The Pt site reactivity of the molecular graphs of Au6Pt isomers

NASA Astrophysics Data System (ADS)

Xu, Tianlv; Jenkins, Samantha; Xiao, Chen-Xia; Maza, Julio R.; Kirk, Steven R.

2013-12-01

Within the framework of the theory of atoms in molecules (QTAIM), in an exploratory study we propose a new measure of site reactivity equivalent to the atomic coordination number based purely on the electronic structure. It was found that the number of ring critical points (NNRCPs) positioned on the boundary of the atomic basin of the dopant (Pt) nucleus correlated very well with the relative zero point energy (ZPE) corrected energies. A weaker condition (i.e. than the number of associated bond paths) for the association of the dopant Pt nucleus with the Au6Pt molecular graph is found for NNRCP = 0.

A rotamer energy level study of sulfuric acid.

PubMed

Partanen, Lauri; Pesonen, Janne; Sjöholm, Elina; Halonen, Lauri

2013-10-14

It is a common approach in quantum chemical calculations for polyatomic molecules to rigidly constrain some of the degrees of freedom in order to make the calculations computationally feasible. However, the presence of the rigid constraints also affects the kinetic energy operator resulting in the frozen mode correction, originally derived by Pesonen [J. Chem. Phys. 139, 144310 (2013)]. In this study, we compare the effects of this correction to several different approximations to the kinetic energy operator used in the literature, in the specific case of the rotamer energy levels of sulfuric acid. The two stable conformers of sulfuric acid are connected by the rotations of the O-S-O-H dihedral angles and possess C2 and Cs symmetry in the order of increasing energy. Our results show that of the models tested, the largest differences with the frozen mode corrected values were obtained by simply omitting the passive degrees of freedom. For the lowest 17 excited states, this inappropriate treatment introduces an increase of 9.6 cm(-1) on average, with an increase of 8.7 cm(-1) in the zero-point energies. With our two-dimensional potential energy surface calculated at the CCSD(T)-F12a/VDZ-F12 level, we observe a radical shift in the density of states compared to the harmonic picture, combined with an increase in zero point energy. Thus, we conclude that the quantum mechanical inclusion of the different conformers of sulfuric acid have a significant effect on its vibrational partition function, suggesting that it will also have an impact on the computational values of the thermodynamic properties of any reactions where sulfuric acid plays a role. Finally, we also considered the effect of the anharmonicities for the other vibrational degrees of freedom with a VSCF-calculation at the DF-MP2-F12/VTZ-F12 level of theory but found that the inclusion of the other conformer had the more important effect on the vibrational partition function.

Computational Prediction of Kinetic Rate Constants

DTIC Science & Technology

2006-11-30

without requiring additional data. Zero-point energy ( ZPE ) anharmonicity has a large effect on the accuracy of approximate partition function estimates. If...the accurate ZPE is taken into account, separable approximation partition functions using the most accurate torsion treatment and harmonic treatments...for the remaining degrees of freedom agree with accurate QM partition functions to within a mean accuracy of 9%. If no ZPE anharmonicity correction

Conductivity of Weakly Disordered Metals Close to a "Ferromagnetic" Quantum Critical Point

NASA Astrophysics Data System (ADS)

Kastrinakis, George

2018-05-01

We calculate analytically the conductivity of weakly disordered metals close to a "ferromagnetic" quantum critical point in the low-temperature regime. Ferromagnetic in the sense that the effective carrier potential V(q,ω ), due to critical fluctuations, is peaked at zero momentum q=0. Vertex corrections, due to both critical fluctuations and impurity scattering, are explicitly considered. We find that only the vertex corrections due to impurity scattering, combined with the self-energy, generate appreciable effects as a function of the temperature T and the control parameter a, which measures the proximity to the critical point. Our results are consistent with resistivity experiments in several materials displaying typical Fermi liquid behaviour, but with a diverging prefactor of the T^2 term for small a.

A Systematic Approach for Computing Zero-Point Energy, Quantum Partition Function, and Tunneling Effect Based on Kleinert's Variational Perturbation Theory.

PubMed

Wong, Kin-Yiu; Gao, Jiali

2008-09-09

In this paper, we describe an automated integration-free path-integral (AIF-PI) method, based on Kleinert's variational perturbation (KP) theory, to treat internuclear quantum-statistical effects in molecular systems. We have developed an analytical method to obtain the centroid potential as a function of the variational parameter in the KP theory, which avoids numerical difficulties in path-integral Monte Carlo or molecular dynamics simulations, especially at the limit of zero-temperature. Consequently, the variational calculations using the KP theory can be efficiently carried out beyond the first order, i.e., the Giachetti-Tognetti-Feynman-Kleinert variational approach, for realistic chemical applications. By making use of the approximation of independent instantaneous normal modes (INM), the AIF-PI method can readily be applied to many-body systems. Previously, we have shown that in the INM approximation, the AIF-PI method is accurate for computing the quantum partition function of a water molecule (3 degrees of freedom) and the quantum correction factor for the collinear H(3) reaction rate (2 degrees of freedom). In this work, the accuracy and properties of the KP theory are further investigated by using the first three order perturbations on an asymmetric double-well potential, the bond vibrations of H(2), HF, and HCl represented by the Morse potential, and a proton-transfer barrier modeled by the Eckart potential. The zero-point energy, quantum partition function, and tunneling factor for these systems have been determined and are found to be in excellent agreement with the exact quantum results. Using our new analytical results at the zero-temperature limit, we show that the minimum value of the computed centroid potential in the KP theory is in excellent agreement with the ground state energy (zero-point energy) and the position of the centroid potential minimum is the expectation value of particle position in wave mechanics. The fast convergent property of the KP theory is further examined in comparison with results from the traditional Rayleigh-Ritz variational approach and Rayleigh-Schrödinger perturbation theory in wave mechanics. The present method can be used for thermodynamic and quantum dynamic calculations, including to systematically determine the exact value of zero-point energy and to study kinetic isotope effects for chemical reactions in solution and in enzymes.

Time delay of critical images in the vicinity of cusp point of gravitational-lens systems

NASA Astrophysics Data System (ADS)

Alexandrov, A.; Zhdanov, V.

2016-12-01

We consider approximate analytical formulas for time-delays of critical images of a point source in the neighborhood of a cusp-caustic. We discuss zero, first and second approximations in powers of a parameter that defines the proximity of the source to the cusp. These formulas link the time delay with characteristics of the lens potential. The formula of zero approximation was obtained by Congdon, Keeton & Nordgren (MNRAS, 2008). In case of a general lens potential we derived first order correction thereto. If the potential is symmetric with respect to the cusp axis, then this correction is identically equal to zero. For this case, we obtained second order correction. The relations found are illustrated by a simple model example.

The ground states of iron(III) porphines: role of entropy-enthalpy compensation, Fermi correlation, dispersion, and zero-point energies.

PubMed

Kepp, Kasper P

2011-10-01

Porphyrins are much studied due to their biochemical relevance and many applications. The density functional TPSSh has previously accurately described the energy of close-lying electronic states of transition metal systems such as porphyrins. However, a recent study questioned this conclusion based on calculations of five iron(III) porphines. Here, we compute the geometries of 80 different electronic configurations and the free energies of the most stable configurations with the functionals TPSSh, TPSS, and B3LYP. Zero-point energies and entropy favor high-spin by ~4kJ/mol and 0-10kJ/mol, respectively. When these effects are included, and all electronic configurations are evaluated, TPSSh correctly predicts the spin of all the four difficult phenylporphine cases and is within the lower bound of uncertainty of any known theoretical method for the fifth, iron(III) chloroporphine. Dispersion computed with DFT-D3 favors low-spin by 3-53kJ/mol (TPSSh) or 4-15kJ/mol (B3LYP) due to the attractive r(-6) term and the shorter distances in low-spin. The very large and diverse corrections from TPSS and TPSSh seem less consistent with the similarity of the systems than when calculated from B3LYP. If the functional-specific corrections are used, B3LYP and TPSSh are of equal accuracy, and TPSS is much worse, whereas if the physically reasonable B3LYP-computed dispersion effect is used for all functionals, TPSSh is accurate for all systems. B3LYP is significantly more accurate when dispersion is added, confirming previous results. Copyright © 2011 Elsevier Inc. All rights reserved.

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

Hoobler, Preston Reece; Turney, Justin Matthew; Schaefer III, Henry

The n-propylperoxy radical has been described as a molecule of critical importance to studies of low temperature combustion. Ab initio methods were used to study this three-carbon alkylperoxy radical, normal propylperoxy. Reliable CCSD(T)/ANO0 geometries were predicted for the molecule's five rotamers. For each rotamer, energetic predictions were made using basis sets as large as the cc-pV5Z in conjunction with coupled cluster levels of theory up to CCSDT(Q). Along with the extrapolations, corrections for relativistic effects, zero-point vibrational energies, and diagonal Born--Oppenheimer corrections were used to further refine energies. The results indicate that the lowest conformer is the gauche-gauche (GG) rotamermore » followed by the gauche-trans (0.12 kcal mol^-1 above GG), trans-gauche (0.44 kcal mol^-1), gauche'-gauche (0.47 kcal mol^-1), and trans-trans (0.57 kcal mol^-1). Fundamental vibrational frequencies were obtained using second-order vibrational perturbation theory (VPT2). This is the first time anharmonic frequencies have been computed for this system. The most intense IR features include all but one of the C-H stretches. The O-O fundamental (1063 cm^-1 for the GG structure) also has a significant IR intensity, 19.6 km mol^-1. The anharmonicity effects on the potential energy surface were also used to compute vibrationally averaged r_g,0 K bond lengths, accounting for zero-point vibrations present within the molecule.« less

Polymeric quantum mechanics and the zeros of the Riemann zeta function

NASA Astrophysics Data System (ADS)

Berra-Montiel, Jasel; Molgado, Alberto

We analyze the Berry-Keating model and the Sierra and Rodríguez-Laguna Hamiltonian within the polymeric quantization formalism. By using the polymer representation, we obtain for both models, the associated polymeric quantum Hamiltonians and the corresponding stationary wave functions. The self-adjointness condition provides a proper domain for the Hamiltonian operator and the energy spectrum, which turned out to be dependent on an introduced scale parameter. By performing a counting of semiclassical states, we prove that the polymer representation reproduces the smooth part of the Riemann-von Mangoldt formula, and also introduces a correction depending on the energy and the scale parameter. This may shed some light on the understanding of the fluctuation behavior of the zeros of the Riemann function from a purely quantum point of view.

Exploring proton transfer in 1,2,3-triazole-triazolium dimer with ab initio method

NASA Astrophysics Data System (ADS)

Li, Ailin; Yan, Tianying; Shen, Panwen

Ab initio calculations are utilized to search for transition state structures for proton transfer in the 1,2,3-triazole-triazolium complexes on the basis of optimized dimers. The result suggests six transition state structures for single proton transfer in the complexes, most of which are coplanar. The energy barriers, between different stable and transition states structures with zero point energy (ZPE) corrections, show that proton transfer occurs at room temperature with coplanar configuration that has the lowest energy. The results clearly support that reorientation gives triazole flexibility for proton transfer.

Structures, energetics, vibrational spectra of NH4+ (H2O)(n=4,6) clusters: Ab initio calculations and first principles molecular dynamics simulations.

PubMed

Karthikeyan, S; Singh, Jiten N; Park, Mina; Kumar, Rajesh; Kim, Kwang S

2008-06-28

Important structural isomers of NH(4) (+)(H(2)O)(n=4,6) have been studied by using density functional theory, Moller-Plesset second order perturbation theory, and coupled-cluster theory with single, double, and perturbative triple excitations [CCSD(T)]. The zero-point energy (ZPE) correction to the complete basis set limit of the CCSD(T) binding energies and free energies is necessary to identify the low energy structures for NH(4) (+)(H(2)O)(n=4,6) because otherwise wrong structures could be assigned for the most probable structures. For NH(4) (+)(H(2)O)(6), the cage-type structure, which is more stable than the previously reported open structure before the ZPE correction, turns out to be less stable after the ZPE correction. In first principles Car-Parrinello molecular dynamics simulations around 100 K, the combined power spectrum of three lowest energy isomers of NH(4) (+)(H(2)O)(4) and two lowest energy isomers of NH(4) (+)(H(2)O)(6) explains each experimental IR spectrum.

Structures, energetics, vibrational spectra of NH4+(H2O)n=4,6 clusters: Ab initio calculations and first principles molecular dynamics simulations

NASA Astrophysics Data System (ADS)

Karthikeyan, S.; Singh, Jiten N.; Park, Mina; Kumar, Rajesh; Kim, Kwang S.

2008-06-01

Important structural isomers of NH4+(H2O)n=4,6 have been studied by using density functional theory, Møller-Plesset second order perturbation theory, and coupled-cluster theory with single, double, and perturbative triple excitations [CCSD(T)]. The zero-point energy (ZPE) correction to the complete basis set limit of the CCSD(T) binding energies and free energies is necessary to identify the low energy structures for NH4+(H2O)n=4,6 because otherwise wrong structures could be assigned for the most probable structures. For NH4+(H2O)6, the cage-type structure, which is more stable than the previously reported open structure before the ZPE correction, turns out to be less stable after the ZPE correction. In first principles Car-Parrinello molecular dynamics simulations around 100 K, the combined power spectrum of three lowest energy isomers of NH4+(H2O)4 and two lowest energy isomers of NH4+(H2O)6 explains each experimental IR spectrum.

XZP + 1d and XZP + 1d-DKH basis sets for second-row elements: application to CCSD(T) zero-point vibrational energy and atomization energy calculations.

PubMed

Campos, Cesar T; Jorge, Francisco E; Alves, Júlia M A

2012-09-01

Recently, segmented all-electron contracted double, triple, quadruple, quintuple, and sextuple zeta valence plus polarization function (XZP, X = D, T, Q, 5, and 6) basis sets for the elements from H to Ar were constructed for use in conjunction with nonrelativistic and Douglas-Kroll-Hess Hamiltonians. In this work, in order to obtain a better description of some molecular properties, the XZP sets for the second-row elements were augmented with high-exponent d "inner polarization functions," which were optimized in the molecular environment at the second-order Møller-Plesset level. At the coupled cluster level of theory, the inclusion of tight d functions for these elements was found to be essential to improve the agreement between theoretical and experimental zero-point vibrational energies (ZPVEs) and atomization energies. For all of the molecules studied, the ZPVE errors were always smaller than 0.5 %. The atomization energies were also improved by applying corrections due to core/valence correlation and atomic spin-orbit effects. This led to estimates for the atomization energies of various compounds in the gaseous phase. The largest error (1.2 kcal mol(-1)) was found for SiH(4).

Phonon self-energy corrections to non-zero wavevector phonon modes in single-layer graphene

NASA Astrophysics Data System (ADS)

Araujo, Paulo; Mafra, Daniela; Sato, Kentaro; Saito, Richiiro; Kong, Jing; Dresselhaus, Mildred

2012-02-01

Phonon self-energy corrections have mostly been studied theoretically and experimentally for phonon modes with zone-center (q = 0) wave-vectors. Here, gate-modulated Raman scattering is used to study phonons of a single layer of graphene (1LG) in the frequency range from 2350 to 2750 cm-1, which shows the G* and the G'-band features originating from a double-resonant Raman process with q 0. The observed phonon renormalization effects are different from what is observed for the zone-center q = 0 case. To explain our experimental findings, we explored the phonon self-energy for the phonons with non-zero wave-vectors (q 0) in 1LG in which the frequencies and decay widths are expected to behave oppositely to the behavior observed in the corresponding zone-center q = 0 processes. Within this framework, we resolve the identification of the phonon modes contributing to the G* Raman feature at 2450 cm-1 to include the iTO+LA combination modes with q 0 and the 2iTO overtone modes with q = 0, showing both to be associated with wave-vectors near the high symmetry point K in the Brillouin zone.

Calibration of the photometric G passband for Gaia Data Release 1

NASA Astrophysics Data System (ADS)

Maíz Apellániz, J.

2017-12-01

Context. On September 2016 the first data from Gaia were released (DR1). The first release included photometry for over 109 sources in the very broad G system. Aims: The aims here are to test the correspondence between G magnitudes in DR1 and the synthetic equivalents derived using spectral energy distributions from observed and model spectrophotometry; to correct the G passband curve; and to measure the zero point in the Vega system. Methods: I have computed the synthetic G and Tycho-2 BTVT photometry for a sample of stars using the Next Generation Spectral Library (NGSL) and the Hubble Space Telescope (HST) CALSPEC spectroscopic standards. Results: I have found that the nominal G passband curve is too blue for the DR1 photometry, as shown by the presence of a color term in the comparison between observed and synthetic magnitudes. A correction to the passband applying a power law in λ with an exponent of 0.783 eliminates the color term. The corrected passband has a Vega zero point of 0.070 ± 0.004 mag. Tables 1 and 2 are only available at the CDS via anonymous ftp to http://cdsarc.u-strasbg.fr (http://130.79.128.5) or via http://cdsarc.u-strasbg.fr/viz-bin/qcat?J/A+A/608/L8

On the contribution of vibrational anharmonicity to the binding energies of water clusters.

PubMed

Diri, Kadir; Myshakin, Evgeniy M; Jordan, Kenneth D

2005-05-05

The second-order vibrational perturbation theory method has been used together with the B3LYP and MP2 electronic structure methods to investigate the effects of anharmonicity on the vibrational zero-point energy (ZPE) contributions to the binding energies of (H2O)n, n = 2-6, clusters. For the low-lying isomers of (H2O)6, the anharmonicity correction to the binding energy is calculated to range from -248 to -355 cm(-1). It is also demonstrated that although high-order electron correlation effects are important for the individual vibrational frequencies, they are relatively unimportant for the net ZPE contributions to the binding energies of water clusters.

Gradient corrections to the exchange-correlation free energy

DOE PAGES

Sjostrom, Travis; Daligault, Jerome

2014-10-07

We develop the first-order gradient correction to the exchange-correlation free energy of the homogeneous electron gas for use in finite-temperature density functional calculations. Based on this, we propose and implement a simple temperature-dependent extension for functionals beyond the local density approximation. These finite-temperature functionals show improvement over zero-temperature functionals, as compared to path-integral Monte Carlo calculations for deuterium equations of state, and perform without computational cost increase compared to zero-temperature functionals and so should be used for finite-temperature calculations. Furthermore, while the present functionals are valid at all temperatures including zero, non-negligible difference with zero-temperature functionals begins at temperatures abovemore » 10 000 K.« less

Investigating the ground-state rotamers of n-propylperoxy radical.

PubMed

Hoobler, Preston R; Turney, Justin M; Schaefer, Henry F

2016-11-07

The n-propylperoxy radical has been described as a molecule of critical importance to studies of low temperature combustion. Ab initio methods were used to study this three-carbon alkylperoxy radical, normal propylperoxy. Reliable CCSD(T) (coupled-cluster theory, incorporating single, double, and perturbative triple)/ANO0 geometries were predicted for the molecule's five rotamers. For each rotamer, energetic predictions were made using basis sets as large as the cc-pV5Z in conjunction with coupled cluster levels of theory up to CCSDT(Q). Along with the extrapolations, corrections for relativistic effects, zero-point vibrational energies, and diagonal Born-Oppenheimer corrections were used to further refine energies. The results indicate that the lowest conformer is the gauche-gauche (GG) rotamer followed by the gauche-trans (0.12 kcal mol -1 above GG), trans-gauche (0.44 kcal mol -1 ), gauche'-gauche (0.47 kcal mol -1 ), and trans-trans (0.57 kcal mol -1 ). Fundamental vibrational frequencies were obtained using second-order vibrational perturbation theory. This is the first time anharmonic frequencies have been computed for this system. The most intense IR features include all but one of the C-H stretches. The O-O fundamental (1063 cm -1 for the GG structure) also has a significant IR intensity, 19.6 km mol -1 . The anharmonicity effects on the potential energy surface were also used to compute vibrationally averaged r g,0K bond lengths, accounting for zero-point vibrations present within the molecule.

Investigating the Ground-State Rotamers of n-Propylperoxy Radical

DOE PAGES

Hoobler, Preston Reece; Turney, Justin Matthew; Schaefer III, Henry

2016-11-01

The n-propylperoxy radical has been described as a molecule of critical importance to studies of low temperature combustion. Ab initio methods were used to study this three-carbon alkylperoxy radical, normal propylperoxy. Reliable CCSD(T)/ANO0 geometries were predicted for the molecule's five rotamers. For each rotamer, energetic predictions were made using basis sets as large as the cc-pV5Z in conjunction with coupled cluster levels of theory up to CCSDT(Q). Along with the extrapolations, corrections for relativistic effects, zero-point vibrational energies, and diagonal Born--Oppenheimer corrections were used to further refine energies. The results indicate that the lowest conformer is the gauche-gauche (GG) rotamermore » followed by the gauche-trans (0.12 kcal mol^-1 above GG), trans-gauche (0.44 kcal mol^-1), gauche'-gauche (0.47 kcal mol^-1), and trans-trans (0.57 kcal mol^-1). Fundamental vibrational frequencies were obtained using second-order vibrational perturbation theory (VPT2). This is the first time anharmonic frequencies have been computed for this system. The most intense IR features include all but one of the C-H stretches. The O-O fundamental (1063 cm^-1 for the GG structure) also has a significant IR intensity, 19.6 km mol^-1. The anharmonicity effects on the potential energy surface were also used to compute vibrationally averaged r_g,0 K bond lengths, accounting for zero-point vibrations present within the molecule.« less

Investigating the ground-state rotamers of n-propylperoxy radical

NASA Astrophysics Data System (ADS)

Hoobler, Preston R.; Turney, Justin M.; Schaefer, Henry F.

2016-11-01

The n-propylperoxy radical has been described as a molecule of critical importance to studies of low temperature combustion. Ab initio methods were used to study this three-carbon alkylperoxy radical, normal propylperoxy. Reliable CCSD(T) (coupled-cluster theory, incorporating single, double, and perturbative triple)/ANO0 geometries were predicted for the molecule's five rotamers. For each rotamer, energetic predictions were made using basis sets as large as the cc-pV5Z in conjunction with coupled cluster levels of theory up to CCSDT(Q). Along with the extrapolations, corrections for relativistic effects, zero-point vibrational energies, and diagonal Born-Oppenheimer corrections were used to further refine energies. The results indicate that the lowest conformer is the gauche-gauche (GG) rotamer followed by the gauche-trans (0.12 kcal mol-1 above GG), trans-gauche (0.44 kcal mol-1), gauche'-gauche (0.47 kcal mol-1), and trans-trans (0.57 kcal mol-1). Fundamental vibrational frequencies were obtained using second-order vibrational perturbation theory. This is the first time anharmonic frequencies have been computed for this system. The most intense IR features include all but one of the C-H stretches. The O-O fundamental (1063 cm-1 for the GG structure) also has a significant IR intensity, 19.6 km mol-1. The anharmonicity effects on the potential energy surface were also used to compute vibrationally averaged rg,0K bond lengths, accounting for zero-point vibrations present within the molecule.

