğlu, Ertuğrul Osman; Öz, Ersoy; Eyecioğlu, Önder; Demir, Mustafa; İçelli, Orhan

2018-05-31

The main purpose of this study was to investigate the relationship between the electron densities and Na/K ratio which has important role in breast cancer disease. Determinations of sodium and potassium concentrations in blood samples performed with inductive coupled plasma-atomic emission spectrometry. Electron density values of blood samples were determined via ZXCOM. Statistical analyses were performed for electron densities and Na/K ratio including Kolmogorov-Smirnov normality tests, Spearman's rank correlation test and Mann-Whitney U test. It was found that the electron densities significantly differ between control and breast cancer groups. In addition, statistically significant positive correlation was found between the electron density and Na/K ratios in breast cancer group.

Single metal catalysis: DFT and CAS modelling of species involved in the Fe cation assisted transformation of acetylene to benzene

NASA Astrophysics Data System (ADS)

Altun, Zikri; Bleda, Erdi; Trindle, Carl

2017-09-01

Gas phase conversion of acetylene to benzene, assisted by a single metal cation such as Fe(+), Ru(+) and Rh(+), offers an attractive prospect for application of computational modelling techniques to catalytic processes. Gas phase processes are not complicated by environmental effects and the participation of a single metal atom is a significant simplification. Still the process is complex, owing to the possibility of several low-energy spin states and the abundance of alternative structures. By density functional theory modelling using recently developed models with range and dispersion corrections, we locate and characterise a number of extreme points on the FeC6H6(+) surface, some of which have not been described previously. These include eta-1, eta-2 and eta-3 complexes of Fe(+) with the C4H4 ring. We identify new FeC6H6(+) structures as well, which may be landmarks for the Fe(+)-catalysed production of benzene from acetylene. The Fe(+) benzene complex is the most stable species on the FeC6H6 cation surface. With the abundant energy of complexation available in the isolated gas phase species, detachment of the Fe(+) and production of benzene can be efficient. We address the issue raised by other investigators whether multi-configurational self-consistent field methods are essential to the proper description of these systems. We find that the relative energy of intrinsically multi-determinant doublets is strongly affected, but judge that the density functional theory (DFT) description provides more accurate estimates of energetics and a more plausible reaction path.

Device and method for electron beam heating of a high density plasma

DOEpatents

Thode, L.E.

A device and method for relativistic electron beam heating of a high density plasma in a small localized region are described. A relativistic electron beam generator produces a high voltage electron beam which propagates along a vacuum drift tube and is modulated to initiate electron bunching within the beam. The beam is then directed through a low density gas chamber which provides isolation between the vacuum modulator and the relativistic electron beam target. The relativistic beam is then applied to a high density target plasma which typically comprises DT, DD, hydrogen boron or similar thermonuclear gas at a density of 10/sup 17/ to 10/sup 20/.

Ultrafast dynamics induced by the interaction of molecules with electromagnetic fields: Several quantum, semiclassical, and classical approaches.

PubMed

Antipov, Sergey V; Bhattacharyya, Swarnendu; El Hage, Krystel; Xu, Zhen-Hao; Meuwly, Markus; Rothlisberger, Ursula; Vaníček, Jiří

2017-11-01

Several strategies for simulating the ultrafast dynamics of molecules induced by interactions with electromagnetic fields are presented. After a brief overview of the theory of molecule-field interaction, we present several representative examples of quantum, semiclassical, and classical approaches to describe the ultrafast molecular dynamics, including the multiconfiguration time-dependent Hartree method, Bohmian dynamics, local control theory, semiclassical thawed Gaussian approximation, phase averaging, dephasing representation, molecular mechanics with proton transfer, and multipolar force fields. In addition to the general overview, some focus is given to the description of nuclear quantum effects and to the direct dynamics, in which the ab initio energies and forces acting on the nuclei are evaluated on the fly. Several practical applications, performed within the framework of the Swiss National Center of Competence in Research "Molecular Ultrafast Science and Technology," are presented: These include Bohmian dynamics description of the collision of H with H 2 , local control theory applied to the photoinduced ultrafast intramolecular proton transfer, semiclassical evaluation of vibrationally resolved electronic absorption, emission, photoelectron, and time-resolved stimulated emission spectra, infrared spectroscopy of H-bonding systems, and multipolar force fields applications in the condensed phase.

Calculating Potential Energy Curves with Quantum Monte Carlo

NASA Astrophysics Data System (ADS)

Powell, Andrew D.; Dawes, Richard

2014-06-01

Quantum Monte Carlo (QMC) is a computational technique that can be applied to the electronic Schrödinger equation for molecules. QMC methods such as Variational Monte Carlo (VMC) and Diffusion Monte Carlo (DMC) have demonstrated the capability of capturing large fractions of the correlation energy, thus suggesting their possible use for high-accuracy quantum chemistry calculations. QMC methods scale particularly well with respect to parallelization making them an attractive consideration in anticipation of next-generation computing architectures which will involve massive parallelization with millions of cores. Due to the statistical nature of the approach, in contrast to standard quantum chemistry methods, uncertainties (error-bars) are associated with each calculated energy. This study focuses on the cost, feasibility and practical application of calculating potential energy curves for small molecules with QMC methods. Trial wave functions were constructed with the multi-configurational self-consistent field (MCSCF) method from GAMESS-US.[1] The CASINO Monte Carlo quantum chemistry package [2] was used for all of the DMC calculations. An overview of our progress in this direction will be given. References: M. W. Schmidt et al. J. Comput. Chem. 14, 1347 (1993). R. J. Needs et al. J. Phys.: Condensed Matter 22, 023201 (2010).

Direct Quantum Dynamics Using Grid-Based Wave Function Propagation and Machine-Learned Potential Energy Surfaces.

PubMed

Richings, Gareth W; Habershon, Scott

2017-09-12

We describe a method for performing nuclear quantum dynamics calculations using standard, grid-based algorithms, including the multiconfiguration time-dependent Hartree (MCTDH) method, where the potential energy surface (PES) is calculated "on-the-fly". The method of Gaussian process regression (GPR) is used to construct a global representation of the PES using values of the energy at points distributed in molecular configuration space during the course of the wavepacket propagation. We demonstrate this direct dynamics approach for both an analytical PES function describing 3-dimensional proton transfer dynamics in malonaldehyde and for 2- and 6-dimensional quantum dynamics simulations of proton transfer in salicylaldimine. In the case of salicylaldimine we also perform calculations in which the PES is constructed using Hartree-Fock calculations through an interface to an ab initio electronic structure code. In all cases, the results of the quantum dynamics simulations are in excellent agreement with previous simulations of both systems yet do not require prior fitting of a PES at any stage. Our approach (implemented in a development version of the Quantics package) opens a route to performing accurate quantum dynamics simulations via wave function propagation of many-dimensional molecular systems in a direct and efficient manner.

Ultrafast dynamics induced by the interaction of molecules with electromagnetic fields: Several quantum, semiclassical, and classical approaches

PubMed Central

Antipov, Sergey V.; Bhattacharyya, Swarnendu; El Hage, Krystel; Xu, Zhen-Hao; Meuwly, Markus; Rothlisberger, Ursula; Vaníček, Jiří

2018-01-01

Several strategies for simulating the ultrafast dynamics of molecules induced by interactions with electromagnetic fields are presented. After a brief overview of the theory of molecule-field interaction, we present several representative examples of quantum, semiclassical, and classical approaches to describe the ultrafast molecular dynamics, including the multiconfiguration time-dependent Hartree method, Bohmian dynamics, local control theory, semiclassical thawed Gaussian approximation, phase averaging, dephasing representation, molecular mechanics with proton transfer, and multipolar force fields. In addition to the general overview, some focus is given to the description of nuclear quantum effects and to the direct dynamics, in which the ab initio energies and forces acting on the nuclei are evaluated on the fly. Several practical applications, performed within the framework of the Swiss National Center of Competence in Research “Molecular Ultrafast Science and Technology,” are presented: These include Bohmian dynamics description of the collision of H with H2, local control theory applied to the photoinduced ultrafast intramolecular proton transfer, semiclassical evaluation of vibrationally resolved electronic absorption, emission, photoelectron, and time-resolved stimulated emission spectra, infrared spectroscopy of H-bonding systems, and multipolar force fields applications in the condensed phase. PMID:29376107

Impacts of hydroxylation on the photophysics of chalcones: insights into the relation between the chemical composition and the electronic structure.

PubMed

Kalchevski, Dobromir A; Petrov, Vesselin; Tadjer, Alia; Nenov, Artur

2018-03-28

A combined theoretical/experimental study of the photoreactivity of two flavylium-derived chalcones, 2,4,4'-trihydroxychalcone and 2,4'-dihydroxychalcone, at the multiconfigurational wavefunction level of theory (CASSCF//CASPT2) in vacuo and in an implicit solvent (water, treated as a polarisable continuum) and by means of linear absorption spectroscopy is presented. The photosensitivity of flavium salts is expressed in the ability of their chalcone form to undergo a cis-trans isomerisation which has found application in logical networks. Despite a considerable amount of experimental data documenting the dependence of the isomerisation on solvent, pH and temperature, the knowledge of how chalcones process energy under various conditions at the molecular level is still scarce. On the example of 2,4,4'-trihydroxychalcone we unravel the complex excited state deactivation mechanism in vacuo involving ultrafast decay through conical intersections, formation of twisted intramolecular charge transfer species, intramolecular proton transfer and inter system crossings. Furthermore, we rationalise the observed discrepancies in the linear absorption spectra of 2,4,4'-trihydroxychalcone and 2,4'-dihydroxychalcone, thereby establishing a link between the functionalisation pattern and the observed spectral properties.

Atomic structure calculations and identification of EUV and SXR spectral lines in Sr XXX

NASA Astrophysics Data System (ADS)

Goyal, Arun; Khatri, Indu; Aggarwal, Sunny; Singh, A. K.; Mohan, Man

2015-08-01

We report an extensive theoretical study of atomic data for Sr XXX in a wide range with L-shell electron excitations to the M-shell. We have calculated energy levels, wave-function compositions and lifetimes for lowest 113 fine structure levels and wavelengths of an extreme Ultraviolet (EUV) and soft X-ray (SXR) transitions. We have employed multi-configuration Dirac Fock method (MCDF) approach within the framework of Dirac-Coulomb Hamiltonian including quantum electrodynamics (QED) and Breit corrections. We have also presented the radiative data for electric and magnetic dipole (E1, M1) and quadrupole (E2, M2) transitions from the ground state. We have made comparisons with available energy levels compiled by NIST and achieve good agreement. But due to inadequate data in the literature, analogous relativistic distorted wave calculations have also been performed using flexible atomic code (FAC) to assess the reliability and accuracy of our results. Additionally, we have provided new atomic data for Sr XXX which is not published elsewhere in the literature and we believe that our results may be beneficial in fusion plasma research and astrophysical investigations and applications.

Theoretical study of the H2 reaction with a Pt4 (111) cluster

NASA Astrophysics Data System (ADS)

Cruz, A.; Bertin, V.; Poulain, E.; Benitez, J. I.; Castillo, S.

2004-04-01

The Cs symmetry reaction of the H2 molecule on a Pt4 (111) clusters, has been studied using ab initio multiconfiguration self-consistent field plus extensive multireference configuration interaction variational and perturbative calculations. The H2 interaction by the vertex and by the base of a tetrahedral Pt4 cluster were studied in ground and excited triplet and singlet states (closed and open shells), where the reaction curves are obtained through many avoided crossings. The Pt4 cluster captures and activates the hydrogen molecule; it shows a similar behavior compared with other Ptn (n=1,2,3) systems. The Pt4 cluster in their lowest five open and closed shell electronic states: 3B2, 1B2, 1A1 3A1, 1A1, respectively, may capture and dissociate the H2 molecule without activation barriers for the hydrogen molecule vertex approach. For the threefolded site reaction, i.e., by the base, the situation is different, the hydrogen adsorption presents some barriers. The potential energy minima occur outside and inside the cluster, with strong activation of the H-H bond. In all cases studied, the Pt4 cluster does not absorb the hydrogen molecule.

Distribution of E/N and N/e/ in a cross-flow electric discharge laser. [electric field to neutral gas density and electron number density

NASA Technical Reports Server (NTRS)

Dunning, J. W., Jr.; Lancashire, R. B.; Manista, E. J.

1976-01-01

Measurements have been conducted of the effect of the convection of ions and electrons on the discharge characteristics in a large scale laser. The results are presented for one particular distribution of ballast resistance. Values of electric field, current density, input power density, ratio of electric field to neutral gas density (E/N), and electron number density were calculated on the basis of measurements of the discharge properties. In a number of graphs, the E/N ratio, current density, power density, and electron density are plotted as a function of row number (downstream position) with total discharge current and gas velocity as parameters. From the dependence of the current distribution on the total current, it appears that the electron production in the first two rows significantly affects the current flowing in the succeeding rows.

Radiation source

DOEpatents

Thode, Lester E.

1981-01-01

A device and method for relativistic electron beam heating of a high-density plasma in a small localized region. A relativistic electron beam generator or accelerator produces a high-voltage electron beam which propagates along a vacuum drift tube and is modulated to initiate electron bunching within the beam. The beam is then directed through a low-density gas chamber which provides isolation between the vacuum modulator and the relativistic electron beam target. The relativistic beam is then applied to a high-density target plasma which typically comprises DT, DD, or similar thermonuclear gas at a density of 10.sup.17 to 10.sup.20 electrons per cubic centimeter. The target gas is ionized prior to application of the relativistic electron beam by means of a laser or other preionization source to form a plasma. Utilizing a relativistic electron beam with an individual particle energy exceeding 3 MeV, classical scattering by relativistic electrons passing through isolation foils is negligible. As a result, relativistic streaming instabilities are initiated within the high-density target plasma causing the relativistic electron beam to efficiently deposit its energy into a small localized region of the high-density plasma target.

Direct comparison of Viking 2.3-GHz signal phase fluctuation and columnar electron density between 2 and 160 solar radii

NASA Technical Reports Server (NTRS)

Berman, A. L.; Wackley, J. A.; Hietzke, W. H.

1982-01-01

The relationship between solar wind induced signal phase fluctuation and solar wind columnar electron density has been the subject of intensive analysis during the last two decades. In this article, a sizeable volume of 2.3-GHz signal phase fluctuation and columnar electron density measurements separately and concurrently inferred from Viking spacecraft signals are compared as a function of solar geometry. These data demonstrate that signal phase fluctuation and columnar electron density are proportional over a very wide span of solar elongation angle. A radially dependent electron density model which provides a good fit to the columnar electron density measurements and, when appropriately scaled, to the signal phase fluctuation measurements, is given. This model is also in good agreement with K-coronameter observations at 2 solar radii (2r0), with pulsar time delay measurements at 10r0, and with spacecraft in situ electron density measurements at 1 AU.

Electron (charge) density studies of cellulose models

USDA-ARS?s Scientific Manuscript database

Introductory material first describes electron density approaches and demonstrates visualization of electron lone pairs and bonding as concentrations of electron density. Then it focuses on the application of Bader’s Quantum Theory of Atoms-in-Molecules (AIM) to cellulose models. The purpose of the ...

Electron densities in the ionosphere of Mars: A comparison of MARSIS and radio occultation measurements

NASA Astrophysics Data System (ADS)

Vogt, Marissa F.; Withers, Paul; Fallows, Kathryn; Flynn, Casey L.; Andrews, David J.; Duru, Firdevs; Morgan, David D.

2016-10-01

Radio occultation electron densities measurements from the Mariner 9 and Viking spacecraft, which orbited Mars in the 1970s, have recently become available in a digital format. These data are highly complementary to the radio occultation electron density profiles from Mars Global Surveyor, which were restricted in solar zenith angle and altitude. We have compiled data from the Mariner 9, Viking, and Mars Global Surveyor radio occultation experiments for comparison to electron density measurements made by Mars Advanced Radar for Subsurface and Ionosphere Sounding (MARSIS), the topside radar sounder on Mars Express, and MARSIS-based empirical density models. We find that the electron densities measured by radio occultation are in generally good agreement with the MARSIS data and model, especially near the altitude of the peak electron density but that the MARSIS data and model display a larger plasma scale height than the radio occultation profiles at altitudes between the peak density and 200 km. Consequently, the MARSIS-measured and model electron densities are consistently larger than radio occultation densities at altitudes 200-300 km. Finally, we have analyzed transitions in the topside ionosphere, at the boundary between the photochemically controlled and transport-controlled regions, and identified the average transition altitude, or altitude at which a change in scale height occurs. The average transition altitude is 200 km in the Mariner 9 and Viking radio occultation profiles and in profiles of the median MARSIS radar sounding electron densities.

The electrons and ion characteristics of Saturn's plasma disk inside the Enceladus orbit

NASA Astrophysics Data System (ADS)

Morooka, Michiko; Wahlund, Jan-Erik; Ye, Sheng-Yi; Kurth, William; Persoon, Ann; Holmberg, Mika

2017-04-01

Cassini observations revealed that Saturn's icy moon Enceladus and surrounding E ring are the significant plasma source of the magnetosphere. However, the observations sometimes show the electron density enhancement even inside the Enceladus orbiting distance, 4RS. Further plasma contribution from the inner rings, the G and the F rings and main A ring are the natural candidate as an additional plasma source. The Cassini/RPWS Langmuir Probe (LP) measurement provides the characteristics of the electrons and ions independently in a cold dense plasma. The observations near the center of the E ring showed that the ion density being larger than the electron density, indicating that there is additional particle as a negative charge carrier. Those are the small nm and μm sized dust grains that are negatively charged by the electron attachments. The faint F and G rings, located at R=2RS and 3RS, consist of small grains and similar electron/ion density discrepancies can be expected. We will show different types of the LP observations when Cassini traveled the equator region of the plasma disk down to 3RS. One with the electron density increasing inside 4RS, and another with the electron density decreasing inside 4RS. During the orbit 016 (2005 doy-284/285), the electron density continued to increase toward the planet. On the other hand, the ion currents, the LP measured currents from the negative bias voltage, turn to decreasing inside 4RS, implying the density decrease of the ions. By comparing the observed LP ion current characteristics and the modeled values using the obtained electron density, we found that the characteristic ion mass can be several times larger than the water ions (AMU=18) that we expected in this region. During the orbit 015 (2005 doy-266/267), on the other hand, the LP observed sharp electron density drop near 3RS. The dust signals from the RPWS antenna showed the density enhancement of the μm sized grains coincide the electron density drop and we have estimated that the characteristic ion mass can exceed AMU=100. Throughout the whole Cassini observation near the equator inside 4RS, we didn't find the case with the ion densities larger than the electron densities as were found near the E ring and the Enceladus plume. We suggest that Saturn's plasmadisk inside the Enceladus orbit is dynamic in ion characteristics where the water molecules coagulate and grow into a small icy dust grains. In the presentation we discuss the relationship between the electron/ion density and the density of the nm and μm sized grains.

Electron density profile measurements at a self-focusing ion beam with high current density and low energy extracted through concave electrodes.

PubMed

Fujiwara, Y; Hirano, Y; Kiyama, S; Nakamiya, A; Koguchi, H; Sakakita, H

2014-02-01

The self-focusing phenomenon has been observed in a high current density and low energy ion beam. In order to study the mechanism of this phenomenon, a special designed double probe to measure the electron density and temperature is installed into the chamber where the high current density ion beam is injected. Electron density profile is successfully measured without the influence of the ion beam components. Estimated electron temperature and density are ∼0.9 eV and ∼8 × 10(8) cm(-3) at the center of ion beam cross section, respectively. It was found that a large amount of electrons are spontaneously accumulated in the ion beam line in the case of self-forcing state.

The molecular and electronic structure of s-tetrazine in the ground and first excited state: A theoretical investigation

NASA Astrophysics Data System (ADS)

Schütz, Martin; Hutter, Jürg; Lüthi, Hans Peter

1995-10-01

The ground- and first excited state of s-tetrazine arising from a π*←n excitation (1Ag,1B3u) have been studied using the complete active space (CASSCF) and the second order multiconfiguration perturbation theory (CASPT2) ab initio methods. The focus of this study is on the effect of the electronic excitation on the molecular structure and on those electronic properties which are important to model the solvatochromatic behavior of the molecule in polymer matrices as used in permanent hole burning experiments. Since the accurate computation of excited state molecular properties represents a major challenge for today's numerical quantum chemistry, some technical aspects are also considered. The present study shows that the change in geometry upon electronic excitation is small. This is in partial contradiction with the experimental studies which however disagree among themselves [see K. K. Innes, I. G. Ross, and W. R. Moomaw, J. Mol. Spectrosc. 132, 492 (1988), and R. E. Smalley, L. Wharton, and D. H. Levi, ibid. 66, 375 (1977)]. This study also confirms that the first excited state equilibrium structure is of D2h symmetry. In an earlier theoretical study it was found that the D2h symmetry structure may represent a saddle point rather than a minimum on the excited state potential surface [see A. C. Scheiner and H. F. Schaefer III, J. Chem. Phys. 87, 3539 (1987)]. In the first excited state, we observe an increase of the mean polarizability of s-tetrazine along with an enhanced anisotropy. The change in the polarizability is almost exclusively in the ``in-plane'' components of the tensor; the polarizability in the vertical direction is nearly unchanged. This observation questions recent experimental results reported for this molecule [see S. Heitz, D. Weidnauer, and A. Hese, J. Chem. Phys. 95, 7952 (1991)].

Transition and Electron Impact Excitation Collision Rates for O III

NASA Astrophysics Data System (ADS)

Tayal, S. S.; Zatsarinny, O.

2017-12-01

Transition probabilities, electron excitation collision strengths, and rate coefficients for a large number of O III lines over a broad wavelength range, from the infrared to ultraviolet, have been reported. The collision strengths have been calculated in the close-coupling approximation using the B-spline Breit-Pauli R-matrix method. The multiconfiguration Hartree-Fock method in combination with B-spline expansions is employed for an accurate representation of the target wave functions. The close-coupling expansion contains 202 O2+ fine-structure levels of the 2{s}22{p}2,2s2{p}3, 2{p}4,2{s}22p3s,3p,3d, 4s,4p,4d,4f,5s, and 2s2{p}33s,3p,3d configurations. The effective collision strengths are obtained by averaging electron excitation collision strengths over a Maxwellian distribution of velocities at electron temperatures ranging from 100 to 100,000 K. The calculated effective collision strengths have been reported for the 20,302 transitions between all 202 fine-structure levels. There is an overall good agreement with the recent R-matrix calculations by Storey et al. for the transitions between all levels of the ground 2{s}22{p}2 configuration, but significant discrepancies have been found with Palay et al. for transitions to the 2{s}22{p}2 1 S 0 level. Line intensity ratios between the optical lines arising from the 2{s}22{p}2{}3{P}{0,1,2} - 1 D 2 transitions have been compared with other calculations and observations from the photoionized gaseous nebulae, and good agreement is found. The present calculations provide the most complete and accurate data sets, which should allow a more detailed treatment of the available measured spectra from different ground and space observatories.

Device and method for relativistic electron beam heating of a high-density plasma to drive fast liners

DOEpatents

Thode, Lester E.

1981-01-01

A device and method for relativistic electron beam heating of a high-density plasma in a small localized region. A relativistic electron beam generator or accelerator produces a high-voltage electron beam which propagates along a vacuum drift tube and is modulated to initiate electron bunching within the beam. The beam is then directed through a low-density gas chamber which provides isolation between the vacuum modulator and the relativistic electron beam target. The relativistic beam is then applied to a high-density target plasma which typically comprises DT, DD, hydrogen boron or similar thermonuclear gas at a density of 10.sup.17 to 10.sup.20 electrons per cubic centimeter. The target gas is ionized prior to application of the electron beam by means of a laser or other preionization source to form a plasma. Utilizing a relativistic electron beam with an individual particle energy exceeding 3 MeV, classical scattering by relativistic electrons passing through isolation foils is negligible. As a result, relativistic streaming instabilities are initiated within the high-density target plasma causing the relativistic electron beam to efficiently deposit its energy and momentum into a small localized region of the high-density plasma target. Fast liners disposed in the high-density target plasma are explosively or ablatively driven to implosion by a heated annular plasma surrounding the fast liner which is generated by an annular relativistic electron beam. An azimuthal magnetic field produced by axial current flow in the annular plasma, causes the energy in the heated annular plasma to converge on the fast liner.

IV INTERNATIONAL CONFERENCE ON ATOM AND MOLECULAR PULSED LASERS (AMPL'99): Critical electron density in a self-contained copper vapour laser in the restricted pulse repetition rate

NASA Astrophysics Data System (ADS)

Yakovlenko, Sergei I.

2000-06-01

One of the mechanisms of the inversion breaking in copper vapour lasers caused by a high prepulse electron density is considered. Inversion breaking occurs at a critical electron density Ne cr. If the prepulse electron density exceeds Ne cr, the electron temperature Te cr cannot reach, during a plasma heating pulse, the temperature of ~2eV required for lasing. A simple estimate of Ne cr is made.

Vertical and Lateral Electron Content in the Martian Ionosphere

NASA Astrophysics Data System (ADS)

Paetzold, M. P.; Peter, K.; Bird, M. K.; Häusler, B.; Tellmann, S.

2016-12-01

The radio-science experiment MaRS (Mars Express Radio Science) on the Mars Express spacecraft sounds the neutral atmosphere and ionosphere of Mars since 2004. Approximately 800 vertical profiles of the ionospheric electron density have been acquired until today. The vertical electron content (TEC) is easily computed from the vertical electron density profile by integrating along the altitude. The TEC is typically a fraction of a TEC unit (1E16 m^-2) and depends on the solar zenith angle. The magnitude of the TEC is however fully dominated by the electron density contained in the main layer M2. The contributions by the M1 layer below M2 or the topside is marginal. MaRS is using two radio frequencies for the sounding of the ionosphere. The directly observed differential Doppler from the two received frequencies is a measure of the lateral electron content that means along the ray path and perpendicular to the vertical electron density profile. Combining both the vertical electron density profile, the vertical TEC and the directly observed lateral TEC describes the lateral electron density distribution in the ionosphere.

Investigation of mid-latitude electron density enhancement using total electron content measurements and FORMOSAT-3/COSMIC electron density profiles

NASA Astrophysics Data System (ADS)

Rajesh, P. K.; Nanan, Balan; Liu, Jann-Yenq; Lin, Charles C. H.; Chang, S. Y.; Chen, Chia-Hung

This study investigates the mid-latitude electron density enhancement (MEDE) using global ionospheric map (GIM) total electron content (TEC) measurements and FORMOSAT-3/COSMIC (F3/C) electron density profiles. Diurnal, seasonal, latitudinal, and solar activity variations in the occurrence and strength of MEDE are examined using global GIM TEC data in the years 2002 and 2009. The results show that MEDE occurrence is pronounced during 2200-0400 LT, the feature also appears during day. The strength of MEDE maximizes around 0400 LT, and is very weak during daytime. The occurrence and strength show significant longitude dependence, and vary with season and solar activity. Concurrent F3/C electron density profiles also reveal enhancement of the peak electron density and total electron content. Further studies are carried out by examining the role of neutral wind in re-organizing the plasma using SAMI2 and HWM93 models. The results indicate that meridional neutral wind could cause the plasma to converge over mid-latitudes, and thus support in maintaining the enhancement.

Analysis of Total Electron Content and Electron Density Profile during Different Geomagnetic Storms

NASA Astrophysics Data System (ADS)

Chapagain, N. P.; Rana, B.; Adhikari, B.

2017-12-01

Total Electron content (TEC) and electron density are the key parameters in the mitigation of ionospheric effects on radio communication system. Detail study of the TEC and electron density variations has been carried out during geomagnetic storms, with longitude and latitude, for four different locations: (13˚N -17˚N, 88˚E -98˚E), (30˚N-50˚N, 120˚W -95˚W), (29˚S-26˚S, 167˚W-163˚W,) and (60˚S-45˚S, 120˚W-105˚W) using the Gravity Recovery and Climate Experiment (GRACE) satellite observations. In order to find the geomagnetic activity, the solar wind parameters such as north-south component of inter planetary magnetic field (Bz), plasma drift velocity (Vsw), flow pressure (nPa), AE, Dst and Kp indices were obtained from Operating Mission as Nodes on the Internet (OMNI) web system. The data for geomagnetic indices have been correlated with the TEC and electron density for four different events of geomagnetic storms on 6 April 2008, 27 March 2008, 4 September 2008, and 11 October 2008. The result illustrates that the observed TEC and electron density profile significantly vary with longitudes and latitudes. This study illustrates that the values of TEC and the vertical electron density profile are influenced by the solar wind parameters associated with solar activities. The peak values of electron density and TEC increase as the geomagnetic storms become stronger. Similarly, the electron density profile varies with altitudes, which peaks around the altitude range of about 250- 350 km, depending on the strength of geomagnetic storms. The results clearly show that the peak electron density shifted to higher altitude (from about 250 km to 350 km) as the geomagnetic disturbances becomes stronger.

Profiles of Ionospheric Storm-enhanced Density during the 17 March 2015 Great Storm

NASA Astrophysics Data System (ADS)

Liu, J.; Wang, W.; Burns, A. G.; Yue, X.; Zhang, S.; Zhang, Y.

2015-12-01

Ionospheric F2 region peak densities (NmF2) are expected to show a positive phase correlation with total electron content (TEC), and electron density is expected to have an anti-correlation with electron temperature near the ionospheric F2 peak. However, we show that, during the 17 March 2015 great storm, TEC and F2 region electron density peak height (hmF2) over Millstone Hill increased, but the F2 region electron density peak (NmF2) decreased significantly during the storm-enhanced density (SED) phase of the storm compared with the quiet-time ionosphere. This SED occurred where there was a negative ionospheric storm near the F2 peak and below it. The weak ionosphere below the F2 peak resulted in much reduced downward heat conduction for the electrons, trapping the heat in the topside. This, in turn, increased the topside scale height, so that, even though electron densities at the F2 peak were depleted, TEC increased in the SED. The depletion in NmF2 was probably caused by an increase in the density of the molecular neutrals, resulting in enhanced recombination. In addition, the storm-time topside ionospheric electron density profile was much closer to diffusive equilibrium than non-storm time profile because of less daytime plasma flow from the ionosphere to the plasmasphere.

SU-G-JeP2-02: A Unifying Multi-Atlas Approach to Electron Density Mapping Using Multi-Parametric MRI for Radiation Treatment Planning

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

Ren, S; Tianjin University, Tianjin; Hara, W

Purpose: MRI has a number of advantages over CT as a primary modality for radiation treatment planning (RTP). However, one key bottleneck problem still remains, which is the lack of electron density information in MRI. In the work, a reliable method to map electron density is developed by leveraging the differential contrast of multi-parametric MRI. Methods: We propose a probabilistic Bayesian approach for electron density mapping based on T1 and T2-weighted MRI, using multiple patients as atlases. For each voxel, we compute two conditional probabilities: (1) electron density given its image intensity on T1 and T2-weighted MR images, and (2)more » electron density given its geometric location in a reference anatomy. The two sources of information (image intensity and spatial location) are combined into a unifying posterior probability density function using the Bayesian formalism. The mean value of the posterior probability density function provides the estimated electron density. Results: We evaluated the method on 10 head and neck patients and performed leave-one-out cross validation (9 patients as atlases and remaining 1 as test). The proposed method significantly reduced the errors in electron density estimation, with a mean absolute HU error of 138, compared with 193 for the T1-weighted intensity approach and 261 without density correction. For bone detection (HU>200), the proposed method had an accuracy of 84% and a sensitivity of 73% at specificity of 90% (AUC = 87%). In comparison, the AUC for bone detection is 73% and 50% using the intensity approach and without density correction, respectively. Conclusion: The proposed unifying method provides accurate electron density estimation and bone detection based on multi-parametric MRI of the head with highly heterogeneous anatomy. This could allow for accurate dose calculation and reference image generation for patient setup in MRI-based radiation treatment planning.« less

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

Finzel, Kati, E-mail: kati.finzel@liu.se

The local conditions for the Pauli potential that are necessary in order to yield self-consistent electron densities from orbital-free calculations are investigated for approximations that are expressed with the help of a local position variable. It is shown that those local conditions also apply when the Pauli potential is given in terms of the electron density. An explicit formula for the Ne atom is given, preserving the local conditions during the iterative procedure. The resulting orbital-free electron density exhibits proper shell structure behavior and is in close agreement with the Kohn-Sham electron density. This study demonstrates that it is possiblemore » to obtain self-consistent orbital-free electron densities with proper atomic shell structure from simple one-point approximations for the Pauli potential at local density level.« less

Relationship between the Geotail spacecraft potential and the magnetospheric electron number density including the distant tail regions

NASA Astrophysics Data System (ADS)

Ishisaka, K.; Okada, T.; Tsuruda, K.; Hayakawa, H.; Mukai, T.; Matsumoto, H.