The structure of N2 adsorbed on the rumpled NaCl(100) surface—A combined LEED and DFT-D study

NASA Astrophysics Data System (ADS)

Vogt, Jochen

2012-11-01

The structure of N2 physisorbed on the NaCl(100) single crystal surface is investigated by means of quantitative low-energy electron diffraction (LEED) in combination with dispersion corrected density functional theory (DFT-D). In the temperature range between 20 K and 45 K, a p(1 × 1) structure is observed in the LEED experiment. According to the structure analysis based on the measured diffraction spot intensity profiles, the N2 molecules are adsorbed over the topmost Na+ ions. The experimental distance of the lower nitrogen to the Na+ ion underneath is (2.55 ± 0.07) Å; the corresponding DFT-D value is 2.65 Å. The axes of the molecules are tilted (26 ± 3)° with respect to the surface normal, while in the zero Kelvin optimum structure from DFT-D, the molecules have a perpendicular orientation. The experimental monolayer heat of adsorption, deduced from a Fowler-Guggenheim kinetic model of adsorption is -(13.6 ± 1.6) kJ mol-1, including a lateral molecule-molecule interaction energy of -(2.0 ± 0.4) kJ mol-1. The zero Kelvin adsorption energy from DFT-D, including zero point energy correction, is -15.6 kJ mol-1; the molecule-molecule interaction is -2.4 kJ mol-1. While the rumpling of the NaCl(100) surface is unchanged upon adsorption of nitrogen, the best-fit root mean square thermal displacements of the ions in the topmost substrate layer are significantly reduced.

The Charge Transfer Efficiency and Calibration of WFPC2

NASA Technical Reports Server (NTRS)

Dolphin, Andrew E.

2000-01-01

A new determination of WFPC2 photometric corrections is presented, using HSTphot reduction of the WFPC2 Omega Centauri and NGC 2419 observations from January 1994 through March 2000 and a comparison with ground-based photometry. No evidence is seen for any position-independent photometric offsets (the "long-short anomaly"); all systematic errors appear to be corrected with the CTE and zero point solution. The CTE loss time dependence is determined to be very significant in the Y direction, causing time-independent CTE solutions to be valid only for a small range of times. On average, the present solution produces corrections similar to Whitmore, Heyer, & Casertano, although with an improved functional form that produces less scatter in the residuals and determined with roughly a year of additional data. In addition to the CTE loss characterization, zero point corrections are also determined as functions of chip, gain, filter, and temperature. Of interest, there are chip-to-chip differences of order 0.01 - 0.02 magnitudes relative to the Holtzman et al. calibrations, and the present study provides empirical zero point determinations for the non-standard filters such as the frequently-used F450W, F606W, and F702W.

Binding matter with antimatter: the covalent positron bond.

PubMed

Charry, Jorge Alfonso; Varella, Marcio T Do N; Reyes, Andrés

2018-05-16

We report sufficient theoretical evidence of the energy stability of the e⁺H₂²⁻ molecule, formed by two H⁻ anions and one positron. Analysis of the electronic and positronic densities of the latter compound undoubtedly points out the formation of a positronic covalent bond between the otherwise repelling hydride anions. The lower limit for the bonding energy of the e⁺H₂²⁻ molecule is 74 kJ/mol (0.77 eV), accounting for the zero-point vibrational correction. The formation of a non electronic covalent bond is fundamentally distinct from positron attachment to stable molecules, as the latter process is characterized by a positron affinity, analogous to the electron affinity. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Communication: A new ab initio potential energy surface for HCl-H2O, diffusion Monte Carlo calculations of D0 and a delocalized zero-point wavefunction.

PubMed

Mancini, John S; Bowman, Joel M

2013-03-28

We report a global, full-dimensional, ab initio potential energy surface describing the HCl-H2O dimer. The potential is constructed from a permutationally invariant fit, using Morse-like variables, to over 44,000 CCSD(T)-F12b∕aug-cc-pVTZ energies. The surface describes the complex and dissociated monomers with a total RMS fitting error of 24 cm(-1). The normal modes of the minima, low-energy saddle point and separated monomers, the double minimum isomerization pathway and electronic dissociation energy are accurately described by the surface. Rigorous quantum mechanical diffusion Monte Carlo (DMC) calculations are performed to determine the zero-point energy and wavefunction of the complex and the separated fragments. The calculated zero-point energies together with a De value calculated from CCSD(T) with a complete basis set extrapolation gives a D0 value of 1348 ± 3 cm(-1), in good agreement with the recent experimentally reported value of 1334 ± 10 cm(-1) [B. E. Casterline, A. K. Mollner, L. C. Ch'ng, and H. Reisler, J. Phys. Chem. A 114, 9774 (2010)]. Examination of the DMC wavefunction allows for confident characterization of the zero-point geometry to be dominant at the C(2v) double-well saddle point and not the C(s) global minimum. Additional support for the delocalized zero-point geometry is given by numerical solutions to the 1D Schrödinger equation along the imaginary-frequency out-of-plane bending mode, where the zero-point energy is calculated to be 52 cm(-1) above the isomerization barrier. The D0 of the fully deuterated isotopologue is calculated to be 1476 ± 3 cm(-1), which we hope will stand as a benchmark for future experimental work.

Accurate ab initio binding energies of the benzene dimer.

PubMed

Park, Young Choon; Lee, Jae Shin

2006-04-20

Accurate binding energies of the benzene dimer at the T and parallel displaced (PD) configurations were determined using the single- and double-coupled cluster method with perturbative triple correction (CCSD(T)) with correlation-consistent basis sets and an effective basis set extrapolation scheme recently devised. The difference between the estimated CCSD(T) basis set limit electronic binding energies for the T and PD shapes appears to amount to more than 0.3 kcal/mol, indicating the PD shape is a more stable configuration than the T shape for this dimer in the gas phase. This conclusion is further strengthened when a vibrational zero-point correction to the electronic binding energies of this dimer is made, which increases the difference between the two configurations to 0.4-0.5 kcal/mol. The binding energies of 2.4 and 2.8 kcal/mol for the T and PD configurations are in good accord with the previous experimental result from ionization potential measurement.

Zero-point energy constraint in quasi-classical trajectory calculations.

PubMed

Xie, Zhen; Bowman, Joel M

2006-04-27

A method to constrain the zero-point energy in quasi-classical trajectory calculations is proposed and applied to the Henon-Heiles system. The main idea of this method is to smoothly eliminate the coupling terms in the Hamiltonian as the energy of any mode falls below a specified value.

Dissociation energies of six NO2 isotopologues by laser induced fluorescence spectroscopy and zero point energy of some triatomic molecules.

PubMed

Michalski, G; Jost, R; Sugny, D; Joyeux, M; Thiemens, M

2004-10-15

We have measured the rotationless photodissociation threshold of six isotopologues of NO2 containing 14N, 15N, 16O, and 18O isotopes using laser induced fluorescence detection and jet cooled NO2 (to avoid rotational congestion). For each isotopologue, the spectrum is very dense below the dissociation energy while fluorescence disappears abruptly above it. The six dissociation energies ranged from 25 128.56 cm(-1) for 14N16O2 to 25 171.80 cm(-1) for 15N18O2. The zero point energy for the NO2 isotopologues was determined from experimental vibrational energies, application of the Dunham expansion, and from canonical perturbation theory using several potential energy surfaces. Using the experimentally determined dissociation energies and the calculated zero point energies of the parent NO2 isotopologue and of the NO product(s) we determined that there is a common De = 26 051.17+/-0.70 cm(-1) using the Born-Oppenheimer approximation. The canonical perturbation theory was then used to calculate the zero point energy of all stable isotopologues of SO2, CO2, and O3, which are compared with previous determinations.

Quasiparticle renormalization in ABC graphene trilayers

NASA Astrophysics Data System (ADS)

Dou, Xu; Jaefari, Akbar; Barlas, Yafis; Uchoa, Bruno

2015-03-01

We investigate the effect of electron-electron interactions in ABC stacked graphene trilayers. In the gapless regime, we show that the self-energy corrections lead to the renormalization of the dynamical exponent z = 3 +α1 / N , with α1 ~ 0 . 52 and N is the number of fermionic species. Although the quasiparticle residue is suppressed near the neutrality point, the lifetime has a sublinear scaling with the energy and the quasiparticles are well defined even at zero energy. We calculate the renormalization of a variety of physical observables, which can be directly measured in experiments. X.D., A.J., and B.U. acknowledge University of Oklahoma for support. B.U. acknowledges NSF Career Grant No. DMR-1352604 for partial support.

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

Engel, Edgar A., E-mail: eae32@cam.ac.uk; Needs, Richard J.; Monserrat, Bartomeu

Surface energies of hexagonal and cubic water ice are calculated using first-principles quantum mechanical methods, including an accurate description of anharmonic nuclear vibrations. We consider two proton-orderings of the hexagonal and cubic ice basal surfaces and three proton-orderings of hexagonal ice prism surfaces, finding that vibrations reduce the surface energies by more than 10%. We compare our vibrational densities of states to recent sum frequency generation absorption measurements and identify surface proton-orderings of experimental ice samples and the origins of characteristic absorption peaks. We also calculate zero point quantum vibrational corrections to the surface electronic band gaps, which range frommore » −1.2 eV for the cubic ice basal surface up to −1.4 eV for the hexagonal ice prism surface. The vibrational corrections to the surface band gaps are up to 12% smaller than for bulk ice.« less

Computed potential energy surfaces for chemical reactions

NASA Technical Reports Server (NTRS)

Walch, Stephen P.

1988-01-01

The minimum energy path for the addition of a hydrogen atom to N2 is characterized in CASSCF/CCI calculations using the (4s3p2d1f/3s2p1d) basis set, with additional single point calculations at the stationary points of the potential energy surface using the (5s4p3d2f/4s3p2d) basis set. These calculations represent the most extensive set of ab initio calculations completed to date, yielding a zero point corrected barrier for HN2 dissociation of approx. 8.5 kcal mol/1. The lifetime of the HN2 species is estimated from the calculated geometries and energetics using both conventional Transition State Theory and a method which utilizes an Eckart barrier to compute one dimensional quantum mechanical tunneling effects. It is concluded that the lifetime of the HN2 species is very short, greatly limiting its role in both termolecular recombination reactions and combustion processes.

A correlated ab initio study of the A2 pi <-- X2 sigma+ transition in MgCCH

NASA Technical Reports Server (NTRS)

Woon, D. E.

1997-01-01

The A2 pi <-- X2 sigma+ transition in MgCCH was studied with correlation consistent basis sets and single- and multireference correlation methods. The A2 pi excited state was characterized in detail; the x2 sigma+ ground state has been described elsewhere recently. The estimated complete basis set (CBS) limits for valence correlation, including zero-point energy corrections, are 22668, 23191, and 22795 for the RCCSD(T), MRCI, and MRCI + Q methods, respectively. A core-valence correction of +162 cm-1 shifts the RCCSD(T) value to 22830 cm-1, in good agreement with the experimental result of 22807 cm-1.

Performance of an Optimally Tuned Range-Separated Hybrid Functional for 0-0 Electronic Excitation Energies.

PubMed

Jacquemin, Denis; Moore, Barry; Planchat, Aurélien; Adamo, Carlo; Autschbach, Jochen

2014-04-08

Using a set of 40 conjugated molecules, we assess the performance of an "optimally tuned" range-separated hybrid functional in reproducing the experimental 0-0 energies. The selected protocol accounts for the impact of solvation using a corrected linear-response continuum approach and vibrational corrections through calculations of the zero-point energies of both ground and excited-states and provides basis set converged data thanks to the systematic use of diffuse-containing atomic basis sets at all computational steps. It turns out that an optimally tuned long-range corrected hybrid form of the Perdew-Burke-Ernzerhof functional, LC-PBE*, delivers both the smallest mean absolute error (0.20 eV) and standard deviation (0.15 eV) of all tested approaches, while the obtained correlation (0.93) is large but remains slightly smaller than its M06-2X counterpart (0.95). In addition, the efficiency of two other recently developed exchange-correlation functionals, namely SOGGA11-X and ωB97X-D, has been determined in order to allow more complete comparisons with previously published data.

DFT studies on the multi-channel reaction of CH3S+NO2

NASA Astrophysics Data System (ADS)

Tang, Yi-Zhen; Sun, Hao; Pan, Ya-Ru; Pan, Xiu-Mei; Wang, Rong-Shun

The mechanisms for the reaction of CH3S with NO2 are investigated at the QCISD(T)/6-311++G(d,p)//B3LYP/6-311++G(d,p) on both single and triple potential energy surfaces (PESs). The geometries, vibrational frequencies, and zero-point energy (ZPE) correction of all stationary points involved in the title reaction are calculated at the B3LYP/6-311++G(d,p) level. More accurate energies are obtained at the QCISD(T)/6-311++G(d,p). The results show that 5 intermediates and 14 transition states are found. The reaction is more predominant on the single PES, while it is negligible on the triple PES. Without any barrier height for the whole process, the main channel of the reaction is to form CH3SONO and then dissociate to CH3SO+NO.

The vibrationally adiabatic torsional potential energy surface of trans-stilbene

NASA Astrophysics Data System (ADS)

Chowdary, Praveen D.; Martinez, Todd J.; Gruebele, Martin

2007-05-01

The effect of vibrational Zero Point Energy (ZPE) on the torsional barriers of trans-stilbene is studied in the adiabatic approximation. The two torsional modes corresponding to phenyl rotation are explicitly separated, and the remaining modes are treated as normal coordinates. ZPE reduces the adiabatic barrier along the in-phase torsion from 198 to 13 cm -1. A one-dimensional adiabatic potential for the anti-phase torsion, including the ZPE of the in-phase torsion, reduces the adiabatic barrier from 260 to 58 cm -1. Comparison with recent electronic structure benchmark calculations suggests that vibrational corrections play a significant role in trans-stilbene's experimentally observed planar structure.

Ca(AlH4)2, CaAlH5, and CaH2+6LiBH4: Calculated dehydrogenation enthalpy, including zero point energy, and the structure of the phonon spectra.

PubMed

Marashdeh, Ali; Frankcombe, Terry J

2008-06-21

The dehydrogenation enthalpies of Ca(AlH(4))(2), CaAlH(5), and CaH(2)+6LiBH(4) have been calculated using density functional theory calculations at the generalized gradient approximation level. Harmonic phonon zero point energy (ZPE) corrections have been included using Parlinski's direct method. The dehydrogenation of Ca(AlH(4))(2) is exothermic, indicating a metastable hydride. Calculations for CaAlH(5) including ZPE effects indicate that it is not stable enough for a hydrogen storage system operating near ambient conditions. The destabilized combination of LiBH(4) with CaH(2) is a promising system after ZPE-corrected enthalpy calculations. The calculations confirm that including ZPE effects in the harmonic approximation for the dehydrogenation of Ca(AlH(4))(2), CaAlH(5), and CaH(2)+6LiBH(4) has a significant effect on the calculated reaction enthalpy. The contribution of ZPE to the dehydrogenation enthalpies of Ca(AlH(4))(2) and CaAlH(5) calculated by the direct method phonon analysis was compared to that calculated by the frozen-phonon method. The crystal structure of CaAlH(5) is presented in the more useful standard setting of P2(1)c symmetry and the phonon density of states of CaAlH(5), significantly different to other common complex metal hydrides, is rationalized.

Ca(AlH4)2, CaAlH5, and CaH2+6LiBH4: Calculated dehydrogenation enthalpy, including zero point energy, and the structure of the phonon spectra

NASA Astrophysics Data System (ADS)

Marashdeh, Ali; Frankcombe, Terry J.

2008-06-01

The dehydrogenation enthalpies of Ca(AlH4)2, CaAlH5, and CaH2+6LiBH4 have been calculated using density functional theory calculations at the generalized gradient approximation level. Harmonic phonon zero point energy (ZPE) corrections have been included using Parlinski's direct method. The dehydrogenation of Ca(AlH4)2 is exothermic, indicating a metastable hydride. Calculations for CaAlH5 including ZPE effects indicate that it is not stable enough for a hydrogen storage system operating near ambient conditions. The destabilized combination of LiBH4 with CaH2 is a promising system after ZPE-corrected enthalpy calculations. The calculations confirm that including ZPE effects in the harmonic approximation for the dehydrogenation of Ca(AlH4)2, CaAlH5, and CaH2+6LiBH4 has a significant effect on the calculated reaction enthalpy. The contribution of ZPE to the dehydrogenation enthalpies of Ca(AlH4)2 and CaAlH5 calculated by the direct method phonon analysis was compared to that calculated by the frozen-phonon method. The crystal structure of CaAlH5 is presented in the more useful standard setting of P21/c symmetry and the phonon density of states of CaAlH5, significantly different to other common complex metal hydrides, is rationalized.

Electromagnetic corrections to the hadronic vacuum polarization of the photon within QEDL and QEDM

NASA Astrophysics Data System (ADS)

Bussone, Andrea; Della Morte, Michele; Janowski, Tadeusz

2018-03-01

We compute the leading QED corrections to the hadronic vacuum polarization (HVP) of the photon, relevant for the determination of leptonic anomalous magnetic moments, al. We work in the electroquenched approximation and use dynamical QCD configurations generated by the CLS initiative with two degenerate flavors of nonperturbatively O(a)-improved Wilson fermions. We consider QEDL and QEDM to deal with the finite-volume zero modes. We compare results for the Wilson loops with exact analytical determinations. In addition we make sure that the volumes and photon masses used in QEDM are such that the correct dispersion relation is reproduced by the energy levels extracted from the charged pions two-point functions. Finally we compare results for pion masses and the HVP between QEDL and QEDM. For the vacuum polarization, corrections with respect to the pure QCD case, at fixed pion masses, turn out to be at the percent level.

Modification of the quantum mechanical flux formula for electron-hydrogen ionization through Bohm's velocity field

NASA Astrophysics Data System (ADS)

Randazzo, J. M.; Ancarani, L. U.

2015-12-01

For the single differential cross section (SDCS) for hydrogen ionization by electron impact (e -H problem), we propose a correction to the flux formula given by R. Peterkop [Theory of Ionization of Atoms by Electron Impact (Colorado Associated University Press, Boulder, 1977)]. The modification is based on an alternative way of defining the kinetic energy fraction, using Bohm's definition of velocities instead of the usual asymptotic kinematical, or geometrical, approximation. It turns out that the solution-dependent, modified energy fraction is equally related to the components of the probability flux. Compared to what is usually observed, the correction yields a finite and well-behaved SDCS value in the asymmetrical situation where one of the continuum electrons carries all the energy while the other has zero energy. We also discuss, within the S -wave model of the e -H ionization process, the continuity of the SDCS derivative at the equal energy sharing point, a property not so clearly observed in published benchmark results obtained with integral and S -matrix formulas with unequal final states.

High-Level ab initio electronic structure calculations of Water Clusters (H2O)16 and (H2O)17: a new global minimum for (H2O)16

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

Yoo, Soohaeng; Apra, Edoardo; Zeng, Xiao Cheng

The lowest-energy structures of water clusters (H2O)16 and (H2O)17 were revisited at the MP2 and CCSD(T) levels of theory. A new global minimum structure for (H2O)16 was found at the MP2 and CCSD(T) levels of theory and the effect of zero-point energy corrections on the relative stability of the low-lying minimum energy structures was assessed. For (H2O)17 the CCSD(T) calculations confirm the previously found at the MP2 level of theory "interior" arrangement (fully coordinated water molecule inside a spherical cluster) as the global minimum.

High-Level ab-initio Electronic Structure Calculations of Water Clusters (H2O)16 and (H2O)17 : a New Global Minimum for (H2O)16

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

Yoo, Soohaeng; Apra, Edoardo; Zeng, X.C.

The lowest-energy structures of water clusters (H2O)16 and (H2O)17 were revisited at the MP2 and CCSD(T) levels of theory. A new global minimum structure for (H2O)16 was found at both the MP2 and CCSD(T) levels of theory, and the effect of zero-point energy corrections on the relative stability of the low-lying minimum energy structures was assessed. For (H2O)17, the CCSD(T) calculations confirm the previously found at the MP2 level of theory interior arrangement (fully coordinated water molecule inside a spherical cluster) as the global minimum

Broken symmetries, zero-energy modes, and quantum transport in disordered graphene: from supermetallic to insulating regimes.

PubMed

Cresti, Alessandro; Ortmann, Frank; Louvet, Thibaud; Van Tuan, Dinh; Roche, Stephan

2013-05-10

The role of defect-induced zero-energy modes on charge transport in graphene is investigated using Kubo and Landauer transport calculations. By tuning the density of random distributions of monovacancies either equally populating the two sublattices or exclusively located on a single sublattice, all conduction regimes are covered from direct tunneling through evanescent modes to mesoscopic transport in bulk disordered graphene. Depending on the transport measurement geometry, defect density, and broken sublattice symmetry, the Dirac-point conductivity is either exceptionally robust against disorder (supermetallic state) or suppressed through a gap opening or by algebraic localization of zero-energy modes, whereas weak localization and the Anderson insulating regime are obtained for higher energies. These findings clarify the contribution of zero-energy modes to transport at the Dirac point, hitherto controversial.

Germylenes: structures, electron affinities, and singlet-triplet gaps of the conventional XGeCY(3) (X = H, F, Cl, Br, and I; Y = F and Cl) species and the unexpected cyclic XGeCY(3) (Y = Br and I) systems.

PubMed

Bundhun, Ashwini; Abdallah, Hassan H; Ramasami, Ponnadurai; Schaefer, Henry F

2010-12-23

A systematic investigation of the X-Ge-CY(3) (X = H, F, Cl, Br, and I; Y = F, Cl, Br, and I) species is carried out using density functional theory. The basis sets used for all atoms (except iodine) in this work are of double-ζ plus polarization quality with additional s- and p-type diffuse functions, and denoted DZP++. Vibrational frequency analyses are performed to evaluate zero-point energy corrections and to determine the nature of the stationary points located. Predicted are four different forms of neutral-anion separations: adiabatic electron affinity (EA(ad)), zero-point vibrational energy corrected EA(ad(ZPVE)), vertical electron affinity (EA(vert)), and vertical detachment energy (VDE). The electronegativity (χ) reactivity descriptor for the halogens (X = F, Cl, Br, and I) is used as a tool to assess the interrelated properties of these germylenes. The topological position of the halogen atom bound to the divalent germanium center is well correlated with the trend in the electron affinities and singlet-triplet gaps. For the expected XGeCY(3) structures (X = H, F, Cl, Br, and I; Y = F and Cl), the predicted trend in the electron affinities is well correlated with simpler germylene derivatives (J. Phys. Chem. A 2009, 113, 8080). The predicted EA(ad(ZPVE)) values with the BHLYP functional range from 1.66 eV (FGeCCl(3)) to 2.20 eV (IGeCF(3)), while the singlet-triplet splittings range from 1.28 eV (HGeCF(3)) to 2.22 eV (FGeCCl(3)). The XGeCY(3) (Y = Br and I) species are most often characterized by three-membered cyclic systems involving the divalent germanium atom, the carbon atom, and a halogen atom.