2001-04-01

The spacecraft potential has been used to derive the electron number density surrounding the spacecraft in the magnetosphere and solar wind. We have investigated the correlation between the spacecraft potential of the Geotail spacecraft and the electron number density derived from the plasma waves in the solar wind and almost all the regions of the magnetosphere, except for the high-density plasmasphere, and obtained an empirical formula to show their relation. The new formula is effective in the range of spacecraft potential from a few volts up to 90 V, corresponding to the electron number density from 0.001 to 50 cm-3. We compared the electron number density obtained by the empirical formula with the density obtained by the plasma wave and plasma particle measurements. On occasions the density determined by plasma wave measurements in the lobe region is different from that calculated by the empirical formula. Using the difference in the densities measured by two methods, we discuss whether or not the lower cutoff frequency of the plasma waves, such as continuum radiation, indicates the local electron density near the spacecraft. Then we applied the new relation to the spacecraft potential measured by the Geotail spacecraft during the period from October 1993 to December 1995, and obtained the electron spatial distribution in the solar wind and magnetosphere, including the distant tail region. Higher electron number density is clearly observed on the dawnside than on the duskside of the magnetosphere in the distant tail beyond 100RE.

[Study on the distribution of plasma parameters in electrodeless lamp using emission spectrometry].

PubMed

Wang, Chang-Quan; Zhang, Gui-Xin; Wang, Xin-Xin; Shao, Ming-Song; Dong, Jin-Yang; Wang, Zan-Ji

2011-09-01

Electrodeless lamp in pear shape was ignited using inductively coupled discharge setup and Ar-Hg mixtures as working gas. The changes in electronic temperature and density with axial and radial positions at 5 s of igniting were studied by means of emission spectrometry. The changes in electronic temperature were obtained according to the Ar line intensity ratio of 425.9 nm/ 750.4 nm. And the variations in electronic density were analyzed using 750.4 nm line intensity. It was found that plasma electronic temperature and density is various at different axial or radial positions. The electronic temperatures first increase, then decrease, and then increase quickly, and finally decline. While the electronic density firstly increase quickly, the decrease, and then rise slowly and finally decline again with axial distance increasing. With radial distance increasing, electronic temperature increases to a stable area, then continues to rise, while electronic density decreases.

The Holographic Electron Density Theorem, de-quantization, re-quantization, and nuclear charge space extrapolations of the Universal Molecule Model

NASA Astrophysics Data System (ADS)

Mezey, Paul G.

2017-11-01

Two strongly related theorems on non-degenerate ground state electron densities serve as the basis of "Molecular Informatics". The Hohenberg-Kohn theorem is a statement on global molecular information, ensuring that the complete electron density contains the complete molecular information. However, the Holographic Electron Density Theorem states more: the local information present in each and every positive volume density fragment is already complete: the information in the fragment is equivalent to the complete molecular information. In other words, the complete molecular information provided by the Hohenberg-Kohn Theorem is already provided, in full, by any positive volume, otherwise arbitrarily small electron density fragment. In this contribution some of the consequences of the Holographic Electron Density Theorem are discussed within the framework of the "Nuclear Charge Space" and the Universal Molecule Model. In the Nuclear Charge Space" the nuclear charges are regarded as continuous variables, and in the more general Universal Molecule Model some other quantized parameteres are also allowed to become "de-quantized and then re-quantized, leading to interrelations among real molecules through abstract molecules. Here the specific role of the Holographic Electron Density Theorem is discussed within the above context.

Analysis of rapid increase in the plasma density during the ramp-up phase in a radio frequency negative ion source by large-scale particle simulation

NASA Astrophysics Data System (ADS)

Yasumoto, M.; Ohta, M.; Kawamura, Y.; Hatayama, A.

2014-02-01

Numerical simulations become useful for the developing RF-ICP (Radio Frequency Inductively Coupled Plasma) negative ion sources. We are developing and parallelizing a two-dimensional three velocity electromagnetic Particle-In-Cell code. The result shows rapid increase in the electron density during the density ramp-up phase. A radial electric field due to the space charge is produced with increase in the electron density and the electron transport in the radial direction is suppressed. As a result, electrons stay for a long period in the region where the inductive electric field is strong, and this leads efficient electron acceleration and a rapid increasing of the electron density.

Gedanken densities and exact constraints in density functional theory.

PubMed

Perdew, John P; Ruzsinszky, Adrienn; Sun, Jianwei; Burke, Kieron

2014-05-14

Approximations to the exact density functional for the exchange-correlation energy of a many-electron ground state can be constructed by satisfying constraints that are universal, i.e., valid for all electron densities. Gedanken densities are designed for the purpose of this construction, but need not be realistic. The uniform electron gas is an old gedanken density. Here, we propose a spherical two-electron gedanken density in which the dimensionless density gradient can be an arbitrary positive constant wherever the density is non-zero. The Lieb-Oxford lower bound on the exchange energy can be satisfied within a generalized gradient approximation (GGA) by bounding its enhancement factor or simplest GGA exchange-energy density. This enhancement-factor bound is well known to be sufficient, but our gedanken density shows that it is also necessary. The conventional exact exchange-energy density satisfies no such local bound, but energy densities are not unique, and the simplest GGA exchange-energy density is not an approximation to it. We further derive a strongly and optimally tightened bound on the exchange enhancement factor of a two-electron density, which is satisfied by the local density approximation but is violated by all published GGA's or meta-GGA's. Finally, some consequences of the non-uniform density-scaling behavior for the asymptotics of the exchange enhancement factor of a GGA or meta-GGA are given.

Effect of channel coupling on the elastic scattering of lithium isotopes

NASA Astrophysics Data System (ADS)

Furumoto, T.; Suhara, T.; Itagaki, N.

2018-04-01

Herein, we investigated the channel coupling (CC) effect on the elastic scatterings of lithium (Li) isotopes (A =6 -9) for 12C and 28Si targets at E /A =50 -60 MeV. The wave functions of the Li isotopes were obtained using the stochastic multi-configuration mixing method based on the microscopic-cluster model. The proton radii of the 7Li, 8Li, and 9Li nuclei became smaller as the number of valence neutrons increased. The valence neutrons in the 8Li and 9Li nuclei exhibited a glue-like behavior, thereby attracting the α and t clusters. Based on the transition densities derived from these microscopic wave functions, the elastic-scattering cross section was calculated using a microscopic coupled-channel method with a complex G -matrix interaction. The existing experimental data for the elastic scatterings of the Li isotopes and 10Be nuclei were well reproduced. The Li isotope elastic cross sections were demonstrated for the 12C and 28Si targets at E /A =53 MeV. The glue-like effect of the valence neutrons on the Li isotope was clearly demonstrated by the CC effect on elastic scattering. Finally, we realize that the valence neutrons stabilized the bindings of the core parts and the CC effect related to core excitation was indeed reduced.

Many-body excitations and deexcitations in trapped ultracold bosonic clouds

NASA Astrophysics Data System (ADS)

Theisen, Marcus; Streltsov, Alexej I.

2016-11-01

We employ the multiconfigurational time-dependent Hartree for bosons (MCTDHB) method to study excited states of interacting Bose-Einstein condensates confined by harmonic and double-well trap potentials. Two approaches to access excitations, one static and the other dynamic, are investigated and contrasted. In static simulations the low-lying excitations are computed by utilizing a linear-response theory constructed on top of a static MCTDHB solution (LR-MCTDHB). Complimentarily, we propose two dynamic protocols that address excitations by propagating the MCTDHB wave function. In particular, we investigate dipolelike oscillations induced by shifting the origin of the confining potential and breathinglike excitations by quenching the frequency of a parabolic part of the trap. To contrast static predictions and dynamic results we compute the time evolution and regard the respective Fourier transform of several local and nonlocal observables. Namely, we study the expectation value of the position operator , its variance Var [x (t )] , and a local density computed at selected positions. We find that the variance is the most sensitive and informative quantity: Along with excitations it contains information about deexcitations even in a linear regime of the induced dynamics. The dynamic protocols are found to access the many-body excitations predicted by the static LR-MCTDHB approach.

Synergy between optical and microwave remote sensing to derive soil and vegetation parameters from MAC Europe 1991 Experiment

NASA Technical Reports Server (NTRS)

Taconet, O.; Benallegue, M.; Vidal, A.; Vidal-Madjar, D.; Prevot, L.; Normand, M.

1993-01-01

The ability of remote sensing for monitoring vegetation density and soil moisture for agricultural applications is extensively studied. In optical bands, vegetation indices (NDVI, WDVI) in visible and near infrared reflectances are related to biophysical quantities as the leaf area index, the biomass. In active microwave bands, the quantitative assessment of crop parameters and soil moisture over agricultural areas by radar multiconfiguration algorithms remains prospective. Furthermore the main results are mostly validated on small test sites, but have still to be demonstrated in an operational way at a regional scale. In this study, a large data set of radar backscattering has been achieved at a regional scale on a French pilot watershed, the Orgeval, along two growing seasons in 1988 and 1989 (mainly wheat and corn). The radar backscattering was provided by the airborne scatterometer ERASME, designed at CRPE, (C and X bands and HH and VV polarizations). Empirical relationships to estimate water crop and soil moisture over wheat in CHH band under actual field conditions and at a watershed scale are investigated. Therefore, the algorithms developed in CHH band are applied for mapping the surface conditions over wheat fields using the AIRSAR and TMS images collected during the MAC EUROPE 1991 experiment. The synergy between optical and microwave bands is analyzed.

Mechanism of the OH Radical Addition to Adenine from Quantum-Chemistry Determinations of Reaction Paths and Spectroscopic Tracking of the Intermediates.

PubMed

Francés-Monerris, Antonio; Merchán, Manuela; Roca-Sanjuán, Daniel

2017-01-06

The OH radical is a well-known mediator in the oxidation of biological structures like DNA. Over the past decades, the precise events taking place after reaction of DNA nucleobases with OH radical have been widely investigated by the scientific community. Thirty years after the proposal of the main routes for the reaction of • OH with adenine ( Vieira , A. ; Steenken , S. J. Am. Chem. Soc. 1990 , 112 , 6986 - 6994 ), the present work demonstrates that the OH radical addition to C4 position is a minor pathway. Instead, the dehydration process is mediated by the A5OH adduct. Conclusions are based on density functional theory calculations for the ground-state reactivity and highly accurate multiconfigurational computations for the excited states of the radical intermediates. The methodology has been also used to study the mechanism giving rise to the mutagens 8-oxoA and FAPyA. Taking into account the agreement between the experimental data and the theoretical results, it is concluded that addition to the C5 and C8 positions accounts for at least ∼44.5% of the total • OH reaction in water solution. Finally, the current findings suggest that hydrophobicity in the DNA/RNA surroundings facilitates the formation of 8-oxoA and FAPyA.

Quantitative electron density characterization of soft tissue substitute plastic materials using grating-based x-ray phase-contrast imaging

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

Sarapata, A.; Chabior, M.; Zanette, I.

2014-10-15

Many scientific research areas rely on accurate electron density characterization of various materials. For instance in X-ray optics and radiation therapy, there is a need for a fast and reliable technique to quantitatively characterize samples for electron density. We present how a precise measurement of electron density can be performed using an X-ray phase-contrast grating interferometer in a radiographic mode of a homogenous sample in a controlled geometry. A batch of various plastic materials was characterized quantitatively and compared with calculated results. We found that the measured electron densities closely match theoretical values. The technique yields comparable results between amore » monochromatic and a polychromatic X-ray source. Measured electron densities can be further used to design dedicated X-ray phase contrast phantoms and the additional information on small angle scattering should be taken into account in order to exclude unsuitable materials.« less

Ion Densities in the Nightside Ionosphere of Mars: Effects of Electron Impact Ionization

NASA Astrophysics Data System (ADS)

Girazian, Z.; Mahaffy, P.; Lillis, R. J.; Benna, M.; Elrod, M.; Fowler, C. M.; Mitchell, D. L.

2017-11-01

We use observations from the Mars Atmosphere and Volatile EvolutioN (MAVEN) mission to show how superthermal electron fluxes and crustal magnetic fields affect ion densities in the nightside ionosphere of Mars. We find that due to electron impact ionization, high electron fluxes significantly increase the CO2+, O+, and O2+ densities below 200 km but only modestly increase the NO+ density. High electron fluxes also produce distinct peaks in the CO2+, O+, and O2+ altitude profiles. We also find that superthermal electron fluxes are smaller near strong crustal magnetic fields. Consequently, nightside ion densities are also smaller near strong crustal fields because they decay without being replenished by electron impact ionization. Furthermore, the NO+/O2+ ratio is enhanced near strong crustal fields because, in the absence of electron impact ionization, O2+ is converted into NO+ and not replenished. Our results show that electron impact ionization is a significant source of CO2+, O+, and O2+ in the nightside ionosphere of Mars.

Temporal-spatial measurement of electron relaxation time in femtosecond laser induced plasma using two-color pump-probe imaging technique

NASA Astrophysics Data System (ADS)

Pan, Changji; Jiang, Lan; Wang, Qingsong; Sun, Jingya; Wang, Guoyan; Lu, Yongfeng

2018-05-01

The femtosecond (fs) laser is a powerful tool to study ultrafast plasma dynamics, especially electron relaxation in strong ionization of dielectrics. Herein, temporal-spatial evolution of femtosecond laser induced plasma in fused silica was investigated using a two-color pump-probe technique (i.e., 400 nm and 800 nm, respectively). We demonstrated that when ionized electron density is lower than the critical density, free electron relaxation time is inversely proportional to electron density, which can be explained by the electron-ion scattering regime. In addition, electron density evolution within plasma was analyzed in an early stage (first 800 fs) of the laser-material interaction.

Ionospheric E-region electron density and neutral atmosphere variations

NASA Technical Reports Server (NTRS)

Stick, T. L.

1976-01-01

Electron density deviations from a basic variation with the solar zenith angle were investigated. A model study was conducted in which the effects of changes in neutral and relative densities of atomic and molecular oxygen on calculated electron densities were compared with incoherent scatter measurements in the height range 100-117 km at Arecibo, Puerto Rico. The feasibility of determining tides in the neutral atmosphere from electron density profiles was studied. It was determined that variations in phase between the density and temperature variation and the comparable magnitudes of their components make it appear improbable that the useful information on tidal modes can be obtained in this way.

Self-focusing and defocusing of Gaussian laser beams in collisional inhomogeneous plasmas with linear density and temperature ramps

NASA Astrophysics Data System (ADS)

Hashemzadeh, M.

2018-01-01

Self-focusing and defocusing of Gaussian laser beams in collisional inhomogeneous plasmas are investigated in the presence of various laser intensities and linear density and temperature ramps. Considering the ponderomotive force and using the momentum transfer and energy equations, the nonlinear electron density is derived. Taking into account the paraxial approximation and nonlinear electron density, a nonlinear differential equation, governing the focusing and defocusing of the laser beam, is obtained. Results show that in the absence of ramps the laser beam is focused between a minimum and a maximum value of laser intensity. For a certain value of laser intensity and initial electron density, the self-focusing process occurs in a temperature range which reaches its maximum at turning point temperature. However, the laser beam is converged in a narrow range for various amounts of initial electron density. It is indicated that the σ2 parameter and its sign can affect the self-focusing process for different values of laser intensity, initial temperature, and initial density. Finally, it is found that although the electron density ramp-down diverges the laser beam, electron density ramp-up improves the self-focusing process.

Molecular Electron Density Theory: A Modern View of Reactivity in Organic Chemistry.

PubMed

Domingo, Luis R

2016-09-30

A new theory for the study of the reactivity in Organic Chemistry, named Molecular Electron Density Theory (MEDT), is proposed herein. MEDT is based on the idea that while the electron density distribution at the ground state is responsible for physical and chemical molecular properties, as proposed by the Density Functional Theory (DFT), the capability for changes in electron density is responsible for molecular reactivity. Within MEDT, the reactivity in Organic Chemistry is studied through a rigorous quantum chemical analysis of the changes of the electron density as well as the energies associated with these changes along the reaction path in order to understand experimental outcomes. Studies performed using MEDT allow establishing a modern rationalisation and to gain insight into molecular mechanisms and reactivity in Organic Chemistry.

Communication: Near-locality of exchange and correlation density functionals for 1- and 2-electron systems

NASA Astrophysics Data System (ADS)

Sun, Jianwei; Perdew, John P.; Yang, Zenghui; Peng, Haowei

2016-05-01

The uniform electron gas and the hydrogen atom play fundamental roles in condensed matter physics and quantum chemistry. The former has an infinite number of electrons uniformly distributed over the neutralizing positively charged background, and the latter only one electron bound to the proton. The uniform electron gas was used to derive the local spin density approximation to the exchange-correlation functional that undergirds the development of the Kohn-Sham density functional theory. We show here that the ground-state exchange-correlation energies of the hydrogen atom and many other 1- and 2-electron systems are modeled surprisingly well by a different local spin density approximation (LSDA0). LSDA0 is constructed to satisfy exact constraints but agrees surprisingly well with the exact results for a uniform two-electron density in a finite, curved three-dimensional space. We also apply LSDA0 to excited or noded 1-electron densities, where it works less well. Furthermore, we show that the localization of the exact exchange hole for a 1- or 2-electron ground state can be measured by the ratio of the exact exchange energy to its optimal lower bound.

Two-dimensional electron density characterisation of arc interruption phenomenon in current-zero phase

NASA Astrophysics Data System (ADS)

Inada, Yuki; Kamiya, Tomoki; Matsuoka, Shigeyasu; Kumada, Akiko; Ikeda, Hisatoshi; Hidaka, Kunihiko

2018-01-01

Two-dimensional electron density imaging over free burning SF6 arcs and SF6 gas-blast arcs was conducted at current zero using highly sensitive Shack-Hartmann type laser wavefront sensors in order to experimentally characterise electron density distributions for the success and failure of arc interruption in the thermal reignition phase. The experimental results under an interruption probability of 50% showed that free burning SF6 arcs with axially asymmetric electron density profiles were interrupted with a success rate of 88%. On the other hand, the current interruption of SF6 gas-blast arcs was reproducibly achieved under locally reduced electron densities and the interruption success rate was 100%.

Photoionization of calcium

NASA Astrophysics Data System (ADS)

Deshmukh, Pranawa C.; Johnson, W. R.

1983-01-01

A study of the photoionization of calcium in the relativistic random-phase approximation is reported. Predictions of photoionization cross sections, angular distribution asymmetry parameters, and spin-polarization parameters for the 4s, 3p, and 3s subshells are made with emphasis on the energy region above the 3p32 threshold where multiconfigurational effects are not expected to be very important. Autoionization resonances below the 3s threshold and between the 3p32 and 3p12 thresholds are analyzed using the relativistic multichannel quantum-defect theory.

Intermittent electron density and temperature fluctuations and associated fluxes in the Alcator C-Mod scrape-off layer

NASA Astrophysics Data System (ADS)

Kube, R.; Garcia, O. E.; Theodorsen, A.; Brunner, D.; Kuang, A. Q.; LaBombard, B.; Terry, J. L.

2018-06-01

The Alcator C-Mod mirror Langmuir probe system has been used to sample data time series of fluctuating plasma parameters in the outboard mid-plane far scrape-off layer. We present a statistical analysis of one second long time series of electron density, temperature, radial electric drift velocity and the corresponding particle and electron heat fluxes. These are sampled during stationary plasma conditions in an ohmically heated, lower single null diverted discharge. The electron density and temperature are strongly correlated and feature fluctuation statistics similar to the ion saturation current. Both electron density and temperature time series are dominated by intermittent, large-amplitude burst with an exponential distribution of both burst amplitudes and waiting times between them. The characteristic time scale of the large-amplitude bursts is approximately 15 μ {{s}}. Large-amplitude velocity fluctuations feature a slightly faster characteristic time scale and appear at a faster rate than electron density and temperature fluctuations. Describing these time series as a superposition of uncorrelated exponential pulses, we find that probability distribution functions, power spectral densities as well as auto-correlation functions of the data time series agree well with predictions from the stochastic model. The electron particle and heat fluxes present large-amplitude fluctuations. For this low-density plasma, the radial electron heat flux is dominated by convection, that is, correlations of fluctuations in the electron density and radial velocity. Hot and dense blobs contribute only a minute fraction of the total fluctuation driven heat flux.

MAVEN Observations of Dayside Peak Electron Densities in the Ionosphere of Mars

NASA Astrophysics Data System (ADS)

Vogt, M. F.; Withers, P.; Andersson, L.; Mahaffy, P. R.; Benna, M.; Elrod, M. K.; Connerney, J. E. P.; Espley, J. R.; Eparvier, F. G.; Jakosky, B. M.

2016-12-01

The peak electron density in the dayside Martian ionosphere is a valuable diagnostic of the state of the ionosphere. Its dependence on factors like the solar zenith angle, ionizing solar irradiance, neutral scale height, and electron temperature has been well studied. The MAVEN spacecraft's September 2015 "deep dip" orbits, in which the orbital periapsis is lowered to 120 km, provided our first opportunity since Viking to sample in situ a complete dayside electron density profiles including the main peak, and the first observations with contemporaneous comprehensive measurements of the local plasma and magnetic field properties. We have analyzed the peak electron density measurements from the MAVEN deep dip orbits and will discuss their variability with various ionospheric properties, including the proximity to regions of large crustal magnetic fields, and external drivers. We will also present observations of the electron temperature and atmospheric neutral and ion composition at the altitude of the peak electron density.

Use of Total Electron Content data to analyze ionosphere electron density gradients

NASA Astrophysics Data System (ADS)

Nava, B.; Radicella, S. M.; Leitinger, R.; Coisson, P.

In presence of electron density gradients the thin shell approximation for the ionosphere used together with a simple mapping function to convert slant Total Electron Content TEC to vertical TEC could lead to TEC conversion errors Therefore these mapping function errors can be used to identify the effects of the electron density gradients in the ionosphere In the present work high precision GPS derived slant TEC data have been used to investigate the effects of the electron density gradients in the middle and low latitude ionosphere under geomagnetic quiet and disturbed conditions In particular the data corresponding to the geographic area of the American sector for the days 5-7 April 2000 have been used to perform a complete analysis of mapping function errors based on the coinciding pierce point technique The results clearly illustrate the electron density gradient effects according to the locations considered and to the actual levels of disturbance of the ionosphere

[Study of the effect of heat source separation distance on plasma physical properties in laser-pulsed GMAW hybrid welding based on spectral diagnosis technique].

PubMed

Liao, Wei; Hua, Xue-Ming; Zhang, Wang; Li, Fang

2014-05-01

In the present paper, the authors calculated the plasma's peak electron temperatures under different heat source separation distance in laser- pulse GMAW hybrid welding based on Boltzmann spectrometry. Plasma's peak electron densities under the corresponding conditions were also calculated by using the Stark width of the plasma spectrum. Combined with high-speed photography, the effect of heat source separation distance on electron temperature and electron density was studied. The results show that with the increase in heat source separation distance, the electron temperatures and electron densities of laser plasma did not changed significantly. However, the electron temperatures of are plasma decreased, and the electron densities of are plasma first increased and then decreased.

Observations of the electron density perturbation in the cusp irregularities during the ICI-2 campaign

NASA Astrophysics Data System (ADS)

Abe, Takumi; Moen, J. I.

The ICI-2 (Investigation of Cusp Irregularities-2) sounding rocket campaign was conducted in Svalbard, Norway on December 2008. The scientific objective of ICI-2 is to investigate genera-tion mechanism(s) of coherent HF radar backscatter targets. Strong coherent HF backscatter echoes are well-known phenomena in the polar ionospheric cusp, and are thought to result from field-aligned plasma irregularities with decameter scale length. However, the generation mech-anism of backscatter targets has not yet been understood, and even the altitude profile of HF cusp backscatter is unknown. The ICI-2 rocket was launched at 10:35:10 UT at Ny-˚lesund, A and reached an apogee of 330 km at about 5 minutes after the launch. All onboard systems functioned flawlessly. A comprehensive measurement of the electron density, low energy elec-tron flux, medium energy particle flux, AC and DC electric fields was conducted to exploit the potential role of the gradient drift instability versus the other suggested mechanisms. We present a result obtained from a Fixed-Biased Probe (FBP) which was aimed at measuring fine-scale (< 1 m) electron density perturbation. Our analysis of the FBP data during the rocket's flight indicates that the rocket traversed HF backscatter regions where the electron density perturbation is relatively large. The power spectrum analysis of the electron density shows that the amplitude increases not only in the decameter wavelength but also in the broad range of frequency. Characteristic features of the electron density perturbation are summarized as follows: 1) A strong perturbation of the electron density was observed by the FBP when the ICI-2 rocket passed through a front side of the poleward moving 630 nm emission region which was identified by the all-sky imager. This means that the electron density perturbation and the 630 nm emission are observed to coexist in the same region. 2) The absolute value of the electron density becomes larger in the disturbed region than in the surrounding region. The electron density gradient in the boundary with the outer region is larger in the equatorward side than in the poleward side. 3) The amplitude of the electron density perturbation is remarkably large in the equatorward edge rather than the poleward boundaries. 4) The FBP identified the electron density perturbation at three different altitudes during the rocket flight. This indicates that the perturbation likely exists not only within the narrow limits but in a larger extent in the vertical direction.

Exchange-correlation energies of atoms from efficient density functionals: influence of the electron density

DOE PAGES

Tao, Jianmin; Ye, Lin -Hui; Duan, Yuhua

2017-11-20

The primary goal of Kohn–Sham density functional theory is to evaluate the exchange-correlation contribution to electronic properties. However, the accuracy of a density functional can be affected by the electron density. Here we apply the nonempirical Tao–Mo (TM) semilocal functional to study the influence of the electron density on the exchange and correlation energies of atoms and ions, and compare the results with the commonly used nonempirical semilocal functionals local spin-density approximation (LSDA), Perdew–Burke–Ernzerhof (PBE), Tao–Perdew–Staroverov–Scuseria (TPSS), and hybrid functional PBE0. We find that the spin-restricted Hartree–Fock density yields the exchange and correlation energies in good agreement with the Optimizedmore » Effective Potential method, particularly for spherical atoms and ions. However, the errors of these semilocal and hybrid functionals become larger for self-consistent densities. We further find that the quality of the electron density have greater effect on the exchange-correlation energies of kinetic energy density-dependent meta-GGA functionals TPSS and TM than on those of the LSDA and GGA, and therefore, should have greater influence on the performance of meta-GGA functionals. Lastly, we show that the influence of the density quality on PBE0 is slightly reduced, compared to that of PBE, due to the exact mixing.« less

Exchange-correlation energies of atoms from efficient density functionals: influence of the electron density

NASA Astrophysics Data System (ADS)

Tao, Jianmin; Ye, Lin-Hui; Duan, Yuhua

2017-12-01

The primary goal of Kohn-Sham density functional theory is to evaluate the exchange-correlation contribution to electronic properties. However, the accuracy of a density functional can be affected by the electron density. Here we apply the nonempirical Tao-Mo (TM) semilocal functional to study the influence of the electron density on the exchange and correlation energies of atoms and ions, and compare the results with the commonly used nonempirical semilocal functionals local spin-density approximation (LSDA), Perdew-Burke-Ernzerhof (PBE), Tao-Perdew-Staroverov-Scuseria (TPSS), and hybrid functional PBE0. We find that the spin-restricted Hartree-Fock density yields the exchange and correlation energies in good agreement with the Optimized Effective Potential method, particularly for spherical atoms and ions. However, the errors of these semilocal and hybrid functionals become larger for self-consistent densities. We further find that the quality of the electron density have greater effect on the exchange-correlation energies of kinetic energy density-dependent meta-GGA functionals TPSS and TM than on those of the LSDA and GGA, and therefore, should have greater influence on the performance of meta-GGA functionals. Finally, we show that the influence of the density quality on PBE0 is slightly reduced, compared to that of PBE, due to the exact mixing.

Exchange-correlation energies of atoms from efficient density functionals: influence of the electron density

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

Tao, Jianmin; Ye, Lin -Hui; Duan, Yuhua

The primary goal of Kohn–Sham density functional theory is to evaluate the exchange-correlation contribution to electronic properties. However, the accuracy of a density functional can be affected by the electron density. Here we apply the nonempirical Tao–Mo (TM) semilocal functional to study the influence of the electron density on the exchange and correlation energies of atoms and ions, and compare the results with the commonly used nonempirical semilocal functionals local spin-density approximation (LSDA), Perdew–Burke–Ernzerhof (PBE), Tao–Perdew–Staroverov–Scuseria (TPSS), and hybrid functional PBE0. We find that the spin-restricted Hartree–Fock density yields the exchange and correlation energies in good agreement with the Optimizedmore » Effective Potential method, particularly for spherical atoms and ions. However, the errors of these semilocal and hybrid functionals become larger for self-consistent densities. We further find that the quality of the electron density have greater effect on the exchange-correlation energies of kinetic energy density-dependent meta-GGA functionals TPSS and TM than on those of the LSDA and GGA, and therefore, should have greater influence on the performance of meta-GGA functionals. Lastly, we show that the influence of the density quality on PBE0 is slightly reduced, compared to that of PBE, due to the exact mixing.« less

Environment, Ram Pressure, and Shell Formation in Holmberg II

NASA Astrophysics Data System (ADS)

Bureau, M.; Carignan, C.

2002-03-01

Neutral hydrogen VLA D-array observations of the dwarf irregular galaxy HoII, a prototype galaxy for studies of shell formation, are presented. These were extracted from the multiconfiguration data set of Puche and colleagues. H I is detected to radii over 16' or 4R25, almost a factor of 2 better than previous studies. The total H I mass MHI=6.44×108 Msolar. The integrated H I map has a comet-like appearance, with a large but faint component extending to the northwest and the H I appearing compressed on the opposite side. This suggests that HoII is affected by ram pressure from an intragroup medium (IGM). The velocity field shows a clear rotating disk pattern, and a rotation curve corrected for asymmetric drift was derived. However, the gas at large radii may not be in equilibrium. Puche and colleagues' multiconfiguration data were also reanalyzed, and it is shown that they overestimated their fluxes by over 20%. The rotation curve derived for HoII is well defined for r<~10 kpc. For 10<~r<~18 kpc, however, velocities are only defined on the approaching side, such that this part of the rotation curve should be used with caution. An analysis of the mass distribution, using the whole extent of this rotation curve, yields a total mass of 6.3×109 Msolar, of which ~80% is dark. Similarly to what is seen in many dwarfs, there is more luminous mass in H I than in stars. One peculiarity, however, is that luminous matter dominates within the optical body of the galaxy and dark matter only in the outer parts, analogous to what is seen in massive spirals rather than dwarfs. HoII lies northeast of the M81 Group's core, along with Kar 52 (M81 dwarf A) and UGC 4483. No signs of interaction are observed, however, and it is argued that HoII is part of the NGC 2403 subgroup, infalling toward M81. A case is made for ram pressure stripping and an IGM in the M81 Group. Stripping of the outer parts of the disk would require an IGM density nIGM>~4.0×10-6 atoms cm-3 at the location of HoII. This corresponds to ~1% of the virial mass of the group uniformly distributed over a volume just enclosing HoII and is consistent with the known X-ray properties of small groups. The H I tail is consistent with additional turbulent viscous stripping and evaporation, at least for low IGM temperatures. It is argued that existing observations of HoII do not support self-propagating star formation scenarios, whereby the H I holes and shells are created by supernova explosions and stellar winds. Many H I holes are located in low surface density regions of the disk, where no star formation is expected or observed. Alternative mechanisms are discussed, and it is suggested that ram pressure can help. Ram pressure has the capacity to enlarge preexisting holes and lower their creation energies, helping to bridge the gap between the observed star formation rate and that required to create the holes.