Vibrational and thermal properties of β-HMX and TATB from dispersion corrected density functional theory

NASA Astrophysics Data System (ADS)

Landerville, Aaron C.; Oleynik, Ivan I.

2017-01-01

Dispersion Corrected Density Functional Theory (DFT+vdW) calculations are performed to predict vibrational and thermal properties of the bulk energetic materials (EMs) β-octahydrocyclotetramethylene-tetranitramine (β-HMX) and triaminotrinitrobenzene (TATB). DFT+vdW calculations of pressure-dependent crystal structure and the hydrostatic equation of state are followed by frozen-phonon calculations of their respective vibration spectra at each pressure. These are then used under the quasi-harmonic approximation to obtain zero-point and thermal free energy contributions to the pressure, resulting in pressure-volume-temperature (PVT) EOS for each material that are in excellent agreement with experiment. Heat capacities, and coefficients of thermal expansion as functions of temperature are also calculated and compared with experiment.

The effect of zero-point energy differences on the isotope dependence of the formation of ozone: a classical trajectory study.

PubMed

Schinke, Reinhard; Fleurat-Lessard, Paul

2005-03-01

The effect of zero-point energy differences (DeltaZPE) between the possible fragmentation channels of highly excited O(3) complexes on the isotope dependence of the formation of ozone is investigated by means of classical trajectory calculations and a strong-collision model. DeltaZPE is incorporated in the calculations in a phenomenological way by adjusting the potential energy surface in the product channels so that the correct exothermicities and endothermicities are matched. The model contains two parameters, the frequency of stabilizing collisions omega and an energy dependent parameter Delta(damp), which favors the lower energies in the Maxwell-Boltzmann distribution. The stabilization frequency is used to adjust the pressure dependence of the absolute formation rate while Delta(damp) is utilized to control its isotope dependence. The calculations for several isotope combinations of oxygen atoms show a clear dependence of relative formation rates on DeltaZPE. The results are similar to those of Gao and Marcus [J. Chem. Phys. 116, 137 (2002)] obtained within a statistical model. In particular, like in the statistical approach an ad hoc parameter eta approximately 1.14, which effectively reduces the formation rates of the symmetric ABA ozone molecules, has to be introduced in order to obtain good agreement with the measured relative rates of Janssen et al. [Phys. Chem. Chem. Phys. 3, 4718 (2001)]. The temperature dependence of the recombination rate is also addressed.

Correction of Thermal Gradient Errors in Stem Thermocouple Hygrometers

PubMed Central

Michel, Burlyn E.

1979-01-01

Stem thermocouple hygrometers were subjected to transient and stable thermal gradients while in contact with reference solutions of NaCl. Both dew point and psychrometric voltages were directly related to zero offset voltages, the latter reflecting the size of the thermal gradient. Although slopes were affected by absolute temperature, they were not affected by water potential. One hygrometer required a correction of 1.75 bars water potential per microvolt of zero offset, a value that was constant from 20 to 30 C. PMID:16660685

Theoretical characterization of the minimum energy path for hydrogen atom addition to N2 - Implications for the unimolecular lifetime of HN2

NASA Technical Reports Server (NTRS)

Walch, Stephen P.; Duchovic, Ronald J.; Rohlfing, Celeste Mcmichael

1989-01-01

Results are reported from CASSCF externally contracted CI ab initio computations of the minimum-energy path for the addition of H to N2. The theoretical basis and numerical implementation of the computations are outlined, and the results are presented in extensive tables and graphs and characterized in detail. The zero-point-corrected barrier for HN2 dissociation is estimated as 8.5 kcal/mol, and the lifetime of the lowest-lying quasi-bound vibrational state of HN2 is found to be between 88 psec and 5.8 nsec (making experimental observation of this species very difficult).

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

Torcellini, Paul A.; Bonnema, Eric; Goldwasser, David

Building energy consumption can only be measured at the site or at the point of utility interconnection with a building. Often, to evaluate the total energy impact, this site-based energy consumption is translated into source energy, that is, the energy at the point of fuel extraction. Consistent with this approach, the U.S. Department of Energy's (DOE) definition of zero energy buildings uses source energy as the metric to account for energy losses from the extraction, transformation, and delivery of energy. Other organizations, as well, use source energy to characterize the energy impacts. Four methods of making the conversion from sitemore » energy to source energy were investigated in the context of the DOE definition of zero energy buildings. These methods were evaluated based on three guiding principles--improve energy efficiency, reduce and stabilize power demand, and use power from nonrenewable energy sources as efficiently as possible. This study examines relative trends between strategies as they are implemented on very low-energy buildings to achieve zero energy. A typical office building was modeled and variations to this model performed. The photovoltaic output that was required to create a zero energy building was calculated. Trends were examined with these variations to study the impacts of the calculation method on the building's ability to achieve zero energy status. The paper will highlight the different methods and give conclusions on the advantages and disadvantages of the methods studied.« less

The main beam correction term in kinetic energy release from metastable peaks.

PubMed

Petersen, Allan Christian

2017-12-01

The correction term for the precursor ion signal width in determination of kinetic energy release is reviewed, and the correction term is formally derived. The derived correction term differs from the traditionally applied term. An experimental finding substantiates the inaccuracy in the latter. The application of the "T-value" to study kinetic energy release is found preferable to kinetic energy release distributions when the metastable peaks are slim and simple Gaussians. For electronically predissociated systems, a "borderline zero" kinetic energy release can be directly interpreted in reaction dynamics with strong curvature in the reaction coordinate. Copyright © 2017 John Wiley & Sons, Ltd.

Interaction of monovalent cations with acetonitrile

NASA Astrophysics Data System (ADS)

Černušák, Ivan; Aranyosiová, Monika; Vollárová, Ol'ga; Velič, Dušan; Kirdajová, Ol'ga; Benko, Ján

Solvation of monovalent cations (Me+) of alkali metals=Na+, K+, Rb+, and Cs+, coinage metals=Cu+, Ag+, Au+, and p-block elements Ga+, In+, and Tl+ with acetonitrile was studied by means of ab initio calculations and time-of-flight secondary ion mass spectrometry (TOF-SIMS). The intermolecular interactions in the complexes Me+···CH3CN were investigated using the coupled clusters theory including single, double, and noniterative triple substitutions (CCSD(T)) in conjunction with the Pol and Pol-dk basis sets. The binding energies of these donor-acceptor complexes were estimated; taking into account the basis set superposition error, zero-point vibrations, correlation contribution, and scalar relativistic corrections. The theoretical ΔG0298 K values based on CCSD(T)/Pol and/or CCSD(T)/Pol-dk binding energies correlated well with experimental transfer Gibbs energies (from water to acetonitrile) for the series of cations. In the case of Au monocation, relativistic correction turned out to be extremely important. Composition of the complex of Ag+ and Na+ with acetonitrile was determined by using SIMS supporting both theoretical and experimental transfer Gibbs energies.

Zero-point corrections for isotropic coupling constants for cyclohexadienyl radical, C₆H₇ and C₆H₆Mu: beyond the bond length change approximation.

PubMed

Hudson, Bruce S; Chafetz, Suzanne K

2013-04-25

Zero-point vibrational level averaging for electron spin resonance (ESR) and muon spin resonance (µSR) hyperfine coupling constants (HFCCs) are computed for H and Mu isotopomers of the cyclohexadienyl radical. A local mode approximation previously developed for computation of the effect of replacement of H by D on ¹³C-NMR chemical shifts is used. DFT methods are used to compute the change in energy and HFCCs when the geometry is changed from the equilibrium values for the stretch and both bend degrees of freedom. This variation is then averaged over the probability distribution for each degree of freedom. The method is tested using data for the methylene group of C₆H₇, cyclohexadienyl radical and its Mu analog. Good agreement is found for the difference between the HFCCs for Mu and H of CHMu and that for H of CHMu and CH₂ of the parent radical methylene group. All three of these HFCCs are the same in the absence of the zero point average, a one-parameter fit of the static HFCC, a(0), can be computed. That value, 45.2 Gauss, is compared to the results of several fixed geometry electronic structure computations. The HFCC values for the ortho, meta and para H atoms are then discussed.

Uncertainty relations, zero point energy and the linear canonical group

NASA Technical Reports Server (NTRS)

Sudarshan, E. C. G.

1993-01-01

The close relationship between the zero point energy, the uncertainty relations, coherent states, squeezed states, and correlated states for one mode is investigated. This group-theoretic perspective enables the parametrization and identification of their multimode generalization. In particular the generalized Schroedinger-Robertson uncertainty relations are analyzed. An elementary method of determining the canonical structure of the generalized correlated states is presented.

Theoretical insight of adsorption thermodynamics of multifunctional molecules on metal surfaces

NASA Astrophysics Data System (ADS)

Loffreda, David

2006-05-01

Adsorption thermodynamics based on density functional theory (DFT) calculations are exposed for the interaction of several multifunctional molecules with Pt and Au(1 1 0)-(1 × 2) surfaces. The Gibbs free adsorption energy explicitly depends on the adsorption internal energy, which is derived from DFT adsorption energy, and the vibrational entropy change during the chemisorption process. Zero-point energy (ZPE) corrections have been systematically applied to the adsorption energy. Moreover the vibrational entropy change has been computed on the basis of DFT harmonic frequencies (gas and adsorbed phases, clean surfaces), which have been extended to all the adsorbate vibrations and the metallic surface phonons. The phase diagrams plotted in realistic conditions of temperature (from 100 to 400 K) and pressure (0.15 atm) show that the ZPE corrected adsorption energy is the main contribution. When strong chemisorption is considered on the Pt surface, the multifunctional molecules are adsorbed on the surface in the considered temperature range. In contrast for weak chemisorption on the Au surface, the thermodynamic results should be held cautiously. The systematic errors of the model (choice of the functional, configurational entropy and vibrational entropy) make difficult the prediction of the adsorption-desorption phase boundaries.

Direct decarbonylation of furfural to furan: A density functional theory study on Pt-graphene

NASA Astrophysics Data System (ADS)

Fellah, Mehmet Ferdi

2017-05-01

The catalytic mechanism of direct decarbonylation of furfural to furan on Pt graphene surface has been investigated by means of density functional theory (DFT) calculations. The main catalytic mechanism proposed in this study has six steps such as furfural adsorption, dissociation of H from adsorbed furfural, dissociation of carbon monoxide (molecularly) from adsorbed complex, furan formation and desorption of products. It has been concluded that the rate determining step for direct decarbonylation of furfural to furan is furan formation step and global activation barrier for this catalytic system is 82 kJ/mol consisting of zero point energy and thermal energy corrections. Pt-graphene structure has an important role on the catalytic decarbonylation of furfural to furan without any other reactants. This accordingly points out that Pt doped graphene structure might be an encouraging catalyst for direct decarbonylation of furfural to furan molecule as a valuable chemical material.

Zero-Point Energy Constraint for Unimolecular Dissociation Reactions. Giving Trajectories Multiple Chances To Dissociate Correctly.

PubMed

Paul, Amit K; Hase, William L

2016-01-28

A zero-point energy (ZPE) constraint model is proposed for classical trajectory simulations of unimolecular decomposition and applied to CH4* → H + CH3 decomposition. With this model trajectories are not allowed to dissociate unless they have ZPE in the CH3 product. If not, they are returned to the CH4* region of phase space and, if necessary, given additional opportunities to dissociate with ZPE. The lifetime for dissociation of an individual trajectory is the time it takes to dissociate with ZPE in CH3, including multiple possible returns to CH4*. With this ZPE constraint the dissociation of CH4* is exponential in time as expected for intrinsic RRKM dynamics and the resulting rate constant is in good agreement with the harmonic quantum value of RRKM theory. In contrast, a model that discards trajectories without ZPE in the reaction products gives a CH4* → H + CH3 rate constant that agrees with the classical and not quantum RRKM value. The rate constant for the purely classical simulation indicates that anharmonicity may be important and the rate constant from the ZPE constrained classical trajectory simulation may not represent the complete anharmonicity of the RRKM quantum dynamics. The ZPE constraint model proposed here is compared with previous models for restricting ZPE flow in intramolecular dynamics, and connecting product and reactant/product quantum energy levels in chemical dynamics simulations.

Rotating Casimir systems: Magnetic-field-enhanced perpetual motion, possible realization in doped nanotubes, and laws of thermodynamics

NASA Astrophysics Data System (ADS)

Chernodub, M. N.

2013-01-01

Recently, we have demonstrated that for a certain class of Casimir-type systems (“devices”) the energy of zero-point vacuum fluctuations reaches its global minimum when the device rotates about a certain axis rather than remains static. This rotational vacuum effect may lead to the emergence of permanently rotating objects provided the negative rotational energy of zero-point fluctuations cancels the positive rotational energy of the device itself. In this paper, we show that for massless electrically charged particles the rotational vacuum effect should be drastically (astronomically) enhanced in the presence of a magnetic field. As an illustration, we show that in a background of experimentally available magnetic fields the zero-point energy of massless excitations in rotating torus-shaped doped carbon nanotubes may indeed overwhelm the classical energy of rotation for certain angular frequencies so that the permanently rotating state is energetically favored. The suggested “zero-point-driven” devices—which have no internally moving parts—correspond to a perpetuum mobile of a new, fourth kind: They do not produce any work despite the fact that their equilibrium (ground) state corresponds to a permanent rotation even in the presence of an external environment. We show that our proposal is consistent with the laws of thermodynamics.

Thermal decomposition of 1,3,3-trinitroazetidine (TNAZ): A density functional theory and ab initio study

NASA Astrophysics Data System (ADS)

Veals, Jeffrey D.; Thompson, Donald L.

2014-04-01

Density functional theory and ab initio methods are employed to investigate decomposition pathways of 1,3,3-trinitroazetidine initiated by unimolecular loss of NO2 or HONO. Geometry optimizations are performed using M06/cc-pVTZ and coupled-cluster (CC) theory with single, double, and perturbative triple excitations, CCSD(T), is used to calculate accurate single-point energies for those geometries. The CCSD(T)/cc-pVTZ energies for NO2 elimination by N-N and C-N bond fission are, including zero-point energy (ZPE) corrections, 43.21 kcal/mol and 50.46 kcal/mol, respectively. The decomposition initiated by trans-HONO elimination can occur by a concerted H-atom and nitramine NO2 group elimination or by a concerted H-atom and nitroalkyl NO2 group elimination via barriers (at the CCSD(T)/cc-pVTZ level with ZPE corrections) of 47.00 kcal/mol and 48.27 kcal/mol, respectively. Thus, at the CCSD(T)/cc-pVTZ level, the ordering of these four decomposition steps from energetically most favored to least favored is: NO2 elimination by N-N bond fission, HONO elimination involving the nitramine NO2 group, HONO elimination involving a nitroalkyl NO2 group, and finally NO2 elimination by C-N bond fission.

Zero-point fluctuations in naphthalene and their effect on charge transport parameters.

PubMed

Kwiatkowski, Joe J; Frost, Jarvist M; Kirkpatrick, James; Nelson, Jenny

2008-09-25

We calculate the effect of vibronic coupling on the charge transport parameters in crystalline naphthalene, between 0 and 400 K. We find that nuclear fluctuations can cause large changes in both the energy of a charge on a molecule and on the electronic coupling between molecules. As a result, nuclear fluctuations cause wide distributions of both energies and couplings. We show that these distributions have a small temperature dependence and that, even at high temperatures, vibronic coupling is dominated by the effect of zero-point fluctuations. Because of the importance of zero-point fluctuations, we find that the distributions of energies and couplings have substantial width, even at 0 K. Furthermore, vibronic coupling with high energy modes may be significant, even though these modes are never thermally activated. Our results have implications for the temperature dependence of charge mobilities in organic semiconductors.

On the contribution of intramolecular zero point energy to the equation of state of solid H2

NASA Technical Reports Server (NTRS)

Chandrasekharan, V.; Etters, R. D.

1978-01-01

Experimental evidence shows that the internal zero-point energy of the H2 molecule exhibits a relatively strong pressure dependence in the solid as well as changing considerably upon condensation. It is shown that these effects contribute about 6% to the total sublimation energy and to the pressure in the solid state. Methods to modify the ab initio isolated pair potential to account for these environmental effects are discussed.

The Strength of Hydrogen Bonds between Fluoro-Organics and Alcohols, a Theoretical Study.

PubMed

Rosenberg, Robert E

2018-05-10

Fluorinated organic compounds are ubiquitous in the pharmaceutical and agricultural industries. To better discern the mode of action of these compounds, it is critical to understand the strengths of hydrogen bonds involving fluorine. There are only a few published examples of the strengths of these bonds. This study provides a high level ab initio study of inter- and intramolecular hydrogen bonds between RF and R'OH, where R and R' are aryl, vinyl, alkyl, and cycloalkyl. Intermolecular binding energies average near 5 kcal/mol, while intramolecular binding energies average about 3 kcal/mol. Inclusion of zero-point energies and applying a counterpoise correction lessen the difference. In both series, modest increases in binding energies are seen with increased acidity of R'OH and increased electron donation of R in RF. In the intramolecular compounds, binding energy increases with the rigidity of the F-(C) n -OH ring. Inclusion of free energy corrections at 298 K results in exoergic binding energies for the intramolecular compounds and endoergic binding energies for the intermolecular compounds. Parameters such as bond lengths, vibrational frequencies, and atomic populations are consistent with formation of a hydrogen bond and with slightly stronger binding in the intermolecular cases over the intramolecular cases. However, these parameters correlated poorly with binding energies.

Nonlinear system guidance in the presence of transmission zero dynamics

NASA Technical Reports Server (NTRS)

Meyer, G.; Hunt, L. R.; Su, R.

1995-01-01

An iterative procedure is proposed for computing the commanded state trajectories and controls that guide a possibly multiaxis, time-varying, nonlinear system with transmission zero dynamics through a given arbitrary sequence of control points. The procedure is initialized by the system inverse with the transmission zero effects nulled out. Then the 'steady state' solution of the perturbation model with the transmission zero dynamics intact is computed and used to correct the initial zero-free solution. Both time domain and frequency domain methods are presented for computing the steady state solutions of the possibly nonminimum phase transmission zero dynamics. The procedure is illustrated by means of linear and nonlinear examples.

The energy separation between the classical and nonclassical isomers of protonated acetylene - An extensive study in one- and n-particle space saturation

NASA Technical Reports Server (NTRS)

Lindh, Roland; Rice, Julia E.; Lee, Timothy J.

1991-01-01

The energy separation between the classical and nonclassical forms of protonated acetylene has been reinvestigated in light of the recent experimentally deduced lower bound to this value of 6.0 kcal/mol. The objective of the present study is to use state-of-the-art ab initio quantum mechanical methods to establish this energy difference to within chemical accuracy (i.e., about 1 kcal/mol). The one-particle basis sets include up to g-type functions and the electron correlation methods include single and double excitation coupled-cluster (CCSD), the CCSD(T) extension, multireference configuration interaction, and the averaged coupled-pair functional methods. A correction for zero-point vibrational energies has also been included, yielding a best estimate for the energy difference between the classical and nonclassical forms of 3.7 + or - 1.3 kcal/mol.

Study of five-dimensional potential-energy surfaces for actinide isotopes by the macroscopic-microscopic method

NASA Astrophysics Data System (ADS)

Fan, T. S.; Wang, Z. M.; Zhu, X.; Zhu, W. J.; Zhong, C. L.

2017-09-01

In this work, the nuclear potential-energy of the deformed nuclei as a function of shape coordinates is calculated in a five-dimensional (5D) parameter space of the axially symmetric generalized Lawrence shapes, on the basis of the macroscopic-microscopic method. The liquid-drop part of the nuclear energy is calculated according to the Myers-Swiatecki model and the Lublin-Strasbourg-drop (LSD) formula. The Woods-Saxon and the folded-Yukawa potentials for deformed nuclei are used for the shell and pairing corrections of the Strutinsky-type. The pairing corrections are calculated at zero temperature, T, related to the excitation energy. The eigenvalues of Hamiltonians for protons and neutrons are found by expanding the eigen-functions in terms of harmonic-oscillator wave functions of a spheroid. Then the BCS pair is applied on the smeared-out single-particle spectrum. By comparing the results obtained by different models, the most favorable combination of the macroscopic-microscopic model is known as the LSD formula with the folded-Yukawa potential. Potential-energy landscapes for actinide isotopes are investigated based on a grid of more than 4,000,000 deformation points and the heights of static fission barriers are obtained in terms of a double-humped structure on the full 5D parameter space. In order to locate the ground state shapes, saddle points, scission points and optimal fission path on the calculated 5D potential-energy surface, the falling rain algorithm and immersion method are designed and implemented. The comparison of our results with available experimental data and others' theoretical results confirms the reliability of our calculations.

Modeling the archetype cysteine protease reaction using dispersion corrected density functional methods in ONIOM-type hybrid QM/MM calculations; the proteolytic reaction of papain.

PubMed

Fekete, Attila; Komáromi, István

2016-12-07

A proteolytic reaction of papain with a simple peptide model substrate N-methylacetamide has been studied. Our aim was twofold: (i) we proposed a plausible reaction mechanism with the aid of potential energy surface scans and second geometrical derivatives calculated at the stationary points, and (ii) we investigated the applicability of the dispersion corrected density functional methods in comparison with the popular hybrid generalized gradient approximations (GGA) method (B3LYP) without such a correction in the QM/MM calculations for this particular problem. In the resting state of papain the ion pair and neutral forms of the Cys-His catalytic dyad have approximately the same energy and they are separated by only a small barrier. Zero point vibrational energy correction shifted this equilibrium slightly to the neutral form. On the other hand, the electrostatic solvation free energy corrections, calculated using the Poisson-Boltzmann method for the structures sampled from molecular dynamics simulation trajectories, resulted in a more stable ion-pair form. All methods we applied predicted at least a two elementary step acylation process via a zwitterionic tetrahedral intermediate. Using dispersion corrected DFT methods the thioester S-C bond formation and the proton transfer from histidine occur in the same elementary step, although not synchronously. The proton transfer lags behind (or at least does not precede) the S-C bond formation. The predicted transition state corresponds mainly to the S-C bond formation while the proton is still on the histidine Nδ atom. In contrast, the B3LYP method using larger basis sets predicts a transition state in which the S-C bond is almost fully formed and the transition state can be mainly featured by the Nδ(histidine) to N(amid) proton transfer. Considerably lower activation energy was predicted (especially by the B3LYP method) for the next amide bond breaking elementary step of acyl-enzyme formation. Deacylation appeared to be a single elementary step process in all the methods we applied.

Water Electrolyzers and the Zero-Point Energy

NASA Astrophysics Data System (ADS)

King, M. B.

The gas emitted from popular water electrolyzer projects manifests unusual energetic anomalies, which include vaporizing tungsten when used in a welding torch and running internal combustion engines on small quantities of the gas. Some claim to run generators in closed loop fashion solely on the gas from the electrolyzer, which is powered solely from the generator. Most investigators believe the energy is from burning hydrogen. A hypothesis is proposed that the dominant energy is not coming from hydrogen, but rather it is coming from charged water gas clusters, which activate and coherently trap zero-point energy.

Progressing beyond SLMTA: Are internal audits and corrective action the key drivers of quality improvement?

PubMed

Maina, Robert N; Mengo, Doris M; Mohamud, Abdikher D; Ochieng, Susan M; Milgo, Sammy K; Sexton, Connie J; Moyo, Sikhulile; Luman, Elizabeth T

2014-01-01

Kenya has implemented the Strengthening Laboratory Management Toward Accreditation (SLMTA) programme to facilitate quality improvement in medical laboratories and to support national accreditation goals. Continuous quality improvement after SLMTA completion is needed to ensure sustainability and continue progress toward accreditation. Audits were conducted by qualified, independent auditors to assess the performance of five enrolled laboratories using the Stepwise Laboratory Quality Improvement Process Towards Accreditation (SLIPTA) checklist. End-of-programme (exit) and one year post-programme (surveillance) audits were compared for overall score, star level (from zero to five, based on scores) and scores for each of the 12 Quality System Essential (QSE) areas that make up the SLIPTA checklist. All laboratories improved from exit to surveillance audit (median improvement 38 percentage points, range 5-45 percentage points). Two laboratories improved from zero to one star, two improved from zero to three stars and one laboratory improved from three to four stars. The lowest median QSE scores at exit were: internal audit; corrective action; and occurrence management and process improvement (< 20%). Each of the 12 QSEs improved substantially at surveillance audit, with the greatest improvement in client management and customer service, internal audit and information management (≥ 50 percentage points). The two laboratories with the greatest overall improvement focused heavily on the internal audit and corrective action QSEs. Whilst all laboratories improved from exit to surveillance audit, those that focused on the internal audit and corrective action QSEs improved substantially more than those that did not; internal audits and corrective actions may have acted as catalysts, leading to improvements in other QSEs. Systematic identification of core areas and best practices to address them is a critical step toward strengthening public medical laboratories.

Progressing beyond SLMTA: Are internal audits and corrective action the key drivers of quality improvement?

PubMed Central

Mengo, Doris M.; Mohamud, Abdikher D.; Ochieng, Susan M.; Milgo, Sammy K.; Sexton, Connie J.; Moyo, Sikhulile; Luman, Elizabeth T.

2014-01-01

Background Kenya has implemented the Strengthening Laboratory Management Toward Accreditation (SLMTA) programme to facilitate quality improvement in medical laboratories and to support national accreditation goals. Continuous quality improvement after SLMTA completion is needed to ensure sustainability and continue progress toward accreditation. Methods Audits were conducted by qualified, independent auditors to assess the performance of five enrolled laboratories using the Stepwise Laboratory Quality Improvement Process Towards Accreditation (SLIPTA) checklist. End-of-programme (exit) and one year post-programme (surveillance) audits were compared for overall score, star level (from zero to five, based on scores) and scores for each of the 12 Quality System Essential (QSE) areas that make up the SLIPTA checklist. Results All laboratories improved from exit to surveillance audit (median improvement 38 percentage points, range 5–45 percentage points). Two laboratories improved from zero to one star, two improved from zero to three stars and one laboratory improved from three to four stars. The lowest median QSE scores at exit were: internal audit; corrective action; and occurrence management and process improvement (< 20%). Each of the 12 QSEs improved substantially at surveillance audit, with the greatest improvement in client management and customer service, internal audit and information management (≥ 50 percentage points). The two laboratories with the greatest overall improvement focused heavily on the internal audit and corrective action QSEs. Conclusion Whilst all laboratories improved from exit to surveillance audit, those that focused on the internal audit and corrective action QSEs improved substantially more than those that did not; internal audits and corrective actions may have acted as catalysts, leading to improvements in other QSEs. Systematic identification of core areas and best practices to address them is a critical step toward strengthening public medical laboratories. PMID:29043193

Semiclassical wave packet treatment of scattering resonances: application to the delta zero-point energy effect in recombination reactions.

PubMed

Vetoshkin, Evgeny; Babikov, Dmitri

2007-09-28

For the first time Feshbach-type resonances important in recombination reactions are characterized using the semiclassical wave packet method. This approximation allows us to determine the energies, lifetimes, and wave functions of the resonances and also to observe a very interesting correlation between them. Most important is that this approach permits description of a quantum delta-zero-point energy effect in recombination reactions and reproduces the anomalous rates of ozone formation.

DFT studies on the mechanism of the reaction of C2H5S with NO2

NASA Astrophysics Data System (ADS)

Tang, Yi-Zhen; Sun, Hao; Pan, Ya-Ru; Pan, Xiu-Mei; Wang, Rong-Shun

The mechanisms for the reaction of C2H5S with NO2 are investigated at the QCISD(T)/6-311++G(d, p)//B3LYP/6-311++G(d, p) level on both single and triple potential energy surfaces. The geometries, vibrational frequencies and zero-point energy (ZPE) corrections of all stationary points involved in the title reaction are calculated at the B3LYP/6-311++G(d, p) level. The results show that the reaction is more predominant on the single potential energy surface, while it is negligible on the triple potential energy surface. Without barrier height in the whole process, the major channel is R ? C2H5SONO (IM1 and IM2) ? P1 (C2H5SO+NO). With much heat released in the formation of C2H5SNO2 (IM3) and the transition state involved in the subsequent step more stable than reactants, P4 (CH3CHS + t-HONO) is subdominant product energetically.

Energy of the quasi-free electron in supercritical krypton near the critical point.

PubMed

Li, Luxi; Evans, C M; Findley, G L

2005-12-01

Field ionization measurements of high-n CH(3)I and C(2)H(5)I Rydberg states doped into krypton are presented as a function of krypton number density along the critical isotherm. These data exhibit a decrease in the krypton-induced shift of the dopant ionization energy near the critical point. This change in shift is modeled to within +/-0.2% of experiment using a theory that accounts for the polarization of krypton by the dopant ion, the polarization of krypton by the quasi-free electron that arises from field ionization of the dopant, and the zero point kinetic energy of the free electron. The overall decrease in the shift of the dopant ionization energy near the critical point of krypton, which is a factor of 2 larger than that observed in argon, is dominated by the increase in the zero point kinetic energy of the quasi-free electron.

Complexes and saddle point structures, vibrational frequencies and relative energies of intermediates for CH2Br + HBr «-» CH3Br + Br

NASA Astrophysics Data System (ADS)

Espinosa-Garcia, J.

Ab initio molecular orbital theory was used to study parts of the reaction between the CH2Br radical and the HBr molecule, and two possibilities were analysed: attack on the hydrogen and attack on the bromine of the HBr molecule. Optimized geometries and harmonic vibrational frequencies were calculated at the second-order Moller-Plesset perturbation theory levels, and comparison with available experimental data was favourable. Then single-point calculations were performed at several higher levels of calculation. In the attack on the hydrogen of HBr, two stationary points were located on the direct hydrogen abstraction reaction path: a very weak hydrogen bonded complex of reactants, C···HBr, close to the reactants, followed by the saddle point (SP). The effects of level of calculation (method + basis set), spin projection, zeropoint energy, thermal corrections (298K), spin-orbit coupling and basis set superposition error (BSSE) on the energy changes were analysed. Taking the reaction enthalpy (298K) as reference, agreement with experiment was obtained only when high correlation energy and large basis sets were used. It was concluded that at room temperature (i.e., with zero-point energy and thermal corrections), when the BSSE was included, the complex disappears and the activation enthalpy (298K) ranges from 0.8kcal mol-1 to 1.4kcal mol-1 above the reactants, depending on the level of calculation. It was concluded also that this result is the balance of a complicated interplay of many factors, which are affected by uncertainties in the theoretical calculations. Finally, another possible complex (X complex), which involves the alkyl radical being attracted to the halogen end of HBr (C···BrH), was explored also. It was concluded that this X complex does not exist at room temperature.

Time delay of critical images of a point source near the gravitational lens fold-caustic

NASA Astrophysics Data System (ADS)

Alexandrov, A.; Zhdanov, V.

2016-06-01

Within the framework of the analytical theory of the gravitational lensing we derive asymptotic formula for the time delay of critical images of apoint source, which is situated near a fold-caustic. We found corrections of the first and second order in powers of a parameter, which describescloseness of the source to the caustic. Our formula modifies earlier result by Congdon, Keeton &Nordgren (MNRAS, 2008) obtained in zero-orderapproximation. We have proved the hypothesis put forward by these authors that the first-order correction to the relative time delay of two criticalmages is identically zero. The contribution of the corrections is illustrated in model example by comparison with exact expression.

Thermodynamic Stability of Ice II and Its Hydrogen-Disordered Counterpart: Role of Zero-Point Energy.

PubMed

Nakamura, Tatsuya; Matsumoto, Masakazu; Yagasaki, Takuma; Tanaka, Hideki

2016-03-03

We investigate why no hydrogen-disordered form of ice II has been found in nature despite the fact that most of hydrogen-ordered ices have hydrogen-disordered counterparts. The thermodynamic stability of a set of hydrogen-ordered ice II variants relative to ice II is evaluated theoretically. It is found that ice II is more stable than the disordered variants so generated as to satisfy the simple ice rule due to the lower zero-point energy as well as the pair interaction energy. The residual entropy of the disordered ice II phase gradually compensates the unfavorable free energy with increasing temperature. The crossover, however, occurs at a high temperature well above the melting point of ice III. Consequently, the hydrogen-disordered phase does not exist in nature. The thermodynamic stability of partially hydrogen-disordered ices is also scrutinized by examining the free-energy components of several variants obtained by systematic inversion of OH directions in ice II. The potential energy of one variant is lower than that of the ice II structure, but its Gibbs free energy is slightly higher than that of ice II due to the zero-point energy. The slight difference in the thermodynamic stability leaves the possibility of the partial hydrogen-disorder in real ice II.

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.

Entanglement of Distillation for Lattice Gauge Theories.

PubMed

Van Acoleyen, Karel; Bultinck, Nick; Haegeman, Jutho; Marien, Michael; Scholz, Volkher B; Verstraete, Frank

2016-09-23

We study the entanglement structure of lattice gauge theories from the local operational point of view, and, similar to Soni and Trivedi [J. High Energy Phys. 1 (2016) 1], we show that the usual entanglement entropy for a spatial bipartition can be written as the sum of an undistillable gauge part and of another part corresponding to the local operations and classical communication distillable entanglement, which is obtained by depolarizing the local superselection sectors. We demonstrate that the distillable entanglement is zero for pure Abelian gauge theories at zero gauge coupling, while it is in general nonzero for the non-Abelian case. We also consider gauge theories with matter, and show in a perturbative approach how area laws-including a topological correction-emerge for the distillable entanglement. Finally, we also discuss the entanglement entropy of gauge fixed states and show that it has no relation to the physical distillable entropy.

Quantum dynamics study of H+NH3-->H2+NH2 reaction.

PubMed

Zhang, Xu Qiang; Cui, Qian; Zhang, John Z H; Han, Ke Li

2007-06-21

We report in this paper a quantum dynamics study for the reaction H+NH3-->NH2+H2 on the potential energy surface of Corchado and Espinosa-Garcia [J. Chem. Phys. 106, 4013 (1997)]. The quantum dynamics calculation employs the semirigid vibrating rotor target model [J. Z. H. Zhang, J. Chem. Phys. 111, 3929 (1999)] and time-dependent wave packet method to propagate the wave function. Initial state-specific reaction probabilities are obtained, and an energy correction scheme is employed to account for zero point energy changes for the neglected degrees of freedom in the dynamics treatment. Tunneling effect is observed in the energy dependency of reaction probability, similar to those found in H+CH4 reaction. The influence of rovibrational excitation on reaction probability and stereodynamical effect are investigated. Reaction rate constants from the initial ground state are calculated and are compared to those from the transition state theory and experimental measurement.

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

Veklenko, B. A., E-mail: veklenkoba@yandex.ru

It is shown theoretically that the electromagnetic background of longitudinal zero oscillations of a temperature-degenerate electron–ion plasma in a thermodynamic equilibrium state resonantly distorts the wave functions of its electrons. This gives rise to a characteristic quantum frequency that nonanalytically depends on Planck’s constant ℏ. Vacuum phenomena in plasma attributed to zero oscillations turn out to be anomalously large. Quantum corrections to the transverse dielectric permittivity of a degenerate electron–ion plasma, which are nonanalytic with respect to ℏ and are attributed to the zero-point oscillations of the plasma, are determined.

Black hole firewalls require huge energy of measurement

NASA Astrophysics Data System (ADS)

Hotta, Masahiro; Matsumoto, Jiro; Funo, Ken

2014-06-01

The unitary moving mirror model is one of the best quantum systems for checking the reasoning of the original firewall paradox of Almheiri et al. [J. High Energy Phys. 02 (2013) 062] in quantum black holes. Though the late-time part of radiations emitted from the mirror is fully entangled with the early part, no firewall exists with a deadly, huge average energy flux in this model. This is because the high-energy entanglement structure of the discretized systems in almost maximally entangled states is modified so as to yield the correct description of low-energy effective field theory. Furthermore, the strong subadditivity paradox of firewalls is resolved using nonlocality of general one-particle states and zero-point fluctuation entanglement. Due to the Reeh-Schlieder theorem in quantum field theory, another firewall paradox is inevitably raised with quantum remote measurements in the model. We resolve this paradox from the viewpoint of the energy cost of measurements. No firewall appears, as long as the energy for the measurement is much smaller than the ultraviolet cutoff scale.

Pyridine adsorption and diffusion on Pt(111) investigated with density functional theory

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

Kolsbjerg, Esben L.; Groves, Michael N.; Hammer, Bjørk, E-mail: hammer@phys.au.dk

2016-04-28

The adsorption, diffusion, and dissociation of pyridine, C{sub 5}H{sub 5}N, on Pt(111) are investigated with van der Waals-corrected density functional theory. An elaborate search for local minima in the adsorption potential energy landscape reveals that the intact pyridine adsorbs with the aromatic ring parallel to the surface. Piecewise interconnections of the local minima in the energy landscape reveal that the most favourable diffusion path for pyridine has a barrier of 0.53 eV. In the preferred path, the pyridine remains parallel to the surface while performing small single rotational steps with a carbon-carbon double bond hinged above a single Pt atom.more » The origin of the diffusion pathway is discussed in terms of the C{sub 2}–Pt π-bond being stronger than the corresponding CN–Pt π-bond. The energy barrier and reaction enthalpy for dehydrogenation of adsorbed pyridine into an adsorbed, upright bound α-pyridyl species are calculated to 0.71 eV and 0.18 eV, respectively (both zero-point energy corrected). The calculations are used to rationalize previous experimental observations from the literature for pyridine on Pt(111).« less

An assessment of mean-field mixed semiclassical approaches: Equilibrium populations and algorithm stability

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

Bellonzi, Nicole; Jain, Amber; Subotnik, Joseph E.

2016-04-21

We study several recent mean-field semiclassical dynamics methods, focusing on the ability to recover detailed balance for long time (equilibrium) populations. We focus especially on Miller and Cotton’s [J. Phys. Chem. A 117, 7190 (2013)] suggestion to include both zero point electronic energy and windowing on top of Ehrenfest dynamics. We investigate three regimes: harmonic surfaces with weak electronic coupling, harmonic surfaces with strong electronic coupling, and anharmonic surfaces with weak electronic coupling. In most cases, recent additions to Ehrenfest dynamics are a strong improvement upon mean-field theory. However, for methods that include zero point electronic energy, we show thatmore » anharmonic potential energy surfaces often lead to numerical instabilities, as caused by negative populations and forces. We also show that, though the effect of negative forces can appear hidden in harmonic systems, the resulting equilibrium limits do remain dependent on any windowing and zero point energy parameters.« less

Comment on ‘The paradoxical zero reflection at zero energy’

NASA Astrophysics Data System (ADS)

van Dijk, W.; Nogami, Y.

2017-05-01

We point out that the anomalous threshold effect in one dimension occurs when the reflection probability at zero energy R(0) has some other value than unity, rather than R(0)=0 or R(0)\\ll 1 as implied by Ahmed et al in their paper entitled ‘The paradoxical zero reflection at zero energy’ (2017 Eur. J. Phys. 38 025401).

Thermal corrections to the Casimir energy in a general weak gravitational field

NASA Astrophysics Data System (ADS)

Nazari, Borzoo

2016-12-01

We calculate finite temperature corrections to the energy of the Casimir effect of a two conducting parallel plates in a general weak gravitational field. After solving the Klein-Gordon equation inside the apparatus, mode frequencies inside the apparatus are obtained in terms of the parameters of the weak background. Using Matsubara’s approach to quantum statistical mechanics gravity-induced thermal corrections of the energy density are obtained. Well-known weak static and stationary gravitational fields are analyzed and it is found that in the low temperature limit the energy of the system increases compared to that in the zero temperature case.

Changes in the zero-point energy of the protons as the source of the binding energy of water to A-phase DNA.

PubMed

Reiter, G F; Senesi, R; Mayers, J

2010-10-01

The measured changes in the zero-point kinetic energy of the protons are entirely responsible for the binding energy of water molecules to A phase DNA at the concentration of 6  water molecules/base pair. The changes in kinetic energy can be expected to be a significant contribution to the energy balance in intracellular biological processes and the properties of nano-confined water. The shape of the momentum distribution in the dehydrated A phase is consistent with coherent delocalization of some of the protons in a double well potential, with a separation of the wells of 0.2 Å.

Effect of Chlorine Substitution on Sulfide Reactivity with OH Radicals

DTIC Science & Technology

2008-09-01

Single point energy: MP2/6-311+G(3df,2p) (LRG) • Zero Point Energy from a vibrational frequency analysis: MP2/6-31++G** ( ZPE ) • Extrapolated energy...E(QCI) + E(LARG) – E(SML) + ZPE • Characterize the TS • Use a three-point fit methodology – fit a harmonic potential to three CCSD single point

A DFT/HF study of the potential energy surface of protonated ethane C2H7+

NASA Astrophysics Data System (ADS)

Hrusak, Jan; Zabka, Jan; Dolejsek, Zdenek; Herman, Zdenek

1997-11-01

Structures and energies of several isomers of the C2H7+ cation have been calculated using the parametrized B3LYP HF/DFT method. The B3LYP/6-31G** geometries of the individual isomers are of at least the same quality as the MP2/6-31G** results. The zero-point-energy corrected relative stabilities of the individual C2H7+ isomers are in excellent agreement with the much more costly MP4SDTQ/6-31G** MO calculations. A structure with a linear C---H---C skeleton and a CC distance of about 2.5 A was found to be a higher order saddle point on the PES resulting from curve crossing between the reactant and product channels CH3+ + CH4; this finding is of importance in interpreting the experimental results on the hydride ion transfer between CH3+ and CH4. The calculations are also consistent with the earlier experimental results on the formation of the products C2H5+ + H2.

A new ab initio potential energy surface of LiClH (1A') system and quantum dynamics calculation for Li + HCl (v = 0, j = 0-2) → LiCl + H reaction

NASA Astrophysics Data System (ADS)

Tan, Rui Shan; Zhai, Huan Chen; Yan, Wei; Gao, Feng; Lin, Shi Ying

2017-04-01

A new ab initio potential energy surface (PES) for the ground state of Li + HCl reactive system has been constructed by three-dimensional cubic spline interpolation of 36 654 ab initio points computed at the MRCI+Q/aug-cc-pV5Z level of theory. The title reaction is found to be exothermic by 5.63 kcal/mol (9 kcal/mol with zero point energy corrections), which is very close to the experimental data. The barrier height, which is 2.99 kcal/mol (0.93 kcal/mol for the vibrationally adiabatic barrier height), and the depth of van der Waals minimum located near the entrance channel are also in excellent agreement with the experimental findings. This study also identified two more van der Waals minima. The integral cross sections, rate constants, and their dependence on initial rotational states are calculated using an exact quantum wave packet method on the new PES. They are also in excellent agreement with the experimental measurements.

Quantum chemical characterization of the X((1)A'), a((3)A'') and A((1)A'') states of CHBr and CHI and computed heats of formation for CHI and CI.

PubMed

Bacskay, George B

2010-08-26

The relative energies of the X, a, and A states of CHBr and CHI and their atomization and dissociation energies in the complete basis limit were determined by extrapolating (R/U)CCSD(T) and Davidson corrected MRCI energies calculated with the aug-cc-pVxZ (x = T,Q,5) basis sets, which were corrected for core-valence correlation, spin-orbit coupling, and zero point energies. The all-electron calculations on the bromine containing molecules were explicitly corrected for scalar relativity, while in the iodo systems they are implicit in the ECP28MDF pseudopotential of iodine. The geometries and vibrational frequencies were calculated at the CASPT2/cc-pVTZ level of theory. The computed singlet-triplet splittings (5.7 and 3.7 kcal mol(-1) for CHBr and CHI respectively) are in close agreement with the recent experimental values, while the predicted A <-- X excitation energies are within approximately 1 kcal mol(-1) of experiment. The barriers to linearity and dissociation on the A surface were also characterized. For CHI and CI, the predicted heats of formation at 298 K are 134.5 +/- 1.0 and 103.9 +/- 1.0 kcal mol(-1), respectively. The spin-orbit splitting in iodomethylidyne (CI) is computed to be 746 cm(-1), although that value may be an underestimate by approximately 20%.

Ab initio study of structural and mechanical property of solid molecular hydrogens

NASA Astrophysics Data System (ADS)

Ye, Yingting; Yang, Li; Yang, Tianle; Nie, Jinlan; Peng, Shuming; Long, Xinggui; Zu, Xiaotao; Du, Jincheng

2015-06-01

Ab initio calculations based on density functional theory (DFT) were performed to investigate the structural and the elastic properties of solid molecular hydrogens (H2). The influence of molecular axes of H2 on structural relative stabilities of hexagonal close-packed (hcp) and face-centered cubic (fcc) structured hydrogen molecular crystals were systematically investigated. Our results indicate that for hcp structures, disordered hydrogen molecule structure is more stable, while for fcc structures, Pa3 hydrogen molecular crystal is most stable. The cohesive energy of fcc H2 crystal was found to be lower than hcp. The mechanical properties of fcc and hcp hydrogen molecular crystals were obtained, with results consistent with previous theoretical calculations. In addition, the effects of zero point energy (ZPE) and van der Waals (vdW) correction on the cohesive energy and the stability of hydrogen molecular crystals were systematically studied and discussed.

Vibrational zero point energy for H-doped silicon

NASA Astrophysics Data System (ADS)

Karazhanov, S. Zh.; Ganchenkova, M.; Marstein, E. S.

2014-05-01

Most of the studies addressed to computations of hydrogen parameters in semiconductor systems, such as silicon, are performed at zero temperature T = 0 K and do not account for contribution of vibrational zero point energy (ZPE). For light weight atoms such as hydrogen (H), however, magnitude of this parameter might be not negligible. This Letter is devoted to clarify the importance of accounting the zero-point vibrations when analyzing hydrogen behavior in silicon and its effect on silicon electronic properties. For this, we estimate the ZPE for different locations and charge states of H in Si. We show that the main contribution to the ZPE is coming from vibrations along the Si-H bonds whereas contributions from other Si atoms apart from the direct Si-H bonds play no role. It is demonstrated that accounting the ZPE reduces the hydrogen formation energy by ˜0.17 eV meaning that neglecting ZPE at low temperatures one can underestimate hydrogen solubility by few orders of magnitude. In contrast, the effect of the ZPE on the ionization energy of H in Si is negligible. The results can have important implications for characterization of vibrational properties of Si by inelastic neutron scattering, as well as for theoretical estimations of H concentration in Si.