Electron energy distribution function in the divertor region of the COMPASS tokamak during neutral beam injection heating

NASA Astrophysics Data System (ADS)

Hasan, E.; Dimitrova, M.; Havlicek, J.; Mitošinková, K.; Stöckel, J.; Varju, J.; Popov, Tsv K.; Komm, M.; Dejarnac, R.; Hacek, P.; Panek, R.; the COMPASS Team

2018-02-01

This paper presents the results from swept probe measurements in the divertor region of the COMPASS tokamak in D-shaped, L-mode discharges, with toroidal magnetic field BT = 1.15 T, plasma current Ip = 180 kA and line-average electron densities varying from 2 to 8×1019 m-3. Using neutral beam injection heating, the electron energy distribution function is studied before and during the application of the beam. The current-voltage characteristics data are processed using the first-derivative probe technique. This technique allows one to evaluate the plasma potential and the real electron energy distribution function (respectively, the electron temperatures and densities). At the low average electron density of 2×1019 m-3, the electron energy distribution function is bi-Maxwellian with a low-energy electron population with temperatures 4-6 eV and a high-energy electron group 12-25 eV. As the line-average electron density is increased, the electron temperatures decrease. At line-average electron densities above 7×1019 m-3, the electron energy distribution function is found to be Maxwellian with a temperature of 6-8.5 eV. The effect of the neutral beam injection heating power in the divertor region is also studied.

Device and method for imploding a microsphere with a fast liner

DOEpatents

Thode, Lester E.

1981-01-01

A device and method for relativistic electron beam heating of a high-density plasma in a small localized region. A relativistic electron beam generator or accelerator produces a high-voltage electron beam which propagates along a vacuum drift tube and is modulated to initiate electron bunching within the beam. The beam is then directed through a low-density gas chamber which provides isolation between the vacuum modulator and the relativistic electron beam target. The relativistic beam is then applied to a high-density target plasma which typically comprises DT, DD, hydrogen boron or similar thermonuclear gas at a density of 10.sup.17 to 10.sup.20 electrons per cubic centimeter. The target gas is ionized prior to application of the electron beam by means of a laser or other preionization source to form a plasma. Utilizing a relativistic electron beam with an individual particle energy exceeding 3 MeV, classical scattering by relativistic electrons passing through isolation foils is negligible. As a result, relativistic streaming instabilities are initiated within the high-density target plasma causing the relativistic electron beam to efficiently deposit its energy and momentum into a small localized region of the high-density plasma target. Fast liners disposed in the high-density target plasma are explosively or ablatively driven to implosion by a heated annular plasma surrounding the fast liner generated by an annular relativistic electron beam. An azimuthal magnetic field produced by axial current flow in the annular plasma, causes the energy in the heated annular plasma to converge on the fast liner to drive the fast liner to implode a microsphere.

Quantitative contribution of molecular orbitals to hydrogen bonding in a water dimer: Electron density projected integral (EDPI) analysis

NASA Astrophysics Data System (ADS)

Zhang, Zhiyuan; Jiang, Wanrun; Wang, Bo; Wang, Zhigang

2017-06-01

We introduce the orbital-resolved electron density projected integral (EDPI) along the H-bond in the real space to quantitatively investigate the specific contribution from the molecular orbitals (MOs) aspect in (H2O)2. Calculation results show that, the electronic occupied orbital (HOMO-4) of (H2O)2 accounts for about surprisingly 40% of the electron density at the bond critical point. Moreover, the electronic density difference analysis visualizes the electron accumulating effect of the orbital interaction within the H-bond between water molecules, supporting its covalent-like character. Our work expands the understanding of H-bond with specific contributions from certain MOs.

2D microwave imaging reflectometer electronics.

PubMed

Spear, A G; Domier, C W; Hu, X; Muscatello, C M; Ren, X; Tobias, B J; Luhmann, N C

2014-11-01

A 2D microwave imaging reflectometer system has been developed to visualize electron density fluctuations on the DIII-D tokamak. Simultaneously illuminated at four probe frequencies, large aperture optics image reflections from four density-dependent cutoff surfaces in the plasma over an extended region of the DIII-D plasma. Localized density fluctuations in the vicinity of the plasma cutoff surfaces modulate the plasma reflections, yielding a 2D image of electron density fluctuations. Details are presented of the receiver down conversion electronics that generate the in-phase (I) and quadrature (Q) reflectometer signals from which 2D density fluctuation data are obtained. Also presented are details on the control system and backplane used to manage the electronics as well as an introduction to the computer based control program.

A tunable electron beam source using trapping of electrons in a density down-ramp in laser wakefield acceleration.

PubMed

Ekerfelt, Henrik; Hansson, Martin; Gallardo González, Isabel; Davoine, Xavier; Lundh, Olle

2017-09-25

One challenge in the development of laser wakefield accelerators is to demonstrate sufficient control and reproducibility of the parameters of the generated bunches of accelerated electrons. Here we report on a numerical study, where we demonstrate that trapping using density down-ramps allows for tuning of several electron bunch parameters by varying the properties of the density down-ramp. We show that the electron bunch length is determined by the difference in density before and after the ramp. Furthermore, the transverse emittance of the bunch is controlled by the steepness of the ramp. Finally, the amount of trapped charge depends both on the density difference and on the steepness of the ramp. We emphasize that both parameters of the density ramp are feasible to vary experimentally. We therefore conclude that this tunable electron accelerator makes it suitable for a wide range of applications, from those requiring short pulse length and low emittance, such as the free-electron lasers, to those requiring high-charge, large-emittance bunches to maximize betatron X-ray generation.

Electron density studies of methyl cellobioside

USDA-ARS?s Scientific Manuscript database

Experimental X-ray diffraction crystallography determines the variations in electron density that result from the periodic array of atoms in a crystal. Normally, the positions and type of atom are determined from the electron density based on an approximation that the atoms are spherical. However, t...

Thermal imaging diagnostics of high-current electron beams.

PubMed

Pushkarev, A; Kholodnaya, G; Sazonov, R; Ponomarev, D

2012-10-01

The thermal imaging diagnostics of measuring pulsed electron beam energy density is presented. It provides control of the electron energy spectrum and a measure of the density distribution of the electron beam cross section, the spatial distribution of electrons with energies in the selected range, and the total energy of the electron beam. The diagnostics is based on the thermal imager registration of the imaging electron beam thermal print in a material with low bulk density and low thermal conductivity. Testing of the thermal imaging diagnostics has been conducted on a pulsed electron accelerator TEU-500. The energy of the electrons was 300-500 keV, the density of the electron current was 0.1-0.4 kA/cm(2), the duration of the pulse (at half-height) was 60 ns, and the energy in the pulse was up to 100 J. To register the thermal print, a thermal imager Fluke-Ti10 was used. Testing showed that the sensitivity of a typical thermal imager provides the registration of a pulsed electron beam heat pattern within one pulse with energy density over 0.1 J/cm(2) (or with current density over 10 A/cm(2), pulse duration of 60 ns and electron energy of 400 keV) with the spatial resolution of 0.9-1 mm. In contrast to the method of using radiosensitive (dosimetric) materials, thermal imaging diagnostics does not require either expensive consumables, or plenty of processing time.

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

Raymund, T.D.

Recently, several tomographic techniques for ionospheric electron density imaging have been proposed. These techniques reconstruct a vertical slice image of electron density using total electron content data. The data are measured between a low orbit beacon satellite and fixed receivers located along the projected orbital path of the satellite. By using such tomographic techniques, it may be possible to inexpensively (relative to incoherent scatter techniques) image the ionospheric electron density in a vertical plane several times per day. The satellite and receiver geometry used to measure the total electron content data causes the data to be incomplete; that is, themore » measured data do not contain enough information to completely specify the ionospheric electron density distribution in the region between the satellite and the receivers. A new algorithm is proposed which allows the incorporation of other complementary measurements, such as those from ionosondes, and also includes ways to include a priori information about the unknown electron density distribution in the reconstruction process. The algorithm makes use of two-dimensional basis functions. Illustrative application of this algorithm is made to simulated cases with good results. The technique is also applied to real total electron content (TEC) records collected in Scandinavia in conjunction with the EISCAT incoherent scatter radar. The tomographic reconstructions are compared with the incoherent scatter electron density images of the same region of the ionosphere.« less

Modeling photoabsorption of the asFP595 chromophore.

PubMed

Bravaya, Ksenia B; Bochenkova, Anastasia V; Granovsky, Alexander A; Savitsky, Alexander P; Nemukhin, Alexander V

2008-09-18

The fluorescent protein asFP595 is a promising photoswitchable biomarker for studying processes in living cells. We present the results of a high level theoretical study of photoabsorption properties of the model asFP595 chromophore molecule in biologically relevant protonation states: anionic, zwitterionic, and neutral. Ground state equilibrium geometry parameters are optimized in the PBE0/(aug)-cc-pVDZ density functional theory approximation. An augmented version of multiconfigurational quasidegenerate perturbation theory (aug-MCQDPT2) following the state-averaged CASSCF/(aug)-cc-pVDZ calculations is used to estimate the vertical S0-S1 excitation energies for all chromophore species. An accuracy of this approach is validated by comparing the computed estimates of the S0-S1 absorption maximum of the closely related chromophore from the DsRed protein to the known experimental value in the gas phase. An influence of the CASSCF active space on the aug-MCQDPT2 excitation energies is analyzed. The zwitterionic form of the asFP595 chromophore is found to be the most sensitive to a particular choice and amount of active orbitals. This observation is explained by the charge-transfer type of the S0-S1 transition involving the entire conjugated pi-electron system for the zwitterionic protonation state. According to the calculation results, the anionic form in the trans conformation is found to possess the most red-shifted absorption band with the maximum located at 543 nm. The bands of the zwitterionic and neutral forms are considerably blue-shifted compared to those of the anionic form. These conclusions are at variance with the results obtained in the TDDFT approximation for the asFP595 chromophore. The absorption wavelengths computed in the aug-MCQDPT2/CASSCF theory are as follows: 543 (535), 470 (476), and 415 (417) nm for the anionic, zwitterionic, and neutral forms of the trans and cis (in parentheses) isomers of the asFP595 chromophore. These data can be used as a reference for further theoretical studies of the asFP595 chromophore in different media and for modeling photoabsorption properties of the asFP595 fluorescent protein.

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

Verheest, Frank, E-mail: frank.verheest@ugent.be; School of Chemistry and Physics, University of KwaZulu-Natal, Durban 4000; Hellberg, Manfred A., E-mail: hellberg@ukzn.ac.za

The propagation of arbitrary amplitude electron-acoustic solitons and double layers is investigated in a plasma containing cold positive ions, cool adiabatic and hot isothermal electrons, with the retention of full inertial effects for all species. For analytical tractability, the resulting Sagdeev pseudopotential is expressed in terms of the hot electron density, rather than the electrostatic potential. The existence domains for Mach numbers and hot electron densities clearly show that both rarefactive and compressive solitons can exist. Soliton limitations come from the cool electron sonic point, followed by the hot electron sonic point, until a range of rarefactive double layers occurs.more » Increasing the relative cool electron density further yields a switch to compressive double layers, which ends when the model assumptions break down. These qualitative results are but little influenced by variations in compositional parameters. A comparison with a Boltzmann distribution for the hot electrons shows that only the cool electron sonic point limit remains, giving higher maximum Mach numbers but similar densities, and a restricted range in relative hot electron density before the model assumptions are exceeded. The Boltzmann distribution can reproduce neither the double layer solutions nor the switch in rarefactive/compressive character or negative/positive polarity.« less

Talbot-Lau x-ray deflectometer electron density diagnostic for laser and pulsed power high energy density plasma experiments (invited).

PubMed

Valdivia, M P; Stutman, D; Stoeckl, C; Mileham, C; Begishev, I A; Theobald, W; Bromage, J; Regan, S P; Klein, S R; Muñoz-Cordovez, G; Vescovi, M; Valenzuela-Villaseca, V; Veloso, F

2016-11-01

Talbot-Lau X-ray deflectometry (TXD) has been developed as an electron density diagnostic for High Energy Density (HED) plasmas. The technique can deliver x-ray refraction, attenuation, elemental composition, and scatter information from a single Moiré image. An 8 keV Talbot-Lau interferometer was deployed using laser and x-pinch backlighters. Grating survival and electron density mapping were demonstrated for 25-29 J, 8-30 ps laser pulses using copper foil targets. Moiré pattern formation and grating survival were also observed using a copper x-pinch driven at 400 kA, ∼1 kA/ns. These results demonstrate the potential of TXD as an electron density diagnostic for HED plasmas.

Talbot-Lau X-ray Deflectometer electron density diagnostic for laser and pulsed power high energy density plasma experiments

DOE PAGES

Valdivia, M. P.; Stutman, D.; Stoeckl, C.; ...

2016-04-21

Talbot-Lau X-ray Deflectometry has been developed as an electron density diagnostic for High Energy Density plasmas. The technique can deliver x-ray refraction, attenuation, elemental composition, and scatter information from a single Moiré image. An 8 keV Talbot-Lau interferometer was deployed using laser and x-pinch backlighters. Grating survival and electron density mapping was demonstrated for 25-29 J, 8-30 ps laser pulses using copper foil targets. Moire pattern formation and grating survival was also observed using a copper x-pinch driven at 400 kA, ~1 kA/ns. Lastly, these results demonstrate the potential of TXD as an electron density diagnostic for HED plasmas.

Tracing the Fingerprint of Chemical Bonds within the Electron Densities of Hydrocarbons: A Comparative Analysis of the Optimized and the Promolecule Densities.

PubMed

Keyvani, Zahra Alimohammadi; Shahbazian, Shant; Zahedi, Mansour

2016-10-18

The equivalence of the molecular graphs emerging from the comparative analysis of the optimized and the promolecule electron densities in two hundred and twenty five unsubstituted hydrocarbons was recently demonstrated [Keyvani et al. Chem. Eur. J. 2016, 22, 5003]. Thus, the molecular graph of an optimized molecular electron density is not shaped by the formation of the C-H and C-C bonds. In the present study, to trace the fingerprint of the C-H and C-C bonds in the electron densities of the same set of hydrocarbons, the amount of electron density and its Laplacian at the (3, -1) critical points associated with these bonds are derived from both optimized and promolecule densities, and compared in a newly proposed comparative analysis. The analysis not only conforms to the qualitative picture of the electron density build up between two atoms upon formation of a bond in between, but also quantifies the resulting accumulation of the electron density at the (3, -1) critical points. The comparative analysis also reveals a unified mode of density accumulation in the case of 2318 studied C-H bonds, but various modes of density accumulation are observed in the case of 1509 studied C-C bonds and they are classified into four groups. The four emerging groups do not always conform to the traditional classification based on the bond orders. Furthermore, four C-C bonds described as exotic bonds in previous studies, for example the inverted C-C bond in 1,1,1-propellane, are naturally distinguished from the analysis. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Modern Possibilities for Calculating Some Properties of Molecules and Crystals from the Experimental Electron Density

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

Stash, A.I.; Tsirelson, V.G.

2005-03-01

Methods for calculating some properties of molecules and crystals from the electron density reconstructed from a precise X-ray diffraction experiment using the multipole model are considered. These properties include, on the one hand, the characteristics of the electron density and the inner-crystal electrostatic field and, on the other hand, the local electronic energies (kinetic, potential, total), the exchange energy density, the electron-pair localization function, the localized-orbital locator, the effective crystal potential, and others. It is shown that the integration of these characteristics over pseudoatomic volumes bounded by the surfaces of the zero flux of the electron density gradient makes itmore » possible to characterize directly from an experiment the properties of molecules and crystals in terms of the atomic contributions. The computer program WinXPRO2004, realizing these possibilities, is briefly described.« less

Topology of the electron density of d0 transition metal compounds at subatomic resolution.

PubMed

Batke, Kilian; Eickerling, Georg

2013-11-14

Accurate X-ray diffraction experiments allow for a reconstruction of the electron density distribution of solids and molecules in a crystal. The basis for the reconstruction of the electron density is in many cases a multipolar expansion of the X-ray scattering factors in terms of spherical harmonics, a so-called multipolar model. This commonly used ansatz splits the total electron density of each pseudoatom in the crystal into (i) a spherical core, (ii) a spherical valence, and (iii) a nonspherical valence contribution. Previous studies, for example, on diamond and α-silicon have already shown that this approximation is no longer valid when ultrahigh-resolution diffraction data is taken into account. We report here the results of an analysis of the calculated electron density distribution in the d(0) transition metal compounds [TMCH3](2+) (TM = Sc, Y, and La) at subatomic resolution. By a detailed molecular orbital analysis, it is demonstrated that due to the radial nodal structure of the 3d, 4d, and 5d orbitals involved in the TM-C bond formation a significant polarization of the electron density in the inner electronic shells of the TM atoms is observed. We further show that these polarizations have to be taken into account by an extended multipolar model in order to recover accurate electron density distributions from high-resolution structure factors calculated for the title compounds.

Use of total electron content data to analyze ionosphere electron density gradients

NASA Astrophysics Data System (ADS)

Nava, B.; Radicella, S. M.; Leitinger, R.; Coïsson, P.

In the presence of electron density gradients the thin shell approximation for the ionosphere, used together with a simple mapping function to convert slant total electron content (TEC) to vertical TEC, could lead to TEC conversion errors. These "mapping function errors" can therefore be used to detect the electron density gradients in the ionosphere. In the present work GPS derived slant TEC data have been used to investigate the effects of the electron density gradients in the middle and low latitude ionosphere under geomagnetic quiet and disturbed conditions. In particular the data corresponding to the geographic area of the American Sector for the days 5-7 April 2000 have been used to perform a complete analysis of mapping function errors based on the "coinciding pierce point technique". The results clearly illustrate the electron density gradient effects according to the locations considered and to the actual levels of disturbance of the ionosphere. In addition, the possibility to assess an ionospheric shell height able to minimize the mapping function errors has been verified.

Atomic data of intermediate autoionzing Rydberg series nf[K]J (n = 4, 5), nd[K]J (n = 5, 6), np[K]J (n = 6, 7) and ns[K]J (n = 7, 8) of neutral argon atom in the multiconfiguration Dirac-Hartree-Fock framework

NASA Astrophysics Data System (ADS)

Hassouneh, Ola; Salah, Wa'el

2017-07-01

We report the results of an accurate computation of the energy levels, oscillator strengths f_{ij}, the radiative transition rates A_{ij}, the Landé g-factor, the magnetic dipole and the electric quadrupole hyperfine constants of the intermediate Rydberg series nf[K]J (n = 4, 5), nd[K]J (n = 5, 6), np[K]J (n = 6, 7) and ns[K]J (n = 7, 8) relative to the ground state 3p6 1S0 for neutral argon atom spectra based on the multiconfiguration Dirac-Hartree-Fock (MCDHF) approach. In this approach, the quantum electrodynamics (QED) effects with transverse photon Breit interaction and vacuum photon polarization self-energy corrections are included. Moreover, the perturbation due to the core-polarization and electron correlation effects are taken into account. We also reported the oscillator strengths and transition rates in Coulomb and Babushkin gauges for the 3p5(2P)3d-3p5(2P)4f, 3p5(2P)3d-3p5(2P)5f, 3p5(2P)4d-3p5(2P)4f, 3p5(2P)4d-3p5(2P)5f, 3p5(2P)5d-3p5(2P)4f, 3p5(2P)5d-3p5(2P)5f, 3p5(2P)6d-3p5(2P)4f and 3p5(2P)6d-3p5(2P)5f transition arrays as well as the 3p5(2P)5d-3p5(2P)6p, 3p5(2P)7s-3p5(2P)6p, 3p5(2P)7s-3p5(2P)7p and 3p5(2P)8s-3p5(2P)7p transition arrays. Insofar as experimental or theoretical values by other authors exist, comparison is made with those values; it turns out that, for most of the levels, a rather satisfying agreement with these experimental and theoretical results is obtained, thus confirming the reliability of our data.

Model studies of hydrogen atom addition and abstraction processes involving ortho-, meta-, and para-benzynes.

PubMed

Clark, A E; Davidson, E R

2001-10-31

H-atom addition and abstraction processes involving ortho-, meta-, and para-benzyne have been investigated by multiconfigurational self-consistent field methods. The H(A) + H(B)...H(C) reaction (where r(BC) is adjusted to mimic the appropriate singlet-triplet energy gap) is shown to effectively model H-atom addition to benzyne. The doublet multiconfiguration wave functions are shown to mix the "singlet" and "triplet" valence bond structures of H(B)...H(C) along the reaction coordinate; however, the extent of mixing is dependent on the singlet-triplet energy gap (DeltaE(ST)) of the H(B)...H(C) diradical. Early in the reaction, the ground-state wave function is essentially the "singlet" VB function, yet it gains significant "triplet" VB character along the reaction coordinate that allows H(A)-H(B) bond formation. Conversely, the wave function of the first excited state is predominantly the "triplet" VB configuration early in the reaction coordinate, but gains "singlet" VB character when the H-atom is close to a radical center. As a result, the potential energy surface (PES) for H-atom addition to triplet H(B)...H(C) diradical is repulsive! The H3 model predicts, in agreement with the actual calculations on benzyne, that the singlet diradical electrons are not coupled strongly enough to give rise to an activation barrier associated with C-H bond formation. Moreover, this model predicts that the PES for H-atom addition to triplet benzyne will be characterized by a repulsive curve early in the reaction coordinate, followed by a potential avoided crossing with the (pi)1(sigma*)1 state of the phenyl radical. In contrast to H-atom addition, large activation barriers characterize the abstraction process in both the singlet ground state and first triplet state. In the ground state, this barrier results from the weakly avoided crossing of the dominant VB configurations in the ground-state singlet (S0) and first excited singlet (S1) because of the large energy gap between S0 and S1 early in the reaction coordinate. Because the S1 state is best described as the combination of the triplet X-H bond and the triplet H(B)...H(C) spin couplings, the activation barrier along the S0 abstraction PES will have much less dependence on the DeltaE(ST) of H(B)...H(C) than previously speculated. For similar reasons, the T1 potential surface is quite comparable to the S0 PES.

Experimental investigation of mode transitions in asymmetric capacitively coupled radio-frequency Ne and CF4 plasmas

NASA Astrophysics Data System (ADS)

Liu, Gang-Hu; Liu, Yong-Xin; Bai, Li-Shui; Zhao, Kai; Wang, You-Nian

2018-02-01

The dependence of the electron density and the emission intensity on external parameters during the transitions of the electron power absorption mode is experimentally studied in asymmetric electropositive (neon) and electronegative (CF4) capacitively coupled radio-frequency plasmas. The spatio-temporal distribution of the emission intensity is measured with phase resolved optical emission spectroscopy and the electron density at the discharge center is measured by utilizing a floating hairpin probe. In neon discharge, the emission intensity increases almost linearly with the rf voltage at all driving frequencies covered here, while the variation of the electron density with the rf voltage behaves differently at different driving frequencies. In particular, the electron density increases linearly with the rf voltage at high driving frequencies, while at low driving frequencies the electron density increases slowly at the low-voltage side and, however, grows rapidly, when the rf voltage is higher than a certain value, indicating a transition from α to γ mode. The rf voltage, at which the mode transition occurs, increases with the decrease of the driving frequency/the working pressure. By contrast, in CF4 discharge, three different electron power absorption modes can be observed and the electron density and emission intensity do not exhibit a simple dependence on the rf voltage. In particular, the electron density exhibits a minimum at a certain rf voltage when the electron power absorption mode is switching from drift-ambipolar to the α/γ mode. A minimum can also be found in the emission intensity at a higher rf voltage when a discharge is switching into the γ mode.

Marshall N. Rosenbluth Outstanding Doctoral Thesis Award Talk: Simultaneous Measurement of Electron Temperature and Density Fluctuations in the Core of DIII-D Plasmas

NASA Astrophysics Data System (ADS)

White, A. E.

2009-11-01

Multi-field fluctuation measurements provide opportunities for rigorous comparison between experiment and nonlinear gyrokinetic turbulence simulations. A unique set of diagnostics on DIII-D allows for simultaneous study of local, long-wavelength (0 < kθρs< 0.5) electron temperature and density fluctuations in the core plasma (0.4 < ρ< 0.8). Previous experiments in L-mode indicate that normalized electron temperature fluctuation levels (40 < f < 400,kHz) increase with radius from ˜0.4% at ρ= 0.5 to ˜2% at ρ=0.8, similar to simultaneously measured density fluctuations. Electron cyclotron heating (ECH) is used to increase Te, which increases electron temperature fluctuation levels and electron heat transport in the experiments. In contrast, long wavelength density fluctuation levels change very little. The different responses are consistent with increased TEM drive relative to ITG-mode drive. A new capability at DIII-D is the measurement of phase angle between electron temperature and density fluctuations using coupled correlation electron cyclotron emission radiometer and reflectometer diagnostics. Linear and nonlinear GYRO runs have been used to design validation experiments that focus on measurements of the phase angle. GYRO shows that if Te and ∇Te increase 50% in a beam-heated L-mode plasma (ρ=0.5), then the phase angle between electron temperature and density fluctuations decreases 30%-50% and electron temperature fluctuation levels increase a factor of two more than density fluctuations. Comparisons between these predictions and experimental results will be presented.

Phosphorus and carrier density of heavily n-type doped germanium

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

Takinai, K.; Wada, K.

2016-05-14

The threshold current density of n-type, tensile-strained Ge lasers strongly depends on the electron density. Although optical net gain analyses indicate that the optimum electron density should be on the order of 1 × 10{sup 20} cm{sup −3} to get the lowest threshold, it is not a simple task to increase the electron density beyond the mid range of 10{sup 19} cm{sup −3}. The present paper analyzes the phenomenon where electron density is not proportional to phosphorus donor density, i.e., “saturation” phenomenon, by applying the so-called amphoteric defect model. The analyses indicate that the saturation phenomenon can be well explained by the charge compensationmore » between the phosphorus donors (P{sup +}) and doubly negative charged Ge vacancies (V{sup 2−}).« less

Viking Doppler noise used to determine the radial dependence of electron density in the extended corona

NASA Technical Reports Server (NTRS)

Berman, A. L.; Wackley, J. A.; Rockwell, S. T.; Kwan, M.

1977-01-01

The common form for radial dependence of electron density in the extended corona is given. By assuming proportionality between Doppler noise and integrated signal path electron density, Viking Doppler noise can be used to solve for a numerical value of X.

Brain Tissue Compartment Density Estimated Using Diffusion-Weighted MRI Yields Tissue Parameters Consistent With Histology

PubMed Central

Sepehrband, Farshid; Clark, Kristi A.; Ullmann, Jeremy F.P.; Kurniawan, Nyoman D.; Leanage, Gayeshika; Reutens, David C.; Yang, Zhengyi

2015-01-01

We examined whether quantitative density measures of cerebral tissue consistent with histology can be obtained from diffusion magnetic resonance imaging (MRI). By incorporating prior knowledge of myelin and cell membrane densities, absolute tissue density values were estimated from relative intra-cellular and intra-neurite density values obtained from diffusion MRI. The NODDI (neurite orientation distribution and density imaging) technique, which can be applied clinically, was used. Myelin density estimates were compared with the results of electron and light microscopy in ex vivo mouse brain and with published density estimates in a healthy human brain. In ex vivo mouse brain, estimated myelin densities in different sub-regions of the mouse corpus callosum were almost identical to values obtained from electron microscopy (Diffusion MRI: 42±6%, 36±4% and 43±5%; electron microscopy: 41±10%, 36±8% and 44±12% in genu, body and splenium, respectively). In the human brain, good agreement was observed between estimated fiber density measurements and previously reported values based on electron microscopy. Estimated density values were unaffected by crossing fibers. PMID:26096639

Self-injection of electrons in a laser-wakefield accelerator by using longitudinal density ripple

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

Dahiya, Deepak; Sharma, A. K.; Sajal, Vivek

By introducing a longitudinal density ripple (periodic modulation in background plasma density), we demonstrate self-injection of electrons in a laser-wakefield accelerator. The wakefield driven plasma wave, in presence of density ripple excites two side band waves of same frequency but different wave numbers. One of these side bands, having smaller phase velocity compared to wakefield driven plasma wave, preaccelerates the background plasma electrons. Significant number of these preaccelerated electrons get trapped in the laser-wakefield and further accelerated to higher energies.

Density functional theory and an experimentally-designed energy functional of electron density.

PubMed

Miranda, David A; Bueno, Paulo R

2016-09-21

We herein demonstrate that capacitance spectroscopy (CS) experimentally allows access to the energy associated with the quantum mechanical ground state of many-electron systems. Priorly, electrochemical capacitance, C [small mu, Greek, macron] [ρ], was previously understood from conceptual and computational density functional theory (DFT) calculations. Thus, we herein propose a quantum mechanical experiment-based variational method for electron charging processes based on an experimentally-designed functional of the ground state electron density. In this methodology, the electron state density, ρ, and an energy functional of the electron density, E [small mu, Greek, macron] [ρ], can be obtained from CS data. CS allows the derivative of the electrochemical potential with respect to the electron density, (δ[small mu, Greek, macron][ρ]/δρ), to be obtained as a unique functional of the energetically minimised system, i.e., β/C [small mu, Greek, macron] [ρ], where β is a constant (associated with the size of the system) and C [small mu, Greek, macron] [ρ] is an experimentally observable quantity. Thus the ground state energy (at a given fixed external potential) can be obtained simply as E [small mu, Greek, macron] [ρ], from the experimental measurement of C [small mu, Greek, macron] [ρ]. An experimental data-set was interpreted to demonstrate the potential of this quantum mechanical experiment-based variational principle.

Evolution of Field-Aligned Electron and Ion Densities From Whistler Mode Radio Soundings During Quiet to Moderately Active Period and Comparisons With SAMI2 Simulations

NASA Astrophysics Data System (ADS)

Reddy, A.; Sonwalkar, V. S.; Huba, J. D.

2018-02-01

Knowledge of field-aligned electron and ion distributions is necessary for understanding the physical processes causing variations in field-aligned electron and ion densities. Using whistler mode sounding by Radio Plasma Imager/Imager for Magnetopause-to-Aurora Global Exploration (RPI/IMAGE), we determined the evolution of dayside electron and ion densities along L ˜ 2 and L ˜ 3 (90-4,000 km) during a 7 day (21-27 November 2005) geomagnetically quiet to moderately active period. Over this period the O+/H+ transition height was ˜880 ± 60 km and ˜1000 ± 100 km, respectively, at L ˜ 2 and L ˜ 3. The electron density varied in a complex manner; it was different at L ˜ 2 and L ˜ 3 and below and above the O+/H+ transition height. The measured electron and ion densities are consistent with those from Challenging Minisatellite Payload (CHAMP) and Defense Meteorological Satellite Program (DMSP) and other past measurements, but they deviated from bottomside sounding and International Reference Ionosphere (IRI) 2012 empirical model results. Using SAMI2 (Naval Research Laboratory (NRL) ionosphere model) with reasonably adjusted values of inputs (neutral densities, winds, electric fields, and photoelectron heating), we simulated the evolution of O+/H+ transition height and field-aligned electron and ion densities so that a fair agreement was obtained between the simulation results and observations. Simulation studies indicated that reduced neutral densities (H and/or O) with time limited O+-H charge exchange process. This reduction in neutral densities combined with changes in neutral winds and plasma temperature led to the observed variations in the electron and ion densities. The observation/simulation method presented here can be extended to investigate the role of neutral densities and composition, disturbed winds, and prompt penetration electric fields in the storm time ionosphere/plasmasphere dynamics.

Characterization of an F-center in an alkali halide cluster

NASA Astrophysics Data System (ADS)

Bader, R. F. W.; Platts, J. A.

1997-11-01

The removal of a fluorine atom from its central position in a cubiclike Li14F13+ cluster creates an F-center vacancy that may or may not be occupied by the remaining odd electron. The topology exhibited by the electron density in Li14F12+, the F-center cluster, enables one to make a clear distinction between the two possible forms that the odd electron can assume. If it possesses a separate identity, then a local maximum in the electron density will be found within the vacancy and the F-center will behave quantum mechanically as an open system, bounded by a surface of local zero flux in the gradient vector field of the electron density. If, however, the density of the odd electron is primarily delocalized onto the neighboring ions, then a cage critical point, a local minimum in the density, will be found at the center of the vacancy. Without an associated local maximum, the vacancy has no boundary and is undefined. Self-consistent field (SCF) calculations with geometry optimization of the Li14F13+ cluster and of the doublet state of Li14F12+ show that the creation of the central vacancy has only a minor effect upon the geometry of the cluster, the result of a local maximum in the electron density being formed within the vacancy. Thus the F-center is the physical manifestation of a non-nuclear attractor in the electron density. It is consequently a proper open system with a definable set of properties, the most characteristic being its low kinetic energy per electron. In addition to determining the properties of the F-center, the effect of its formation on the energies, volumes, populations, both electron and spin, and electron localizations of the ions in the cluster are determined.

Cyclic evolution of the electron temperature and density in dusty low-pressure radio frequency plasmas with pulsed injection of hexamethyldisiloxane

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

Garofano, V.; Stafford, L., E-mail: luc.stafford@umontreal.ca, E-mail: kremena.makasheva@laplace.univ-tlse.fr; Despax, B.