Stable long-time semiclassical description of zero-point energy in high-dimensional molecular systems.

PubMed

Garashchuk, Sophya; Rassolov, Vitaly A

2008-07-14

Semiclassical implementation of the quantum trajectory formalism [J. Chem. Phys. 120, 1181 (2004)] is further developed to give a stable long-time description of zero-point energy in anharmonic systems of high dimensionality. The method is based on a numerically cheap linearized quantum force approach; stabilizing terms compensating for the linearization errors are added into the time-evolution equations for the classical and nonclassical components of the momentum operator. The wave function normalization and energy are rigorously conserved. Numerical tests are performed for model systems of up to 40 degrees of freedom.

Zero field reversal probability in thermally assisted magnetization reversal

NASA Astrophysics Data System (ADS)

Prasetya, E. B.; Utari; Purnama, B.

2017-11-01

This paper discussed about zero field reversal probability in thermally assisted magnetization reversal (TAMR). Appearance of reversal probability in zero field investigated through micromagnetic simulation by solving stochastic Landau-Lifshitz-Gibert (LLG). The perpendicularly anisotropy magnetic dot of 50×50×20 nm3 is considered as single cell magnetic storage of magnetic random acces memory (MRAM). Thermally assisted magnetization reversal was performed by cooling writing process from near/almost Curie point to room temperature on 20 times runs for different randomly magnetized state. The results show that the probability reversal under zero magnetic field decreased with the increase of the energy barrier. The zero-field probability switching of 55% attained for energy barrier of 60 k B T and the reversal probability become zero noted at energy barrier of 2348 k B T. The higest zero-field switching probability of 55% attained for energy barrier of 60 k B T which corespond to magnetif field of 150 Oe for switching.

Role of zero-point effects in stabilizing the ground state structure of bulk Fe2P

NASA Astrophysics Data System (ADS)

Bhat, Soumya S.; Gupta, Kapil; Bhattacharjee, Satadeep; Lee, Seung-Cheol

2018-05-01

Structural stability of Fe2P is investigated in detail using first-principles calculations based on density functional theory. While the orthorhombic C23 phase is found to be energetically more stable, the experiments suggest it to be hexagonal C22 phase. In the present study, we show that in order to obtain the correct ground state structure of Fe2P from the first-principles based methods it is utmost necessary to consider the zero-point effects such as zero-point vibrations and spin fluctuations. This study demonstrates an exceptional case where a bulk material is stabilized by quantum effects, which are usually important in low-dimensional materials. Our results also indicate the possibility of magnetic field induced structural quantum phase transition in Fe2P, which should form the basis for further theoretical and experimental efforts.

Investigating the significance of zero-point motion in small molecular clusters of sulphuric acid and water

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

Stinson, Jake L.; Kathmann, Shawn M.; Ford, Ian J.

2014-01-14

The nucleation of particles from trace gases in the atmosphere is an important source of cloud condensation nuclei (CCN), and these are vital for the formation of clouds in view of the high supersaturations required for homogeneous water droplet nucleation. The methods of quantum chemistry have increasingly been employed to model nucleation due to their high accuracy and efficiency in calculating configurational energies; and nucleation rates can be obtained from the associated free energies of particle formation. However, even in such advanced approaches, it is typically assumed that the nuclei have a classical nature, which is questionable for some systems.more » The importance of zero-point motion (also known as quantum nuclear dynamics) in modelling small clusters of sulphuric acid and water is tested here using the path integral molecular dynamics (PIMD) method at the density functional theory (DFT) level of theory. We observe a small zero-point effect on the the equilibrium structures of certain clusters. One configuration is found to display a bimodal behaviour at 300 K in contrast to the stable ionised state suggested from a zero temperature classical geometry optimisation. The general effect of zero-point motion is to promote the extent of proton transfer with respect to classical behaviour. We thank Prof. Angelos Michaelides and his group in University College London (UCL) for practical advice and helpful discussions. This work benefited from interactions with the Thomas Young Centre through seminar and discussions involving the PIMD method. SMK was supported by the U.S. Department of Energy, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences. JLS and IJF were supported by the IMPACT scheme at UCL and by the U.S. Department of Energy, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences. We are grateful for use of the UCL Legion High Performance Computing Facility and the resources of the National Energy Research Scientific Computing Center (NERSC), which is supported by the U.S. Department of Energy, Office of Science of the under Contract No. DE-AC02-05CH11231.« less

Measurements of the electric field of zero-point optical phonons in GaAs quantum wells support the Urbach rule for zero-temperature lifetime broadening.

PubMed

Bhattacharya, Rupak; Mondal, Richarj; Khatua, Pradip; Rudra, Alok; Kapon, Eli; Malzer, Stefan; Döhler, Gottfried; Pal, Bipul; Bansal, Bhavtosh

2015-01-30

We study a specific type of lifetime broadening resulting in the well-known exponential "Urbach tail" density of states within the energy gap of an insulator. After establishing the frequency and temperature dependence of the Urbach edge in GaAs quantum wells, we show that the broadening due to the zero-point optical phonons is the fundamental limit to the Urbach slope in high-quality samples. In rough analogy with Welton's heuristic interpretation of the Lamb shift, the zero-temperature contribution to the Urbach slope can be thought of as arising from the electric field of the zero-point longitudinal-optical phonons. The value of this electric field is experimentally measured to be 3  kV cm-1, in excellent agreement with the theoretical estimate.

Rate constants for the slow Mu + propane abstraction reaction at 300 K by diamagnetic RF resonance.

PubMed

Fleming, Donald G; Cottrell, Stephen P; McKenzie, Iain; Ghandi, Khashayar

2015-08-14

The study of kinetic isotope effects for H-atom abstraction rates by incident H-atoms from the homologous series of lower mass alkanes (CH4, C2H6 and, here, C3H8) provides important tests of reaction rate theory on polyatomic systems. With a mass of only 0.114 amu, the most sensitive test is provided by the rates of the Mu atom. Abstraction of H by Mu can be highly endoergic, due to the large zero-point energy shift in the MuH bond formed, which also gives rise to high activation energies from similar zero-point energy corrections at the transition state. Rates are then far too slow near 300 K to be measured by conventional TF-μSR techniques that follow the disappearance of the spin-polarised Mu atom with time. Reported here is the first measurement of a slow Mu reaction rate in the gas phase by the technique of diamagnetic radio frequency (RF) resonance, where the amplitude of the MuH product formed in the Mu + C3H8 reaction is followed with time. The measured rate constant, kMu = (6.8 ± 0.5) × 10(-16) cm(3) s(-1) at 300 K, is surprisingly only about a factor of three slower than that expected for H + C3H8, indicating a dominant contribution from quantum tunneling in the Mu reaction, consistent with elementary transition state theory calculations of the kMu/kH kinetic isotope effect.

Can two H2 molecules be inserted into C60 - an accurate first-principles exploration of structural, energetic and vibrational properties of the 2H2@C60 complex

NASA Astrophysics Data System (ADS)

Dolgonos, Grygoriy A.; Peslherbe, Gilles H.

2016-10-01

The 2H2@C60 minimum structure of C2 symmetry has been fully characterized at the density-fitting local second-order Møller-Plesset (DF-LMP2) level of theory. Its uncorrected and zero-point energy (ZPE) corrected complexation energies equal 1.9 and 6.2 kcal/mol, respectively, confirming the instability of the complex. This structure exhibits the largest intermolecular host-guest and guest-guest separations among all the complexes studied in this work. The calculated infrared spectrum of 2H2@C60 does not show any frequency shifts for the modes associated with radial or tangential displacements in C60 (except for one mode), but shows a weak red Hsbnd H vibrational frequency shift.

On the flux of fluctuation energy in a collisional grain flow at a flat, frictional wall

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

Jenkins, J.T.; Louge, M.Y.

We consider a flow of colliding spheres that interacts with a flat, frictional wall and calculate the flux of fluctuation energy in two limits. In the first limit, all spheres slide upon contact with the wall. Here, we refine the calculations of Jenkins [J. Appl. Mech. {bold 59}, 120 (1992)] and show that a correlation between two orthogonal components of the fluctuation velocity of the point of contact of the grains with the wall provides a substantial correction to the flux originally predicted. In the other limit, the granular material is agitated but the mean velocity of the contact pointsmore » with respect to the wall is zero and Jenkins{close_quote} earlier calculation is improved by distinguishing between those contacts that slide in a collision and those that stick. The new expressions for the flux agree well with the computer simulations of Louge [Phys. Fluids {bold 6}, 2253 (1994)]. Finally, we extend the expression for zero mean sliding to incorporate small sliding and obtain an approximate expression for the flux between the two limits. {copyright} {ital 1997 American Institute of Physics.}« less

Rotational barriers. 1. 1,2-dihaloethanes

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

Wiberg, K.B.; Murcko, M.A.

1987-06-18

The rotational barrier about the C-C bond of 1,2-dichloroethane has been calculated by using several basis sets (4-31G, 6-31G*, 6-31+G*, and 6-31++G**) and including electron correlation. Corrections for zero-point energy differences, and the differences in enthalpy change from 0 to 298 K, were made by using the calculated geometries and vibrational frequencies. The trans/gauche energy difference was found to be 1.39 kcal/mol as compared to the observed value, 1.1 +/- 0.1 kcal/mol. The intramolecular interactions in the several rotamers are discussed. The trans/gauche energy difference for 1,2-difluoroethane also was calculated (MP3/6-311++G**) and was found to be 0.76 kcal/mol favoring themore » gauche conformer, again in good agreement with the experimental value of 0.57 +/- 0.09 kcal/mol. The trend in trans/gauche energy differences in the series n-butane, 1,2-dichloroethane, 1,2-difluoroethane is noted.« less

Ubiquity of quantum zero-point fluctuations in dislocation glide

NASA Astrophysics Data System (ADS)

Landeiro Dos Reis, Marie; Choudhury, Anshuman; Proville, Laurent

2017-03-01

Modeling the dislocation glide through atomic scale simulations in Al, Cu, and Ni and in solid solution alloys Al(Mg) and Cu(Ag), we show that in the course of the plastic deformation the variation of the crystal zero-point energy (ZPE) and the dislocation potential energy barriers are of opposite sign. The multiplicity of situations where we have observed the same trend allows us to conclude that quantum fluctuations, giving rise to the crystal ZPE, make easier the dislocation glide in most materials, even those constituted of atoms heavier than H and He.

The lowest-lying electronic singlet and triplet potential energy surfaces for the HNO-NOH system: energetics, unimolecular rate constants, tunneling and kinetic isotope effects for the isomerization and dissociation reactions.

PubMed

Bozkaya, Uğur; Turney, Justin M; Yamaguchi, Yukio; Schaefer, Henry F

2012-04-28

The lowest-lying electronic singlet and triplet potential energy surfaces (PES) for the HNO-NOH system have been investigated employing high level ab initio quantum chemical methods. The reaction energies and barriers have been predicted for two isomerization and four dissociation reactions. Total energies are extrapolated to the complete basis set limit applying focal point analyses. Anharmonic zero-point vibrational energies, diagonal Born-Oppenheimer corrections, relativistic effects, and core correlation corrections are also taken into account. On the singlet PES, the (1)HNO → (1)NOH endothermicity including all corrections is predicted to be 42.23 ± 0.2 kcal mol(-1). For the barrierless decomposition of (1)HNO to H + NO, the dissociation energy is estimated to be 47.48 ± 0.2 kcal mol(-1). For (1)NOH → H + NO, the reaction endothermicity and barrier are 5.25 ± 0.2 and 7.88 ± 0.2 kcal mol(-1). On the triplet PES the reaction energy and barrier including all corrections are predicted to be 7.73 ± 0.2 and 39.31 ± 0.2 kcal mol(-1) for the isomerization reaction (3)HNO → (3)NOH. For the triplet dissociation reaction (to H + NO) the corresponding results are 29.03 ± 0.2 and 32.41 ± 0.2 kcal mol(-1). Analogous results are 21.30 ± 0.2 and 33.67 ± 0.2 kcal mol(-1) for the dissociation reaction of (3)NOH (to H + NO). Unimolecular rate constants for the isomerization and dissociation reactions were obtained utilizing kinetic modeling methods. The tunneling and kinetic isotope effects are also investigated for these reactions. The adiabatic singlet-triplet energy splittings are predicted to be 18.45 ± 0.2 and 16.05 ± 0.2 kcal mol(-1) for HNO and NOH, respectively. Kinetic analyses based on solution of simultaneous first-order ordinary-differential rate equations demonstrate that the singlet NOH molecule will be difficult to prepare at room temperature, while the triplet NOH molecule is viable with respect to isomerization and dissociation reactions up to 400 K. Hence, our theoretical findings clearly explain why (1)NOH has not yet been observed experimentally.

On the global Casimir effect in the Schwarzschild spacetime

NASA Astrophysics Data System (ADS)

Muniz, C. R.; Tahim, M. O.; Cunha, M. S.; Vieira, H. S.

2018-01-01

In this paper we study the vacuum quantum fluctuations of the stationary modes of an uncharged scalar field with mass m around a Schwarzschild black hole with mass M, at zero and non-zero temperatures. The procedure consists of calculating the energy eigenvalues starting from the exact solutions found for the dynamics of the scalar field, considering a frequency cutoff in which the particle is not absorbed by the black hole. From this result, we obtain the exterior contributions for the vacuum energy associated to the stationary states of the scalar field, by considering the half-summing of the levels of energy and taking into account the respective degeneracies, in order to better capture the nontrivial topology of the black hole spacetime. Then we use the Riemann's zeta function to regularize the vacuum energy thus found. Such a regularized quantity is the Casimir energy, whose analytic computation we show to yield a convergent series. The Casimir energy obtained does not take into account any boundaries artificially imposed on the system, just the nontrivial spacetime topology associated to the source and its singularity. We suggest that this latter manifests itself through the vacuum tension calculated on the event horizon. We also investigate the problem by considering the thermal corrections via Helmholtz free energy calculation, computing the Casimir internal energy, the corresponding tension on the event horizon, the Casimir entropy, and the thermal capacity of the regularized quantum vacuum, analyzing their behavior at low and high temperatures, pointing out the thermodynamic instability of the system in the considered regime, i.e. mMll 1.

Communication: Prediction of the rate constant of bimolecular hydrogen exchange in the water dimer using an ab initio potential energy surface.

PubMed

Wang, Yimin; Bowman, Joel M; Huang, Xinchuan

2010-09-21

We report the properties of two novel transition states of the bimolecular hydrogen exchange reaction in the water dimer, based on an ab initio water dimer potential [A. Shank et al., J. Chem. Phys. 130, 144314 (2009)]. The realism of the two transition states is assessed by comparing structures, energies, and harmonic frequencies obtained from the potential energy surface and new high-level ab initio calculations. The rate constant for the exchange is obtained using conventional transition state theory with a tunneling correction. We employ a one-dimensional approach for the tunneling calculations using a relaxed potential from the full-dimensional potential in the imaginary-frequency normal mode of the saddle point, Q(im). The accuracy of this one-dimensional approach has been shown for the ground-state tunneling splittings for H and D-transfer in malonaldehyde and for the D+H(2) reaction [Y. Wang and J. M. Bowman, J. Chem. Phys. 129, 121103 (2008)]. This approach is applied to calculate the rate constant for the H(2)O+H(2)O exchange and also for H(2)O+D(2)O→2HOD. The local zero-point energy is also obtained using diffusion Monte Carlo calculations in the space of real-frequency-saddle-point normal modes, as a function of Q(im).

19 CFR 351.224 - Disclosure of calculations and procedures for the correction of ministerial errors.

Code of Federal Regulations, 2012 CFR

2012-04-01

... least five absolute percentage points in, but not less than 25 percent of, the weighted-average dumping... margin or countervailable subsidy rate (whichever is applicable) of zero (or de minimis) and a weighted...

19 CFR 351.224 - Disclosure of calculations and procedures for the correction of ministerial errors.

Code of Federal Regulations, 2010 CFR

2010-04-01

... least five absolute percentage points in, but not less than 25 percent of, the weighted-average dumping... margin or countervailable subsidy rate (whichever is applicable) of zero (or de minimis) and a weighted...

19 CFR 351.224 - Disclosure of calculations and procedures for the correction of ministerial errors.

Code of Federal Regulations, 2014 CFR

2014-04-01

... least five absolute percentage points in, but not less than 25 percent of, the weighted-average dumping... margin or countervailable subsidy rate (whichever is applicable) of zero (or de minimis) and a weighted...

19 CFR 351.224 - Disclosure of calculations and procedures for the correction of ministerial errors.

Code of Federal Regulations, 2013 CFR

2013-04-01

... least five absolute percentage points in, but not less than 25 percent of, the weighted-average dumping... margin or countervailable subsidy rate (whichever is applicable) of zero (or de minimis) and a weighted...

19 CFR 351.224 - Disclosure of calculations and procedures for the correction of ministerial errors.

Code of Federal Regulations, 2011 CFR

2011-04-01

... least five absolute percentage points in, but not less than 25 percent of, the weighted-average dumping... margin or countervailable subsidy rate (whichever is applicable) of zero (or de minimis) and a weighted...

Gravity and Zero Point Energy

NASA Astrophysics Data System (ADS)

Massie, U. W.

When Planck introduced the 1/2 hv term to his 1911 black body equation he showed that there is a residual energy remaining at zero degree K after all thermal energy ceased. Other investigators, including Lamb, Casimir, and Dirac added to this information. Today zero point energy (ZPE) is accepted as an established condition. The purpose of this paper is to demonstrate that the density of the ZPE is given by the gravity constant (G) and the characteristics of its particles are revealed by the cosmic microwave background (CMB). Eddies of ZPE particles created by flow around mass bodies reduce the pressure normal to the eddy flow and are responsible for the force of gravity. Helium atoms resonate with ZPE particles at low temperature to produce superfluid helium. High velocity micro vortices of ZPE particles about a basic particle or particles are responsible for electromagnetic forces. The speed of light is the speed of the wave front in the ZPE and its value is a function of the temperature and density of the ZPE.

Zero-point term and quantum effects in the Johnson noise of resistors: a critical appraisal

NASA Astrophysics Data System (ADS)

Kish, Laszlo B.; Niklasson, Gunnar A.; Granqvist, Claes G.

2016-05-01

There is a longstanding debate about the zero-point term in the Johnson noise voltage of a resistor. This term originates from a quantum-theoretical treatment of the fluctuation-dissipation theorem (FDT). Is the zero-point term really there, or is it only an experimental artifact, due to the uncertainty principle, for phase-sensitive amplifiers? Could it be removed by renormalization of theories? We discuss some historical measurement schemes that do not lead to the effect predicted by the FDT, and we analyse new features that emerge when the consequences of the zero-point term are measured via the mean energy and force in a capacitor shunting the resistor. If these measurements verify the existence of a zero-point term in the noise, then two types of perpetual motion machines can be constructed. Further investigation with the same approach shows that, in the quantum limit, the Johnson-Nyquist formula is also invalid under general conditions even though it is valid for a resistor-antenna system. Therefore we conclude that in a satisfactory quantum theory of the Johnson noise, the FDT must, as a minimum, include also the measurement system used to evaluate the observed quantities. Issues concerning the zero-point term may also have implications for phenomena in advanced nanotechnology.

Lifshitz transitions and zero point lattice fluctuations in sulfur hydride showing near room temperature superconductivity

NASA Astrophysics Data System (ADS)

Bianconi, Antonio; Jarlborg, Thomas

2015-11-01

Emerets's experiments on pressurized sulfur hydride have shown that H3S metal has the highest known superconducting critical temperature Tc = 203 K. The Emerets data show pressure induced changes of the isotope coefficient between 0.25 and 0.5, in disagreement with Eliashberg theory which predicts a nearly constant isotope coefficient.We assign the pressure dependent isotope coefficient to Lifshitz transitions induced by pressure and zero point lattice fluctuations. It is known that pressure could induce changes of the topology of the Fermi surface, called Lifshitz transitions, but were neglected in previous papers on the H3S superconductivity issue. Here we propose thatH3S is a multi-gap superconductor with a first condensate in the BCS regime (located in the large Fermi surface with high Fermi energy) which coexists with second condensates in the BCS-BEC crossover regime (located on the Fermi surface spots with small Fermi energy) near the and Mpoints.We discuss the Bianconi-Perali-Valletta (BPV) superconductivity theory to understand superconductivity in H3S since the BPV theory includes the corrections of the chemical potential due to pairing and the configuration interaction between different condensates, neglected by the Eliashberg theory. These two terms in the BPV theory give the shape resonance in superconducting gaps, similar to Feshbach resonance in ultracold fermionic gases, which is known to amplify the critical temperature. Therefore this work provides some key tools useful in the search for new room temperature superconductors.

Zero-point Energy is Needed in Molecular Dynamics Calculations to Access the Saddle Point for H+HCN→H2CN* and cis/trans-HCNH* on a New Potential Energy Surface.

PubMed

Wang, Xiaohong; Bowman, Joel M

2013-02-12

We calculate the probabilities for the association reactions H+HCN→H2CN* and cis/trans-HCNH*, using quasiclassical trajectory (QCT) and classical trajectory (CT) calculations, on a new global ab initio potential energy surface (PES) for H2CN including the reaction channels. The surface is a linear least-squares fit of roughly 60 000 CCSD(T)-F12b/aug-cc-pVDZ electronic energies, using a permutationally invariant basis with Morse-type variables. The reaction probabilities are obtained at a variety of collision energies and impact parameters. Large differences in the threshold energies in the two types of dynamics calculations are traced to the absence of zero-point energy in the CT calculations. We argue that the QCT threshold energy is the realistic one. In addition, trajectories find a direct pathway to trans-HCNH, even though there is no obvious transition state (TS) for this pathway. Instead the saddle point (SP) for the addition to cis-HCNH is evidently also the TS for direct formation of trans-HCNH.

Comment on 'Controversy concerning the definition of quark and gluon angular momentum' by Elliot Leader [PRD 83, 096012 (2011)

NASA Astrophysics Data System (ADS)

Lin, Huey-Wen; Liu, Keh-Fei

2012-03-01

It is argued by the author that the canonical form of the quark energy-momentum tensor with a partial derivative instead of the covariant derivative is the correct definition for the quark momentum and angular momentum fraction of the nucleon in covariant quantization. Although it is not manifestly gauge-invariant, its matrix elements in the nucleon will be nonvanishing and are gauge-invariant. We test this idea in the path-integral quantization by calculating correlation functions on the lattice with a gauge-invariant nucleon interpolation field and replacing the gauge link in the quark lattice momentum operator with unity, which corresponds to the partial derivative in the continuum. We find that the ratios of three-point to two-point functions are zero within errors for both the u and d quarks, contrary to the case without setting the gauge links to unity.