2015-11-02

Optical emission spectroscopy was used to analyze the very-low-frequency cyclic evolution of the electron energy and density caused by repetitive formation and loss of dust nanoparticles in argon plasmas with pulsed injection of hexamethyldisiloxane (HMDSO, [CH{sub 3}]{sub 6}Si{sub 2}O). After elaborating a Boltzmann diagram for Ar high-lying levels and a collisional-radiative model for Ar 2p (Paschen notation) states, temperatures characterizing the low- and high-energy parts of the electron population were calculated. Relative electron densities were also estimated from relative line emission intensities. Both temperatures increase when the dust occupation increases, and then decrease when dust is lost. The opposite trendmore » was observed for the electron density. Such cyclic behaviors of the electron energy and electron density in the HMDSO-containing plasmas are in good agreement with the evolution processes in dusty plasmas, in which the formation of negative ions followed by an electron attachment on the surfaces of the nanoparticles is a critical phenomenon driving dust growth.« less

Effective mass in bilayer graphene at low carrier densities: The role of potential disorder and electron-electron interaction

NASA Astrophysics Data System (ADS)

Li, J.; Tan, L. Z.; Zou, K.; Stabile, A. A.; Seiwell, D. J.; Watanabe, K.; Taniguchi, T.; Louie, Steven G.; Zhu, J.

2016-10-01

In a two-dimensional electron gas, the electron-electron interaction generally becomes stronger at lower carrier densities and renormalizes the Fermi-liquid parameters, such as the effective mass of carriers. We combine experiment and theory to study the effective masses of electrons and holes me* and mh* in bilayer graphene in the low carrier density regime on the order of 1 ×1011c m-2 . Measurements use temperature-dependent low-field Shubnikov-de Haas oscillations observed in high-mobility hexagonal boron nitride supported samples. We find that while me* follows a tight-binding description in the whole density range, mh* starts to drop rapidly below the tight-binding description at a carrier density of n =6 ×1011c m-2 and exhibits a strong suppression of 30% when n reaches 2 ×1011c m-2 . Contributions from the electron-electron interaction alone, evaluated using several different approximations, cannot explain the experimental trend. Instead, the effect of the potential fluctuation and the resulting electron-hole puddles play a crucial role. Calculations including both the electron-electron interaction and disorder effects explain the experimental data qualitatively and quantitatively. This Rapid Communication reveals an unusual disorder effect unique to two-dimensional semimetallic systems.

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

DOE PAGES

Hubertus J. J. van Dam

2016-04-27

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

Robust Estimation of Electron Density From Anatomic Magnetic Resonance Imaging of the Brain Using a Unifying Multi-Atlas Approach

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

Ren, Shangjie; Department of Radiation Oncology, Stanford University School of Medicine, Palo Alto, California; Hara, Wendy

Purpose: To develop a reliable method to estimate electron density based on anatomic magnetic resonance imaging (MRI) of the brain. Methods and Materials: We proposed a unifying multi-atlas approach for electron density estimation based on standard T1- and T2-weighted MRI. First, a composite atlas was constructed through a voxelwise matching process using multiple atlases, with the goal of mitigating effects of inherent anatomic variations between patients. Next we computed for each voxel 2 kinds of conditional probabilities: (1) electron density given its image intensity on T1- and T2-weighted MR images; and (2) electron density given its spatial location in a referencemore » anatomy, obtained by deformable image registration. These were combined into a unifying posterior probability density function using the Bayesian formalism, which provided the optimal estimates for electron density. We evaluated the method on 10 patients using leave-one-patient-out cross-validation. Receiver operating characteristic analyses for detecting different tissue types were performed. Results: The proposed method significantly reduced the errors in electron density estimation, with a mean absolute Hounsfield unit error of 119, compared with 140 and 144 (P<.0001) using conventional T1-weighted intensity and geometry-based approaches, respectively. For detection of bony anatomy, the proposed method achieved an 89% area under the curve, 86% sensitivity, 88% specificity, and 90% accuracy, which improved upon intensity and geometry-based approaches (area under the curve: 79% and 80%, respectively). Conclusion: The proposed multi-atlas approach provides robust electron density estimation and bone detection based on anatomic MRI. If validated on a larger population, our work could enable the use of MRI as a primary modality for radiation treatment planning.« less

Experimental charge density analysis of a gallium(I) N-heterocyclic carbene analogue.

PubMed

Overgaard, Jacob; Jones, Cameron; Dange, Deepak; Platts, James A

2011-09-05

The experimental electron density of the only known example of a four-membered Ga(I) N-heterocyclic carbene analogue has been determined by multipole modeling of 90 K X-ray diffraction data and compared to theoretical data. In order to obtain a satisfactory model, it is necessary to modify the radial dependency of the core electrons of Ga using two separate scaling parameters for s,p- and d-electrons. Evidence for significant lone-pair density on Ga is found in the electron density and derived properties despite the partial positive charge of this atom. Static deformation density and molecular electrostatic potential clearly show a directional lone pair on Ga, whereas the Laplacian of the total electron density does not; this feature is, however, present in the Laplacian of the valence-only density. The Ga center also acts as an acceptor in four intramolecular C-H···Ga contacts, whose nature is probed by density properties. Substantial covalent character is apparent in the Ga-N bonds, but no sign of donation from filled N p-orbitals to empty Ga p-orbitals is found, whereas π-delocalization over the organic ligand is evident. This study highlights the utility of experimental charge density analysis as a technique to investigate the unusual bonding and electronic characteristics of low oxidation state/low coordinate p-block complexes.

Use of large-scale multi-configuration EMI measurements to characterize heterogeneous subsurface structures and their impact on crop productivity

NASA Astrophysics Data System (ADS)

Brogi, Cosimo; Huisman, Johan Alexander; Kaufmann, Manuela Sarah; von Hebel, Christian; van der Kruk, Jan; Vereecken, Harry

2017-04-01

Soil subsurface structures can play a key role in crop performance, especially during water stress periods. Geophysical techniques like electromagnetic induction EMI have been shown to be able of providing information about dominant shallow subsurface features. However, previous work with EMI has typically not reached beyond the field scale. The objective of this study is to use large-scale multi-configuration EMI to characterize patterns of soil structural organization (layering and texture) and the associated impact on crop vegetation at the km2 scale. For this, we carried out an intensive measurement campaign and collected high spatial resolution multi-configuration EMI data on an agricultural area of approx. 1 km2 (102 ha) near Selhausen (North Rhine-Westphalia, Germany) with a maximum depth of investigation of around 2.5 m. We measured using two EMI instruments simultaneously with a total of nine coil configurations. The instruments were placed inside polyethylene sleds that were pulled by an all-terrain-vehicle along parallel lines with a spacing of 2 to 2.5 m. The driving speed was between 5 and 7 km h-1 and we used a 0.2 Hz sampling frequency to obtain an in-line resolution of approximately 0.3 m. The survey area consists of almost 50 different fields managed in different way. The EMI measurements were collected between April and December 2016 within a few days after the harvest of each field. After data acquisition, EMI data were automatically filtered, temperature corrected, and interpolated onto a common grid. The resulting EMI maps allowed us to identify three main areas with different subsurface heterogeneities. The differences between these areas are likely related to the late quaternary geological history (Pleistocene and Holocene) of the area that resulted in spatially variable soil texture and layering, which has a strong impact on spatio-temporal soil water content variability. The high resolution surveys also allowed us to identify small scale geomorphological structures as well as anthropogenic activities such as soil management and drainage networks carried out in the last 150 years. To identify areas with similar subsurface structures with high spatial resolution, we applied multiband image classification using the nine coil configurations as bands of a single image. We compared both supervised and unsupervised classification and obtained promising preliminary results showing a good degree of conformity between EMI supervised classification maps and observed patterns in plant productivity.

Novel quantitative calibration approach for multi-configuration electromagnetic induction (EMI) systems using data acquired at multiple elevations

NASA Astrophysics Data System (ADS)

Tan, Xihe; Mester, Achim; von Hebel, Christian; van der Kruk, Jan; Zimmermann, Egon; Vereecken, Harry; van Waasen, Stefan

2017-04-01

Electromagnetic induction (EMI) systems offer a great potential to obtain highly resolved layered electrical conductivity models of the shallow subsurface. State-of-the-art inversion procedures require quantitative calibration of EMI data, especially for short-offset EMI systems where significant data shifts are often observed. These shifts are caused by external influences such as the presence of the operator, zero-leveling procedures, the field setup used to move the EMI system and/or cables close by. Calibrations can be performed by using collocated electrical resistivity measurements or taking soil samples, however, these two methods take a lot of time in the field. To improve the calibration in a fast and concise way, we introduce a novel on-site calibration method using a series of apparent electrical conductivity (ECa) values acquired at multiple elevations for a multi-configuration EMI system. No additional instrument or pre-knowledge of the subsurface is needed to acquire quantitative ECa data. By using this calibration method, we correct each coil configuration, i.e., transmitter and receiver coil separation and the horizontal or vertical coplanar (HCP or VCP) coil orientation with a unique set of calibration parameters. A multi-layer soil structure at the corresponding measurement location is inverted together with the calibration parameters using full-solution Maxwell equations for the forward modelling within the shuffled complex evolution (SCE) algorithm to find the optimum solution under a user-defined parameter space. Synthetic data verified the feasibility for calibrating HCP and VCP measurements of a custom made six-coil EMI system with coil offsets between 0.35 m and 1.8 m for quantitative data inversions. As a next step, we applied the calibration approach on acquired experimental data from a bare soil test field (Selhausen, Germany) for the considered EMI system. The obtained calibration parameters were applied to measurements over a 30 m transect line that covers a range of conductivities between 5 and 40 mS/m. Inverted calibrated EMI data of the transect line showed very similar electrical conductivity distributions and layer interfaces of the subsurface compared to reference data obtained from vertical electrical sounding (VES) measurements. These results show that a combined calibration and inversion of multi-configuration EMI data is possible when including measurements at different elevations, which will speed up the measurement process to obtain quantitative EMI data since the labor intensive electrical resistivity measurement or soil coring is not necessary anymore.

Teaching Chemistry with Electron Density Models.

ERIC Educational Resources Information Center

Shusterman, Gwendolyn P.; Shusterman, Alan J.

1997-01-01

Describes a method for teaching electronic structure and its relevance to chemical phenomena that relies on computer-generated three-dimensional models of electron density distributions. Discusses the quantum mechanical background needed and presents ways of using models of electronic ground states to teach electronic structure, bonding concepts,…

Peculiarities of electron density distribution in bismuth chalcogenides, iron pnictides, cuprates and related unconventional superconductors

NASA Astrophysics Data System (ADS)

Orlov, V. G.; Sergeev, G. S.

2018-05-01

With the aim to reveal the origin of instabilities in the electron subsystem of unconventional superconductors, such as stripes or nematic symmetry breaking, electron band structure calculations were performed for a number of bismuth chalcogenides, bismuth oxide, iron pnictides, as well as for Bi2Sr2CaCu2O8, YBa2Cu3O7 and La2CuO4. It was found that bond critical points in the electron density distribution ρ(r) of all the studied compounds were characterized by positive sign of electron density Laplacian evidencing on depletion of electron charge from the area of bond critical points. A correlation was found between the Tc and the value of electron density Laplacian in the strongest bond critical points of superconductors and related substances.

Uncovering the nonadiabatic response of geosynchronous electrons to geomagnetic disturbance

USGS Publications Warehouse

Gannon, Jennifer; Elkington, Scot R.; Onsager, Terrance G.

2012-01-01

We describe an energy spectrum method for scaling electron integral flux, which is measured at a constant energy, to phase space density at a constant value of the first adiabatic invariant which removes much of the variation due to reversible adiabatic effects. Applying this method to nearly a solar cycle (1995 - 2006) of geosynchronous electron integral flux (E>2.0MeV) from the GOES satellites, we see that much of the diurnal variation in electron phase space density at constant energy can be removed by the transformation to phase space density at constant μ (4000 MeV/G). This allows us a clearer picture of underlying non-adiabatic electron population changes due to geomagnetic activity. Using scaled phase space density, we calculate the percentage of geomagnetic storms resulting in an increase, decrease or no change in geosynchronous electrons as 38%, 7%, and 55%, respectively. We also show examples of changes in the electron population that may be different than the unscaled fluxes alone suggest. These examples include sudden electron enhancements during storms which appear during the peak of negative Dst for μ-scaled phase space density, contrary to the slow increase seen during the recovery phase for unscaled phase space density for the same event.

Experimental investigations of driving frequency effect in low-pressure capacitively coupled oxygen discharges

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

Liu, Jia; Liu, Yong-Xin; Liu, Gang-Hu

2015-04-14

The effect of driving frequency on the electron density is investigated in low-pressure capacitively coupled oxygen plasmas by utilizing a floating hairpin probe. The power absorbed by the plasma is investigated and it is found that the power lost in the matching network can reach 50% or higher under certain conditions. The effect of driving frequency on the electron density is studied from two aspects, i.e., constant absorbed power and electrode voltage. In the former case, the electron density increases with the driving frequency increasing from 13.56 to 40.68 MHz and slightly changes depending on the gas pressures with the frequencymore » further increasing to 100 MHz. In the latter case, the electron density rapidly increases when the driving frequency increases from 13.56 to 40.68 MHz, and then decreases with the frequency further increasing to 100 MHz. The electron series resonance is observed at 40.68 MHz and can be attributed to the higher electron density. And the standing wave effect also plays an important role in increasing electron density at 100 MHz and 2.6 Pa.« less

The impact of spherical symmetry assumption on radio occultation data inversion in the ionosphere: An assessment study

NASA Astrophysics Data System (ADS)

Shaikh, M. M.; Notarpietro, R.; Nava, B.

2014-02-01

'Onion-peeling' is a very common technique used to invert Radio Occultation (RO) data in the ionosphere. Because of the implicit assumption of spherical symmetry for the electron density (N(e)) distribution in the ionosphere, the standard Onion-peeling algorithm could give erroneous concentration values in the retrieved electron density profile. In particular, this happens when strong horizontal ionospheric electron density gradients are present, like for example in the Equatorial Ionization Anomaly (EIA) region during high solar activity periods. In this work, using simulated RO Total Electron Content (TEC) data computed by means of the NeQuick2 ionospheric electron density model and ideal RO geometries, we tried to formulate and evaluate an asymmetry level index for quasi-horizontal TEC observations. The asymmetry index is based on the electron density variation that a signal may experience along its path (satellite to satellite link) in a RO event and is strictly dependent on the occultation geometry (e.g. azimuth of the occultation plane). A very good correlation has been found between the asymmetry index and errors related to the inversion products, in particular those concerning the peak electron density NmF2 estimate and the Vertical TEC (VTEC) evaluation.

Hyperfine induced transition probabilities from 4{f}^{14}5s5p{}^{3}{{\\rm{P}}}_{0,2}^{o} states in Sm-like ions

NASA Astrophysics Data System (ADS)

Zhou, Fuyang; Li, Jiguang; Qu, Yizhi; Wang, Jianguo

2017-11-01

The hyperfine induced 4{f}145s5p{}3{{{P}}}0,2o-4{f}145{s}2{}1{{{S}}}0 transition probabilities for highly charged Sm-like ions are calculated within the framework of the multiconfiguration Dirac-Hartree-Fock method. Electron correlation, the Breit interaction and quantum electrodynamical effects are taken into account. For ions ranging from Z = 79 to Z=94,4{f}145s5p{}3{{{P}}}0o is the first excited state, and the hyperfine induced transition (HIT) is a dominant decay channel. For the 4{f}145s5p{}3{{{P}}}2o state, the HIT rates of Sm-like ions with Z=82-94 are reported as well as the magnetic dipole (M1) {}3{{{P}}}2o-{}3{{{P}}}1o, the electric quadrupole (E2) {}3{{{P}}}2o-{}3{{{P}}}0,1o, and the magnetic quadrupole (M2) {}3{{{P}}}2o-{}1{{{S}}}0 transition probabilities. It is found that M1 transition from the 4{f}145s5p{}3{{{P}}}2o state is the most important decay channel in this range on Z≥slant 82.

Modeling Photoelectron Spectra of CuO, Cu2O, and CuO2 Anions with Equation-of-Motion Coupled-Cluster Methods: An Adventure in Fock Space.

PubMed

Orms, Natalie; Krylov, Anna I

2018-04-12

The experimental photoelectron spectra of di- and triatomic copper oxide anions have been reported previously. We present an analysis of the experimental spectra of the CuO - , Cu 2 O - , and CuO 2 - anions using equation-of-motion coupled-cluster (EOM-CC) methods. The open-shell electronic structure of each molecule demands a unique combination of EOM-CC methods to achieve an accurate and balanced representation of the multiconfigurational anionic- and neutral-state manifolds. Analysis of the Dyson orbitals associated with photodetachment from CuO - reveals the strong non-Koopmans character of the CuO states. For the lowest detachment energy, a good agreement between theoretical and experimental values is obtained with CCSD(T) (coupled-cluster with single and double excitations and perturbative account of triple excitations). The (T) correction is particularly important for Cu 2 O - . Use of a relativistic pseudopotential and matching basis set improves the quality of results in most cases. EOM-DIP-CCSD analysis of the low-lying states of CuO 2 - reveals multiple singlet and triplet anionic states near the triplet ground state, adding an extra layer of complexity to the interpretation of the experimental CuO 2 - photoelectron spectrum.

Extreme ultraviolet and soft x-ray spectral lines in Rb XXIX

NASA Astrophysics Data System (ADS)

Indu, Khatri; Arun, Goyal; Sunny, Aggarwal; A, K. Singh; Man, Mohan

2016-03-01

An extensive theoretical set of atomic data for Rb XXIX in a wide range with L-shell electron excitations to the M-shell has been reported. We have computed energy levels for the lowest 113 fine structure levels of Rb XXIX. The fully relativistic multiconfigurational Dirac-Fock method (MCDF) within the framework of Dirac-Coulomb Hamiltonian taking quantum electrodynamics (QED) and Breit corrections into account has been adopted for calculations. Radiative data are reported for electric dipole (E1), magnetic dipole (M1), electric quadrupole (E2), and magnetic quadrupole (M2) transitions from the ground level, although calculations have been performed for a much larger number of levels. To assess the accuracy of results, we performed analogous calculations using flexible atomic code (FAC). Comparisons are made with existing available results and a good agreement has been achieved. Most of the wavelengths calculated lie in the soft x-ray (SXR) region. Lifetimes for all 113 levels have also been provided for the first time. Additionally, we have provided the spectra for allowed transitions from n = 2 to n = 3 within the x-ray region and also compared our SXR photon wavelengths with experimentally recognized wavelengths. We hope that our results will be beneficial in fusion plasma research and astrophysical applications.

Orbital order and effective mass enhancement in t2 g two-dimensional electron gases

NASA Astrophysics Data System (ADS)

Tolsma, John; Principi, Alessandro; Polini, Marco; MacDonald, Allan

2015-03-01

It is now possible to prepare d-electron two-dimensional electron gas systems that are confined near oxide heterojunctions and contain t2 g electrons with a density much smaller than one electron per metal atom. I will discuss a generic model that captures all qualitative features of electron-electron interaction physics in t2 g two-dimensional electron gas systems, and the use of a GW approximation to explore t2 g quasiparticle properties in this new context. t2 g electron gases contain a high density isotropic light mass xy component and low-density xz and yz anisotropic components with light and heavy masses in orthogonal directions. The high density light mass band screens interactions within the heavy bands. As a result the wave vector dependence of the self-energy is reduced and the effective mass is increased. When the density in the heavy bands is low, the difference in anisotropy between the two heavy bands favors orbital order. When orbital order does not occur, interactions still reshape the heavy-band Fermi surfaces. I will discuss these results in the context of recently reported magnetotransport experiments.

Effects of meteoric smoke particles on the D region ion chemistry

NASA Astrophysics Data System (ADS)

Baumann, Carsten; Rapp, Markus; Anttila, Milla; Kero, Antti; Verronen, Pekka T.

2015-12-01

This study focuses on meteor smoke particle (MSP) induced effects on the D region ion chemistry. Hereby, MSPs, represented with an 11 bin size distribution, have been included as an active component into the Sodankyä Ion and Neutral Chemistry model. By doing that, we model the diurnal variation of the negatively and positively charged MSPs as well as ions and the electron density under quiet ionospheric conditions. Two distinct points in time are studied in more detail, i.e., one for sunlit conditions (Solar zenith angle is 72°) and one for dark conditions (Solar zenith angle is 103°). We find nightly decrease of free electrons and negative ions, the positive ion density is enhanced at altitudes above 80 km and reduced below. During sunlit conditions the electron density is enhanced between 60 and 70 km altitude, while there is a reduction in negative and positive ions densities. In general, the MSP influence on the ion chemistry is caused by changes in the electron density. On the one hand, these changes occur due to nightly electron scavenging by MSPs resulting in a reduced electron-ion recombination. As a consequence positive ion density increase, especially water cluster ions are highly affected. On the other hand, the electron density is slightly increased during daytime by a MSP-related production due to solar radiation. Thus, more electrons attach to neutrals and short-lived negative ions increase in number density. The direct attachment of ions to MSPs is a minor process, but important for long living ions.

Variations of plasmaspheric field-aligned electron and ion densities (90-4000 km) during quiet to moderately active (Kp < 4) geomagnetic conditions

NASA Astrophysics Data System (ADS)

Sonwalkar, V. S.; Reddy, A.

2017-12-01

Variation in field-aligned electron and ion densities as a function of geomagnetic activity are important parameters in the physics of the thermosphere-ionosphere-magnetosphere coupling. Using whistler mode sounding from IMAGE, we report variations in field-aligned electron density and O+/H+ transition height (HT) during two periods (16-23 Aug 2005; 24 Sep-06 Oct 2005) when geomagnetic conditions were quiet (maximum Kp in the past 24 hours, Kpmax,24 ≤ 2) to moderately active (2 < Kpmax,24 <4). The measurements were obtained in the L=1.7 to 3.3 range (90- 4000 km, 13 or 15 MLT). Our results show that, under similar geomagnetic activity, at similar L-shells but with different geographic longitudes and MLTs, the O+/H+ transition height varied within ±12% of 1100 km at L 2 and within ±8% of 1350 km at L 3. The electron densities along flux tubes varied within 30% and 20%, respectively, below (including F2 peak) and above HT. With increasing L shell: (a) O+/H+ transition height increased; (b) electron density variations below HT including F2 peak showed no trend; (c) electron density above HT decreased. For flux tubes at similar longitudes, L-shells, and MLT's, relative to quiet time, during moderate geomagnetic activity: (1) O+/H+ transition height was roughly same; (2) electron density variations below HT showed no trend; (3) electron density above HT increased ( 10-40 %). The measured electron density is in agreement with in situ measurements from CHAMP (350 km) and DMSP (850 km) and past space borne (e. g., ISIS) measurements but the F2 peak density is a factor of 2 lower relative to that measured by ground ionosondes and that predicted by IRI-2012 empirical model. The measured transition height is consistent with OGO 4, Explorer 31, and C/NOFS measurements but is lower than that from IRI-2012. The observed variations in electron density at F2 peak are consistent with past work and are attributed to solar, geomagnetic, and meteorological causes [e. g. Risibeth and Mendillo, 2001; Forbes et al., 2000]. To the best of our knowledge, variations in field-aligned electron density above transition height at mid-latitudes during quiet to moderately active periods have not been reported in the past. Further investigation using physics based models (e. g., SAMI3) is required to explain the observed variations.

Talbot-Lau x-ray deflectometer electron density diagnostic for laser and pulsed power high energy density plasma experiments (invited)

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

Valdivia, M. P., E-mail: mpvaldivia@pha.jhu.edu; Stutman, D.; Stoeckl, C.

2016-11-15

Talbot-Lau X-ray deflectometry (TXD) has been developed as an electron density diagnostic for High Energy Density (HED) plasmas. The technique can deliver x-ray refraction, attenuation, elemental composition, and scatter information from a single Moiré image. An 8 keV Talbot-Lau interferometer was deployed using laser and x-pinch backlighters. Grating survival and electron density mapping were demonstrated for 25–29 J, 8–30 ps laser pulses using copper foil targets. Moiré pattern formation and grating survival were also observed using a copper x-pinch driven at 400 kA, ∼1 kA/ns. These results demonstrate the potential of TXD as an electron density diagnostic for HED plasmas.

Electron density measurements in STPX plasmas

NASA Astrophysics Data System (ADS)

Clark, Jerry; Williams, R.; Titus, J. B.; Mezonlin, E. D.; Akpovo, C.; Thomas, E.

2017-10-01

Diagnostics have been installed to measure the electron density of Spheromak Turbulent Physics Experiment (STPX) plasmas at Florida A. & M. University. An insertable probe, provided by Auburn University, consisting of a combination of a triple-tipped Langmuir probe and a radial array consisting of three ion saturation current / floating potential rings has been installed to measure instantaneous plasma density, temperature and plasma potential. As the ramp-up of the experimental program commences, initial electron density measurements from the triple-probe show that the electron density is on the order of 1019 particles/m3. For a passive measurement, a CO2 interferometer system has been designed and installed for measuring line-averaged densities and to corroborate the Langmuir measurements. We describe the design, calibration, and performance of these diagnostic systems on large volume STPX plasmas.

Using Satellite Radio-Sounding Data to Investigate Variations in the Earth's Topside Ionosphere Electron Density Profiles in the Polar Regions

NASA Astrophysics Data System (ADS)

Detweiler, L. G.; Glocer, A.; Benson, R. F.; Fung, S. F.

2016-12-01

In order to investigate and understand the role that different drivers play on the electron density altitude profile in the topside ionosphere of the polar regions, we used satellite radio-sounding data collected during the 1960s, 1970s, and 1980s to construct a series of graphs of electron density as a function of altitude and solar zenith angle. These data were gathered by the swept-frequency topside sounders from four of the satellites from the International Satellites for Ionospheric Studies (ISIS) program: Alouette 1 and 2, and ISIS 1 and 2, and were obtained from the NASA Space Physics Data Facility. In order to control for phenomenon known to effect electron density, we restricted our data set to data collected during a specific DST range (between -10 and 40 nT), and roughly constant solar radio flux values (between 40 and 90 W*m-2*Hz-1). To look at the effect of electron precipitation, we examine two separate cases, one above an invariant latitude of 60°, which includes precipitation, and one above 75°, which excludes precipitation. Under these restrictions we gathered a total of 407,500 altitude, solar zenith angle, and electron density data pairs. We then sorted these data pairs into bins of altitude and solar zenith angle, and present graphs of the medians of these binned data. We then fit our binned data to an exponential function representing hydrostatic equilibrium in the ionosphere presented in Kitamura et. al [2011]. We present graphs which show how well this best fit equation fits our data. Our results clearly show the strong dependence of electron density with respect to solar zenith angle, and demonstrates that electron precipitation can also influence the electron density profile, particularly on the nightside. We also examine how seasonal effects, via differences in the neutral thermosphere, can affect the electron density profiles. This study provides a climatological picture of what drives the topside electron density profile in the polar regions, and could be useful in future studies for model validation.

First spin-resolved electron distributions in crystals from combined polarized neutron and X-ray diffraction experiments.

PubMed

Deutsch, Maxime; Gillon, Béatrice; Claiser, Nicolas; Gillet, Jean-Michel; Lecomte, Claude; Souhassou, Mohamed

2014-05-01

Since the 1980s it has been possible to probe crystallized matter, thanks to X-ray or neutron scattering techniques, to obtain an accurate charge density or spin distribution at the atomic scale. Despite the description of the same physical quantity (electron density) and tremendous development of sources, detectors, data treatment software etc., these different techniques evolved separately with one model per experiment. However, a breakthrough was recently made by the development of a common model in order to combine information coming from all these different experiments. Here we report the first experimental determination of spin-resolved electron density obtained by a combined treatment of X-ray, neutron and polarized neutron diffraction data. These experimental spin up and spin down densities compare very well with density functional theory (DFT) calculations and also confirm a theoretical prediction made in 1985 which claims that majority spin electrons should have a more contracted distribution around the nucleus than minority spin electrons. Topological analysis of the resulting experimental spin-resolved electron density is also briefly discussed.

On the electron density localization in elemental cubic ceramic and FCC transition metals by means of a localized electrons detector.

PubMed

Aray, Yosslen; Paredes, Ricardo; Álvarez, Luis Javier; Martiz, Alejandro

2017-06-14

The electron density localization in insulator and semiconductor elemental cubic materials with diamond structure, carbon, silicon, germanium, and tin, and good metallic conductors with face centered cubic structure such as α-Co, Ni, Cu, Rh, Pd, Ag, Ir, Pt, and Au, was studied using a localized electrons detector defined in the local moment representation. Our results clearly show an opposite pattern of the electron density localization for the cubic ceramic and transition metal materials. It was found that, for the elemental ceramic materials, the zone of low electron localization is very small and is mainly localized on the atomic basin edges. On the contrary, for the transition metals, there are low-valued localized electrons detector isocontours defining a zone of highly delocalized electrons that extends throughout the material. We have found that the best conductors are those in which the electron density at this low-value zone is the lowest.

The influence of the Ar/O2 ratio on the electron density and electron temperature in microwave discharges

NASA Astrophysics Data System (ADS)

Espinho, S.; Hofmann, S.; Palomares, J. M.; Nijdam, S.

2017-10-01

The aim of this work is to study the properties of Ar-O2 microwave driven surfatron plasmas as a function of the Ar/O2 ratio in the gas mixture. The key parameters are the plasma electron density and electron temperature, which are estimated with Thomson scattering (TS) for O2 contents up to 50% of the total gas flow. A sharp drop in the electron density from {10}20 {{{m}}}-3 to approximately {10}18 {{{m}}}-3 is estimated as the O2 content in the gas mixture is increased up to 15%. For percentages of O2 lower than 10%, the electron temperature is estimated to be about 2-3 times higher than in the case of a pure argon discharge in the same conditions ({T}{{e}}≈ 1 eV) and gradually decreases as the O2 percentage is raised to 50%. However, for O2 percentages above 30%, the scattering spectra become Raman dominated, resulting in large uncertainties in the estimated electron densities and temperatures. The influence of photo-detached electrons from negative ions caused by the typical TS laser fluences is also likely to contribute to the uncertainty in the measured electron densities for high O2 percentages. Moreover, the detection limit of the system is reached for percentages of O2 higher than 25%. Additionally, both the electron density and temperature of microwave discharges with large Ar/O2 ratios are more sensitive to gas pressure variations.

Shape information from a critical point analysis of calculated electron density maps: application to DNA-drug systems

NASA Astrophysics Data System (ADS)

Leherte, L.; Allen, F. H.; Vercauteren, D. P.

1995-04-01

A computational method is described for mapping the volume within the DNA double helix accessible to a groove-binding antibiotic, netropsin. Topological critical point analysis is used to locate maxima in electron density maps reconstructed from crystallographically determined atomic coordinates. The peaks obtained in this way are represented as ellipsoids with axes related to local curvature of the electron density function. Combining the ellipsoids produces a single electron density function which can be probed to estimate effective volumes of the interacting species. Close complementarity between host and ligand in this example shows the method to be a good representation of the electron density function at various resolutions; while at the atomic level the ellipsoid method gives results which are in close agreement with those from the conventional, spherical, van der Waals approach.

Shape information from a critical point analysis of calculated electron density maps: Application to DNA-drug systems

NASA Astrophysics Data System (ADS)

Leherte, Laurence; Allen, Frank H.

1994-06-01

A computational method is described for mapping the volume within the DNA double helix accessible to the groove-binding antibiotic netropsin. Topological critical point analysis is used to locate maxima in electron density maps reconstructed from crystallographically determined atomic coordinates. The peaks obtained in this way are represented as ellipsoids with axes related to local curvature of the electron density function. Combining the ellipsoids produces a single electron density function which can be probed to estimate effective volumes of the interacting species. Close complementarity between host and ligand in this example shows the method to give a good representation of the electron density function at various resolutions. At the atomic level, the ellipsoid method gives results which are in close agreement with those from the conventional spherical van der Waals approach.

Electronic structure and electron momentum densities of Ag2CrO4

NASA Astrophysics Data System (ADS)

Meena, Seema Kumari; Ahuja, B. L.

2018-05-01

We present the first-ever experimental electron momentum density of Ag2CrO4 using 661.65 keV γ-rays from 20 Ci 137Cs source. To validate our experimental data, we have also deduced theoretical Compton profiles, energy bands and density of states using linear combination of atomic orbitals (LCAO) method in the framework of density functional theory. It is seen that the DFT-LDA gives a better agreement with experimental data than free atom model. The energy bands and density of states are also discussed.

High-latitude electron density observations from the IMAGE radio plasma imager

NASA Astrophysics Data System (ADS)

Henize, Vance Karl

2003-11-01

Before the IMAGE mission, electron densities in the high latitude, high altitude region of the magnetosphere were measured exclusively by in situ means. The Radio Plasma Imager instrument onboard IMAGE is capable of remotely observing electron densities between 0.01 and 100,000 e-/cm-3 from distances of several Earth radii or more. This allows a global view of the high latitude region that has a far greater accuracy than was previously possible. Soundings of the terrestrial magnetic cusp provide the first remote observations of the dynamics and poleward density profile of this feature continuously over a 60- minute interval. During steady quiet-time solar wind and interplanetary magnetic field conditions, the cusp is shown to be stable in both position and density structure with only slight variations in both. Peak electron densities within the cusp during this time are found to be somewhat higher than predicted. New procedures for deriving electron densities from radio sounding measurements are developed. The addition of curve fitting algorithms significantly increases the amount of useable data. Incorporating forward modeling techniques greatly reduces the computational time over traditional inversion methods. These methods are described in detail. A large number high latitude observations of ducted right-hand extraordinary mode waves made over the course of one year of the IMAGE mission are used to create a three dimensional model of the electron density profile of the terrestrial polar cap region. The dependence of electron density in the polar cap on average geocentric distance (d) is found to vary as d-6.6. This is a significantly steeper gradient than cited in earlier works such as Persoon et al., although the introduction of an asymptotic term provides for basic agreement in the limited region of their joint validity. Latitudinal and longitudinal variations are found to be insignificant. Both the mean profile power law index of the electron density profile and, to a stronger degree, its variance show dependence with the DST index.

Local and linear chemical reactivity response functions at finite temperature in density functional theory

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

Franco-Pérez, Marco, E-mail: francopj@mcmaster.ca, E-mail: ayers@mcmaster.ca, E-mail: jlgm@xanum.uam.mx, E-mail: avela@cinvestav.mx; Departamento de Química, Universidad Autónoma Metropolitana-Iztapalapa, Av. San Rafael Atlixco 186, México, D.F. 09340; Ayers, Paul W., E-mail: francopj@mcmaster.ca, E-mail: ayers@mcmaster.ca, E-mail: jlgm@xanum.uam.mx, E-mail: avela@cinvestav.mx

2015-12-28

We explore the local and nonlocal response functions of the grand canonical potential density functional at nonzero temperature. In analogy to the zero-temperature treatment, local (e.g., the average electron density and the local softness) and nonlocal (e.g., the softness kernel) intrinsic response functions are defined as partial derivatives of the grand canonical potential with respect to its thermodynamic variables (i.e., the chemical potential of the electron reservoir and the external potential generated by the atomic nuclei). To define the local and nonlocal response functions of the electron density (e.g., the Fukui function, the linear density response function, and the dualmore » descriptor), we differentiate with respect to the average electron number and the external potential. The well-known mathematical relationships between the intrinsic response functions and the electron-density responses are generalized to nonzero temperature, and we prove that in the zero-temperature limit, our results recover well-known identities from the density functional theory of chemical reactivity. Specific working equations and numerical results are provided for the 3-state ensemble model.« less

Local and linear chemical reactivity response functions at finite temperature in density functional theory.

PubMed

Franco-Pérez, Marco; Ayers, Paul W; Gázquez, José L; Vela, Alberto

2015-12-28

We explore the local and nonlocal response functions of the grand canonical potential density functional at nonzero temperature. In analogy to the zero-temperature treatment, local (e.g., the average electron density and the local softness) and nonlocal (e.g., the softness kernel) intrinsic response functions are defined as partial derivatives of the grand canonical potential with respect to its thermodynamic variables (i.e., the chemical potential of the electron reservoir and the external potential generated by the atomic nuclei). To define the local and nonlocal response functions of the electron density (e.g., the Fukui function, the linear density response function, and the dual descriptor), we differentiate with respect to the average electron number and the external potential. The well-known mathematical relationships between the intrinsic response functions and the electron-density responses are generalized to nonzero temperature, and we prove that in the zero-temperature limit, our results recover well-known identities from the density functional theory of chemical reactivity. Specific working equations and numerical results are provided for the 3-state ensemble model.

LPWA using supersonic gas jet with tailored density profile

NASA Astrophysics Data System (ADS)

Kononenko, O.; Bohlen, S.; Dale, J.; D'Arcy, R.; Dinter, M.; Erbe, J. H.; Indorf, G.; di Lucchio, L.; Goldberg, L.; Gruse, J. N.; Karstensen, S.; Libov, V.; Ludwig, K.; Martinez de La Ossa, A.; Marutzky, F.; Niroula, A.; Osterhoff, J.; Quast, M.; Schaper, L.; Schwinkendorf, J.-P.; Streeter, M.; Tauscher, G.; Weichert, S.; Palmer, C.; Horbatiuk, Taras

2016-10-01

Laser driven plasma wakefield accelerators have been explored as a potential compact, reproducible source of relativistic electron bunches, utilising an electric field of many GV/m. Control over injection of electrons into the wakefield is of crucial importance in producing stable, mono-energetic electron bunches. Density tailoring of the target, to control the acceleration process, can also be used to improve the quality of the bunch. By using gas jets to provide tailored targets it is possible to provide good access for plasma diagnostics while also producing sharp density gradients for density down-ramp injection. OpenFOAM hydrodynamic simulations were used to investigate the possibility of producing tailored density targets in a supersonic gas jet. Particle-in-cell simulations of the resulting density profiles modelled the effect of the tailored density on the properties of the accelerated electron bunch. Here, we present the simulation results together with preliminary experimental measurements of electron and x-ray properties from LPWA experiments using gas jet targets and a 25 TW, 25 fs Ti:Sa laser system at DESY.

Ionization balance in Titan's nightside ionosphere

NASA Astrophysics Data System (ADS)

Vigren, E.; Galand, M.; Yelle, R. V.; Wellbrock, A.; Coates, A. J.; Snowden, D.; Cui, J.; Lavvas, P.; Edberg, N. J. T.; Shebanits, O.; Wahlund, J.-E.; Vuitton, V.; Mandt, K.

2015-03-01

Based on a multi-instrumental Cassini dataset we make model versus observation comparisons of plasma number densities, nP = (nenI)1/2 (ne and nI being the electron number density and total positive ion number density, respectively) and short-lived ion number densities (N+, CH2+, CH3+, CH4+) in the southern hemisphere of Titan's nightside ionosphere over altitudes ranging from 1100 and 1200 km and from 1100 to 1350 km, respectively. The nP model assumes photochemical equilibrium, ion-electron pair production driven by magnetospheric electron precipitation and dissociative recombination as the principal plasma neutralization process. The model to derive short-lived-ion number densities assumes photochemical equilibrium for the short-lived ions, primary ion production by electron-impact ionization of N2 and CH4 and removal of the short-lived ions through reactions with CH4. It is shown that the models reasonably reproduce the observations, both with regards to nP and the number densities of the short-lived ions. This is contrasted by the difficulties in accurately reproducing ion and electron number densities in Titan's sunlit ionosphere.

A theoretical-electron-density databank using a model of real and virtual spherical atoms.

PubMed

Nassour, Ayoub; Domagala, Slawomir; Guillot, Benoit; Leduc, Theo; Lecomte, Claude; Jelsch, Christian

2017-08-01

A database describing the electron density of common chemical groups using combinations of real and virtual spherical atoms is proposed, as an alternative to the multipolar atom modelling of the molecular charge density. Theoretical structure factors were computed from periodic density functional theory calculations on 38 crystal structures of small molecules and the charge density was subsequently refined using a density model based on real spherical atoms and additional dummy charges on the covalent bonds and on electron lone-pair sites. The electron-density parameters of real and dummy atoms present in a similar chemical environment were averaged on all the molecules studied to build a database of transferable spherical atoms. Compared with the now-popular databases of transferable multipolar parameters, the spherical charge modelling needs fewer parameters to describe the molecular electron density and can be more easily incorporated in molecular modelling software for the computation of electrostatic properties. The construction method of the database is described. In order to analyse to what extent this modelling method can be used to derive meaningful molecular properties, it has been applied to the urea molecule and to biotin/streptavidin, a protein/ligand complex.

Transition properties of the Be-like Kα X-ray from Mg IX

NASA Astrophysics Data System (ADS)

Hu, Feng; Zhang, Shufang; Sun, Yan; Mei, Maofei; Sang, Cuicui; Yang, Jiamin

2017-12-01

Energy levels among the lowest 40 fine-structure levels in Be-like Mg IX are calculated using grasp2K code. The wavelengths, oscillator strengths, radiative rates and lifetimes for all possible Kα transitions have been calculated using the multiconfiguration Dirac-Fock method. The accuracy of the results is determined through extensive comparisons with the existing laboratory measurements and theoretical results. The present data can be used reliably for many purposes, such as the line identification of the observed spectra, and modelling and diagnostics of magnesium plasma.

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

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

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

2016-03-25

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

Multiconfigurational quantum propagation with trajectory-guided generalized coherent states

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

Grigolo, Adriano, E-mail: agrigolo@ifi.unicamp.br; Aguiar, Marcus A. M. de, E-mail: aguiar@ifi.unicamp.br; Viscondi, Thiago F., E-mail: viscondi@if.usp.br

2016-03-07

A generalized version of the coupled coherent states method for coherent states of arbitrary Lie groups is developed. In contrast to the original formulation, which is restricted to frozen-Gaussian basis sets, the extended method is suitable for propagating quantum states of systems featuring diversified physical properties, such as spin degrees of freedom or particle indistinguishability. The approach is illustrated with simple models for interacting bosons trapped in double- and triple-well potentials, most adequately described in terms of SU(2) and SU(3) bosonic coherent states, respectively.

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

NASA Technical Reports Server (NTRS)

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

1984-01-01

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

Measurement of electron density using reactance cutoff probe

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

You, K. H.; Seo, B. H.; Kim, J. H.

2016-05-15

This paper proposes a new measurement method of electron density using the reactance spectrum of the plasma in the cutoff probe system instead of the transmission spectrum. The highly accurate reactance spectrum of the plasma-cutoff probe system, as expected from previous circuit simulations [Kim et al., Appl. Phys. Lett. 99, 131502 (2011)], was measured using the full two-port error correction and automatic port extension methods of the network analyzer. The electron density can be obtained from the analysis of the measured reactance spectrum, based on circuit modeling. According to the circuit simulation results, the reactance cutoff probe can measure themore » electron density more precisely than the previous cutoff probe at low densities or at higher pressure. The obtained results for the electron density are presented and discussed for a wide range of experimental conditions, and this method is compared with previous methods (a cutoff probe using the transmission spectrum and a single Langmuir probe).« less

Effect of electron-phonon coupling on energy and density of states renormalizations of dynamically screened graphene

NASA Astrophysics Data System (ADS)

Leblanc, J. P. F.; Carbotte, J. P.; Nicol, E. J.

2012-02-01

Motivated by recent tunneling and angle-resolved photoemission (ARPES) work [1,2], we explore the combined effect of electron-electron and electron-phonon couplings on the renormalized energy dispersion, the spectral function, and the density of states of doped graphene. We find that the plasmarons seen in ARPES are also observable in the density of states and appear as structures with quadratic dependence on energy about the minima. Further, we illustrate how knowledge of the slopes of both the density of states and the renormalized dispersion near the Fermi level can allow for the separation of momentum and frequency dependent renormalizations to the Fermi velocity. This analysis should allow for the isolation of the renormalization due to the electron-phonon interaction from that of the electron-electron interaction. [4pt] [1] Brar et al. Phys. Rev. Lett. 104, 036805 (2010) [2] Bostwick et al. Science 328, p.999 (2010)

Dayside ionosphere of Titan: Impact on calculated plasma densities due to variations in the model parameters

NASA Astrophysics Data System (ADS)

Mukundan, Vrinda; Bhardwaj, Anil

2018-01-01

A one dimensional photochemical model for the dayside ionosphere of Titan has been developed for calculating the density profiles of ions and electrons under steady state photochemical equilibrium condition. We concentrated on the T40 flyby of Cassini orbiter and used the in-situ measurements from instruments onboard Cassini as input to the model. An energy deposition model is employed for calculating the attenuated photon flux and photoelectron flux at different altitudes in Titan's ionosphere. We used the Analytical Yield Spectrum approach for calculating the photoelectron fluxes. Volume production rates of major primary ions, like, N2+, N+ , CH4+, CH3+, etc due to photon and photoelectron impact are calculated and used as input to the model. The modeled profiles are compared with the Cassini Ion Neutral Mass Spectrometer (INMS) and Langmuir Probe (LP) measurements. The calculated electron density is higher than the observation by a factor of 2 to 3 around the peak. We studied the impact of different model parameters, viz. photoelectron flux, ion production rates, electron temperature, dissociative recombination rate coefficients, neutral densities of minor species, and solar flux on the calculated electron density to understand the possible reasons for this discrepancy. Recent studies have shown that there is an overestimation in the modeled photoelectron flux and N2+ ion production rates which may contribute towards this disagreement. But decreasing the photoelectron flux (by a factor of 3) and N2+ ion production rate (by a factor of 2) decreases the electron density only by 10 to 20%. Reduction in the measured electron temperature by a factor of 5 provides a good agreement between the modeled and observed electron density. The change in HCN and NH3 densities affects the calculated densities of the major ions (HCNH+ , C2H5+, and CH5+); however the overall impact on electron density is not appreciable ( < 20%). Even though increasing the dissociative recombination rate coefficients of the ions C2H5+ and CH5+ by a factor of 10 reduces the difference between modeled and observed densities of the major ions, the modeled electron density is still higher than the observation by ∼ 60% at the peak. We suggest that there might be some unidentified chemical reactions that may account for the additional loss of plasma in Titan's ionosphere.

Use of micro-photoluminescence as a contactless measure of the 2D electron density in a GaAs quantum well

NASA Astrophysics Data System (ADS)

Kamburov, D.; Baldwin, K. W.; West, K. W.; Lyon, S.; Pfeiffer, L. N.; Pinczuk, A.

2017-06-01

We compare micro-photoluminescence (μPL) as a measure of the electron density in a clean, two-dimensional (2D) system confined in a GaAs quantum well (QW) to the standard magneto-transport technique. Our study explores the PL shape evolution across a number of molecular beam epitaxy-grown samples with different QW widths and 2D electron densities and notes its correspondence with the density obtained in magneto-transport measurements on these samples. We also measure the 2D density in a top-gated quantum well sample using both PL and transport and find that the two techniques agree to within a few percent over a wide range of gate voltages. We find that the PL measurements are sensitive to gate-induced 2D density changes on the order of 109 electrons/cm2. The spatial resolution of the PL density measurement in our experiments is 40 μm, which is already substantially better than the millimeter-scale resolution now possible in spatial density mapping using magneto-transport. Our results establish that μPL can be used as a reliable high spatial resolution technique for future contactless measurements of density variations in a 2D electron system.

Self consistent solution of Schrödinger Poisson equations and some electronic properties of ZnMgO/ZnO hetero structures

NASA Astrophysics Data System (ADS)

Uslu, Salih; Yarar, Zeki

2017-02-01

The epitaxial growth of quantum wells composed of high quality allows the production and application to their device of new structures in low dimensions. The potential profile at the junction is determined by free carriers and by the level of doping. Therefore, the shape of potential is obtained by the electron density. Energy level determines the number of electrons that can be occupied at every level. Energy levels and electron density values of each level must be calculated self consistently. Starting with V(z) test potential, wave functions and electron densities for each energy levels can be calculated to solve Schrödinger equation. If Poisson's equation is solved with the calculated electron density, the electrostatic potential can be obtained. The new V(z) potential can be calculated with using electrostatic potential found beforehand. Thus, the obtained values are calculated self consistently to a certain error criterion. In this study, the energy levels formed in the interfacial potential, electron density in each level and the wave function dependence of material parameters were investigated self consistently.

Laser collisional induced fluorescence electron density measurements as a function of ring bias and the onset of anode spot formation in a ring cusp magnetic field

NASA Astrophysics Data System (ADS)

Arthur, N. A.; Foster, J. E.; Barnat, E. V.

2018-05-01

Two-dimensional electron density measurements are made in a magnetic ring cusp discharge using laser collisional induced fluorescence. The magnet rings are isolated from the anode structure such that they can be biased independently in order to modulate electron flows through the magnetic cusps. Electron density images are captured as a function of bias voltage in order to assess the effects of current flow through the cusp on the spatial extent of the cusp. We anticipated that for a fixed current density being funneled through the magnetic cusp, the leak width would necessarily increase. Unexpectedly, the leak width, as measured by LCIF images, does not increase. This suggests that the current density is not constant, and that possibly either electrons are being heated or additional ionization events are occurring within the cusp. Spatially resolving electron temperature would be needed to determine if electrons are being heated within the cusp. We also observe breakdown of the anode magnetosheath and formation of anode spots at high bias voltage.

Detection of an electron beam in a high density plasma via an electrostatic probe

NASA Astrophysics Data System (ADS)

Majeski, Stephen; Yoo, Jongsoo; Zweben, Stewart; Yamada, Masaaki

2018-07-01

An electron beam is detected by a 1D floating potential probe array in a relatively high density (1012–1013 cm‑3) and low temperature (∼5 eV) plasma of the Magnetic Reconnection Experiment. Clear perturbations in the floating potential profile by the electron beam are observed. Based on the floating potential profile and a current balance equation to the probe array tips, the effective width of the electron beam is determined, from which we determine the radial and toroidal beam current density profiles. After the profile of the electron beam is specified from the measured beam current, we demonstrate the consistency of the current balance equation and the location of the perturbation is also in agreement with field line mapping. No significant broadening of the electron beam is observed after the beam propagates for tens of centimeters through the high density plasma. These results prove that the field line mapping is, in principle, possible in high density plasmas.

Detection of an electron beam in a high density plasma via an electrostatic probe

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

Majeski, Stephen; Yoo, Jongsoo; Zweben, Stewart

Here, an electron beam is detected by a 1D floating potential probe array in a relatively high density (10 12–10 13 cm -3) and low temperature (~5 eV) plasma of the Magnetic Reconnection Experiment. Clear perturbations in the floating potential profile by the electron beam are observed. Based on the floating potential profile and a current balance equation to the probe array tips, the effective width of the electron beam is determined, from which we determine the radial and toroidal beam current density profiles. After the profile of the electron beam is specified from the measured beam current, we demonstratemore » the consistency of the current balance equation and the location of the perturbation is also in agreement with field line mapping. No significant broadening of the electron beam is observed after the beam propagates for tens of centimeters through the high density plasma. These results prove that the field line mapping is, in principle, possible in high density plasmas.« less

Density Functionals of Chemical Bonding

PubMed Central

Putz, Mihai V.

2008-01-01

The behavior of electrons in general many-electronic systems throughout the density functionals of energy is reviewed. The basic physico-chemical concepts of density functional theory are employed to highlight the energy role in chemical structure while its extended influence in electronic localization function helps in chemical bonding understanding. In this context the energy functionals accompanied by electronic localization functions may provide a comprehensive description of the global-local levels electronic structures in general and of chemical bonds in special. Becke-Edgecombe and author’s Markovian electronic localization functions are discussed at atomic, molecular and solid state levels. Then, the analytical survey of the main workable kinetic, exchange, and correlation density functionals within local and gradient density approximations is undertaken. The hierarchy of various energy functionals is formulated by employing both the parabolic and statistical correlation degree of them with the electronegativity and chemical hardness indices by means of quantitative structure-property relationship (QSPR) analysis for basic atomic and molecular systems. PMID:19325846

Approaching an experimental electron density model of the biologically active trans -epoxysuccinyl amide group-Substituent effects vs. crystal packing

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

Shi, Ming W.; Stewart, Scott G.; Sobolev, Alexandre N.

The trans-epoxysuccinyl amide group as a biologically active moiety in cysteine protease inhibitors such as loxistatin acid E64c has been used as a benchmark system for theoretical studies of environmental effects on the electron density of small active ingredients in relation to their biological activity. Here, the synthesis and the electronic properties of the smallest possible active site model compound are reported to close the gap between the unknown experimental electron density of trans-epoxysuccinyl amides and the well-known function of related drugs. Intramolecular substituent effects are separated from intermolecular crystal packing effects on the electron density, which allows us tomore » predict the conditions under which an experimental electron density investigation on trans-epoxysuccinyl amides will be possible. In this context, the special importance of the carboxylic acid function in the model compound for both crystal packing and biological activity is revealed through the novel tool of model energy analysis.« less

Detection of an electron beam in a high density plasma via an electrostatic probe

DOE PAGES

Majeski, Stephen; Yoo, Jongsoo; Zweben, Stewart; ...

2018-05-08

Here, an electron beam is detected by a 1D floating potential probe array in a relatively high density (10 12–10 13 cm -3) and low temperature (~5 eV) plasma of the Magnetic Reconnection Experiment. Clear perturbations in the floating potential profile by the electron beam are observed. Based on the floating potential profile and a current balance equation to the probe array tips, the effective width of the electron beam is determined, from which we determine the radial and toroidal beam current density profiles. After the profile of the electron beam is specified from the measured beam current, we demonstratemore » the consistency of the current balance equation and the location of the perturbation is also in agreement with field line mapping. No significant broadening of the electron beam is observed after the beam propagates for tens of centimeters through the high density plasma. These results prove that the field line mapping is, in principle, possible in high density plasmas.« less

A Non-Neutral Plasma Device: Electron Beam Penning Trap

NASA Astrophysics Data System (ADS)

Zhuang, Ge; Liu, Wan-dong; Zheng, Jian; Fu, Cheng-jiang; Bai, Bo; Chi, Ji; Zhao, Kai; Xie, Jin-lin; Liang, Xiao-ping; Yu, Chang-xuan

1999-12-01

An electron beam Penning trap (EBPT) non- neutral plasma system, built to investigate the formation of a dense electron core with the density beyond Brillouin limit and possible application to fusion research, has been described. The density in the center of the EBPT has been verified to be up to 10 times of Brillouin density limit.

The 1973 solar occultation of the Crab Nebula pulsar

NASA Technical Reports Server (NTRS)

Weisberg, J. M.

1975-01-01

The mean electron density of the solar corona was determined by measuring the dispersion of radiofrequency pulses from pulsar NP 0532 during the June 1973 solar occultation. Trends continued which were noticed in 1971 as solar activity declined. Model fitting results suggest that the corona continued to become even more concentrated toward the equator in 1973 than in 1971. The number density of electrons in most regions decreased. The best model of the distribution of corona electrons is suggested to be one with zero density at the poles. K-corona isophotes and contours of equal path-integrated density are presented for several models. Electron density versus date and position in the corona are tabulated. It is seen that there is no simple relationship between the onset of major solar activity and density or scattering enhancements.

Talbot-Lau x-ray deflectometry phase-retrieval methods for electron density diagnostics in high-energy density experiments.

PubMed

Valdivia, Maria Pia; Stutman, Dan; Stoeckl, Christian; Mileham, Chad; Begishev, Ildar A; Bromage, Jake; Regan, Sean P

2018-01-10

Talbot-Lau x-ray interferometry uses incoherent x-ray sources to measure refraction index changes in matter. These measurements can provide accurate electron density mapping through phase retrieval. An adaptation of the interferometer has been developed in order to meet the specific requirements of high-energy density experiments. This adaptation is known as a moiré deflectometer, which allows for single-shot capabilities in the form of interferometric fringe patterns. The moiré x-ray deflectometry technique requires a set of object and reference images in order to provide electron density maps, which can be costly in the high-energy density environment. In particular, synthetic reference phase images obtained ex situ through a phase-scan procedure, can provide a feasible solution. To test this procedure, an object phase map was retrieved from a single-shot moiré image obtained from a plasma-produced x-ray source. A reference phase map was then obtained from phase-stepping measurements using a continuous x-ray tube source in a small laboratory setting. The two phase maps were used to retrieve an electron density map. A comparison of the moiré and phase-stepping phase-retrieval methods was performed to evaluate single-exposure plasma electron density mapping for high-energy density and other transient plasma experiments. It was found that a combination of phase-retrieval methods can deliver accurate refraction angle mapping. Once x-ray backlighter quality is optimized, the ex situ method is expected to deliver electron density mapping with improved resolution. The steps necessary for improved diagnostic performance are discussed.

Precision Electron Density Measurements in the SSX MHD Wind Tunnel

NASA Astrophysics Data System (ADS)

Suen-Lewis, Emma M.; Barbano, Luke J.; Shrock, Jaron E.; Kaur, Manjit; Schaffner, David A.; Brown, Michael R.

2017-10-01

We characterize fluctuations of the line averaged electron density of Taylor states produced by the magnetized coaxial plasma gun of the SSX device using a 632.8 nm HeNe laser interferometer. The analysis method uses the electron density dependence of the refractive index of the plasma to determine the electron density of the Taylor states. Typical magnetic field and density values in the SSX device approach about B ≅ 0.3 T and n = 0 . 4 ×1016 cm-3 . Analysis is improved from previous density measurement methods by developing a post-processing method to remove relative phase error between interferometer outputs and to account for approximately linear phase drift due to low-frequency mechanical vibrations of the interferometer. Precision density measurements coupled with local measurements of the magnetic field will allow us to characterize the wave composition of SSX plasma via density vs. magnetic field correlation analysis, and compare the wave composition of SSX plasma with that of the solar wind. Preliminary results indicate that density and magnetic field appear negatively correlated. Work supported by DOE ARPA-E ALPHA program.

Measurement of electron density and electron temperature of a cascaded arc plasma using laser Thomson scattering compared to an optical emission spectroscopic approach

NASA Astrophysics Data System (ADS)

Yong, WANG; Cong, LI; Jielin, SHI; Xingwei, WU; Hongbin, DING

2017-11-01

As advanced linear plasma sources, cascaded arc plasma devices have been used to generate steady plasma with high electron density, high particle flux and low electron temperature. To measure electron density and electron temperature of the plasma device accurately, a laser Thomson scattering (LTS) system, which is generally recognized as the most precise plasma diagnostic method, has been established in our lab in Dalian University of Technology. The electron density has been measured successfully in the region of 4.5 × 1019 m-3 to 7.1 × 1020 m-3 and electron temperature in the region of 0.18 eV to 0.58 eV. For comparison, an optical emission spectroscopy (OES) system was established as well. The results showed that the electron excitation temperature (configuration temperature) measured by OES is significantly higher than the electron temperature (kinetic electron temperature) measured by LTS by up to 40% in the given discharge conditions. The results indicate that the cascaded arc plasma is recombining plasma and it is not in local thermodynamic equilibrium (LTE). This leads to significant error using OES when characterizing the electron temperature in a non-LTE plasma.

Diurnal evolution of the F region electron density local time gradient at low and middle latitudes resolved by the Swarm constellation

NASA Astrophysics Data System (ADS)

Xiong, Chao; Zhou, Yun-Liang; Lühr, Hermann; Ma, Shu-Ying

2016-09-01

In this study we have provided new insights into the local time gradient of F region electron density (ΔNe) derived from the lower pair of Swarm satellites flying side by side. Our result shows that the electron density (Ne) increase starts just at sunrise, around 06:00 LT, simultaneously at low and middle latitudes due to the increased photoionization. At equatorial latitudes the increase in electron density gets even steeper after 07:00 LT, and the steepest increase of electron density (about 3 · 1010 m-3 within 6 min) occurs around 09:00 LT. We suggest that the upward vertical plasma drift in connection with the buildup of the equatorial fountain effect plays a major role. We also found that the local time variations of the equatorial ionization anomaly (EIA) crest electron density during daytime are similar to the respective evolutions at the equator, but about 1-2 h delayed. We relate this delay to the response time between the equatorial electric field and the buildup of the plasma fountain. At equinox months a fast decrease of the F region electron density is seen at the EIA trough region during the prereversal enhancement, while an increase is found meanwhile at crest regions. Afterward, a fast decrease of the EIA crest electron density occurs between 19:00 and 23:00 LT, with seasonal dependence. The local time gradient between Swarm A and C shows also prominent longitudinal wave-4 pattern around August months, and the phase of DE3 in ΔNe is found to be delayed by 6 h compared to that in Ne.

A technique for routinely updating the ITU-R database using radio occultation electron density profiles

NASA Astrophysics Data System (ADS)

Brunini, Claudio; Azpilicueta, Francisco; Nava, Bruno

2013-09-01

Well credited and widely used ionospheric models, such as the International Reference Ionosphere or NeQuick, describe the variation of the electron density with height by means of a piecewise profile tied to the F2-peak parameters: the electron density,, and the height, . Accurate values of these parameters are crucial for retrieving reliable electron density estimations from those models. When direct measurements of these parameters are not available, the models compute the parameters using the so-called ITU-R database, which was established in the early 1960s. This paper presents a technique aimed at routinely updating the ITU-R database using radio occultation electron density profiles derived from GPS measurements gathered from low Earth orbit satellites. Before being used, these radio occultation profiles are validated by fitting to them an electron density model. A re-weighted Least Squares algorithm is used for down-weighting unreliable measurements (occasionally, entire profiles) and to retrieve and values—together with their error estimates—from the profiles. These values are used to monthly update the database, which consists of two sets of ITU-R-like coefficients that could easily be implemented in the IRI or NeQuick models. The technique was tested with radio occultation electron density profiles that are delivered to the community by the COSMIC/FORMOSAT-3 mission team. Tests were performed for solstices and equinoxes seasons in high and low-solar activity conditions. The global mean error of the resulting maps—estimated by the Least Squares technique—is between and elec/m for the F2-peak electron density (which is equivalent to 7 % of the value of the estimated parameter) and from 2.0 to 5.6 km for the height (2 %).

Comparisons of ionospheric electron density distributions reconstructed by GPS computerized tomography, backscatter ionograms, and vertical ionograms

NASA Astrophysics Data System (ADS)

Zhou, Chen; Lei, Yong; Li, Bofeng; An, Jiachun; Zhu, Peng; Jiang, Chunhua; Zhao, Zhengyu; Zhang, Yuannong; Ni, Binbin; Wang, Zemin; Zhou, Xuhua

2015-12-01

Global Positioning System (GPS) computerized ionosphere tomography (CIT) and ionospheric sky wave ground backscatter radar are both capable of measuring the large-scale, two-dimensional (2-D) distributions of ionospheric electron density (IED). Here we report the spatial and temporal electron density results obtained by GPS CIT and backscatter ionogram (BSI) inversion for three individual experiments. Both the GPS CIT and BSI inversion techniques demonstrate the capability and the consistency of reconstructing large-scale IED distributions. To validate the results, electron density profiles obtained from GPS CIT and BSI inversion are quantitatively compared to the vertical ionosonde data, which clearly manifests that both methods output accurate information of ionopsheric electron density and thereby provide reliable approaches to ionospheric soundings. Our study can improve current understanding of the capability and insufficiency of these two methods on the large-scale IED reconstruction.

Electron Densities Near Io from Galileo Plasma Wave Observations

NASA Technical Reports Server (NTRS)

Gurnett, D. A.; Persoon, A. M.; Kurth, W. S.; Roux, A.; Bolton, S. J.

2001-01-01

This paper presents an overview of electron densities obtained near Io from the Galileo plasma wave instrument during the first four flybys of Io. These flybys were Io, which was a downstream wake pass that occurred on December 7, 1995; I24, which was an upstream pass that occurred on October 11, 1999; I25, which was a south polar pass that occurred on November 26, 1999; and I27, which was an upstream pass that occurred on February 22, 2000. Two methods were used to measure the electron density. The first was based on the frequency of upper hybrid resonance emissions, and the second was based on the low-frequency cutoff of electromagnetic radiation at the electron plasma frequency. For three of the flybys, Io, I25, and I27, large density enhancements were observed near the closest approach to Io. The peak electron densities ranged from 2.1 to 6.8 x 10(exp 4) per cubic centimeters. These densities are consistent with previous radio occultation measurements of Io's ionosphere. No density enhancement was observed during the I24 flyby, most likely because the spacecraft trajectory passed too far upstream to penetrate Io's ionosphere. During two of the flybys, I25 and I27, abrupt step-like changes were observed at the outer boundaries of the region of enhanced electron density. Comparisons with magnetic field models and energetic particle measurements show that the abrupt density steps occur as the spacecraft penetrated the boundary of the Io flux tube, with the region of high plasma density on the inside of the flux tube. Most likely the enhanced electron density within the Io flux tube is associated with magnetic field lines that are frozen to Io by the high conductivity of Io's atmosphere, thereby enhancing the escape of plasma along the magnetic field lines that pass through Io's ionosphere.