Isotope effects in liquid water probed by transmission mode x-ray absorption spectroscopy at the oxygen K-edge.

PubMed

Schreck, Simon; Wernet, Philippe

2016-09-14

The effects of isotope substitution in liquid water are probed by x-ray absorption spectroscopy at the O K-edge as measured in transmission mode. Confirming earlier x-ray Raman scattering experiments, the D2O spectrum is found to be blue shifted with respect to H2O, and the D2O spectrum to be less broadened. Following the earlier interpretations of UV and x-ray Raman spectra, the shift is related to the difference in ground-state zero-point energies between D2O and H2O, while the difference in broadening is related to the difference in ground-state vibrational zero-point distributions. We demonstrate that the transmission-mode measurements allow for determining the spectral shapes with unprecedented accuracy. Owing in addition to the increased spectral resolution and signal to noise ratio compared to the earlier measurements, the new data enable the stringent determination of blue shift and broadening in the O K-edge x-ray absorption spectrum of liquid water upon isotope substitution. The results are compared to UV absorption data, and it is discussed to which extent they reflect the differences in zero-point energies and vibrational zero-point distributions in the ground-states of the liquids. The influence of the shape of the final-state potential, inclusion of the Franck-Condon structure, and differences between liquid H2O and D2O resulting from different hydrogen-bond environments in the liquids are addressed. The differences between the O K-edge absorption spectra of water from our transmission-mode measurements and from the state-of-the-art x-ray Raman scattering experiments are discussed in addition. The experimentally extracted values of blue shift and broadening are proposed to serve as a test for calculations of ground-state zero-point energies and vibrational zero-point distributions in liquid H2O and D2O. This clearly motivates the need for new calculations of the O K-edge x-ray absorption spectrum of liquid water.

Sensing Atomic Motion from the Zero Point to Room Temperature with Ultrafast Atom Interferometry.

PubMed

Johnson, K G; Neyenhuis, B; Mizrahi, J; Wong-Campos, J D; Monroe, C

2015-11-20

We sense the motion of a trapped atomic ion using a sequence of state-dependent ultrafast momentum kicks. We use this atom interferometer to characterize a nearly pure quantum state with n=1 phonon and accurately measure thermal states ranging from near the zero-point energy to n[over ¯]~10^{4}, with the possibility of extending at least 100 times higher in energy. The complete energy range of this method spans from the ground state to far outside of the Lamb-Dicke regime, where atomic motion is greater than the optical wavelength. Apart from thermometry, these interferometric techniques are useful for characterizing ultrafast entangling gates between multiple trapped ions.

Quantum heating as an alternative of reheating

NASA Astrophysics Data System (ADS)

Akhmedov, Emil T.; Bascone, Francesco

2018-02-01

To model a realistic situation for the beginning we consider massive real scalar ϕ4 theory in a (1 +1 )-dimensional asymptotically static Minkowski spacetime with an intermediate stage of expansion. To have an analytic headway we assume that scalars have a big mass. At past and future infinities of the background we have flat Minkowski regions which are joint by the inflationary expansion region. We use the tree-level Keldysh propagator in the theory in question to calculate the expectation value of the stress-energy tensor which is, thus, due to the excitations of the zero-point fluctuations. Then we show that even for large mass, if the de Sitter expansion stage is long enough, the quantum loop corrections to the expectation value of the stress-energy tensor are not negligible in comparison with the tree-level contribution. That is revealed itself via the excitation of the higher-point fluctuations of the exact modes: during the expansion stage a nonzero particle number density for the exact modes is generated. This density is not Planckian and serves as a quench which leads to a thermalization in the out Minkowski stage.

An accurate global potential energy surface, dipole moment surface, and rovibrational frequencies for NH3

NASA Astrophysics Data System (ADS)

Huang, Xinchuan; Schwenke, David W.; Lee, Timothy J.

2008-12-01

A global potential energy surface (PES) that includes short and long range terms has been determined for the NH3 molecule. The singles and doubles coupled-cluster method that includes a perturbational estimate of connected triple excitations and the internally contracted averaged coupled-pair functional electronic structure methods have been used in conjunction with very large correlation-consistent basis sets, including diffuse functions. Extrapolation to the one-particle basis set limit was performed and core correlation and scalar relativistic contributions were included directly, while the diagonal Born-Oppenheimer correction was added. Our best purely ab initio PES, denoted "mixed," is constructed from two PESs which differ in whether the ic-ACPF higher-order correlation correction was added or not. Rovibrational transition energies computed from the mixed PES agree well with experiment and the best previous theoretical studies, but most importantly the quality does not deteriorate even up to 10300cm-1 above the zero-point energy (ZPE). The mixed PES was improved further by empirical refinement using the most reliable J =0-2 rovibrational transitions in the HITRAN 2004 database. Agreement between high-resolution experiment and rovibrational transition energies computed from our refined PES for J =0-6 is excellent. Indeed, the root mean square (rms) error for 13 HITRAN 2004 bands for J =0-2 is 0.023cm-1 and that for each band is always ⩽0.06cm-1. For J =3-5 the rms error is always ⩽0.15cm-1. This agreement means that transition energies computed with our refined PES should be useful in the assignment of new high-resolution NH3 spectra and in correcting mistakes in previous assignments. Ideas for further improvements to our refined PES and for extension to other isotopolog are discussed.

The emergence of gravity as a retro-causal post-inflation macro-quantum-coherent holographic vacuum Higgs-Goldstone field

NASA Astrophysics Data System (ADS)

Sarfatti, Jack; Levit, Creon

2009-06-01

We present a model for the origin of gravity, dark energy and dark matter: Dark energy and dark matter are residual pre-inflation false vacuum random zero point energy (w = - 1) of large-scale negative, and short-scale positive pressure, respectively, corresponding to the "zero point" (incoherent) component of a superfluid (supersolid) ground state. Gravity, in contrast, arises from the 2nd order topological defects in the post-inflation virtual "condensate" (coherent) component. We predict, as a consequence, that the LHC will never detect exotic real on-mass-shell particles that can explain dark matter ΩMDM approx 0.23. We also point out that the future holographic dark energy de Sitter horizon is a total absorber (in the sense of retro-causal Wheeler-Feynman action-at-a-distance electrodynamics) because it is an infinite redshift surface for static detectors. Therefore, the advanced Hawking-Unruh thermal radiation from the future de Sitter horizon is a candidate for the negative pressure dark vacuum energy.

Large entropy derived from low-frequency vibrations and its implications for hydrogen storage

NASA Astrophysics Data System (ADS)

Wang, Xiaoxia; Chen, Hongshan

2018-02-01

Adsorption and desorption are driven by the energy and entropy competition, but the entropy effect is often ignored in hydrogen storage and the optimal adsorption strength for the ambient storage is controversial in the literature. This letter investigated the adsorption states of the H2 molecule on M-B12C6N6 (M = Li, Na, Mg, Ca, and Sc) and analyzed the correlation among the zero point energy (ZPE), the entropy change, and the adsorption energy and their effects on the delivery capacities. The ZPE has large correction to the adsorption energy due to the light mass of hydrogen. The computations show that the potential energies along the spherical surface centered at the alkali metals are very flat and it leads to large entropy (˜70 J/mol.K) of the adsorbed H2 molecules. The entropy change can compensate the enthalpy change effectively, and the ambient storage can be realized with relatively weak adsorption of ΔH = -12 kJ/mol. The results are encouraging and instructive for the design of hydrogen storage materials.

Two-Point Orientation Discrimination Versus the Traditional Two-Point Test for Tactile Spatial Acuity Assessment

PubMed Central

Tong, Jonathan; Mao, Oliver; Goldreich, Daniel

2013-01-01

Two-point discrimination is widely used to measure tactile spatial acuity. The validity of the two-point threshold as a spatial acuity measure rests on the assumption that two points can be distinguished from one only when the two points are sufficiently separated to evoke spatially distinguishable foci of neural activity. However, some previous research has challenged this view, suggesting instead that two-point task performance benefits from an unintended non-spatial cue, allowing spuriously good performance at small tip separations. We compared the traditional two-point task to an equally convenient alternative task in which participants attempt to discern the orientation (vertical or horizontal) of two points of contact. We used precision digital readout calipers to administer two-interval forced-choice versions of both tasks to 24 neurologically healthy adults, on the fingertip, finger base, palm, and forearm. We used Bayesian adaptive testing to estimate the participants’ psychometric functions on the two tasks. Traditional two-point performance remained significantly above chance levels even at zero point separation. In contrast, two-point orientation discrimination approached chance as point separation approached zero, as expected for a valid measure of tactile spatial acuity. Traditional two-point performance was so inflated at small point separations that 75%-correct thresholds could be determined on all tested sites for fewer than half of participants. The 95%-correct thresholds on the two tasks were similar, and correlated with receptive field spacing. In keeping with previous critiques, we conclude that the traditional two-point task provides an unintended non-spatial cue, resulting in spuriously good performance at small spatial separations. Unlike two-point discrimination, two-point orientation discrimination rigorously measures tactile spatial acuity. We recommend the use of two-point orientation discrimination for neurological assessment. PMID:24062677

Inelastic neutron scattering, Raman, vibrational analysis with anharmonic corrections, and scaled quantum mechanical force field for polycrystalline L-alanine

NASA Astrophysics Data System (ADS)

Williams, Robert W.; Schlücker, Sebastian; Hudson, Bruce S.

2008-01-01

A scaled quantum mechanical harmonic force field (SQMFF) corrected for anharmonicity is obtained for the 23 K L-alanine crystal structure using van der Waals corrected periodic boundary condition density functional theory (DFT) calculations with the PBE functional. Scale factors are obtained with comparisons to inelastic neutron scattering (INS), Raman, and FT-IR spectra of polycrystalline L-alanine at 15-23 K. Calculated frequencies for all 153 normal modes differ from observed frequencies with a standard deviation of 6 wavenumbers. Non-bonded external k = 0 lattice modes are included, but assignments to these modes are presently ambiguous. The extension of SQMFF methodology to lattice modes is new, as are the procedures used here for providing corrections for anharmonicity and van der Waals interactions in DFT calculations on crystals. First principles Born-Oppenheimer molecular dynamics (BOMD) calculations are performed on the L-alanine crystal structure at a series of classical temperatures ranging from 23 K to 600 K. Corrections for zero-point energy (ZPE) are estimated by finding the classical temperature that reproduces the mean square displacements (MSDs) measured from the diffraction data at 23 K. External k = 0 lattice motions are weakly coupled to bonded internal modes.

Toward simulating complex systems with quantum effects

NASA Astrophysics Data System (ADS)

Kenion-Hanrath, Rachel Lynn

Quantum effects like tunneling, coherence, and zero point energy often play a significant role in phenomena on the scales of atoms and molecules. However, the exact quantum treatment of a system scales exponentially with dimensionality, making it impractical for characterizing reaction rates and mechanisms in complex systems. An ongoing effort in the field of theoretical chemistry and physics is extending scalable, classical trajectory-based simulation methods capable of capturing quantum effects to describe dynamic processes in many-body systems; in the work presented here we explore two such techniques. First, we detail an explicit electron, path integral (PI)-based simulation protocol for predicting the rate of electron transfer in condensed-phase transition metal complex systems. Using a PI representation of the transferring electron and a classical representation of the transition metal complex and solvent atoms, we compute the outer sphere free energy barrier and dynamical recrossing factor of the electron transfer rate while accounting for quantum tunneling and zero point energy effects. We are able to achieve this employing only a single set of force field parameters to describe the system rather than parameterizing along the reaction coordinate. Following our success in describing a simple model system, we discuss our next steps in extending our protocol to technologically relevant materials systems. The latter half focuses on the Mixed Quantum-Classical Initial Value Representation (MQC-IVR) of real-time correlation functions, a semiclassical method which has demonstrated its ability to "tune'' between quantum- and classical-limit correlation functions while maintaining dynamic consistency. Specifically, this is achieved through a parameter that determines the quantumness of individual degrees of freedom. Here, we derive a semiclassical correction term for the MQC-IVR to systematically characterize the error introduced by different choices of simulation parameters, and demonstrate the ability of this approach to optimize MQC-IVR simulations.

Molecular structure of the trans and cis isomers of metal-free phthalocyanine studied by gas-phase electron diffraction and high-level quantum chemical calculations: NH tautomerization and calculated vibrational frequencies.

PubMed

Strenalyuk, Tatyana; Samdal, Svein; Volden, Hans Vidar

2008-05-29

The molecular structure of the trans isomer of metal-free phthalocyanine (H2Pc) is determined using the gas electron diffraction (GED) method and high-level quantum chemical calculations. B3LYP calculations employing the basis sets 6-31G**, 6-311++G**, and cc-pVTZ give two tautomeric isomers for the inner H atoms, a trans isomer having D2h symmetry and a cis isomer having C2v symmetry. The trans isomer is calculated to be 41.6 (B3LYP/6-311++G**, zero-point corrected) and 37.3 kJ/mol (B3LYP/cc-pVTZ, not zero-point corrected) more stable than the cis isomer. However, Hartree-Fock (HF) calculations using different basis sets predict that cis is preferred and that trans does not exist as a stable form of the molecule. The equilibrium composition in the gas phase at 471 degrees C (the temperature of the GED experiment) calculated at the B3LYP/6-311++G** level is 99.8% trans and 0.2% cis. This is in very good agreement with the GED data, which indicate that the mole fraction of the cis isomer is close to zero. The transition states for two mechanisms of the NH tautomerization have been characterized. A concerted mechanism where the two H atoms move simultaneously yields a transition state of D2h symmetry and an energy barrier of 95.8 kJ/mol. A two-step mechanism where a trans isomer is converted to a cis isomer, which is converted into another trans isomer, proceeds via two transition states of C(s) symmetry and an energy barrier of 64.2 kJ/mol according to the B3LYP/6-311++G** calculation. The molecular geometry determined from GED is in very good agreement with the geometry obtained from the quantum chemical calculations. Vibrational frequencies, IR, and Raman intensities have been calculated using B3LYP/6-311++G**. These calculations indicate that the molecule is rather flexible with six vibrational frequencies in the range of 20-84 cm(-1) for the trans isomer. The cis isomer might be detected by infrared matrix spectroscopy since the N-H stretching frequencies are very different for the two isomers.

Thermoelectricity near Anderson localization transitions

NASA Astrophysics Data System (ADS)

Yamamoto, Kaoru; Aharony, Amnon; Entin-Wohlman, Ora; Hatano, Naomichi

2017-10-01

The electronic thermoelectric coefficients are analyzed in the vicinity of one and two Anderson localization thresholds in three dimensions. For a single mobility edge, we correct and extend previous studies and find universal approximants which allow us to deduce the critical exponent for the zero-temperature conductivity from thermoelectric measurements. In particular, we find that at nonzero low temperatures the Seebeck coefficient and the thermoelectric efficiency can be very large on the "insulating" side, for chemical potentials below the (zero-temperature) localization threshold. Corrections to the leading power-law singularity in the zero-temperature conductivity are shown to introduce nonuniversal temperature-dependent corrections to the otherwise universal functions which describe the Seebeck coefficient, the figure of merit, and the Wiedemann-Franz ratio. Next, the thermoelectric coefficients are shown to have interesting dependences on the system size. While the Seebeck coefficient decreases with decreasing size, the figure of merit first decreases but then increases, while the Wiedemann-Franz ratio first increases but then decreases as the size decreases. Small (but finite) samples may thus have larger thermoelectric efficiencies. In the last part we study thermoelectricity in systems with a pair of localization edges, the ubiquitous situation in random systems near the centers of electronic energy bands. As the disorder increases, the two thresholds approach each other, and then the Seebeck coefficient and the figure of merit increase significantly, as expected from the general arguments of Mahan and Sofo [J. D. Mahan and J. O. Sofo, Proc. Natl. Acad. Sci. USA 93, 7436 (1996), 10.1073/pnas.93.15.7436] for a narrow energy range of the zero-temperature metallic behavior.

Mass, radius and composition of the outer crust of nonaccreting cold neutron stars

NASA Astrophysics Data System (ADS)

Hempel, Matthias; Schaffner-Bielich, Jürgen

2008-01-01

The properties and composition of the outer crust of nonaccreting cold neutron stars are studied by applying the model of Baym, Pethick and Sutherland, which was extended by including higher order corrections of the atomic binding, screening, exchange and zero-point energy. The most recent experimental nuclear data from the atomic mass table of Audi, Wapstra and Thibault from 2003 are used. Extrapolation to the drip line is utilized by various state-of-the-art theoretical nuclear models (finite range droplet, relativistic nuclear field and non-relativistic Skyrme Hartree Fock parameterizations). The different nuclear models are compared with respect to the mass and radius of the outer crust for different neutron star configurations and the nuclear compositions of the outer crust.

A new approach to detecting gravitational waves via the coupling of gravity to the zero-point energy of the phonon modes of a superconductor

NASA Astrophysics Data System (ADS)

Inan, Nader A.

The response of a superconductor to a gravitational wave is shown to obey a London-like constituent equation. The Cooper pairs are described by the Ginzburg-Landau free energy density embedded in curved spacetime. The lattice ions are modeled by quantum harmonic oscillators characterized by quasi-energy eigenvalues. This formulation is shown to predict a dynamical Casimir effect since the zero-point energy of the ionic lattice phonons is modulated by the gravitational wave. It is also shown that the response to a gravitational wave is far less for the Cooper pair density than for the ionic lattice. This predicts a “charge separation effect” which can be used to detect the passage of a gravitational wave.

A benchmark theoretical study of the electronic ground state and of the singlet-triplet split of benzene and linear acenes

NASA Astrophysics Data System (ADS)

Hajgató, B.; Szieberth, D.; Geerlings, P.; De Proft, F.; Deleuze, M. S.

2009-12-01

A benchmark theoretical study of the electronic ground state and of the vertical and adiabatic singlet-triplet (ST) excitation energies of benzene (n =1) and n-acenes (C4n+2H2n+4) ranging from naphthalene (n =2) to heptacene (n =7) is presented, on the ground of single- and multireference calculations based on restricted or unrestricted zero-order wave functions. High-level and large scale treatments of electronic correlation in the ground state are found to be necessary for compensating giant but unphysical symmetry-breaking effects in unrestricted single-reference treatments. The composition of multiconfigurational wave functions, the topologies of natural orbitals in symmetry-unrestricted CASSCF calculations, the T1 diagnostics of coupled cluster theory, and further energy-based criteria demonstrate that all investigated systems exhibit a A1g singlet closed-shell electronic ground state. Singlet-triplet (S0-T1) energy gaps can therefore be very accurately determined by applying the principles of a focal point analysis onto the results of a series of single-point and symmetry-restricted calculations employing correlation consistent cc-pVXZ basis sets (X=D, T, Q, 5) and single-reference methods [HF, MP2, MP3, MP4SDQ, CCSD, CCSD(T)] of improving quality. According to our best estimates, which amount to a dual extrapolation of energy differences to the level of coupled cluster theory including single, double, and perturbative estimates of connected triple excitations [CCSD(T)] in the limit of an asymptotically complete basis set (cc-pV∞Z), the S0-T1 vertical excitation energies of benzene (n =1) and n-acenes (n =2-7) amount to 100.79, 76.28, 56.97, 40.69, 31.51, 22.96, and 18.16 kcal/mol, respectively. Values of 87.02, 62.87, 46.22, 32.23, 24.19, 16.79, and 12.56 kcal/mol are correspondingly obtained at the CCSD(T)/cc-pV∞Z level for the S0-T1 adiabatic excitation energies, upon including B3LYP/cc-PVTZ corrections for zero-point vibrational energies. In line with the absence of Peierls distortions, extrapolations of results indicate a vanishingly small S0-T1 energy gap of 0 to ˜4 kcal/mol (˜0.17 eV) in the limit of an infinitely large polyacene.

Structure, Stabilities, Thermodynamic Properties, and IR Spectra of Acetylene Clusters (C2H2)n=2-5.

PubMed

Karthikeyan, S; Lee, Han Myoung; Kim, Kwang S

2010-10-12

There are no clear conclusions over the structures of the acetylene clusters. In this regard, we have carried out high-level calculations for acetylene clusters (C2H2)2-5 using dispersion-corrected density functional theory (DFT-D), Møller-Plesset second-order perturbation theory (MP2); and coupled-cluster theory with single, double, and perturbative triple excitations [CCSD(T)] at the complete basis set limit. The lowest energy structure of the acetylene dimer has a T-shaped structure of C2v symmetry, but it is nearly isoenergetic to the displaced stacked structure of C2h symmetry. We find that the structure shows the quantum statistical distribution for configurations between the T-shaped and displaced stacked structures for which the average angle (|θ̃|) between two acetylene molecules would be 53-78°, close to the T-shaped structure. The trimer has a triangular structure of C3h symmetry. The tetramer has two lowest energy isomers of S4 and C2h symmetry in zero-point energy (ZPE)-uncorrected energy (ΔEe), but one lowest energy isomer of C2v symmetry in ZPE-corrected energy (ΔE0). For the pentamer, the global minimum structure is C1 symmetry with eight sets of T-type π-H interactions and a set of π-π interactions. Our high-level ab initio calculations are consistent with available experimental data.

Spectroscopy and heats of formation of CXI (X = Br, Cl, F) iodocarbenes: quantum chemical characterisation of the ?, ? and ? states

NASA Astrophysics Data System (ADS)

Bacskay, George B.

2015-07-01

The equilibrium energies of the iodocarbenes CXI (X = Br, Cl, F) in their ?, ? and ? states and their atomisation and dissociation energies in the complete basis limit were determined by extrapolating valence correlated (R/U)CCSD(T) and Davidson corrected multi-reference configuration interaction (MRCI) energies calculated with the aug-cc-pVxZ (x = T,Q,5) basis sets and the ECP28MDF pseudopotential of iodine plus corrections for core and core-valence correlation, scalar relativity, spin-orbit coupling and zero-point energies. Spin-orbit energies were computed in a large basis of configurations chosen so as to accurately describe dissociation to the 3P and 2P states of C and of the halogens X and I, respectively. The computed singlet-triplet splittings are 13.6, 14.4 and 27.3 kcal mol-1 for X = Br, Cl and F, respectively. The enthalpies of formation at 0 K are predicted to be 97.4, 82.6 and 38.1 kcal mol-1 with estimated errors of ±1.0 kcal mol-1. The ? excitation energies (T00) in CBrI and CClI are calculated to be 41.1 and 41.7 kcal mol-1, respectively. The Renner-Teller intersections in both molecules are predicted to be substantially higher than the dissociation barriers on the ? surfaces. By contrast, in CFI the ? state is found to be unbound with respect to dissociation.

High-energy zero-norm states and symmetries of string theory.