Anisotropic high-harmonic generation in bulk crystals

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

You, Yong Sing; Reis, David A.; Ghimire, Shambhu

2016-11-21

The microscopic valence electron density determines the optical, electronic, structural and thermal properties of materials. However, current techniques for measuring this electron charge density are limited: for example, scanning tunnelling microscopy is confined to investigations at the surface, and electron diffraction requires very thin samples to avoid multiple scattering. Therefore, an optical method is desirable for measuring the valence charge density of bulk materials. Since the discovery of high-harmonic generation (HHG) in solids, there has been growing interest in using HHG to probe the electronic structure of solids. Here, using single-crystal MgO, we demonstrate that high-harmonic generation in solids ismore » sensitive to interatomic bonding. We find that harmonic efficiency is enhanced (diminished) for semi-classical electron trajectories that connect (avoid) neighbouring atomic sites in the crystal. Finally, these results indicate the possibility of using materials’ own electrons for retrieving the interatomic potential and thus the valence electron density, and perhaps even wavefunctions, in an all-optical setting.« less

Decay of the electron number density in the nitrogen afterglow using a hairpin resonator probe

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

Siefert, Nicholas S.; Ganguly, Biswa N.; Sands, Brian L.

A hairpin resonator was used to measure the electron number density in the afterglow of a nitrogen glow discharge (p=0.25-0.75 Torr). Electron number densities were measured using a time-dependent approach similar to the approach used by Spencer et al. [J. Phys. D 20, 923 (1987)]. The decay time of the electron number density was used to determine the electron temperature in the afterglow, assuming a loss of electrons via ambipolar diffusion to the walls. The electron temperature in the near afterglow remained between 0.4 and 0.6 eV, depending on pressure. This confirms the work by Guerra et al. [IEEE Trans.more » Plasma. Sci. 31, 542 (2003)], who demonstrated experimentally and numerically that the electron temperature stays significantly above room temperature via superelastic collisions with highly vibrationally excited ground state molecules and metastables, such as A {sup 3}{sigma}{sub u}{sup +}.« less

Quantum electronic stress: density-functional-theory formulation and physical manifestation.

PubMed

Hu, Hao; Liu, Miao; Wang, Z F; Zhu, Junyi; Wu, Dangxin; Ding, Hepeng; Liu, Zheng; Liu, Feng

2012-08-03

The concept of quantum electronic stress (QES) is introduced and formulated within density functional theory to elucidate extrinsic electronic effects on the stress state of solids and thin films in the absence of lattice strain. A formal expression of QES (σ(QE)) is derived in relation to deformation potential of electronic states (Ξ) and variation of electron density (Δn), σ(QE) = ΞΔn as a quantum analog of classical Hooke's law. Two distinct QES manifestations are demonstrated quantitatively by density functional theory calculations: (1) in the form of bulk stress induced by charge carriers and (2) in the form of surface stress induced by quantum confinement. Implications of QES in some physical phenomena are discussed to underlie its importance.

Excited level populations and excitation kinetics of nonequilibrium ionizing argon discharge plasma of atmospheric pressure

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

Akatsuka, Hiroshi

2009-04-15

Population densities of excited states of argon atoms are theoretically examined for ionizing argon plasma in a state of nonequilibrium under atmospheric pressure from the viewpoint of elementary processes with collisional radiative model. The dependence of excited state populations on the electron and gas temperatures is discussed. Two electron density regimes are found, which are distinguished by the population and depopulation mechanisms for the excited states in problem. When the electron impact excitation frequency for the population or depopulation is lower than the atomic impact one, the electron density of the plasma is considered as low to estimate the populationmore » and depopulation processes. Some remarkable characteristics of population and depopulation mechanisms are found for the low electron density atmospheric plasma, where thermal relaxation by atomic collisions becomes the predominant process within the group of close-energy states in the ionizing plasma of atmospheric pressure, and the excitation temperature is almost the same as the gas temperature. In addition to the collisional relaxation by argon atoms, electron impact excitation from the ground state is also an essential population mechanism. The ratios of population density of the levels pairs, between which exists a large energy gap, include information on the electron collisional kinetics. For high electron density, the effect of atomic collisional relaxation becomes weak. For this case, the excitation mechanism is explained as electron impact ladderlike excitation similar to low-pressure ionizing plasma, since the electron collision becomes the dominant process for the population and depopulation kinetics.« less

Independent control of electron energy and density using a rotating magnetic field in inductively coupled plasmas

NASA Astrophysics Data System (ADS)

Kondo, Takahiro; Ohta, Masayuki; Ito, Tsuyohito; Okada, Shigefumi

2013-09-01

Effects of a rotating magnetic field (RMF) on the electron energy distribution function (EEDF) and on the electron density are investigated with the aim of controlling the radical composition of inductively coupled plasmas. By adjusting the RMF frequency and generation power, the desired electron density and electron energy shift are obtained. Consequently, the amount and fraction of high-energy electrons, which are mostly responsible for direct dissociation processes of raw molecules, will be controlled externally. This controllability, with no electrode exposed to plasma, will enable us to control radical components and their flux during plasma processing.

Wavefront-sensor-based electron density measurements for laser-plasma accelerators.

PubMed

Plateau, G R; Matlis, N H; Geddes, C G R; Gonsalves, A J; Shiraishi, S; Lin, C; van Mourik, R A; Leemans, W P

2010-03-01

Characterization of the electron density in laser produced plasmas is presented using direct wavefront analysis of a probe laser beam. The performance of a laser-driven plasma-wakefield accelerator depends on the plasma wavelength and hence on the electron density. Density measurements using a conventional folded-wave interferometer and using a commercial wavefront sensor are compared for different regimes of the laser-plasma accelerator. It is shown that direct wavefront measurements agree with interferometric measurements and, because of the robustness of the compact commercial device, offer greater phase sensitivity and straightforward analysis, improving shot-to-shot plasma density diagnostics.

Wavefront-sensor-based electron density measurements for laser-plasma accelerators

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

Plateau, Guillaume; Matlis, Nicholas; Geddes, Cameron

2010-02-20

Characterization of the electron density in laser produced plasmas is presented using direct wavefront analysis of a probe laser beam. The performance of a laser-driven plasma-wakefield accelerator depends on the plasma wavelength, hence on the electron density. Density measurements using a conventional folded-wave interferometer and using a commercial wavefront sensor are compared for different regimes of the laser-plasma accelerator. It is shown that direct wavefront measurements agree with interferometric measurements and, because of the robustness of the compact commercial device, have greater phase sensitivity, straightforward analysis, improving shot-to-shot plasma-density diagnostics.

Support for the existence of invertible maps between electronic densities and non-analytic 1-body external potentials in non-relativistic time-dependent quantum mechanics

NASA Astrophysics Data System (ADS)

Mosquera, Martín A.

2017-10-01

Provided the initial state, the Runge-Gross theorem establishes that the time-dependent (TD) external potential of a system of non-relativistic electrons determines uniquely their TD electronic density, and vice versa (up to a constant in the potential). This theorem requires the TD external potential and density to be Taylor-expandable around the initial time of the propagation. This paper presents an extension without this restriction. Given the initial state of the system and evolution of the density due to some TD scalar potential, we show that a perturbative (not necessarily weak) TD potential that induces a non-zero divergence of the external force-density, inside a small spatial subset and immediately after the initial propagation time, will cause a change in the density within that subset, implying that the TD potential uniquely determines the TD density. In this proof, we assume unitary evolution of wavefunctions and first-order differentiability (which does not imply analyticity) in time of the internal and external force-densities, electronic density, current density, and their spatial derivatives over the small spatial subset and short time interval.

Determining Core Plasmaspheric Electron Densities with the Van Allen Probes

NASA Astrophysics Data System (ADS)

De Pascuale, S.; Hartley, D.; Kurth, W. S.; Kletzing, C.; Thaller, S. A.; Wygant, J. R.

2016-12-01

We survey three methods for obtaining electron densities inside of the core plasmasphere region (L < 4) to the perigee of the Van Allen Probes (L 1.1) from September 2012 to December 2014. Using the EMFISIS instrument on board the Van Allen Probes, electron densities are extracted from the upper hybrid resonance to an uncertainty of 10%. Some measurements are subject to larger errors given interpretational issues, especially at low densities (L > 4) resulting from geomagnetic activity. At high densities EMFISIS is restricted by an upper observable limit near 3000 cm-3. As this limit is encountered above perigee, we employ two additional methods validated against EMFISIS measurements to determine electron densities deep within the plasmasphere (L < 2). EMFISIS can extrapolate density estimates to lower L by calculating high densities, in good agreement with the upper hybrid technique when applicable, from plasma wave properties. Calibrated measurements, from the Van Allen Probes EFW potential instrument, also extend into this range. In comparison with the published EMFISIS database we provide a metric for the validity of core plasmaspheric density measurements obtained from these methods and an empirical density model for use in wave and particle simulations.

Measurement of electron density profiles on HT-6M tokamak by 7-channel FIR HCN laser interferometer

NASA Astrophysics Data System (ADS)

Xiang, Gao; Qiliang, Guo

1990-12-01

Electron density measurements are periormed on HT-6M tokamak using a 7 channel Far-Infrared HCN laser interferometer. From the measured line integrals--7 channel phase shifts the electron density profile is reconstructed by a fit procedure. Results were tested by comparison to Abel inverted. Some recent interesting experimental results were reported.

Synopsis of D- and E-region electron densities during the energy budget campaign

NASA Technical Reports Server (NTRS)

Friedrich, M.; Baker, K. D.; Brekke, A.; Dickinson, P. H. G.; Dumbs, A.; Grandal, B.; Thrane, E. V.; Smith, L. G.; Torkar, K. M.

1982-01-01

Electron density profiles from ground-based and rocket-borne measurements conducted at three sites in northern Scandinavia under various degrees of geophysical disturbances are presented. These data are checked against an instantaneous picture of the ionospheric absorption obtained via the dense riometer network. A map of the riometer absorption and measured electron densities over Scandinavia is given.

Nature of non-nuclear (3, -3) π-attractor and π-bonding: Theoretical analysis on π-electron density

NASA Astrophysics Data System (ADS)

Lv, Jiao; Yang, Lihua; Sun, Zheng; Meng, Lingpeng; Li, Xiaoyan

2018-01-01

Understanding the nature of π-electron density is important to characterize the conjugate π molecular systems. In this work, the π-electron densities of some typical conjugated π molecular systems were separated from their total electron densities; the positions and natures of non-nuclear (3, -3) π-attractors and the π-bond critical points (π-BCPs) are investigated. The calculated results show that for the same element, the position of the π-attractor is constant, regardless of the chemical surroundings. The position of the π-BCP is closer to the atom with the larger electronegativity.

December anomaly in ionosphere using FORMOSAT-3/COSMIC electron density profiles

NASA Astrophysics Data System (ADS)

Dashnyam, G.; Lin, C. C. H.; Rajesh, P. K.; Lin, J. T.

2017-12-01

December anomaly in ionosphere refers to the observation of greater value of global average ionospheric peak electron density (NmF2) in December-January months than in June-July months. So far there has been no satisfactory explanation to account for this difference, which is also known as annual asymmetry, leading to the speculation that forcing from lower atmosphere may be important. In this work, FORMOSAT-3/COSMIC electron density profiles are used to investigate the characteristics of December anomaly at different local times and longitudes in varying levels of solar activity. The observations in the years 2008, 2009 and 2012 are used for the study. The results suggest that the anomaly exists in all the three years, and is pronounced during day. Detailed analysis is carried out using latitude-altitude electron density profiles at selected longitude sectors, revealing that neutral wind may play dominant role. SAMI2 model is used to further examine the role of neutral wind influencing the electron density in different solstices. Tidal decomposition of the wind is carried out to understand the dominant tidal components that give rise to the larger electron density in the December-January months.

[Research on electron density in DC needle-plate corona discharge at atmospheric pressure].

PubMed

Liu, Zhi-Qiang; Guo, Wei; Liu, Tao-Tao; Wu, Wen-Shuo; Liu, Shu-Min

2013-11-01

Using needle-plate discharge device, corona discharge experiment was done in the atmosphere. Through photo of spot size of light-emitting area, the relationship between the voltage and thickness of corona layer was discussed. When the distance between tip and plate is fixed, the thickness of corona layer increases with the increase in voltage; when the voltage is fixed, the thickness of corona layer decreases with the increase in the distance between tip and plate. As spectral intensity of N2 (C3pi(u)) (337.1 nm)reflects high energy electron density, it was measured with emission spectrometry. The results show that high energy electron density is the biggest near the needle tip and the relationship between high energy electron density and voltage is basically linear increasing. Fixing voltage, high energy electron density decreases with the increase in the distance between tip and plate. When the voltage and the distance between tip and plate are fixed, the high energy electron density increases with the decrease in the curvature radius of needle tip. These results are of great importance for the study of plasma parameters of corona discharge.

Statistical analysis of suprathermal electron drivers at 67P/Churyumov-Gerasimenko

NASA Astrophysics Data System (ADS)

Broiles, Thomas W.; Burch, J. L.; Chae, K.; Clark, G.; Cravens, T. E.; Eriksson, A.; Fuselier, S. A.; Frahm, R. A.; Gasc, S.; Goldstein, R.; Henri, P.; Koenders, C.; Livadiotis, G.; Mandt, K. E.; Mokashi, P.; Nemeth, Z.; Odelstad, E.; Rubin, M.; Samara, M.

2016-11-01

We use observations from the Ion and Electron Sensor (IES) on board the Rosetta spacecraft to study the relationship between the cometary suprathermal electrons and the drivers that affect their density and temperature. We fit the IES electron observations with the summation of two kappa distributions, which we characterize as a dense and warm population (˜10 cm-3 and ˜16 eV) and a rarefied and hot population (˜0.01 cm-3 and ˜43 eV). The parameters of our fitting technique determine the populations' density, temperature, and invariant kappa index. We focus our analysis on the warm population to determine its origin by comparing the density and temperature with the neutral density and magnetic field strength. We find that the warm electron population is actually two separate sub-populations: electron distributions with temperatures above 8.6 eV and electron distributions with temperatures below 8.6 eV. The two sub-populations have different relationships between their density and temperature. Moreover, the two sub-populations are affected by different drivers. The hotter sub-population temperature is strongly correlated with neutral density, while the cooler sub-population is unaffected by neutral density and is only weakly correlated with magnetic field strength. We suggest that the population with temperatures above 8.6 eV is being heated by lower hybrid waves driven by counterstreaming solar wind protons and newly formed, cometary ions created in localized, dense neutral streams. To the best of our knowledge, this represents the first observations of cometary electrons heated through wave-particle interactions.

First-principles method for calculating the rate constants of internal-conversion and intersystem-crossing transitions.

PubMed

Valiev, R R; Cherepanov, V N; Baryshnikov, G V; Sundholm, D

2018-02-28

A method for calculating the rate constants for internal-conversion (k IC ) and intersystem-crossing (k ISC ) processes within the adiabatic and Franck-Condon (FC) approximations is proposed. The applicability of the method is demonstrated by calculation of k IC and k ISC for a set of organic and organometallic compounds with experimentally known spectroscopic properties. The studied molecules were pyrromethene-567 dye, psoralene, hetero[8]circulenes, free-base porphyrin, naphthalene, and larger polyacenes. We also studied fac-Alq 3 and fac-Ir(ppy) 3 , which are important molecules in organic light emitting diodes (OLEDs). The excitation energies were calculated at the multi-configuration quasi-degenerate second-order perturbation theory (XMC-QDPT2) level, which is found to yield excitation energies in good agreement with experimental data. Spin-orbit coupling matrix elements, non-adiabatic coupling matrix elements, Huang-Rhys factors, and vibrational energies were calculated at the time-dependent density functional theory (TDDFT) and complete active space self-consistent field (CASSCF) levels. The computed fluorescence quantum yields for the pyrromethene-567 dye, psoralene, hetero[8]circulenes, fac-Alq 3 and fac-Ir(ppy) 3 agree well with experimental data, whereas for the free-base porphyrin, naphthalene, and the polyacenes, the obtained quantum yields significantly differ from the experimental values, because the FC and adiabatic approximations are not accurate for these molecules.

[The Spectral Analysis of Laser-Induced Plasma in Laser Welding with Various Protecting Conditions].

PubMed

Du, Xiao; Yang, Li-jun; Liu, Tong; Jiao, Jiao; Wang, Hui-chao

2016-01-01

The shielding gas plays an important role in the laser welding process and the variation of the protecting conditions has an obvious effect on the welding quality. This paper studied the influence of the change of protecting conditions on the parameters of laser-induced plasma such as electron temperature and electron density during the laser welding process by designing some experiments of reducing the shielding gas flow rate step by step and simulating the adverse conditions possibly occurring in the actual Nd : YAG laser welding process. The laser-induced plasma was detected by a fiber spectrometer to get the spectral data. So the electron temperature of laser-induced plasma was calculated by using the method of relative spectral intensity and the electron density by the Stark Broadening. The results indicated that the variation of protecting conditions had an important effect on the electron temperature and the electron density in the laser welding. When the protecting conditions were changed, the average electron temperature and the average electron density of the laser-induced plasma would change, so did their fluctuation range. When the weld was in a good protecting condition, the electron temperature, the electron density and their fluctuation were all low. Otherwise, the values would be high. These characteristics would have contribution to monitoring the process of laser welding.

Measurement of Electron Density Using the Multipole Resonance Probe, Langmuir Probe and Optical Emission Spectroscopy in Low Pressure Plasmas with Different Electron Energy Distribution Functions

NASA Astrophysics Data System (ADS)

Oberberg, Moritz; Bibinov, Nikita; Ries, Stefan; Awakowicz, Peter; Institute of Electrical Engineering; Plasma Technology Team

2016-09-01

In recently publication, the young diagnostic tool Multipole Resonance Probe (MRP) for electron density measurements was introduced. It is based on active plasma resonance spectroscopy (APRS). The probe was simulated und evaluated for different devices. The geometrical and electrical symmetry simplifies the APRS model, so that the electron density can be easily calculated from the measured resonance. In this work, low pressure nitrogen mixture plasmas with different electron energy distribution functions (EEDF) are investigated. The results of the MRP measurement are compared with measurements of a Langmuir Probe (LP) and Optical Emission Spectroscopy (OES). Probes and OES measure in different regimes of kinetic electron energy. Both probes measure electrons with low kinetic energy (<10 eV), whereas the OES is influenced by electrons with high kinetic energy which are needed for transitions of molecule bands. By the determination of the absolute intensity of N2(C-B) and N2+(B-X)electron temperature and density can be calculated. In a non-maxwellian plasma, all plasma diagnostics need to be combined.

Structural changes induced by lattice-electron interactions: SiO2 stishovite and FeTiO3 ilmenite.

PubMed

Yamanaka, Takamitsu

2005-09-01

The bright source and highly collimated beam of synchrotron radiation offers many advantages for single-crystal structure analysis under non-ambient conditions. The structure changes induced by the lattice-electron interaction under high pressure have been investigated using a diamond anvil pressure cell. The pressure dependence of electron density distributions around atoms is elucidated by a single-crystal diffraction study using deformation electron density analysis and the maximum entropy method. In order to understand the bonding electrons under pressure, diffraction intensity measurements of FeTiO3 ilmenite and gamma-SiO2 stishovite single crystals at high pressures were made using synchrotron radiation. Both diffraction studies describe the electron density distribution including bonding electrons and provide the effective charge of the cations. In both cases the valence electrons are more localized around the cations with increasing pressure. This is consistent with molecular orbital calculations, proving that the bonding electron density becomes smaller with pressure. The thermal displacement parameters of both samples are reduced with increasing pressure.

Probing the solar corona with very long baseline interferometry.

PubMed

Soja, B; Heinkelmann, R; Schuh, H

2014-06-20

Understanding and monitoring the solar corona and solar wind is important for many applications like telecommunications or geomagnetic studies. Coronal electron density models have been derived by various techniques over the last 45 years, principally by analysing the effect of the corona on spacecraft tracking. Here we show that recent observational data from very long baseline interferometry (VLBI), a radio technique crucial for astrophysics and geodesy, could be used to develop electron density models of the Sun's corona. The VLBI results agree well with previous models from spacecraft measurements. They also show that the simple spherical electron density model is violated by regional density variations and that on average the electron density in active regions is about three times that of low-density regions. Unlike spacecraft tracking, a VLBI campaign would be possible on a regular basis and would provide highly resolved spatial-temporal samplings over a complete solar cycle.

Electron-density-sensitive Line Ratios of Fe XIII– XVI from Laboratory Sources Compared to CHIANTI

NASA Astrophysics Data System (ADS)

Weller, M. E.; Beiersdorfer, P.; Soukhanovskii, V. A.; Scotti, F.; LeBlanc, B. P.

2018-02-01

We present electron-density-sensitive line ratios for Fe XIII– XVI measured in the spectral wavelength range of 200–440 Å and an electron density range of (1–4) × 1013 cm‑3. The results provide a test at the high-density limit of density-sensitive line ratios useful for astrophysical studies. The measurements were performed on the National Spherical Torus Experiment-Upgrade, where electron densities were measured independently by the laser Thomson scattering diagnostic. Spectra were collected with a flat-field grazing-incidence spectrometer, which provided a spectral resolution of up to 0.3 Å, i.e., high resolution across the broad wavelength range. The response of the instrument was relatively calibrated using spectroscopic techniques in order to improve accuracy. The line ratios are compared to other laboratory sources and the latest version of CHIANTI (8.0.2), and an agreement within 30% is found.

Density functional theory calculations of the water interactions with ZrO2 nanoparticles Y2O3 doped

NASA Astrophysics Data System (ADS)

Subhoni, Mekhrdod; Kholmurodov, Kholmirzo; Doroshkevich, Aleksandr; Asgerov, Elmar; Yamamoto, Tomoyuki; Lyubchyk, Andrei; Almasan, Valer; Madadzada, Afag

2018-03-01

Development of a new electricity generation techniques is one of the most relevant tasks, especially nowadays under conditions of extreme growth in energy consumption. The exothermic heterogeneous electrochemical energy conversion to the electric energy through interaction of the ZrO2 based nanopowder system with atmospheric moisture is one of the ways of electric energy obtaining. The questions of conversion into the electric form of the energy of water molecules adsorption in 3 mol% Y2O3 doped ZrO2 nanopowder systems were investigated using the density functional theory calculations. The density functional theory calculations has been realized as in the Kohn-Sham formulation, where the exchange-correlation potential is approximated by a functional of the electronic density. The electronic density, total energy and band structure calculations are carried out using the all-electron, full potential, linear augmented plane wave method of the electronic density and related approximations, i.e. the local density, the generalized gradient and their hybrid approximations.

Exact differential equation for the density and ionization energy of a many-particle system

NASA Technical Reports Server (NTRS)

Levy, M.; Perdew, J. P.; Sahni, V.

1984-01-01

The present investigation is concerned with relations studied by Hohenberg and Kohn (1964) and Kohn and Sham (1965). The properties of a ground-state many-electron system are determined by the electron density. The correct differential equation for the density, as dictated by density-functional theory, is presented. It is found that the ground-state density n of a many-electron system obeys a Schroedinger-like differential equation which may be solved by standard Kohn-Sham programs. Results are connected to the traditional exact Kohn-Sham theory. It is pointed out that the results of the current investigations are readily extended to spin-density functional theory.

Basis convergence of range-separated density-functional theory.

PubMed

Franck, Odile; Mussard, Bastien; Luppi, Eleonora; Toulouse, Julien

2015-02-21

Range-separated density-functional theory (DFT) is an alternative approach to Kohn-Sham density-functional theory. The strategy of range-separated density-functional theory consists in separating the Coulomb electron-electron interaction into long-range and short-range components and treating the long-range part by an explicit many-body wave-function method and the short-range part by a density-functional approximation. Among the advantages of using many-body methods for the long-range part of the electron-electron interaction is that they are much less sensitive to the one-electron atomic basis compared to the case of the standard Coulomb interaction. Here, we provide a detailed study of the basis convergence of range-separated density-functional theory. We study the convergence of the partial-wave expansion of the long-range wave function near the electron-electron coalescence. We show that the rate of convergence is exponential with respect to the maximal angular momentum L for the long-range wave function, whereas it is polynomial for the case of the Coulomb interaction. We also study the convergence of the long-range second-order Møller-Plesset correlation energy of four systems (He, Ne, N2, and H2O) with cardinal number X of the Dunning basis sets cc - p(C)V XZ and find that the error in the correlation energy is best fitted by an exponential in X. This leads us to propose a three-point complete-basis-set extrapolation scheme for range-separated density-functional theory based on an exponential formula.

Measurement of a density profile of a hot-electron plasma in RT-1 with three-chord interferometry

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

Saitoh, H.; Yano, Y.; Yoshida, Z.

2015-02-15

The electron density profile of a plasma in a magnetospheric dipole field configuration was measured with a multi-chord interferometry including a relativistic correction. In order to improve the accuracy of density reconstruction, a 75 GHz interferometer was installed at a vertical chord of the Ring Trap 1 (RT-1) device in addition to previously installed ones at tangential and another vertical chords. The density profile was calculated by using the data of three-chord interferometry including relativistic effects for a plasma consisting of hot and cold electrons generated by electron cyclotron resonance heating (ECH). The results clearly showed the effects of density peakingmore » and magnetic mirror trapping in a strongly inhomogeneous dipole magnetic field.« less

Ponderomotive force on solitary structures created during radiation pressure acceleration of thin foils

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

Tripathi, Vipin K.; Sharma, Anamika

2013-05-15

We estimate the ponderomotive force on an expanded inhomogeneous electron density profile, created in the later phase of laser irradiated diamond like ultrathin foil. When ions are uniformly distributed along the plasma slab and electron density obeys the Poisson's equation with space charge potential equal to negative of ponderomotive potential, φ=−φ{sub p}=−(mc{sup 2}/e)(γ−1), where γ=(1+|a|{sup 2}){sup 1/2}, and |a| is the normalized local laser amplitude inside the slab; the net ponderomotive force on the slab per unit area is demonstrated analytically to be equal to radiation pressure force for both overdense and underdense plasmas. In case electron density is takenmore » to be frozen as a Gaussian profile with peak density close to relativistic critical density, the ponderomotive force has non-monotonic spatial variation and sums up on all electrons per unit area to equal radiation pressure force at all laser intensities. The same result is obtained for the case of Gaussian ion density profile and self consistent electron density profile, obeying Poisson's equation with φ=−φ{sub p}.« less

Role of density gradient driven trapped electron mode turbulence in the H-mode inner core with electron heating

DOE PAGES

Ernst, D. R.; Burrell, K. H.; Guttenfelder, W.; ...

2016-05-10

In a series of DIII-D [J. L. Luxon, Nucl. Fusion 42 614 (2002)] low torque quiescent H-mode experiments show that density gradient driven TEM (DGTEM) turbulence dominates the inner core of H-Mode plasmas during strong electron cyclotron heating (ECH). By adding 3.4 MW ECH doubles T e/T i from 0.5 to 1.0, which halves the linear DGTEM critical density gradient, locally reducing density peaking, while transport in all channels displays extreme stiffness in the density gradient. This then suggests fusion -heating may degrade inner core confinement in H-Mode plasmas with moderate density peaking and low collisionality, with equal electron andmore » ion temperatures, key conditions expected in burning plasmas. Gyrokinetic simulations using GYRO [J. Candy and R. E. Waltz, J. Comp. Phys. 186 545 (2003)] (and GENE [F. Jenko et al., Phys. Plasmas 7, 1904 (2000)]) closely match not only particle, energy, and momentum fluxes, but also density fluctuation spectra from Doppler Backscattering (DBS), with and without ECH. Inner core DBS density fluctuations display discrete frequencies with adjacent toroidal mode numbers, which we identify as DGTEMs. GS2 [W. Dorland et al., Phys. Rev. Lett. 85 5579 (2000)] predictions show the DGTEM can be suppressed, to avoid degradation with electron heating, by broadening the current density profile to attain q 0 > q min > 1.« less

Nonadiabatic effects in C-Br bond scission in the photodissociation of bromoacetyl chloride

NASA Astrophysics Data System (ADS)

Valero, Rosendo; Truhlar, Donald G.

2006-11-01

Bromoacetyl chloride photodissociation has been interpreted as a paradigmatic example of a process in which nonadiabatic effects play a major role. In molecular beam experiments by Butler and co-workers [J. Chem. Phys. 95, 3848 (1991); J. Chem. Phys. 97, 355 (1992)], BrCH2C(O )Cl was prepared in its ground electronic state (S0) and excited with a laser at 248nm to its first excited singlet state (S1). The two main ensuing photoreactions are the ruptures of the C-Cl bond and of the C-Br bond. A nonadiabatic model was proposed in which the C-Br scission is strongly suppressed due to nonadiabatic recrossing at the barrier formed by the avoided crossing between the S1 and S2 states. Recent reduced-dimensional dynamical studies lend support to this model. However, another interpretation that has been given for the experimental results is that the reduced probability of C-Br scission is a consequence of incomplete intramolecular energy redistribution. To provide further insight into this problem, we have studied the energetically lowest six singlet electronic states of bromoacetyl chloride by using an ab initio multiconfigurational perturbative electronic structure method. Stationary points (minima and saddle points) and minimum energy paths have been characterized on the S0 and S1 potential energy surfaces. The fourfold way diabatization method has been applied to transform five adiabatic excited electronic states to a diabatic representation. The diabatic potential energy matrix of the first five excited singlet states has been constructed along several cuts of the potential energy hypersurfaces. The thermochemistry of the photodissociation reactions and a comparison with experimental translational energy distributions strongly suggest that nonadiabatic effects dominate the C-Br scission, but that the reaction proceeds along the energetically allowed diabatic pathway to excited-state products instead of being nonadiabatically suppressed. This conclusion is also supported by the low values of the diabatic couplings on the C-Br scission reaction path. The methodology established in the present study will be used for the construction of global potential energy surfaces suitable for multidimensional dynamics simulations to test these preliminary interpretations.

Exact analytical solutions of continuity equation for electron beams precipitating in Coulomb collisions

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

Dobranskis, R. R.; Zharkova, V. V., E-mail: valentina.zharkova@northumbria.ac.uk

2014-06-10

The original continuity equation (CE) used for the interpretation of the power law energy spectra of beam electrons in flares was written and solved for an electron beam flux while ignoring an additional free term with an electron density. In order to remedy this omission, the original CE for electron flux, considering beam's energy losses in Coulomb collisions, was first differentiated by the two independent variables: depth and energy leading to partial differential equation for an electron beam density instead of flux with the additional free term. The analytical solution of this partial differential continuity equation (PDCE) is obtained bymore » using the method of characteristics. This solution is further used to derive analytical expressions for mean electron spectra for Coulomb collisions and to carry out numeric calculations of hard X-ray (HXR) photon spectra for beams with different parameters. The solutions revealed a significant departure of electron densities at lower energies from the original results derived from the CE for the flux obtained for Coulomb collisions. This departure is caused by the additional exponential term that appeared in the updated solutions for electron differential density leading to its faster decrease at lower energies (below 100 keV) with every precipitation depth similar to the results obtained with numerical Fokker-Planck solutions. The effects of these updated solutions for electron densities on mean electron spectra and HXR photon spectra are also discussed.« less

Increasing positive ion number densities below the peak of ion-electron pair production in Titan's ionosphere

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

Vigren, E.; Galand, M.; Shebanits, O.