PubMed

Chan, Chuan-Tsung; Ho, Pei-Ming; Lee, Jen-Chi; Teraguchi, Shunsuke; Yang, Yi

2006-05-05

High-energy limit of zero-norm states in the old covariant first quantized spectrum of the 26D open bosonic string, together with the assumption of a smooth behavior of string theory in this limit, are used to derive infinitely many linear relations among the leading high-energy, fixed-angle behavior of four-point functions of different string states. As a result, ratios among all high-energy scattering amplitudes of four arbitrary string states can be calculated algebraically and the leading order amplitudes can be expressed in terms of that of four tachyons as conjectured by Gross in 1988. A dual calculation can also be performed and equivalent results are obtained by taking the high-energy limit of Virasoro constraints. Finally, we compute all high-energy scattering amplitudes of three tachyons and one massive state at the leading order by saddle-point approximation to verify our results.

Many-body effects and ultraviolet renormalization in three-dimensional Dirac materials

NASA Astrophysics Data System (ADS)

Throckmorton, Robert E.; Hofmann, Johannes; Barnes, Edwin; Das Sarma, S.

2015-09-01

We develop a theory for electron-electron interaction-induced many-body effects in three-dimensional Weyl or Dirac semimetals, including interaction corrections to the polarizability, electron self-energy, and vertex function, up to second order in the effective fine-structure constant of the Dirac material. These results are used to derive the higher-order ultraviolet renormalization of the Fermi velocity, effective coupling, and quasiparticle residue, revealing that the corrections to the renormalization group flows of both the velocity and coupling counteract the leading-order tendencies of velocity enhancement and coupling suppression at low energies. This in turn leads to the emergence of a critical coupling above which the interaction strength grows with decreasing energy scale. In addition, we identify a range of coupling strengths below the critical point in which the Fermi velocity varies nonmonotonically as the low-energy, noninteracting fixed point is approached. Furthermore, we find that while the higher-order correction to the flow of the coupling is generally small compared to the leading order, the corresponding correction to the velocity flow carries an additional factor of the Dirac cone flavor number (the multiplicity of electron species, e.g. ground-state valley degeneracy arising from the band structure) relative to the leading-order result. Thus, for materials with a larger multiplicity, the regime of velocity nonmonotonicity is reached for modest values of the coupling strength. This is in stark contrast to an approach based on a large-N expansion or the random phase approximation (RPA), where higher-order corrections are strongly suppressed for larger values of the Dirac cone multiplicity. This suggests that perturbation theory in the coupling constant (i.e., the loop expansion) and the RPA/large-N expansion are complementary in the sense that they are applicable in different parameter regimes of the theory. We show how our results for the ultraviolet renormalization of quasiparticle properties can be tested experimentally through measurements of quantities such as the optical conductivity or dielectric function (with carrier density or temperature acting as the scale being varied to induce the running coupling). Although experiments typically access the finite-density regime, we show that our zero-density results still capture clear many-body signatures that should be visible at higher temperatures even in real systems with disorder and finite doping.

Applicability of Quantum Thermal Baths to Complex Many-Body Systems with Various Degrees of Anharmonicity.

PubMed

Hernández-Rojas, Javier; Calvo, Florent; Noya, Eva Gonzalez

2015-03-10

The semiclassical method of quantum thermal baths by colored noise thermostats has been used to simulate various atomic systems in the molecular and bulk limits, at finite temperature and in moderately to strongly anharmonic regimes. In all cases, the method performs relatively well against alternative approaches in predicting correct energetic properties, including in the presence of phase changes, provided that vibrational delocalization is not too strong-neon appearing already as an upper limiting case. In contrast, the dynamical behavior inferred from global indicators such as the root-mean-square bond length fluctuation index or the vibrational spectrum reveals more marked differences caused by zero-point energy leakage, except in the case of isolated molecules with well separated vibrational modes. To correct for such deficiencies and reduce the undesired transfer among modes, empirical modifications of the noise power spectral density were attempted to better describe thermal equilibrium but still failed when used as semiclassical preparation for microcanonical trajectories.

Symmetry breaking in the zero-energy Landau level in bilayer graphene.

PubMed

Zhao, Y; Cadden-Zimansky, P; Jiang, Z; Kim, P

2010-02-12

The quantum Hall effect near the charge neutrality point in bilayer graphene is investigated in high magnetic fields of up to 35 T using electronic transport measurements. In the high-field regime, the eightfold degeneracy in the zero-energy Landau level is completely lifted, exhibiting new quantum Hall states corresponding to filling factors nu=0, 1, 2, and 3. Measurements of the activation energy gaps for the nu=2 and 3 filling factors in tilted magnetic fields exhibit no appreciable dependence on the in-plane magnetic field, suggesting that these Landau level splittings are independent of spin. In addition, measurements taken at the nu=0 charge neutral point show that, similar to single layer graphene, the bilayer becomes insulating at high fields.

Bound state potential energy surface construction: ab initio zero-point energies and vibrationally averaged rotational constants.

PubMed

Bettens, Ryan P A

2003-01-15

Collins' method of interpolating a potential energy surface (PES) from quantum chemical calculations for reactive systems (Jordan, M. J. T.; Thompson, K. C.; Collins, M. A. J. Chem. Phys. 1995, 102, 5647. Thompson, K. C.; Jordan, M. J. T.; Collins, M. A. J. Chem. Phys. 1998, 108, 8302. Bettens, R. P. A.; Collins, M. A. J. Chem. Phys. 1999, 111, 816) has been applied to a bound state problem. The interpolation method has been combined for the first time with quantum diffusion Monte Carlo calculations to obtain an accurate ground state zero-point energy, the vibrationally average rotational constants, and the vibrationally averaged internal coordinates. In particular, the system studied was fluoromethane using a composite method approximating the QCISD(T)/6-311++G(2df,2p) level of theory. The approach adopted in this work (a) is fully automated, (b) is fully ab initio, (c) includes all nine nuclear degrees of freedom, (d) requires no assumption of the functional form of the PES, (e) possesses the full symmetry of the system, (f) does not involve fitting any parameters of any kind, and (g) is generally applicable to any system amenable to quantum chemical calculations and Collins' interpolation method. The calculated zero-point energy agrees to within 0.2% of its current best estimate. A0 and B0 are within 0.9 and 0.3%, respectively, of experiment.

Wave-packet formation at the zero-dispersion point in the Gardner-Ostrovsky equation.

PubMed

Whitfield, A J; Johnson, E R

2015-05-01

The long-time effect of weak rotation on an internal solitary wave is the decay into inertia-gravity waves and the eventual emergence of a coherent, steadily propagating, nonlinear wave packet. There is currently no entirely satisfactory explanation as to why these wave packets form. Here the initial value problem is considered within the context of the Gardner-Ostrovsky, or rotation-modified extended Korteweg-de Vries, equation. The linear Gardner-Ostrovsky equation has maximum group velocity at a critical wave number, often called the zero-dispersion point. It is found here that a nonlinear splitting of the wave-number spectrum at the zero-dispersion point, where energy is shifted into the modulationally unstable regime of the Gardner-Ostrovsky equation, is responsible for the wave-packet formation. Numerical comparisons of the decay of a solitary wave in the Gardner-Ostrovsky equation and a derived nonlinear Schrödinger equation at the zero-dispersion point are used to confirm the spectral splitting.

Quantum effects of translational motions in solid para-hydrogen and ortho-deuterium: anharmonic extension of the Einstein model.

PubMed

Kühn, O; Manz, J; Schild, A

2010-04-07

An anharmonic extension of the Einstein model is developed in order to describe the effect of translational zero point motion on structural and thermodynamic properties of para-H(2) and ortho-D(2) crystals in the zero temperature limit. Accordingly, the molecules carry out large amplitude translational motions in their matrix cage, which are formed by the frozen environment of all other molecules. These translations lead from the molecular equilibrium positions via the harmonic to the anharmonic domain of the potential energy surface. The resulting translational distributions are roughly isotropic, and they have approximately Gaussian shapes, with rather broad full widths at half-maximum, FWHM(para-H(2)/ortho-D(2)) = 1.36/1.02 Å. The translational zero point energies induce expansions of the crystals, in nearly quantitative agreement with experimental results. Furthermore, they make significant contributions to the sublimation energies and zero pressure bulk moduli. These quantum effects decrease with heavier molecular masses. The corresponding isotope effects for ortho-D(2) compared to para-H(2) are confirmed by application of the model to Ar crystals. The results imply consequences for laser induced reaction dynamics of dopants with their host crystals.

Electronic Zero-Point Oscillations in the Strong-Interaction Limit of Density Functional Theory.

PubMed

Gori-Giorgi, Paola; Vignale, Giovanni; Seidl, Michael

2009-04-14

The exchange-correlation energy in Kohn-Sham density functional theory can be expressed exactly in terms of the change in the expectation of the electron-electron repulsion operator when, in the many-electron Hamiltonian, this same operator is multiplied by a real parameter λ varying between 0 (Kohn-Sham system) and 1 (physical system). In this process, usually called adiabatic connection, the one-electron density is kept fixed by a suitable local one-body potential. The strong-interaction limit of density functional theory, defined as the limit λ→∞, turns out to be like the opposite noninteracting Kohn-Sham limit (λ→0) mathematically simpler than the physical (λ = 1) case and can be used to build an approximate interpolation formula between λ→0 and λ→∞ for the exchange-correlation energy. Here we extend the systematic treatment of the λ→∞ limit [Phys. Rev. A 2007, 75, 042511] to the next leading term, describing zero-point oscillations of strictly correlated electrons, with numerical examples for small spherical atoms. We also propose an improved approximate functional for the zero-point term and a revised interpolation formula for the exchange-correlation energy satisfying more exact constraints.

Two-point correlation function for Dirichlet L-functions

NASA Astrophysics Data System (ADS)

Bogomolny, E.; Keating, J. P.

2013-03-01

The two-point correlation function for the zeros of Dirichlet L-functions at a height E on the critical line is calculated heuristically using a generalization of the Hardy-Littlewood conjecture for pairs of primes in arithmetic progression. The result matches the conjectured random-matrix form in the limit as E → ∞ and, importantly, includes finite-E corrections. These finite-E corrections differ from those in the case of the Riemann zeta-function, obtained in Bogomolny and Keating (1996 Phys. Rev. Lett. 77 1472), by certain finite products of primes which divide the modulus of the primitive character used to construct the L-function in question.

Improving Photometric Calibration of Meteor Video Camera Systems

NASA Technical Reports Server (NTRS)

Ehlert, Steven; Kingery, Aaron; Suggs, Robert

2016-01-01

We present the results of new calibration tests performed by the NASA Meteoroid Environment Oce (MEO) designed to help quantify and minimize systematic uncertainties in meteor photometry from video camera observations. These systematic uncertainties can be categorized by two main sources: an imperfect understanding of the linearity correction for the MEO's Watec 902H2 Ultimate video cameras and uncertainties in meteor magnitudes arising from transformations between the Watec camera's Sony EX-View HAD bandpass and the bandpasses used to determine reference star magnitudes. To address the rst point, we have measured the linearity response of the MEO's standard meteor video cameras using two independent laboratory tests on eight cameras. Our empirically determined linearity correction is critical for performing accurate photometry at low camera intensity levels. With regards to the second point, we have calculated synthetic magnitudes in the EX bandpass for reference stars. These synthetic magnitudes enable direct calculations of the meteor's photometric ux within the camera band-pass without requiring any assumptions of its spectral energy distribution. Systematic uncertainties in the synthetic magnitudes of individual reference stars are estimated at 0:20 mag, and are limited by the available spectral information in the reference catalogs. These two improvements allow for zero-points accurate to 0:05 ?? 0:10 mag in both ltered and un ltered camera observations with no evidence for lingering systematics.

Derivation of the cut-off length from the quantum quadratic enhancement of a mass in vacuum energy constant Lambda

NASA Astrophysics Data System (ADS)

Fukushima, Kimichika; Sato, Hikaru

2018-04-01

Ultraviolet self-interaction energies in field theory sometimes contain meaningful physical quantities. The self-energies in such as classical electrodynamics are usually subtracted from the rest mass. For the consistent treatment of energies as sources of curvature in the Einstein field equations, this study includes these subtracted self-energies into vacuum energy expressed by the constant Lambda (used in such as Lambda-CDM). In this study, the self-energies in electrodynamics and macroscopic classical Einstein field equations are examined, using the formalisms with the ultraviolet cut-off scheme. One of the cut-off formalisms is the field theory in terms of the step-function-type basis functions, developed by the present authors. The other is a continuum theory of a fundamental particle with the same cut-off length. Based on the effectiveness of the continuum theory with the cut-off length shown in the examination, the dominant self-energy is the quadratic term of the Higgs field at a quantum level (classical self-energies are reduced to logarithmic forms by quantum corrections). The cut-off length is then determined to reproduce today's tiny value of Lambda for vacuum energy. Additionally, a field with nonperiodic vanishing boundary conditions is treated, showing that the field has no zero-point energy.

Effective response theory for zero-energy Majorana bound states in three spatial dimensions

NASA Astrophysics Data System (ADS)

Lopes, Pedro L. e. S.; Teo, Jeffrey C. Y.; Ryu, Shinsei

2015-05-01

We propose a gravitational response theory for point defects (hedgehogs) binding Majorana zero modes in (3 + 1)-dimensional superconductors. Starting in 4 + 1 dimensions, where the point defect is extended into a line, a coupling of the bulk defect texture with the gravitational field is introduced. Diffeomorphism invariance then leads to an S U (2) 2 Kac-Moody current running along the defect line. The S U (2) 2 Kac-Moody algebra accounts for the non-Abelian nature of the zero modes in 3 + 1 dimensions. It is then shown to also encode the angular momentum density which permeates throughout the bulk between hedgehog-antihedgehog pairs.

Coupled-cluster and explicitly correlated perturbation-theory calculations of the uracil anion.

PubMed

Bachorz, Rafał A; Klopper, Wim; Gutowski, Maciej

2007-02-28

A valence-type anion of the canonical tautomer of uracil has been characterized using explicitly correlated second-order Moller-Plesset perturbation theory (RI-MP2-R12) in conjunction with conventional coupled-cluster theory with single, double, and perturbative triple excitations. At this level of electron-correlation treatment and after inclusion of a zero-point vibrational energy correction, determined in the harmonic approximation at the RI-MP2 level of theory, the valence anion is adiabatically stable with respect to the neutral molecule by 40 meV. The anion is characterized by a vertical detachment energy of 0.60 eV. To obtain accurate estimates of the vertical and adiabatic electron binding energies, a scheme was applied in which electronic energy contributions from various levels of theory were added, each of them extrapolated to the corresponding basis-set limit. The MP2 basis-set limits were also evaluated using an explicitly correlated approach, and the results of these calculations are in agreement with the extrapolated values. A remarkable feature of the valence anionic state is that the adiabatic electron binding energy is positive but smaller than the adiabatic electron binding energy of the dipole-bound state.

The Schrödinger Equation, the Zero-Point Electromagnetic Radiation, and the Photoelectric Effect

NASA Astrophysics Data System (ADS)

França, H. M.; Kamimura, A.; Barreto, G. A.

2016-04-01

A Schrödinger type equation for a mathematical probability amplitude Ψ( x, t) is derived from the generalized phase space Liouville equation valid for the motion of a microscopic particle, with mass M and charge e, moving in a potential V( x). The particle phase space probability density is denoted Q( x, p, t), and the entire system is immersed in the "vacuum" zero-point electromagnetic radiation. We show, in the first part of the paper, that the generalized Liouville equation is reduced to a simpler Liouville equation in the equilibrium limit where the small radiative corrections cancel each other approximately. This leads us to a simpler Liouville equation that will facilitate the calculations in the second part of the paper. Within this second part, we address ourselves to the following task: Since the Schrödinger equation depends on hbar , and the zero-point electromagnetic spectral distribution, given by ρ 0{(ω )} = hbar ω 3/2 π 2 c3, also depends on hbar , it is interesting to verify the possible dynamical connection between ρ 0( ω) and the Schrödinger equation. We shall prove that the Planck's constant, present in the momentum operator of the Schrödinger equation, is deeply related with the ubiquitous zero-point electromagnetic radiation with spectral distribution ρ 0( ω). For simplicity, we do not use the hypothesis of the existence of the L. de Broglie matter-waves. The implications of our study for the standard interpretation of the photoelectric effect are discussed by considering the main characteristics of the phenomenon. We also mention, briefly, the effects of the zero-point radiation in the tunneling phenomenon and the Compton's effect.

Dynamically biased statistical model for the ortho/para conversion in the H2 + H3+ → H3+ + H2 reaction.

PubMed

Gómez-Carrasco, Susana; González-Sánchez, Lola; Aguado, Alfredo; Sanz-Sanz, Cristina; Zanchet, Alexandre; Roncero, Octavio

2012-09-07

In this work we present a dynamically biased statistical model to describe the evolution of the title reaction from statistical to a more direct mechanism, using quasi-classical trajectories (QCT). The method is based on the one previously proposed by Park and Light [J. Chem. Phys. 126, 044305 (2007)]. A recent global potential energy surface is used here to calculate the capture probabilities, instead of the long-range ion-induced dipole interactions. The dynamical constraints are introduced by considering a scrambling matrix which depends on energy and determine the probability of the identity/hop/exchange mechanisms. These probabilities are calculated using QCT. It is found that the high zero-point energy of the fragments is transferred to the rest of the degrees of freedom, what shortens the lifetime of H(5)(+) complexes and, as a consequence, the exchange mechanism is produced with lower proportion. The zero-point energy (ZPE) is not properly described in quasi-classical trajectory calculations and an approximation is done in which the initial ZPE of the reactants is reduced in QCT calculations to obtain a new ZPE-biased scrambling matrix. This reduction of the ZPE is explained by the need of correcting the pure classical level number of the H(5)(+) complex, as done in classical simulations of unimolecular processes and to get equivalent quantum and classical rate constants using Rice-Ramsperger-Kassel-Marcus theory. This matrix allows to obtain a ratio of hop/exchange mechanisms, α(T), in rather good agreement with recent experimental results by Crabtree et al. [J. Chem. Phys. 134, 194311 (2011)] at room temperature. At lower temperatures, however, the present simulations predict too high ratios because the biased scrambling matrix is not statistical enough. This demonstrates the importance of applying quantum methods to simulate this reaction at the low temperatures of astrophysical interest.

Dynamically biased statistical model for the ortho/para conversion in the H2+H3+ --> H3++ H2 reaction

NASA Astrophysics Data System (ADS)

Gómez-Carrasco, Susana; González-Sánchez, Lola; Aguado, Alfredo; Sanz-Sanz, Cristina; Zanchet, Alexandre; Roncero, Octavio

2012-09-01

In this work we present a dynamically biased statistical model to describe the evolution of the title reaction from statistical to a more direct mechanism, using quasi-classical trajectories (QCT). The method is based on the one previously proposed by Park and Light [J. Chem. Phys. 126, 044305 (2007), 10.1063/1.2430711]. A recent global potential energy surface is used here to calculate the capture probabilities, instead of the long-range ion-induced dipole interactions. The dynamical constraints are introduced by considering a scrambling matrix which depends on energy and determine the probability of the identity/hop/exchange mechanisms. These probabilities are calculated using QCT. It is found that the high zero-point energy of the fragments is transferred to the rest of the degrees of freedom, what shortens the lifetime of H_5^+ complexes and, as a consequence, the exchange mechanism is produced with lower proportion. The zero-point energy (ZPE) is not properly described in quasi-classical trajectory calculations and an approximation is done in which the initial ZPE of the reactants is reduced in QCT calculations to obtain a new ZPE-biased scrambling matrix. This reduction of the ZPE is explained by the need of correcting the pure classical level number of the H_5^+ complex, as done in classical simulations of unimolecular processes and to get equivalent quantum and classical rate constants using Rice-Ramsperger-Kassel-Marcus theory. This matrix allows to obtain a ratio of hop/exchange mechanisms, α(T), in rather good agreement with recent experimental results by Crabtree et al. [J. Chem. Phys. 134, 194311 (2011), 10.1063/1.3587246] at room temperature. At lower temperatures, however, the present simulations predict too high ratios because the biased scrambling matrix is not statistical enough. This demonstrates the importance of applying quantum methods to simulate this reaction at the low temperatures of astrophysical interest.

Reaction mechanism of guanidinoacetate methyltransferase, concerted or step-wise.

PubMed

Zhang, Xiaodong; Bruice, Thomas C

2006-10-31

We describe a quantum mechanics/molecular mechanics investigation of the guanidinoacetate methyltransferase catalyzed reaction, which shows that proton transfer from guanidinoacetate (GAA) to Asp-134 and methyl transfer from S-adenosyl-L-methionine (AdoMet) to GAA are concerted. By self-consistent-charge density functional tight binding/molecular mechanics, the bond lengths in the concerted mechanism's transition state are 1.26 A for both the OD1 (Asp-134)-H(E) (GAA) and H(E) (GAA)-N(E) (GAA) bonds, and 2.47 and 2.03 A for the S8 (AdoMet)-C9 (AdoMet) and C9 (AdoMet)-N(E) (GAA) bonds, respectively. The potential-energy barrier (DeltaE++) determined by single-point B3LYP/6-31+G*//MM is 18.9 kcal/mol. The contributions of the entropy (-TDeltaS++) and zero-point energy corrections Delta(ZPE)++ by normal mode analysis are 2.3 kcal/mol and -1.7 kcal/mol, respectively. Thus, the activation enthalpy of this concerted mechanism is predicted to be DeltaH++ = DeltaE++ plus Delta(ZPE)++ = 17.2 kcal/mol. The calculated free-energy barrier for the concerted mechanism is DeltaG++ = 19.5 kcal/mol, which is in excellent agreement with the value of 19.0 kcal/mol calculated from the experimental rate constant (3.8 +/- 0.2.min(-1)).

A converged calculation of the energy barrier to internal rotation in the ethylene-sulfur dioxide dimer

NASA Astrophysics Data System (ADS)

Resende, Stella M.; De Almeida, Wagner B.; van Duijneveldt-van de Rijdt, Jeanne G. C. M.; van Duijneveldt, Frans B.

2001-08-01

Geometrical parameters for the equilibrium (MIN) and lowest saddle-point (TS) geometries of the C2H4⋯SO2 dimer, and the corresponding binding energies, were calculated using the Hartree-Fock and correlated levels of ab initio theory, in basis sets ranging from the D95(d,p) double-zeta basis set to the aug-cc-pVQZ correlation consistent basis set. An assessment of the effect of the basis set superposition error (BSSE) on these results was made. The dissociation energy from the lowest vibrational state was estimated to be 705±100 cm-1 at the basis set limit, which is well within the range expected from experiment. The barrier to internal rotation was found to be 53±5 cm-1, slightly higher than the (revised) experimental result of 43 cm-1, probably due to zero-point vibrational effects. Our results clearly show that, in direct contrast with recent ideas, the BSSE correction affects differentially the MIN and TS binding energies and so has to be included in the calculation of small energy barriers such as that in the C2H4⋯SO2 dimer. Previous reports of positive MP2 frozen-core binding energies for this complex in basis D95(d,p) are confirmed. The anomalies are shown to be an artifact arising from an incorrect removal of virtual orbitals by the default frozen-core option in the GAUSSIAN program.

Thermodynamics of finite systems: a key issues review

NASA Astrophysics Data System (ADS)

Swendsen, Robert H.