2014-05-01

We combine derived ion-electron pair formation rates with Cassini Radio Plasma Wave Science Langmuir Probe measurements of electron and positive ion number densities in Titan's sunlit ionosphere. We show that positive ion number densities in Titan's sunlit ionosphere can increase toward significantly lower altitudes than the peak of ion-electron pair formation despite that the effective ion-electron recombination coefficient increases. This is explained by the increased mixing ratios of negative ions, which are formed by electron attachment to neutrals. While such a process acts as a sink for free electrons, the positive ions become longer-lived as the rate coefficients for ion-anionmore » neutralization reactions are smaller than those for ion-electron dissociative recombination reactions.« less

High-efficiency acceleration in the laser wakefield by a linearly increasing plasma density

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

Dong, Kegong; Wu, Yuchi; Zhu, Bin

The acceleration length and the peak energy of the electron beam are limited by the dephasing effect in the laser wakefield acceleration with uniform plasma density. Based on 2D-3V particle in cell simulations, the effects of a linearly increasing plasma density on the electron acceleration are investigated broadly. Comparing with the uniform plasma density, because of the prolongation of the acceleration length and the gradually increasing accelerating field due to the increasing plasma density, the electron beam energy is twice higher in moderate nonlinear wakefield regime. Because of the lower plasma density, the linearly increasing plasma density can also avoidmore » the dark current caused by additional injection. At the optimal acceleration length, the electron energy can be increased from 350 MeV (uniform) to 760 MeV (linearly increasing) with the energy spread of 1.8%, the beam duration is 5 fs and the beam waist is 1.25 μm. This linearly increasing plasma density distribution can be achieved by a capillary with special gas-filled structure, and is much more suitable for experiment.« less

Plasma characteristics of direct current enhanced cylindrical inductively coupled plasma source

NASA Astrophysics Data System (ADS)

Yue, HUA; Jian, SONG; Zeyu, HAO; Chunsheng, REN

2018-06-01

Experimental results of a direct current enhanced inductively coupled plasma (DCE-ICP) source which consists of a typical cylindrical ICP source and a plate-to-grid DC electrode are reported. With the use of this new source, the plasma characteristic parameters, namely, electron density, electron temperature and plasma uniformity, are measured by Langmuir floating double probe. It is found that DC discharge enhances the electron density and decreases the electron temperature, dramatically. Moreover, the plasma uniformity is obviously improved with the operation of DC and radio frequency (RF) hybrid discharge. Furthermore, the nonlinear enhancement effect of electron density with DC + RF hybrid discharge is confirmed. The presented observation indicates that the DCE-ICP source provides an effective method to obtain high-density uniform plasma, which is desirable for practical industrial applications.

The structural, electronic and optical properties of Au-ZnO interface structure from the first-principles calculation

NASA Astrophysics Data System (ADS)

Huo, Jin-Rong; Li, Lu; Cheng, Hai-Xia; Wang, Xiao-Xu; Zhang, Guo-Hua; Qian, Ping

2018-03-01

The interface structure, electronic and optical properties of Au-ZnO are studied using the first-principles calculation based on density functional theory (DFT). Given the interfacial distance, bonding configurations and terminated surface, we built the optimal interface structure and calculated the electronic and optical properties of the interface. The total density of states, partial electronic density of states, electric charge density and atomic populations (Mulliken) are also displayed. The results show that the electrons converge at O atoms at the interface, leading to a stronger binding of interfaces and thereby affecting the optical properties of interface structures. In addition, we present the binding energies of different interface structures. When the interface structure of Au-ZnO gets changed, furthermore, varying optical properties are exhibited.

Probing the Milky Way electron density using multi-messenger astronomy

NASA Astrophysics Data System (ADS)

Breivik, Katelyn; Larson, Shane

2015-04-01

Multi-messenger observations of ultra-compact binaries in both gravitational waves and electromagnetic radiation supply highly complementary information, providing new ways of characterizing the internal dynamics of these systems, as well as new probes of the galaxy itself. Electron density models, used in pulsar distance measurements via the electron dispersion measure, are currently not well constrained. Simultaneous radio and gravitational wave observations of pulsars in binaries provide a method of measuring the average electron density along the line of sight to the pulsar, thus giving a new method for constraining current electron density models. We present this method and assess its viability with simulations of the compact binary component of the Milky Way using the public domain binary evolution code, BSE. This work is supported by NASA Award NNX13AM10G.

Structure, initial excited-state relaxation, and energy storage of rhodopsin resolved at the multiconfigurational perturbation theory level

PubMed Central

Andruniów, Tadeusz; Ferré, Nicolas; Olivucci, Massimo

2004-01-01

We demonstrate that a “brute force” quantum chemical calculation based on an ab initio multiconfigurational second order perturbation theory approach implemented in a quantum mechanics/molecular mechanics strategy can be applied to the investigation of the excited state of the visual pigment rhodopsin (Rh) with a computational error <5 kcal·mol-1. As a consequence, the simulation of the absorption and fluorescence of Rh and its retinal chromophore in solution allows for a nearly quantitative analysis of the factors determining the properties of the protein environment. More specifically, we demonstrate that the Rh environment is more similar to the “gas phase” than to the solution environment and that the so-called “opsin shift” originates from the inability of the solvent to effectively “shield” the chromophore from its counterion. The same strategy is used to investigate three transient structures involved in the photoisomerization of Rh under the assumption that the protein cavity does not change shape during the reaction. Accordingly, the analysis of the initially relaxed excited-state structure, the conical intersection driving the excited-state decay, and the primary isolable bathorhodopsin intermediate supports a mechanism where the photoisomerization coordinate involves a “motion” reminiscent of the so-called bicycle-pedal reaction coordinate. Most importantly, it is shown that the mechanism of the ∼30 kcal·mol-1 photon energy storage observed for Rh is not consistent with a model based exclusively on the change of the electrostatic interaction of the chromophore with the protein/counterion environment. PMID:15604139

Features of Electron Density Distribution in Delafossite Cualo2

NASA Astrophysics Data System (ADS)

Pogoreltsev, A. I.; Schmidt, S. V.; Gavrilenko, A. N.; Shulgin, D. A.; Korzun, B. V.; Matukhin, V. L.

2015-07-01

We have used pulsed 63,65Cu nuclear quadrupole resonance at room temperature to study the semiconductor compound CuAlO2 with a delafossite crystal structure, and we have determined the quadrupole frequency νQ = 28.12 MHz and the asymmetry parameter η ~ 0, which we used to study the features of the electron density distribution in the vicinity of the quadrupolar nucleus. In order to take into account the influence of correlation effects on the electric field gradient, we carried out ab initio calculations within the density functional theory (DFT) approximation using a set of correlation functionals VWN1RPA, VWN5, PW91LDA, CPW91, and B3LYP1. We mapped the electron density distribution in the vicinity of the quadrupolar copper nucleus for the Cu7Al6o{14/- 1} cluster and we calculated the size of the LUMO-HOMO gap, Δ ~ 3.33 eV. We established the anisotropy of the spatial electron density distribution. Based on analysis of the electron density distribution obtained, we suggest that the bond in CuAlO2 is not purely covalent.

LSMS

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

Eisenbach, Markus; Li, Ying Wai; Liu, Xianglin

2017-12-01

LSMS is a first principles, Density Functional theory based, electronic structure code targeted mainly at materials applications. LSMS calculates the local spin density approximation to the diagonal part of the electron Green's function. The electron/spin density and energy are easily determined once the Green's function is known. Linear scaling with system size is achieved in the LSMS by using several unique properties of the real space multiple scattering approach to the Green's function.

Compression of a mixed antiproton and electron non-neutral plasma to high densities

NASA Astrophysics Data System (ADS)

Aghion, Stefano; Amsler, Claude; Bonomi, Germano; Brusa, Roberto S.; Caccia, Massimo; Caravita, Ruggero; Castelli, Fabrizio; Cerchiari, Giovanni; Comparat, Daniel; Consolati, Giovanni; Demetrio, Andrea; Di Noto, Lea; Doser, Michael; Evans, Craig; Fanì, Mattia; Ferragut, Rafael; Fesel, Julian; Fontana, Andrea; Gerber, Sebastian; Giammarchi, Marco; Gligorova, Angela; Guatieri, Francesco; Haider, Stefan; Hinterberger, Alexander; Holmestad, Helga; Kellerbauer, Alban; Khalidova, Olga; Krasnický, Daniel; Lagomarsino, Vittorio; Lansonneur, Pierre; Lebrun, Patrice; Malbrunot, Chloé; Mariazzi, Sebastiano; Marton, Johann; Matveev, Victor; Mazzotta, Zeudi; Müller, Simon R.; Nebbia, Giancarlo; Nedelec, Patrick; Oberthaler, Markus; Pacifico, Nicola; Pagano, Davide; Penasa, Luca; Petracek, Vojtech; Prelz, Francesco; Prevedelli, Marco; Rienaecker, Benjamin; Robert, Jacques; Røhne, Ole M.; Rotondi, Alberto; Sandaker, Heidi; Santoro, Romualdo; Smestad, Lillian; Sorrentino, Fiodor; Testera, Gemma; Tietje, Ingmari C.; Widmann, Eberhard; Yzombard, Pauline; Zimmer, Christian; Zmeskal, Johann; Zurlo, Nicola; Antonello, Massimiliano

2018-04-01

We describe a multi-step "rotating wall" compression of a mixed cold antiproton-electron non-neutral plasma in a 4.46 T Penning-Malmberg trap developed in the context of the AEḡIS experiment at CERN. Such traps are routinely used for the preparation of cold antiprotons suitable for antihydrogen production. A tenfold antiproton radius compression has been achieved, with a minimum antiproton radius of only 0.17 mm. We describe the experimental conditions necessary to perform such a compression: minimizing the tails of the electron density distribution is paramount to ensure that the antiproton density distribution follows that of the electrons. Such electron density tails are remnants of rotating wall compression and in many cases can remain unnoticed. We observe that the compression dynamics for a pure electron plasma behaves the same way as that of a mixed antiproton and electron plasma. Thanks to this optimized compression method and the high single shot antiproton catching efficiency, we observe for the first time cold and dense non-neutral antiproton plasmas with particle densities n ≥ 1013 m-3, which pave the way for an efficient pulsed antihydrogen production in AEḡIS.

Changes in divertor conditions in response to changing core density with RMPs

DOE PAGES

Briesemeister, Alexis R.; Ahn, Joon -Wook; Canik, John M.; ...

2017-06-07

The effects of changes in core density on divertor electron temperature, density and heat flux when resonant magnetic perturbations (RMPs) are applied are presented, notably a reduction in RMP induced secondary radial peaks in the electron temperature profile at the target plate is observed when the core density is increased, which is consistent with modeling. RMPs is used here to indicated non-axisymmetric magnetic field perturbations, created using in-vessel control coils, which have components which has at least one but typically many resonances with the rotational transform of the plasma. RMPs are found to alter inter-ELM heat flux to the divertormore » by modifying the core plasma density. It is shown that applying RMPs reduces the core density and increases the inter-ELM heat flux to both the inner and outer targets. Using gas puffing to return the core density to the pre-RMP levels more than eliminates the increase in inter-ELM heat flux, but a broadening of the heat flux to the outer target remains. These measurements were made at a single toroidal location, but the peak in the heat flux profile was found near the outer strike point where simulations indicate little toroidal variation should exist and tangentially viewing diagnostics showed no evidence of strong asymmetries. In experiments where divertor Thomson scattering measurements were available it is shown that, local secondary peaks in the divertor electron temperature profile near the target plate are reduced as the core density is increased, while peaks in the divertor electron density profile near the target are increased. Furthermore, these trends observed in the divertor electron temperature and density are qualitatively reproduced by scanning the upstream density in EMC3-Eirene modeling. Measurements are presented showing that higher densities are needed to induce detachment of the outer strike point in a case where an increase in electron temperature, likely due to a change in MHD activity, is seen after RMPs are applied.« less

Changes in divertor conditions in response to changing core density with RMPs

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

Briesemeister, Alexis R.; Ahn, Joon -Wook; Canik, John M.

The effects of changes in core density on divertor electron temperature, density and heat flux when resonant magnetic perturbations (RMPs) are applied are presented, notably a reduction in RMP induced secondary radial peaks in the electron temperature profile at the target plate is observed when the core density is increased, which is consistent with modeling. RMPs is used here to indicated non-axisymmetric magnetic field perturbations, created using in-vessel control coils, which have components which has at least one but typically many resonances with the rotational transform of the plasma. RMPs are found to alter inter-ELM heat flux to the divertormore » by modifying the core plasma density. It is shown that applying RMPs reduces the core density and increases the inter-ELM heat flux to both the inner and outer targets. Using gas puffing to return the core density to the pre-RMP levels more than eliminates the increase in inter-ELM heat flux, but a broadening of the heat flux to the outer target remains. These measurements were made at a single toroidal location, but the peak in the heat flux profile was found near the outer strike point where simulations indicate little toroidal variation should exist and tangentially viewing diagnostics showed no evidence of strong asymmetries. In experiments where divertor Thomson scattering measurements were available it is shown that, local secondary peaks in the divertor electron temperature profile near the target plate are reduced as the core density is increased, while peaks in the divertor electron density profile near the target are increased. Furthermore, these trends observed in the divertor electron temperature and density are qualitatively reproduced by scanning the upstream density in EMC3-Eirene modeling. Measurements are presented showing that higher densities are needed to induce detachment of the outer strike point in a case where an increase in electron temperature, likely due to a change in MHD activity, is seen after RMPs are applied.« less

One-electron reduced density matrices of strongly correlated harmonium atoms.

PubMed

Cioslowski, Jerzy

2015-03-21

Explicit asymptotic expressions are derived for the reduced one-electron density matrices (the 1-matrices) of strongly correlated two- and three-electron harmonium atoms in the ground and first excited states. These expressions, which are valid at the limit of small confinement strength ω, yield electron densities and kinetic energies in agreement with the published values. In addition, they reveal the ω(5/6) asymptotic scaling of the exchange components of the electron-electron repulsion energies that differs from the ω(2/3) scaling of their Coulomb and correlation counterparts. The natural orbitals of the totally symmetric ground state of the two-electron harmonium atom are found to possess collective occupancies that follow a mixed power/Gaussian dependence on the angular momentum in variance with the simple power-law prediction of Hill's asymptotics. Providing rigorous constraints on energies as functionals of 1-matrices, these results are expected to facilitate development of approximate implementations of the density matrix functional theory and ensure their proper description of strongly correlated systems.

Role of Excited Nitrogen In The Ionosphere

NASA Astrophysics Data System (ADS)

Campbell, L.; Brunger, M. J.; Cartwright, D. C.; Bolorizadeh, M. A.

2006-12-01

Sunlight photoionises atoms and molecules in the Earth's upper atmosphere, producing ions and photoelectrons. The photoelectrons then produce further ionisation by electron impact. These processes produce the ionosphere, which contains various positive ions, such as NO+, N+, and O+, and an equal density of free electrons. O+(4S) ions are long-lived and so the electron density is determined mainly by the density of O+(4S). This density is dependent on ambipolar diffusion and on loss processes, which are principally reactions with O2 and N2. The reaction with N2 is known to be strongly dependent on the vibrational state of N2 but the rate constants are not well determined for the ionosphere. Vibrational excitation of N2 is produced by direct excitation by thermal electrons and photoelectrons and by cascade from the excited states of N2 that are produced by photoelectron impact. It can also be produced by a chemical reaction and by vibrational-translational transitions. The vibrational excitation is lost by deexcitation by electron impact, by step-wise quenching in collisions with O atoms, and in the reaction with O+(4S). The distribution of vibrational levels is rearranged by vibrational-vibrational transitions, and by molecular diffusion vertically in the atmosphere. A computational model that includes these processes and predicts the electron density as a function of height in the ionosphere is described. This model is a combination of a "statistical equilibrium" calculation, which is used to predict the populations of the excited states of N2, and a time-step calculation of the atmospheric reactions and processes. The latter includes a calculation of photoionisation down through the atmosphere as a function of time of day and solar activity, and calculations at 0.1 s intervals of the changing densities of positive ions, electrons and N2 in the different vibrational levels. The validity of the model is tested by comparison of the predicted electron densities with the International Reference Ionosphere (IRI) of electron density measurements. The contribution of various input parameters can be investigated by their effect on the accuracy of the calculated electron densities. Here the effects of two different sets of rate constants for the reaction of vibrationally excited N2 with O+(4S) are investigated. For reference, predictions using the different sets are compared with laboratory measurements. Then the effect of using the different sets in the computational model of the ionosphere is investigated. It is shown that one set gives predictions of electron densities that are in reasonable agreement with the IRI, while the other set does not. Both sets result in underestimation of the electron density at the height of the peak electron density in the atmosphere, suggesting that either the amount of vibrational excitation or the rate constants may be overestimated. Our comparison is made for two cases with different conditions, to give an indication of the limitations of the atmospheric modeling and also insight into ways in which the sets of rate constants may be deficient.

Optimization of plasma parameters with magnetic filter field and pressure to maximize H{sup −} ion density in a negative hydrogen ion source

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

Cho, Won-Hwi; Dang, Jeong-Jeung; Kim, June Young

2016-02-15

Transverse magnetic filter field as well as operating pressure is considered to be an important control knob to enhance negative hydrogen ion production via plasma parameter optimization in volume-produced negative hydrogen ion sources. Stronger filter field to reduce electron temperature sufficiently in the extraction region is favorable, but generally known to be limited by electron density drop near the extraction region. In this study, unexpected electron density increase instead of density drop is observed in front of the extraction region when the applied transverse filter field increases monotonically toward the extraction aperture. Measurements of plasma parameters with a movable Langmuirmore » probe indicate that the increased electron density may be caused by low energy electron accumulation in the filter region decreasing perpendicular diffusion coefficients across the increasing filter field. Negative hydrogen ion populations are estimated from the measured profiles of electron temperatures and densities and confirmed to be consistent with laser photo-detachment measurements of the H{sup −} populations for various filter field strengths and pressures. Enhanced H{sup −} population near the extraction region due to the increased low energy electrons in the filter region may be utilized to increase negative hydrogen beam currents by moving the extraction position accordingly. This new finding can be used to design efficient H{sup −} sources with an optimal filtering system by maximizing high energy electron filtering while keeping low energy electrons available in the extraction region.« less

Real-Space Multiple-Scattering Theory and Its Applications at Exascale

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

Eisenbach, Markus; Wang, Yang

In recent decades, the ab initio methods based on density functional theory (DFT) (Hohenberg and Kohn 1964, Kohn and Sham 1965) have become a widely used tool in computational materials science, which allows theoretical prediction of physical properties of materials from the first principles and theoretical interpretation of new physical phenomena found in experiments. In the framework of DFT, the original problem that requires solving a quantum mechanical equation for a many-electron system is reduced to a one-electron problem that involves an electron moving in an effective field, while the effective field potential is made up of an electrostatic potential,more » also known as Hartree potential, arising from the electronic and ion charge distribution in space and an exchange–correlation potential, which is a function of the electron density and encapsulates the exchange and correlation effects of the many-electron system. Even though the exact functional form of the exchange-correlation potential is formally unknown, a local density approximation (LDA) or a generalized gradient approximation (GGA) is usually applied so that the calculation of the exchange–correlation potential, as well as the exchange–correlation energy, becomes tractable while a required accuracy is retained. Based on DFT, ab initio electronic structure calculations for a material generally involve a self-consistent process that iterates between two computational tasks: (1) solving an one-electron Schrödinger equation, also known as Kohn–Sham equation, to obtain the electron density and, if needed, the magnetic moment density, and (2) solving the Poisson equation to obtain the electrostatic potential corresponding to the electron density and constructing the effective potential by adding the exchange–correlation potential to the electrostatic potential. This self-consistent process proceeds until a convergence criteria is reached.« less

Validation of Ionosonde Electron Density Reconstruction Algorithms with IONOLAB-RAY in Central Europe

NASA Astrophysics Data System (ADS)

Gok, Gokhan; Mosna, Zbysek; Arikan, Feza; Arikan, Orhan; Erdem, Esra

2016-07-01

Ionospheric observation is essentially accomplished by specialized radar systems called ionosondes. The time delay between the transmitted and received signals versus frequency is measured by the ionosondes and the received signals are processed to generate ionogram plots, which show the time delay or reflection height of signals with respect to transmitted frequency. The critical frequencies of ionospheric layers and virtual heights, that provide useful information about ionospheric structurecan be extracted from ionograms . Ionograms also indicate the amount of variability or disturbances in the ionosphere. With special inversion algorithms and tomographical methods, electron density profiles can also be estimated from the ionograms. Although structural pictures of ionosphere in the vertical direction can be observed from ionosonde measurements, some errors may arise due to inaccuracies that arise from signal propagation, modeling, data processing and tomographic reconstruction algorithms. Recently IONOLAB group (www.ionolab.org) developed a new algorithm for effective and accurate extraction of ionospheric parameters and reconstruction of electron density profile from ionograms. The electron density reconstruction algorithm applies advanced optimization techniques to calculate parameters of any existing analytical function which defines electron density with respect to height using ionogram measurement data. The process of reconstructing electron density with respect to height is known as the ionogram scaling or true height analysis. IONOLAB-RAY algorithm is a tool to investigate the propagation path and parameters of HF wave in the ionosphere. The algorithm models the wave propagation using ray representation under geometrical optics approximation. In the algorithm , the structural ionospheric characteristics arerepresented as realistically as possible including anisotropicity, inhomogenity and time dependence in 3-D voxel structure. The algorithm is also used for various purposes including calculation of actual height and generation of ionograms. In this study, the performance of electron density reconstruction algorithm of IONOLAB group and standard electron density profile algorithms of ionosondes are compared with IONOLAB-RAY wave propagation simulation in near vertical incidence. The electron density reconstruction and parameter extraction algorithms of ionosondes are validated with the IONOLAB-RAY results both for quiet anddisturbed ionospheric states in Central Europe using ionosonde stations such as Pruhonice and Juliusruh . It is observed that IONOLAB ionosonde parameter extraction and electron density reconstruction algorithm performs significantly better compared to standard algorithms especially for disturbed ionospheric conditions. IONOLAB-RAY provides an efficient and reliable tool to investigate and validate ionosonde electron density reconstruction algorithms, especially in determination of reflection height (true height) of signals and critical parameters of ionosphere. This study is supported by TUBITAK 114E541, 115E915 and Joint TUBITAK 114E092 and AS CR 14/001 projects.

Symmetry properties of the electron density and following from it limits on the KS-DFT applications

NASA Astrophysics Data System (ADS)

Kaplan, Ilya G.

2018-03-01

At present, the Density Functional Theory (DFT) approach elaborated by Kohn with co-authors more than 50 years ago became the most widely used method for study molecules and solids. Using modern computation facilities, it can be applied to systems with million atoms. In the atmosphere of such great popularity, it is particularly important to know the limits of the applicability of DFT methods. In this report, I will discuss two cases when the conventional DFT approaches, using only electron density ρ and its gradients, cannot be applied (I will not consider the Ψ-versions of DFT). The first case is quite evident. In the degenerated states, the electron density may not be defined, since electronic and nuclear motions cannot be separated, the vibronic interaction mixed them. The second case is related to the spin of the state. As it was rigorously proved by group theoretical methods at the theorem level, the electron density does not depend on the total spin S of the arbitrary N-electron state. It means that the Kohn-Sham equations have the same form for states with different S. The critical survey of elaborated DFT procedures, taking into account spin, shows that they modified only exchange functionals, the correlation functionals do not correspond to the spin of the state. The point is that the conception of spin cannot be defined in the framework of the electron density formalism, which corresponds to the one-particle reduced density matrix. This is the main reason of the problems arising in the study by DFT of magnetic properties of the transition metals. The possible way of resolving these problems can be found in the two-particle reduced density matrix formulation of DFT.

The Relationship between Ionospheric Slab Thickness and the Peak Density Height, hmF2

NASA Astrophysics Data System (ADS)

Meehan, J.; Sojka, J. J.

2017-12-01

The electron density profile is one of the most critical elements in the ionospheric modeling-related applications today. Ionosphere parameters, hmF2, the height of the peak density layer, and slab thickness, the ratio of the total electron content, TEC, to the peak density value, NmF2, are generally obtained from any global sounding observation network and are easily incorporated into models, theoretical or empirical, as numerical representations. Slab thickness is a convenient one-parameter summary of the electron density profile and can relate a variety of elements of interest that effect the overall electron profile shape, such as the neutral and ionospheric temperatures and gradients, the ionospheric composition, and dynamics. Using ISR data from the 2002 Millstone Hill ISR data campaign, we found, for the first time, slab thickness to be correlated to hmF2. For this, we introduce a new ionospheric index, k, which ultimately relates electron density parameters and can be a very useful tool for describing the topside ionosphere shape. Our study is an initial one location, one season, 30-day study, and future work is needed to verify the robustness of our claim. Generally, the ionospheric profile shape, requires knowledge of several ionospheric parameters: electron, ion and neutral temperatures, ion composition, electric fields, and neutral winds, and is dependent upon seasons, local time, location, and the level of solar and geomagnetic activity; however, with this new index, only readily-available, ionospheric density information is needed. Such information, as used in this study, is obtained from a bottomside electron density profile provided by an ionosonde, and TEC data provided by a local, collocated GPS receiver.

Plasma response to the injection of an electron beam

NASA Technical Reports Server (NTRS)

Singh, N.; Schunk, R. W.

1984-01-01

The results of Vlasov-Poisson-solver numerical simulations of the detailed temporal response of a Maxwellian plasma to the sudden injection of an electron beam are presented in graphs and maps and discussed. Phenomena characterized include ion bursts, electron shocks and holes, plasma heating and expulsion, density gradients; cavitons, deep-density-front and solitary-pulse propagation down the density gradient, and Bunemann-mode excitation leading to formation of a virtual cathode and double layers which are at first monotonic or have low-potential-side dips or high-potential-side bumps and become strong as the electron-current density decreases. The strength of the double layer is found to be roughly proportional to the beam energy.

Measuring the density of a molecular cluster injector via visible emission from an electron beam.

PubMed

Lundberg, D P; Kaita, R; Majeski, R; Stotler, D P

2010-10-01

A method to measure the density distribution of a dense hydrogen gas jet is presented. A Mach 5.5 nozzle is cooled to 80 K to form a flow capable of molecular cluster formation. A 250 V, 10 mA electron beam collides with the jet and produces H(α) emission that is viewed by a fast camera. The high density of the jet, several 10(16) cm(-3), results in substantial electron depletion, which attenuates the H(α) emission. The attenuated emission measurement, combined with a simplified electron-molecule collision model, allows us to determine the molecular density profile via a simple iterative calculation.

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

Sun, Jianwei; Yang, Zenghui; Peng, Haowei

The uniform electron gas and the hydrogen atom play fundamental roles in condensed matter physics and quantum chemistry. The former has an infinite number of electrons uniformly distributed over the neutralizing positively charged background, and the latter only one electron bound to the proton. The uniform electron gas was used to derive the local spin density approximation to the exchange-correlation functional that undergirds the development of the Kohn-Sham density functional theory. We show here that the ground-state exchange-correlation energies of the hydrogen atom and many other 1- and 2-electron systems are modeled surprisingly well by a different local spin densitymore » approximation (LSDA0). LSDA0 is constructed to satisfy exact constraints but agrees surprisingly well with the exact results for a uniform two-electron density in a finite, curved three-dimensional space. We also apply LSDA0 to excited or noded 1-electron densities, where it works less well. Furthermore, we show that the localization of the exact exchange hole for a 1- or 2-electron ground state can be measured by the ratio of the exact exchange energy to its optimal lower bound.« less

Optical Diagnostics in the Gaseous Electronics Conference Reference Cell

PubMed Central

Hebner, G. A.; Greenberg, K. E.

1995-01-01

A number of laser-induced fluorescence and absorption spectroscopy studies have been conducted using Gaseous Electronics Conference Reference Cells. Laser-induced fluorescence has been used to measure hydrogen atom densities, to measure argon metastable spatial profiles, to determine the sheath electric field, and to infer the electron density and temperature. Absorption spectroscopy, using lamp sources and diode lasers, has been used to measure metastable atom densities in helium and argon discharges and fluorocarbon densities in silicon etching discharges. The experimental techniques and sample results of these investigations are reviewed. PMID:29151748

Electron momentum density and band structure calculations of α- and β-GeTe

NASA Astrophysics Data System (ADS)

Vadkhiya, Laxman; Arora, Gunjan; Rathor, Ashish; Ahuja, B. L.

2011-12-01

We have measured isotropic experimental Compton profile of α-GeTe by employing high energy (662 keV) γ-radiation from a 137Cs isotope. To compare our experiment, we have also computed energy bands, density of states, electron momentum densities and Compton profiles of α- and β-phases of GeTe using the linear combination of atomic orbitals method. The electron momentum density is found to play a major role in understanding the topology of bands in the vicinity of the Fermi level. It is seen that the density functional theory (DFT) with generalised gradient approximation is relatively in better agreement with the experiment than the local density approximation and hybrid Hartree-Fock/DFT.

Proportionality between Doppler noise and integrated signal path electron density validated by differenced S-X range

NASA Technical Reports Server (NTRS)

Berman, A. L.

1977-01-01

Observations of Viking differenced S-band/X-band (S-X) range are shown to correlate strongly with Viking Doppler noise. A ratio of proportionality between downlink S-band plasma-induced range error and two-way Doppler noise is calculated. A new parameter (similar to the parameter epsilon which defines the ratio of local electron density fluctuations to mean electron density) is defined as a function of observed data sample interval (Tau) where the time-scale of the observations is 15 Tau. This parameter is interpreted to yield the ratio of net observed phase (or electron density) fluctuations to integrated electron density (in RMS meters/meter). Using this parameter and the thin phase-changing screen approximation, a value for the scale size L is calculated. To be consistent with Doppler noise observations, it is seen necessary for L to be proportional to closest approach distance a, and a strong function of the observed data sample interval, and hence the time-scale of the observations.

Influence of the electron density on the characteristics of terahertz waves generated under laser–cluster interaction

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

Frolov, A. A., E-mail: frolov@ihed.ras.ru

2016-12-15

A theory of generation of terahertz radiation under laser–cluster interaction, developed earlier for an overdense cluster plasma [A. A. Frolov, Plasma Phys. Rep. 42. 637 (2016)], is generalized for the case of arbitrary electron density. The spectral composition of radiation is shown to substantially depend on the density of free electrons in the cluster. For an underdense cluster plasma, there is a sharp peak in the terahertz spectrum at the frequency of the quadrupole mode of a plasma sphere. As the electron density increases to supercritical values, this spectral line vanishes and a broad maximum at the frequency comparable withmore » the reciprocal of the laser pulse duration appears in the spectrum. The dependence of the total energy of terahertz radiation on the density of free electrons is analyzed. The radiation yield is shown to increase significantly under resonance conditions, when the laser frequency is close to the eigenfrequency of the dipole or quadrupole mode of a plasma sphere.« less

Bottomside Ionospheric Electron Density Specification using Passive High Frequency Signals

NASA Astrophysics Data System (ADS)

Kaeppler, S. R.; Cosgrove, R. B.; Mackay, C.; Varney, R. H.; Kendall, E. A.; Nicolls, M. J.

2016-12-01

The vertical bottomside electron density profile is influenced by a variety of natural sources, most especially traveling ionospheric disturbances (TIDs). These disturbances cause plasma to be moved up or down along the local geomagnetic field and can strongly impact the propagation of high frequency radio waves. While the basic physics of these perturbations has been well studied, practical bottomside models are not well developed. We present initial results from an assimilative bottomside ionosphere model. This model uses empirical orthogonal functions based on the International Reference Ionosphere (IRI) to develop a vertical electron density profile, and features a builtin HF ray tracing function. This parameterized model is then perturbed to model electron density perturbations associated with TIDs or ionospheric gradients. Using the ray tracing feature, the model assimilates angle of arrival measurements from passive HF transmitters. We demonstrate the effectiveness of the model using angle of arrival data. Modeling results of bottomside electron density specification are compared against suitable ancillary observations to quantify accuracy of our model.

Solar corona electron density distribution

NASA Astrophysics Data System (ADS)

Esposito, P. B.; Edenhofer, P.; Lueneburg, E.

1980-07-01

The paper discusses the three and one-half months of single-frequency time delay data which were acquired from the Helios 2 spacecraft around the time of its solar occultation. The excess time delay due to integrated effect of free electrons along the signal's ray path could be separated and modeled following the determination of the spacecraft trajectory. An average solar corona and equatorial electron density profile during solar minimum were deduced from the time delay measurements acquired within 5-60 solar radii of the sun. As a point of reference at 10 solar radii from the sun, an average electron density was 4500 el/cu cm. However, an asymmetry was found in the electron density as the ray path moved from the west to east solar limb. This may be related to the fact that during entry into occultation the heliographic latitude of the ray path was about 6 deg, while during exit it was 7 deg. The Helios density model is compared with similar models deduced from different experimental techniques.

Fast electron microscopy via compressive sensing

DOEpatents

Larson, Kurt W; Anderson, Hyrum S; Wheeler, Jason W

2014-12-09

Various technologies described herein pertain to compressive sensing electron microscopy. A compressive sensing electron microscope includes a multi-beam generator and a detector. The multi-beam generator emits a sequence of electron patterns over time. Each of the electron patterns can include a plurality of electron beams, where the plurality of electron beams is configured to impart a spatially varying electron density on a sample. Further, the spatially varying electron density varies between each of the electron patterns in the sequence. Moreover, the detector collects signals respectively corresponding to interactions between the sample and each of the electron patterns in the sequence.

Density functional and theoretical study of the temperature and pressure dependency of the plasmon energy of solids

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

Attarian Shandiz, M., E-mail: mohammad.attarianshandiz@mail.mcgill.ca; Gauvin, R.

The temperature and pressure dependency of the volume plasmon energy of solids was investigated by density functional theory calculations. The volume change of crystal is the major factor responsible for the variation of valence electron density and plasmon energy in the free electron model. Hence, to introduce the effect of temperature and pressure for the density functional theory calculations of plasmon energy, the temperature and pressure dependency of lattice parameter was used. Also, by combination of the free electron model and the equation of state based on the pseudo-spinodal approach, the temperature and pressure dependency of the plasmon energy wasmore » modeled. The suggested model is in good agreement with the results of density functional theory calculations and available experimental data for elements with the free electron behavior.« less

Laser induced photo-detachment of O2 in DC discharge

NASA Astrophysics Data System (ADS)

J, R. LEGORRETA; J, L. PATIÑO; F, B. YOUSIF

2018-07-01

Determination of the negative ion number density of {{{O}}}{{2}}- and {{{O}}}- in a DC discharge of oxygen plasma was made employing Langmuir probe in conjunction with eclipse laser photo-detachment technique. The temporal evolution of the extra electrons resulting from the photo-detachment of {{{O}}}{{2}}- and {{{O}}}- were used to evaluate the negative ion number density. The ratio of {{{O}}}{{2}}- number density to {{{O}}}- varied from 0.03 to 0.22. Number density of both {{{O}}}{{2}}- and {{{O}}}- increased with increasing power and decreased as the pressure was increased. Electron number density was evaluated from the electron energy distribution function (EEDF) using the I–V recorded characteristic curves. Electron temperature between 2 and 2.7 eV were obtained. Influence of the {{{O}}}{{2}}({a}{{1}}{{{Δ }}}{{g}}) metastable state is discussed.

Measuring the Density of States of the Inner and Outer Wall of Double-Walled Carbon Nanotubes.

PubMed

Chambers, Benjamin A; Shearer, Cameron J; Yu, LePing; Gibson, Christopher T; Andersson, Gunther G

2018-06-19

The combination of ultraviolet photoelectron spectroscopy and metastable helium induced electron spectroscopy is used to determine the density of states of the inner and outer coaxial carbon nanotubes. Ultraviolet photoelectron spectroscopy typically measures the density of states across the entire carbon nanotube, while metastable helium induced electron spectroscopy measures the density of states of the outermost layer alone. The use of double-walled carbon nanotubes in electronic devices allows for the outer wall to be functionalised whilst the inner wall remains defect free and the density of states is kept intact for electron transport. Separating the information of the inner and outer walls enables development of double-walled carbon nanotubes to be independent, such that the charge transport of the inner wall is maintained and confirmed whilst the outer wall is modified for functional purposes.

Probing Electron Dynamics with the Laplacian of the Momentum Density

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

Sukumar, N.; MacDougall, Preston J.; Levit, M. Creon

2012-09-24

This chapter in the above-titled monograph presents topological analysis of the Laplacian of the electron momentum density in organic molecules. It relates topological features in this distribution to chemical and physical properties, particularly aromaticity and electron transport.

Density functional theory of electron transfer beyond the Born-Oppenheimer approximation: Case study of LiF

NASA Astrophysics Data System (ADS)

Li, Chen; Requist, Ryan; Gross, E. K. U.

2018-02-01

We perform model calculations for a stretched LiF molecule, demonstrating that nonadiabatic charge transfer effects can be accurately and seamlessly described within a density functional framework. In alkali halides like LiF, there is an abrupt change in the ground state electronic distribution due to an electron transfer at a critical bond length R = Rc, where an avoided crossing of the lowest adiabatic potential energy surfaces calls the validity of the Born-Oppenheimer approximation into doubt. Modeling the R-dependent electronic structure of LiF within a two-site Hubbard model, we find that nonadiabatic electron-nuclear coupling produces a sizable elongation of the critical Rc by 0.5 bohr. This effect is very accurately captured by a simple and rigorously derived correction, with an M-1 prefactor, to the exchange-correlation potential in density functional theory, M = reduced nuclear mass. Since this nonadiabatic term depends on gradients of the nuclear wave function and conditional electronic density, ∇Rχ(R) and ∇Rn(r, R), it couples the Kohn-Sham equations at neighboring R points. Motivated by an observed localization of nonadiabatic effects in nuclear configuration space, we propose a local conditional density approximation—an approximation that reduces the search for nonadiabatic density functionals to the search for a single function y(n).

Development of a Nomarski-type multi-frame interferometer as a time and space resolving diagnostics for the free electron density of laser-generated plasma

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

Boerner, M.; Frank, A.; Pelka, A.

2012-04-15

This article reports on the development and set-up of a Nomarski-type multi-frame interferometer as a time and space resolving diagnostics of the free electron density in laser-generated plasma. The interferometer allows the recording of a series of 4 images within 6 ns of a single laser-plasma interaction. For the setup presented here, the minimal accessible free electron density is 5 x 10{sup 18} cm{sup -3}, the maximal one is 2 x 10{sup 20} cm{sup -3}. Furthermore, it provides a resolution of the electron density in space of 50 {mu}m and in time of 0.5 ns for one image with amore » customizable magnification in space for each of the 4 images. The electron density was evaluated from the interferograms using an Abel inversion algorithm. The functionality of the system was proven during first experiments and the experimental results are presented and discussed. A ray tracing procedure was realized to verify the interferometry pictures taken. In particular, the experimental results are compared to simulations and show excellent agreement, providing a conclusive picture of the evolution of the electron density distribution.« less

Rocket observations of the ionosphere during the eclipse of 26 February 1979

NASA Technical Reports Server (NTRS)

Mcinerney, M. K.; Smith, L. G.

1984-01-01

Electron density profiles and energetic particle fluxes were determined from two rockets launched, respectively, at the beginning and end of totality during the solar eclipse of 26 February 1979. These, and one other rocket at the same time of day on 24 February 1979, were launched from near Red Lake, Ontario. The electron density profile from 24 February shows the electron density to be normal above 110 km, to rocket apogee. Below 110 km, the electron density is enhanced, by an order of magnitude in the D region, compared with data from Wallops Island at the same solar zenith angle (63 deg). The enhancement is qualitatively explained by the large flux of field aligned energetic particles observed on the same rocket. During totality (on 26 February) the electron density above 110 km to rocket apogee is reduced by a factor of about three. Below 110 km, the electron density is much greater than observed during previous eclipses. The particle flux measured on the 26 February was an order of magnitude less than that on the 24 February but showed greater variability, particularly at the higher energies (100 keV). A feature of the particle flux is that, for the two rockets that were separated horizontally by 38 km while above the absorbing region, the variations are uncorrelated.

Two-Dimensional Electron Density Measurement of Positive Streamer Discharge in Atmospheric-Pressure Air

NASA Astrophysics Data System (ADS)

Inada, Yuki; Ono, Ryo; Kumada, Akiko; Hidaka, Kunihiko; Maeyama, Mitsuaki

2016-09-01

The electron density of streamer discharges propagating in atmospheric-pressure air is crucially important for systematic understanding of the production mechanisms of reactive species utilized in wide ranging applications such as medical treatment, plasma-assisted ignition and combustion, ozone production and environmental pollutant processing. However, electron density measurement during the propagation of the atmospheric-pressure streamers is extremely difficult by using the conventional localized type measurement systems due to the streamer initiation jitters and the irreproducibility in the discharge paths. In order to overcome the difficulties, single-shot two-dimensional electron density measurement was conducted by using a Shack-Hartmann type laser wavefront sensor. The Shack-Hartmann sensor with a temporal resolution of 2 ns was applied to pulsed positive streamer discharges generated in an air gap between pin-to-plate electrodes. The electron density a few ns after the streamer initiation was 7*1021m-3 and uniformly distributed along the streamer channel. The electron density and its distribution profile were compared with a previous study simulating similar streamers, demonstrating good agreement. This work was supported in part by JKA and its promotion funds from KEIRIN RACE. The authors like to thank Mr. Kazuaki Ogura and Mr. Kaiho Aono of The University of Tokyo for their support during this work.

On the origin of red and blue shifts of X-H and C-H stretching vibrations in formic acid (formate ion) and proton donor complexes.

PubMed

Tâme Parreira, Renato Luis; Galembeck, Sérgio Emanuel; Hobza, Pavel

2007-01-08

Complexes between formic acid or formate anion and various proton donors (HF, H(2)O, NH(3), and CH(4)) are studied by the MP2 and B3LYP methods with the 6-311++G(3df,3pd) basis set. Formation of a complex is characterized by electron-density transfer from electron donor to ligands. This transfer is much larger with the formate anion, for which it exceeds 0.1 e. Electron-density transfer from electron lone pairs of the electron donor is directed into sigma* antibonding orbitals of X--H bonds of the electron acceptor and leads to elongation of the bond and a red shift of the X--H stretching frequency (standard H-bonding). However, pronounced electron-density transfer from electron lone pairs of the electron donor also leads to reorganization of the electron density in the electron donor, which results in changes in geometry and vibrational frequency. These changes are largest for the C--H bonds of formic acid and formate anion, which do not participate in H-bonding. The resulting blue shift of this stretching frequency is substantial and amounts to almost 35 and 170 cm(-1), respectively.

Self-consistent many-electron theory of electron work functions and surface potential characteristics for selected metals

NASA Technical Reports Server (NTRS)

Smith, J. R.

1969-01-01

Electron work functions, surface potentials, and electron number density distributions and electric fields in the surface region of 26 metals were calculated from first principles within the free electron model. Calculation proceeded from an expression of the total energy as a functional of the electron number density, including exchange and correlation energies, as well as a first inhomogeneity term. The self-consistent solution was obtained via a variational procedure. Surface barriers were due principally to many-body effects; dipole barriers were small only for some alkali metals, becoming quite large for the transition metals. Surface energies were inadequately described by this model, which neglects atomistic effects. Reasonable results were obtained for electron work functions and surface potential characteristics, maximum electron densities varying by a factor of over 60.

Beta electron fluxes inside a magnetic plasma cavern: Calculation and comparison with experiment

NASA Astrophysics Data System (ADS)

Stupitskii, E. L.; Smirnov, E. V.; Kulikova, N. A.

2010-12-01

We study the possibility of electrostatic blanking of beta electrons in the expanding spherical blob of a radioactive plasma in a rarefied ionosphere. From numerical studies on the dynamics of beta electrons departing a cavern, we obtain the form of a function that determines the portion of departing electrons and calculate the flux density of beta electrons inside the cavern in relation to the Starfish Prime nuclear blast. We show that the flux density of electrons in geomagnetic flux tubes and inside the cavern depend on a correct allowance for the quantity of beta electrons returning to the cavern. On the basis of a physical analysis, we determine the approximate criterion for the return of electrons from a geomagnetic flux tube to the cavern. We compare calculation results in terms of the flux density of beta electrons inside the cavern with the recently published experimental results from operation Starfish Prime.

Application of the weighted-density approximation to the accurate description of electron-positron correlation effects in materials

NASA Astrophysics Data System (ADS)

Callewaert, Vincent; Saniz, Rolando; Barbiellini, Bernardo; Bansil, Arun; Partoens, Bart

2017-08-01

We discuss positron-annihilation lifetimes for a set of illustrative bulk materials within the framework of the weighted-density approximation (WDA). The WDA can correctly describe electron-positron correlations in strongly inhomogeneous systems, such as surfaces, where the applicability of (semi-)local approximations is limited. We analyze the WDA in detail and show that the electrons which cannot screen external charges efficiently, such as the core electrons, cannot be treated accurately via the pair correlation of the homogeneous electron gas. We discuss how this problem can be addressed by reducing the screening in the homogeneous electron gas by adding terms depending on the gradient of the electron density. Further improvements are obtained when core electrons are treated within the LDA and the valence electron using the WDA. Finally, we discuss a semiempirical WDA-based approach in which a sum rule is imposed to reproduce the experimental lifetimes.

The preplasma effect on the properties of the shock wave driven by a fast electron beam

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

Llor Aisa, E.; Ribeyre, X.; Tikhonchuk, V. T.

2016-08-15

Strong shock wave generation by a mono-energetic fast electron beam in a plasma with an increasing density profile is studied theoretically. The proposed analytical model describes the shock wave characteristics for a homogeneous plasma preceded by a low density precursor. The shock pressure and the time of shock formation depend on the ratio of the electron stopping length to the preplasma areal density and on the initial energy of injected electrons. The conclusions of theoretical model are confirmed in numerical simulations.

Window for Optimal Frequency Operation and Reliability of 3DEG and 2DEG Channels for Oxide Microwave MESFETs and HFETs

DTIC Science & Technology

2016-04-01

noise, and energy relaxation for doped zinc-oxide and structured ZnO transistor materials with a 2-D electron gas (2DEG) channel subjected to a strong...function on the time delay. Closed symbols represent the Monte Carlo data with hot-phonon effect at different electron gas density: 1•1017 cm-3...Monte Carlo simulation is performed for electron gas density of 1•1018 cm-3. Figure 18. Monte Carlo simulation of density-dependent hot-electron energy

Spectral density method to Anderson-Holstein model

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

Chebrolu, Narasimha Raju, E-mail: narasimharaju.phy@gmail.com; Chatterjee, Ashok

Two-parameter spectral density function of a magnetic impurity electron in a non-magnetic metal is calculated within the framework of the Anderson-Holstein model using the spectral density approximation method. The effect of electron-phonon interaction on the spectral function is investigated.

A tale of two theories: How the adiabatic response and ULF waves affect relativistic electrons

NASA Astrophysics Data System (ADS)

Green, J. C.; Kivelson, M. G.

2001-11-01

Using data from the Comprehensive Energetic Particle and Pitch Angle Distribution (CEPPAD)-High Sensitivity Telescope (HIST) instrument on the Polar spacecraft and ground magnetometer data from the 210 meridian magnetometer chain, we test the ULF wave drift resonance theory proposed to explain relativistic electron phase space density enhancements. We begin by investigating changes in electron flux due to the ``Dst effect.'' The Dst effect refers to the adiabatic response of relativistic electrons to changes in the magnetic field characterized by the Dst index. The Dst effect, assuming no loss or addition of new electrons, produces reversible order of magnitude changes in relativistic electrons flux measured at fixed energy, but it cannot account for the flux enhancement that occurs in the recovery phase of most storms. Liouville's theorem states that phase space density expressed in terms of constant adiabatic invariants is unaffected by adiabatic field changes and thus is insensitive to the Dst effect. It is therefore useful to express flux measurements in terms of phase space densities at constant first, second and third adiabatic invariants. The phase space density is determined from the CEPPAD-HIST electron detector that measures differential directional flux of electrons from 0.7 to 9 MeV and the Tsyganenko 96 field model. The analysis is done for January to June 1997. The ULF wave drift resonance theory that we test proposes that relativistic electrons are accelerated by an m=2 toroidal or poloidal mode wave whose frequency equals the drift frequency of the electron. The theory is tested by comparing the relativistic electron phase space densities to wave power determined at three ground stations with L* values of 4.0, 5.7 and 6.2. Comparison of the wave data to the phase space densities shows that five out of nine storm events are consistent with the ULF wave drift resonance mechanism, three out of nine give ambiguous support to the model, and one event has high ULF wave power at the drift frequency of the electrons but no corresponding phase space density enhancement suggesting that ULF wave power alone is not sufficient to cause an electron response. Two explanations of the anomalous event are investigated including excessive loss of electrons to the magnetopause and wave duration.

Basis convergence of range-separated density-functional theory

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

Franck, Odile, E-mail: odile.franck@etu.upmc.fr; Mussard, Bastien, E-mail: bastien.mussard@upmc.fr; CNRS, UMR 7616, Laboratoire de Chimie Théorique, F-75005 Paris

2015-02-21

Range-separated density-functional theory (DFT) is an alternative approach to Kohn-Sham density-functional theory. The strategy of range-separated density-functional theory consists in separating the Coulomb electron-electron interaction into long-range and short-range components and treating the long-range part by an explicit many-body wave-function method and the short-range part by a density-functional approximation. Among the advantages of using many-body methods for the long-range part of the electron-electron interaction is that they are much less sensitive to the one-electron atomic basis compared to the case of the standard Coulomb interaction. Here, we provide a detailed study of the basis convergence of range-separated density-functional theory. Wemore » study the convergence of the partial-wave expansion of the long-range wave function near the electron-electron coalescence. We show that the rate of convergence is exponential with respect to the maximal angular momentum L for the long-range wave function, whereas it is polynomial for the case of the Coulomb interaction. We also study the convergence of the long-range second-order Møller-Plesset correlation energy of four systems (He, Ne, N{sub 2}, and H{sub 2}O) with cardinal number X of the Dunning basis sets cc − p(C)V XZ and find that the error in the correlation energy is best fitted by an exponential in X. This leads us to propose a three-point complete-basis-set extrapolation scheme for range-separated density-functional theory based on an exponential formula.« less

Global multi-dimensional modeling of ionospheric electron density using GNSS measurements and IRI model

NASA Astrophysics Data System (ADS)

Alizadeh, M.; Schuh, H.; Schmidt, M. G.

2012-12-01

In the last decades Global Navigation Satellite System (GNSS) has turned into a promising tool for probing the ionosphere. The classical input data for developing Global Ionosphere Maps (GIM) is obtained from the dual-frequency GNSS observations. Simultaneous observations of GNSS code or carrier phase at each frequency is used to form a geometric-free linear combination which contains only the ionospheric refraction term and the differential inter-frequency hardware delays. To relate the ionospheric observable to the electron density, a model is used that represents an altitude-dependent distribution of the electron density. This study aims at developing a global multi-dimensional model of the electron density using simulated GNSS observations from about 150 International GNSS Service (IGS) ground stations. Due to the fact that IGS stations are in-homogenously distributed around the world and the accuracy and reliability of the developed models are considerably lower in the area not well covered with IGS ground stations, the International Reference Ionosphere (IRI) model has been used as a background model. The correction term is estimated by applying spherical harmonics expansion to the GNSS ionospheric observable. Within this study this observable is related to the electron density using different functions for the bottom-side and top-side ionosphere. The bottom-side ionosphere is represented by an alpha-Chapman function and the top-side ionosphere is represented using the newly proposed Vary-Chap function.aximum electron density, IRI background model (elec/m3), day 202 - 2010, 0 UT eight of maximum electron density, IRI background model (km), day 202 - 2010, 0 UT

The correlated blanching of synaptic bodies and reduction in afferent firing rates caused by transmitter-depleting agents in the frog semicircular canal

NASA Technical Reports Server (NTRS)

Guth, P.; Norris, C.; Fermin, C. D.; Pantoja, M.

1993-01-01

Synaptic bodies (SBs) associated with rings of synaptic vesicles and well-defined, pre- and post-synaptic membrane structures are indicators of maturity in most hair cell-afferent nerve junctions. The role of the SBs remains elusive despite several experiments showing that they may be involved in storage of neurotransmitter. Our results demonstrate that SBs of the adult posterior semicircular canal (SCC) cristae hair cells become less electron dense following incubation of the SCC with the transmitter-depleting drug tetrabenazine (TBZ). Objective quantification and comparison of the densities of the SBs in untreated and TBZ-treated frog SCC demonstrated that TBZ significantly decreased the electron density of SBs. This reduction in electron density was accompanied by a reduction in firing rates of afferent fibers innervating the posterior SCC. A second transmitter-depleting drug, guanethidine, previously shown to reduce the electron density of hair cell SBs, also reduced the firing rates of afferent fibers innervating the posterior SCC. In contrast, the electron density of dense granules (DG), similar in size and shape to synaptic bodies (SB) in hair cells, did not change after incubation in TBZ, thus indicating that granules and SBs are not similar in regard to their electron density. The role of SBs in synaptic transmission and the transmitter, if any, stored in the SBs remain unknown. Nonetheless, the association of the lessening of electron density with a reduction in afferent firing rate provides impetus for the further investigation of the SB's role in neurotransmission.

Tissue heterogeneity in the anterior chest wall and its influence on radiation therapy of the internal mammary lymph nodes.

PubMed

Lindskoug, B; Hultborn, A

1976-04-01

The density (g cm-3) and electron density (cm-3) of material from the anterior chest wall was determined. On the average, the difference in density between rib bone and intercostal soft tissue amounted to 17 per cent, while the difference in electron density was 7 per cent. The attenuation of high-energy electrons in specimens of rib bone, costal cartilage and sternum was determined by an experimental technique, using dosimeters of TLD material. The results of determinations of attenuation of 10 and 13 MeV electrons in fresh specimens are presented. It is concluded that electron radiation in the energy range of 10 to 13 MeV can be utilized for irradiation of lymph glands along the internal thoracic vessels without risk of underdosage.

Path Integrals for Electronic Densities, Reactivity Indices, and Localization Functions in Quantum Systems

PubMed Central

Putz, Mihai V.

2009-01-01

The density matrix theory, the ancestor of density functional theory, provides the immediate framework for Path Integral (PI) development, allowing the canonical density be extended for the many-electronic systems through the density functional closure relationship. Yet, the use of path integral formalism for electronic density prescription presents several advantages: assures the inner quantum mechanical description of the system by parameterized paths; averages the quantum fluctuations; behaves as the propagator for time-space evolution of quantum information; resembles Schrödinger equation; allows quantum statistical description of the system through partition function computing. In this framework, four levels of path integral formalism were presented: the Feynman quantum mechanical, the semiclassical, the Feynman-Kleinert effective classical, and the Fokker-Planck non-equilibrium ones. In each case the density matrix or/and the canonical density were rigorously defined and presented. The practical specializations for quantum free and harmonic motions, for statistical high and low temperature limits, the smearing justification for the Bohr’s quantum stability postulate with the paradigmatic Hydrogen atomic excursion, along the quantum chemical calculation of semiclassical electronegativity and hardness, of chemical action and Mulliken electronegativity, as well as by the Markovian generalizations of Becke-Edgecombe electronic focalization functions – all advocate for the reliability of assuming PI formalism of quantum mechanics as a versatile one, suited for analytically and/or computationally modeling of a variety of fundamental physical and chemical reactivity concepts characterizing the (density driving) many-electronic systems. PMID:20087467

Path integrals for electronic densities, reactivity indices, and localization functions in quantum systems.

PubMed

Putz, Mihai V

2009-11-10

The density matrix theory, the ancestor of density functional theory, provides the immediate framework for Path Integral (PI) development, allowing the canonical density be extended for the many-electronic systems through the density functional closure relationship. Yet, the use of path integral formalism for electronic density prescription presents several advantages: assures the inner quantum mechanical description of the system by parameterized paths; averages the quantum fluctuations; behaves as the propagator for time-space evolution of quantum information; resembles Schrödinger equation; allows quantum statistical description of the system through partition function computing. In this framework, four levels of path integral formalism were presented: the Feynman quantum mechanical, the semiclassical, the Feynman-Kleinert effective classical, and the Fokker-Planck non-equilibrium ones. In each case the density matrix or/and the canonical density were rigorously defined and presented. The practical specializations for quantum free and harmonic motions, for statistical high and low temperature limits, the smearing justification for the Bohr's quantum stability postulate with the paradigmatic Hydrogen atomic excursion, along the quantum chemical calculation of semiclassical electronegativity and hardness, of chemical action and Mulliken electronegativity, as well as by the Markovian generalizations of Becke-Edgecombe electronic focalization functions - all advocate for the reliability of assuming PI formalism of quantum mechanics as a versatile one, suited for analytically and/or computationally modeling of a variety of fundamental physical and chemical reactivity concepts characterizing the (density driving) many-electronic systems.

Electron density and gas density measurements in a millimeter-wave discharge

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

Schaub, S. C., E-mail: sschaub@mit.edu; Hummelt, J. S.; Guss, W. C.

2016-08-15

Electron density and neutral gas density have been measured in a non-equilibrium air breakdown plasma using optical emission spectroscopy and two-dimensional laser interferometry, respectively. A plasma was created with a focused high frequency microwave beam in air. Experiments were run with 110 GHz and 124.5 GHz microwaves at powers up to 1.2 MW. Microwave pulses were 3 μs long at 110 GHz and 2.2 μs long at 124.5 GHz. Electron density was measured over a pressure range of 25 to 700 Torr as the input microwave power was varied. Electron density was found to be close to the critical density, where the collisional plasma frequency is equal tomore » the microwave frequency, over the pressure range studied and to vary weakly with input power. Neutral gas density was measured over a pressure range from 150 to 750 Torr at power levels high above the threshold for initiating breakdown. The two-dimensional structure of the neutral gas density was resolved. Intense, localized heating was found to occur hundreds of nanoseconds after visible plasma formed. This heating led to neutral gas density reductions of greater than 80% where peak plasma densities occurred. Spatial structure and temporal dynamics of gas heating at atmospheric pressure were found to agree well with published numerical simulations.« less

Electron-density-sensitive Line Ratios of Fe xiii– xvi from Laboratory Sources Compared to CHIANTI

DOE PAGES

Weller, M. E.; Beiersdorfer, P.; Soukhanovskii, V. A.; ...

2018-02-15

We present electron-density-sensitive line ratios for Fe xiii– xvi measured in the spectral wavelength range of 200–440 Å and an electron density range of (1-4) × 10 13 cm -3. The results provide a test at the high-density limit of density-sensitive line ratios useful for astrophysical studies. The measurements were performed on the National Spherical Torus Experiment-Upgrade, where electron densities were measured independently by the laser Thomson scattering diagnostic. Spectra were collected with a flat-field grazing-incidence spectrometer, which provided a spectral resolution of up to 0.3 Å, i.e., high resolution across the broad wavelength range. The response of the instrumentmore » was relatively calibrated using spectroscopic techniques in order to improve accuracy. Lastly, the line ratios are compared to other laboratory sources and the latest version of CHIANTI (8.0.2), and an agreement within 30% is found.« less

Ab-initio study on electronic properties of rocksalt SnAs

NASA Astrophysics Data System (ADS)

Babariya, Bindiya; Vaghela, M. V.; Gajjar, P. N.

2018-05-01

Within the frame work of Local Density Approximation of Exchange and Correlation, ab-initio method of density functional theory with Abinit code is used to compute electronic energy band structure, density of States and charge density of SnAs in rocksalt phase. Our result after optimization for lattice constant agrees with experimental value within 0.59% deviation. The computed electronic energy bands in high symmetry directions Γ→K→X→Γ→L→X→W→L→U shown metallic nature. The lowest band in the electronic band structure is showing band-gap approximately 1.70 eV from next higher band and no crossing between lowest two bands are seen. The density of states revels p-p orbit hybridization between Sn and As atoms. The spherical contour around Sn and As in the charge density plot represent partly ionic and partly covalent bonding. Fermi surface topology is the resultant effect of the single band crossing along L direction at Ef.

Saturn's ionosphere - Inferred electron densities

NASA Technical Reports Server (NTRS)

Kaiser, M. L.; Desch, M. D.; Connerney, J. E. P.

1984-01-01

During the two Voyager encounters with Saturn, radio bursts were detected which appear to have originated from atmospheric lightning storms. Although these bursts generally extended over frequencies from as low as 100 kHz to the upper detection limit of the instrument, 40 MHz, they often exhibited a sharp but variable low frequency cutoff below which bursts were not detected. We interpret the variable low-frequency extent of these bursts to be due to the reflection of the radio waves as they propagate through an ionosphere which varies with local time. We obtain estimates of electron densities at a variety of latitude and local time locations. These compare well with the dawn and dusk densities measured by the Pioneer 11 Voyager Radio Science investigations, and with model predictions for dayside densities. However, we infer a two-order-of-magnitude diurnal variation of electron density, which had not been anticipated by theoretical models of Saturn's ionosphere, and an equally dramatic extinction of ionospheric electron density by Saturn's rings. Previously announced in STAR as N84-17102

An x-ray backlit Talbot-Lau deflectometer for high-energy-density electron density diagnostics.

PubMed

Valdivia, M P; Stutman, D; Stoeckl, C; Theobald, W; Mileham, C; Begishev, I A; Bromage, J; Regan, S P

2016-02-01

X-ray phase-contrast techniques can measure electron density gradients in high-energy-density plasmas through refraction induced phase shifts. An 8 keV Talbot-Lau interferometer consisting of free standing ultrathin gratings was deployed at an ultra-short, high-intensity laser system using K-shell emission from a 1-30 J, 8 ps laser pulse focused on thin Cu foil targets. Grating survival was demonstrated for 30 J, 8 ps laser pulses. The first x-ray deflectometry images obtained under laser backlighting showed up to 25% image contrast and thus enabled detection of electron areal density gradients with a maximum value of 8.1 ± 0.5 × 10(23) cm(-3) in a low-Z millimeter sized sample. An electron density profile was obtained from refraction measurements with an error of <8%. The 50 ± 15 μm spatial resolution achieved across the full field of view was found to be limited by the x-ray source-size, similar to conventional radiography.

Saturn's ionosphere: Inferred electron densities

NASA Technical Reports Server (NTRS)

Kaiser, M. L.; Desch, M. D.; Connerney, J. E. P.

1983-01-01

During the two Voyager encounters with Saturn, radio bursts were detected which appear to have originated from atmospheric lightning storms. Although these bursts generally extended over frequencies from as low as 100 kHz to the upper detection limit of the instrument, 40 MHz, they often exhibited a sharp but variable low frequency cutoff below which bursts were not detected. We interpret the variable low-frequency extent of these bursts to be due to the reflection of the radio waves as they propagate through an ionosphere which varies with local time. We obtain estimates of electron densities at a variety of latitude and local time locations. These compare well with the dawn and dusk densitis measured by the Pioneer 11 Voyager Radio Science investigations, and with model predictions for dayside densities. However, we infer a two-order-of-magnitude diurnal variation of electron density, which had not been anticipated by theoretical models of Saturn's ionosphere, and an equally dramatic extinction of ionospheric electron density by Saturn's rings.

Electron-density-sensitive Line Ratios of Fe xiii– xvi from Laboratory Sources Compared to CHIANTI

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

Weller, M. E.; Beiersdorfer, P.; Soukhanovskii, V. A.

We present electron-density-sensitive line ratios for Fe xiii– xvi measured in the spectral wavelength range of 200–440 Å and an electron density range of (1-4) × 10 13 cm -3. The results provide a test at the high-density limit of density-sensitive line ratios useful for astrophysical studies. The measurements were performed on the National Spherical Torus Experiment-Upgrade, where electron densities were measured independently by the laser Thomson scattering diagnostic. Spectra were collected with a flat-field grazing-incidence spectrometer, which provided a spectral resolution of up to 0.3 Å, i.e., high resolution across the broad wavelength range. The response of the instrumentmore » was relatively calibrated using spectroscopic techniques in order to improve accuracy. Lastly, the line ratios are compared to other laboratory sources and the latest version of CHIANTI (8.0.2), and an agreement within 30% is found.« less

Investigation of reliability of the cutoff probe by a comparison with Thomson scattering in high density processing plasmas

NASA Astrophysics Data System (ADS)

Seo, Byonghoon; Kim, Dae-Woong; Kim, Jung-Hyung; You, Shinjae

2017-12-01

A "cutoff probe" uses microwaves to measure the electron density in a plasma. It is particularly attractive because it is easy to fabricate and use, its measurement is immune to surface contamination by dielectric materials, and it has a straightforward analysis to measure electron density in real time. In this work, we experimentally investigate the accuracy of the cutoff probe through a detailed comparison with Thomson scattering in a low temperature, high density processing plasma. The result shows that the electron density measured by the cutoff probe is lower than that by Thomson scattering and that the discrepancy of the two results becomes smaller as the gap between the two tips increases and/or the neutral gas pressure decreases. The underestimated electron density found by the cutoff probe can be explained by the influence of the probe holder, which becomes important as the pressure increases and the gap gets closer.

Preliminary Study of a Hybrid Helicon-ECR Plasma Source

NASA Astrophysics Data System (ADS)

M. Hala, A.; Oksuz, L.; Ximing, Zhu

2016-08-01

A new type of hybrid discharge is experimentally investigated in this work. A helicon source and an electron cyclotron resonance (ECR) source were combined to produce plasma. As a preliminary study of this type of plasma, the optical emission spectroscopy (OES) method was used to obtain values of electron temperature and density under a series of typical conditions. Generally, it was observed that the electron temperature decreases and the electron density increases as the pressure increased. When increasing the applied power at a certain pressure, the average electron density at certain positions in the discharge does not increase significantly possibly due to the high degree of neutral depletion. Electron temperature increased with power in the hybrid mode. Possible mechanisms of these preliminary observations are discussed.