2018-07-01

A little over ten years ago, Campisi, and Dunkel and Hilbert, published papers claiming that the Gibbs (volume) entropy of a classical system was correct, and that the Boltzmann (surface) entropy was not. They claimed further that the quantum version of the Gibbs entropy was also correct, and that the phenomenon of negative temperatures was thermodynamically inconsistent. Their work began a vigorous debate of exactly how the entropy, both classical and quantum, should be defined. The debate has called into question the basis of thermodynamics, along with fundamental ideas such as whether heat always flows from hot to cold. The purpose of this paper is to sum up the present status—admittedly from my point of view. I will show that standard thermodynamics, with some minor generalizations, is correct, and the alternative thermodynamics suggested by Hilbert, Hänggi, and Dunkel is not. Heat does not flow from cold to hot. Negative temperatures are thermodynamically consistent. The small ‘errors’ in the Boltzmann entropy that started the whole debate are shown to be a consequence of the micro-canonical assumption of an energy distribution of zero width. Improved expressions for the entropy are found when this assumption is abandoned.

Rocksalt or cesium chloride: Investigating the relative stability of the cesium halide structures with random phase approximation based methods

NASA Astrophysics Data System (ADS)

Nepal, Niraj K.; Ruzsinszky, Adrienn; Bates, Jefferson E.

2018-03-01

The ground state structural and energetic properties for rocksalt and cesium chloride phases of the cesium halides were explored using the random phase approximation (RPA) and beyond-RPA methods to benchmark the nonempirical SCAN meta-GGA and its empirical dispersion corrections. The importance of nonadditivity and higher-order multipole moments of dispersion in these systems is discussed. RPA generally predicts the equilibrium volume for these halides within 2.4% of the experimental value, while beyond-RPA methods utilizing the renormalized adiabatic LDA (rALDA) exchange-correlation kernel are typically within 1.8%. The zero-point vibrational energy is small and shows that the stability of these halides is purely due to electronic correlation effects. The rAPBE kernel as a correction to RPA overestimates the equilibrium volume and could not predict the correct phase ordering in the case of cesium chloride, while the rALDA kernel consistently predicted results in agreement with the experiment for all of the halides. However, due to its reasonable accuracy with lower computational cost, SCAN+rVV10 proved to be a good alternative to the RPA-like methods for describing the properties of these ionic solids.

Benchmark of Dynamic Electron Correlation Models for Seniority-Zero Wave Functions and Their Application to Thermochemistry.

PubMed

Boguslawski, Katharina; Tecmer, Paweł

2017-12-12

Wave functions restricted to electron-pair states are promising models to describe static/nondynamic electron correlation effects encountered, for instance, in bond-dissociation processes and transition-metal and actinide chemistry. To reach spectroscopic accuracy, however, the missing dynamic electron correlation effects that cannot be described by electron-pair states need to be included a posteriori. In this Article, we extend the previously presented perturbation theory models with an Antisymmetric Product of 1-reference orbital Geminal (AP1roG) reference function that allows us to describe both static/nondynamic and dynamic electron correlation effects. Specifically, our perturbation theory models combine a diagonal and off-diagonal zero-order Hamiltonian, a single-reference and multireference dual state, and different excitation operators used to construct the projection manifold. We benchmark all proposed models as well as an a posteriori Linearized Coupled Cluster correction on top of AP1roG against CR-CC(2,3) reference data for reaction energies of several closed-shell molecules that are extrapolated to the basis set limit. Moreover, we test the performance of our new methods for multiple bond breaking processes in the homonuclear N 2 , C 2 , and F 2 dimers as well as the heteronuclear BN, CO, and CN + dimers against MRCI-SD, MRCI-SD+Q, and CR-CC(2,3) reference data. Our numerical results indicate that the best performance is obtained from a Linearized Coupled Cluster correction as well as second-order perturbation theory corrections employing a diagonal and off-diagonal zero-order Hamiltonian and a single-determinant dual state. These dynamic corrections on top of AP1roG provide substantial improvements for binding energies and spectroscopic properties obtained with the AP1roG approach, while allowing us to approach chemical accuracy for reaction energies involving closed-shell species.

A density functional theory based approach for predicting melting points of ionic liquids

DOE PAGES

Chen, Lihua; Bryantsev, Vyacheslav S.

2017-01-17

Accurate prediction of melting points of ILs is important both from the fundamental point of view and from the practical perspective for screening ILs with low melting points and broadening their utilization in a wider temperature range. In this work, we present an ab initio approach to calculating melting points of ILs with known crystal structures and illustrate its application for a series of 11 ILs containing imidazolium/pyrrolidinium cations and halide/polyatomic fluoro-containing anions. The melting point is determined as a temperature at which the Gibbs free energy of fusion is zero. The Gibbs free energy of fusion can be expressedmore » through the use of the Born-Fajans-Haber cycle via the lattice free energy of forming a solid IL from gaseous phase ions and the sum of the solvation free energies of ions comprising IL. Dispersion-corrected density functional theory (DFT) involving (semi)local (PBE-D3) and hybrid exchange-correlation (HSE06-D3) functionals is applied to estimate the lattice enthalpy, entropy, and free energy. The ions solvation free energies are calculated with the SMD-generic-IL solvation model at the M06-2X/6-31+G(d) level of theory under standard conditions. The melting points of ILs computed with the HSE06-D3 functional are in good agreement with the experimental data, with a mean absolute error of 30.5 K and a mean relative error of 8.5%. The model is capable of accurately reproducing the trends in melting points upon variation of alkyl substituents in organic cations and replacement one anion by another. The results verify that the lattice energies of ILs containing polyatomic fluoro-containing anions can be approximated reasonably well using the volume-based thermodynamic approach. However, there is no correlation of the computed lattice energies with molecular volume for ILs containing halide anions. Moreover, entropies of solid ILs follow two different linear relationships with molecular volume for halides and polyatomic fluoro-containing anions. As a result, continuous progress in predicting crystal structures of organic salts with halide anions will be a key factor for successful prediction of melting points with no prior knowledge of the crystal structure.« less

A density functional theory based approach for predicting melting points of ionic liquids

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

Chen, Lihua; Bryantsev, Vyacheslav S.

Accurate prediction of melting points of ILs is important both from the fundamental point of view and from the practical perspective for screening ILs with low melting points and broadening their utilization in a wider temperature range. In this work, we present an ab initio approach to calculating melting points of ILs with known crystal structures and illustrate its application for a series of 11 ILs containing imidazolium/pyrrolidinium cations and halide/polyatomic fluoro-containing anions. The melting point is determined as a temperature at which the Gibbs free energy of fusion is zero. The Gibbs free energy of fusion can be expressedmore » through the use of the Born-Fajans-Haber cycle via the lattice free energy of forming a solid IL from gaseous phase ions and the sum of the solvation free energies of ions comprising IL. Dispersion-corrected density functional theory (DFT) involving (semi)local (PBE-D3) and hybrid exchange-correlation (HSE06-D3) functionals is applied to estimate the lattice enthalpy, entropy, and free energy. The ions solvation free energies are calculated with the SMD-generic-IL solvation model at the M06-2X/6-31+G(d) level of theory under standard conditions. The melting points of ILs computed with the HSE06-D3 functional are in good agreement with the experimental data, with a mean absolute error of 30.5 K and a mean relative error of 8.5%. The model is capable of accurately reproducing the trends in melting points upon variation of alkyl substituents in organic cations and replacement one anion by another. The results verify that the lattice energies of ILs containing polyatomic fluoro-containing anions can be approximated reasonably well using the volume-based thermodynamic approach. However, there is no correlation of the computed lattice energies with molecular volume for ILs containing halide anions. Moreover, entropies of solid ILs follow two different linear relationships with molecular volume for halides and polyatomic fluoro-containing anions. As a result, continuous progress in predicting crystal structures of organic salts with halide anions will be a key factor for successful prediction of melting points with no prior knowledge of the crystal structure.« less

Meshless Local Petrov-Galerkin Method for Solving Contact, Impact and Penetration Problems

DTIC Science & Technology

2006-11-30

Crack Growth 3 point of view, this approach makes the full use of the ex- isting FE models to avoid any model regeneration , which is extremely high in...process, at point C, the pressure reduces to zero, but the volumet- ric strain does not go to zero due to the collapsed void volume. 2.2 Damage...lease rate to go beyond the critical strain energy release rate. Thus, the micro-cracks begin to growth inside these areas. At 10 micro-seconds, these

Reducing injection loss in drill strings

DOEpatents

Drumheller, Douglas S.

2004-09-14

A system and method for transferring wave energy into or out of a periodic structure having a characteristic wave impedance profile at a prime frequency, the characteristic wave impedance profile comprising a real portion and an imaginary portion, comprising: locating one or more energy transfer elements each having a wave impedance at the prime frequency approximately equal to the real portion of the characteristic wave impedance at one or more points on the periodic structure with the imaginary portion approximately equaling zero; and employing the one or more energy transfer elements to transfer wave energy into or out of the periodic structure. The energy transfer may be repeaters. Quarter-wave transformers can be provided at one or more points on the periodic structure with the imaginary portion approximately equaling zero to transmit waves across one or more discontinuities. A terminator can be employed for cancellation of waves. The invention substantially eliminates reflections of the wave energy at the prime frequency by joints between sections of the periodic structure.

Analytic second derivatives of the energy in the fragment molecular orbital method

NASA Astrophysics Data System (ADS)

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

2013-04-01

We developed the analytic second derivatives of the energy for the fragment molecular orbital (FMO) method. First we derived the analytic expressions and then introduced some approximations related to the first and second order coupled perturbed Hartree-Fock equations. We developed a parallel program for the FMO Hessian with approximations in GAMESS and used it to calculate infrared (IR) spectra and Gibbs free energies and to locate the transition states in SN2 reactions. The accuracy of the Hessian is demonstrated in comparison to ab initio results for polypeptides and a water cluster. By using the two residues per fragment division, we achieved the accuracy of 3 cm-1 in the reduced mean square deviation of vibrational frequencies from ab initio for all three polyalanine isomers, while the zero point energy had the error not exceeding 0.3 kcal/mol. The role of the secondary structure on IR spectra, zero point energies, and Gibbs free energies is discussed.

Vibrational treatment of the formic acid double minimum case in valence coordinates

NASA Astrophysics Data System (ADS)

Richter, Falk; Carbonnière, P.

2018-02-01

One single full dimensional valence coordinate HCOOH ground state potential energy surface accurate for both cis and trans conformers for all levels up to 6000 cm-1 relative to trans zero point energy has been generated at CCSD(T)-F12a/aug-cc-pVTZ level. The fundamentals and a set of eigenfunctions complete up to about 3120 and 2660 cm-1 for trans- and cis-HCOOH, respectively, have been calculated and assigned using the improved relaxation method of the Heidelberg multi-configuration time-dependent Hartree package and an exact expression for the kinetic energy in valence coordinates generated by the TANA program. The calculated trans fundamental transition frequencies agree with experiment to within 5 cm-1. A few reassignments are suggested. Our results discard any cis trans delocalization effects for vibrational eigenfunctions up to 3640 cm-1 relative to trans zero point energy.

Scalable designs for quasiparticle-poisoning-protected topological quantum computation with Majorana zero modes

NASA Astrophysics Data System (ADS)

Karzig, Torsten; Knapp, Christina; Lutchyn, Roman M.; Bonderson, Parsa; Hastings, Matthew B.; Nayak, Chetan; Alicea, Jason; Flensberg, Karsten; Plugge, Stephan; Oreg, Yuval; Marcus, Charles M.; Freedman, Michael H.

2017-06-01

We present designs for scalable quantum computers composed of qubits encoded in aggregates of four or more Majorana zero modes, realized at the ends of topological superconducting wire segments that are assembled into superconducting islands with significant charging energy. Quantum information can be manipulated according to a measurement-only protocol, which is facilitated by tunable couplings between Majorana zero modes and nearby semiconductor quantum dots. Our proposed architecture designs have the following principal virtues: (1) the magnetic field can be aligned in the direction of all of the topological superconducting wires since they are all parallel; (2) topological T junctions are not used, obviating possible difficulties in their fabrication and utilization; (3) quasiparticle poisoning is abated by the charging energy; (4) Clifford operations are executed by a relatively standard measurement: detection of corrections to quantum dot energy, charge, or differential capacitance induced by quantum fluctuations; (5) it is compatible with strategies for producing good approximate magic states.

Hypercalibration: A Pan-STARRS1-Based Recalibration of the Sloan Digital Sky Survey Photometry

DOE PAGES

Finkbeiner, Douglas P.; Schlafly, Edward F.; Schlegel, David J.; ...

2016-05-05

In this paper, we present a recalibration of the Sloan Digital Sky Survey (SDSS) photometry with new flat fields and zero points derived from Pan-STARRS1. Using point-spread function (PSF) photometry of 60 million stars with 16 < r < 20, we derive a model of amplifier gain and flat-field corrections with per-run rms residuals of 3 millimagnitudes (mmag) in griz bands and 15 mmag in u band. The new photometric zero points are adjusted to leave the median in the Galactic north unchanged for compatibility with previous SDSS work. We also identify transient non-photometric periods in SDSS ("contrails") based onmore » photometric deviations co-temporal in SDSS bands. Finally, the recalibrated stellar PSF photometry of SDSS and PS1 has an rms difference of {9, 7, 7, 8} mmag in griz, respectively, when averaged over 15' regions.« less

Thermal form factor approach to the ground-state correlation functions of the XXZ chain in the antiferromagnetic massive regime

NASA Astrophysics Data System (ADS)

Dugave, Maxime; Göhmann, Frank; Kozlowski, Karol K.; Suzuki, Junji

2016-09-01

We use the form factors of the quantum transfer matrix in the zero-temperature limit in order to study the two-point ground-state correlation functions of the XXZ chain in the antiferromagnetic massive regime. We obtain novel form factor series representations of the correlation functions which differ from those derived either from the q-vertex-operator approach or from the algebraic Bethe Ansatz approach to the usual transfer matrix. We advocate that our novel representations are numerically more efficient and allow for a straightforward calculation of the large-distance asymptotic behaviour of the two-point functions. Keeping control over the temperature corrections to the two-point functions we see that these are of order {T}∞ in the whole antiferromagnetic massive regime. The isotropic limit of our result yields a novel form factor series representation for the two-point correlation functions of the XXX chain at zero magnetic field. Dedicated to the memory of Petr Petrovich Kulish.

The ground state tunneling splitting and the zero point energy of malonaldehyde: a quantum Monte Carlo determination.

PubMed

Viel, Alexandra; Coutinho-Neto, Maurício D; Manthe, Uwe

2007-01-14

Quantum dynamics calculations of the ground state tunneling splitting and of the zero point energy of malonaldehyde on the full dimensional potential energy surface proposed by Yagi et al. [J. Chem. Phys. 1154, 10647 (2001)] are reported. The exact diffusion Monte Carlo and the projection operator imaginary time spectral evolution methods are used to compute accurate benchmark results for this 21-dimensional ab initio potential energy surface. A tunneling splitting of 25.7+/-0.3 cm-1 is obtained, and the vibrational ground state energy is found to be 15 122+/-4 cm-1. Isotopic substitution of the tunneling hydrogen modifies the tunneling splitting down to 3.21+/-0.09 cm-1 and the vibrational ground state energy to 14 385+/-2 cm-1. The computed tunneling splittings are slightly higher than the experimental values as expected from the potential energy surface which slightly underestimates the barrier height, and they are slightly lower than the results from the instanton theory obtained using the same potential energy surface.

Zero point energy of polyhedral water clusters.

PubMed

Anick, David J

2005-06-30

Polyhedral water clusters (PWCs) are cage-like (H2O)n clusters where every O participates in exactly three H bonds. For a database of 83 PWCs, 8 < or = n < or = 20, geometry was optimized and zero point energy (ZPE) was calculated at the B3LYP/6-311++G** level. ZPE correlates negatively with electronic energy (E0): each increase of 1 kcal/mol in E0 corresponds to a decrease of about 0.11 kcal/mol in ZPE. For each n, a set of four connectivity parameters accounts for 98% or more of the variance in ZPE. Linear regression of ZPE against n and this set gives an RMS error of 0.13 kcal/mol. The contributions to ZPE from stretch modes only (ZPE(S)) and from torsional modes only (ZPE(T)) also correlate strongly with E0 and with each other.

On-line calibration of high-response pressure transducers during jet-engine testing

NASA Technical Reports Server (NTRS)

Armentrout, E. C.

1974-01-01

Jet engine testing is reported concerned with the effect of inlet pressure and temperature distortions on engine performance and involves the use of numerous miniature pressure transducers. Despite recent improvements in the manufacture of miniature pressure transducers, they still exhibit sensitivity change and zero-shift with temperature and time. To obtain meaningful data, a calibration system is needed to determine these changes. A system has been developed which provides for computer selection of appropriate reference pressures selected from nine different sources to provide a two- or three-point calibration. Calibrations are made on command, before and sometimes after each data point. A unique no leak matrix valve design is used in the reference pressure system. Zero-shift corrections are measured and the values are automatically inserted into the data reduction program.

The structure and energetics of the HCN → HNC transition state

NASA Astrophysics Data System (ADS)

Lee, Timothy J.; Rendell, Alistair P.

1991-03-01

The optimum geometries and quadratic force constants of HCN, HNC and the transition state connecting them have been determined at the single and double excitation coupled-cluster (CCSD) and CCSD(T) levels of theory. Energy differences were evaluated using the CCSD and CCSD(T) methods in conjunction with large atomic natural orbital basis sets containing g-type basis functions on the heavy atoms and f-type functions on hydrogen. The most reliable structure obtained for the transition state has bond distances of 1.194, 1.188 and 1.389 Å for rCN, rCH and rNH, respectively. Including a correction for zero-point vibrational energies, the transition state is predicted to be 44.6 ± 1.0 kcal/mol above the HCN isomer, while HNC is predicted to be 14.4 ± 1.0 kcal/mol above HCN. The latter value is in excellent agreement with the most recent experimental determination (14.8 ± 2.0 kcal/mol).

Energetics and solvation structure of a dihalogen dopant (I2) in (4)He clusters.

PubMed

Pérez de Tudela, Ricardo; Barragán, Patricia; Valdés, Álvaro; Prosmiti, Rita

2014-08-21

The energetics and structure of small HeNI2 clusters are analyzed as the size of the system changes, with N up to 38. The full interaction between the I2 molecule and the He atoms is based on analytical ab initio He-I2 potentials plus the He-He interaction, obtained from first-principle calculations. The most stable structures, as a function of the number of solvent He atoms, are obtained by employing an evolutionary algorithm and compared with CCSD(T) and MP2 ab initio computations. Further, the classical description is completed by explicitly including thermal corrections and quantum features, such as zero-point-energy values and spatial delocalization. From quantum PIMC calculations, the binding energies and radial/angular probability density distributions of the thermal equilibrium state for selected-size clusters are computed at a low temperature. The sequential formation of regular shell structures is analyzed and discussed for both classical and quantum treatments.

Fission barriers at the end of the chart of the nuclides

NASA Astrophysics Data System (ADS)

Möller, Peter; Sierk, Arnold J.; Ichikawa, Takatoshi; Iwamoto, Akira; Mumpower, Matthew

2015-02-01

We present calculated fission-barrier heights for 5239 nuclides for all nuclei between the proton and neutron drip lines with 171 ≤A ≤330 . The barriers are calculated in the macroscopic-microscopic finite-range liquid-drop model with a 2002 set of macroscopic-model parameters. The saddle-point energies are determined from potential-energy surfaces based on more than 5 000 000 different shapes, defined by five deformation parameters in the three-quadratic-surface shape parametrization: elongation, neck diameter, left-fragment spheroidal deformation, right-fragment spheroidal deformation, and nascent-fragment mass asymmetry. The energy of the ground state is determined by calculating the lowest-energy configuration in both the Nilsson perturbed-spheroid (ɛ ) and the spherical-harmonic (β ) parametrizations, including axially asymmetric deformations. The lower of the two results (correcting for zero-point motion) is defined as the ground-state energy. The effect of axial asymmetry on the inner barrier peak is calculated in the (ɛ ,γ ) parametrization. We have earlier benchmarked our calculated barrier heights to experimentally extracted barrier parameters and found average agreement to about 1 MeV for known data across the nuclear chart. Here we do additional benchmarks and investigate the qualitative and, when possible, quantitative agreement and/or consistency with data on β -delayed fission, isotope generation along prompt-neutron-capture chains in nuclear-weapons tests, and superheavy-element stability. These studies all indicate that the model is realistic at considerable distances in Z and N from the region of nuclei where its parameters were determined.

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

Möller, Peter; Sierk, Arnold J.; Ichikawa, Takatoshi

We present calculated fission-barrier heights for 5239 nuclides for all nuclei between the proton and neutron drip lines with 171 ≤ A ≤ 330. The barriers are calculated in the macroscopic-microscopic finite-range liquid-drop (FRLDM) with a 2002 set of macroscopic-model parameters. The saddle-point energies are determined from potential-energy surfaces based on more than five million different shapes, defined by five deformation parameters in the three-quadratic-surface shape parametrization: elongation, neck diameter, left-fragment spheroidal deformation, right-fragment spheroidal deformation, and nascent-fragment mass asymmetry. The energy of the ground state is determined by calculating the lowest-energy configuration in both the Nilsson perturbed-spheroid (ϵ) andmore » the spherical-harmonic (β) parametrizations, including axially asymmetric deformations. The lower of the two results (correcting for zero-point motion) is defined as the ground-state energy. The effect of axial asymmetry on the inner barrier peak is calculated in the (ϵ,γ) parametrization. We have earlier benchmarked our calculated barrier heights to experimentally extracted barrier parameters and found average agreement to about one MeV for known data across the nuclear chart. Here we do additional benchmarks and investigate the qualitative and, when possible, quantitative agreement and/or consistency with data on β-delayed fission, isotope generation along prompt-neutron-capture chains in nuclear-weapons tests, and superheavy-element stability. In addition these studies all indicate that the model is realistic at considerable distances in Z and N from the region of nuclei where its parameters were determined.« less

Accurate coupled cluster reaction enthalpies and activation energies for X+H2 --> XH+H (X=F, OH, NH2, and CH3)

NASA Astrophysics Data System (ADS)

Kraka, Elfi; Gauss, Jürgen; Cremer, Dieter

1993-10-01

Coupled cluster calculations at the CCSD(T)/[5s4p3d/4s3p] and CCSD(T)/[5s4p3d2 f1g/4s3p2d] level of theory are reported for reactions X+H2→XH+H [X=F (1a), OH (1b), NH2 (1c), and CH3 (1d)] utilizing analytical energy gradients for geometry, frequency, charge distribution, and dipole moment calculations of reactants, transition states, and products. A careful analysis of vibrational corrections leads to reaction enthalpies at 300 K, which are within 0.04, 0.15, 0.62, and 0.89 kcal/mol of experimental values. For reaction (1a) a bent transition state and for reactions (1b) and (1c) transition states with a cis arrangement of the reactants are calculated. The cis forms of transition states (1b) and (1c) are energetically favored because of electrostatic interactions, in particular dipole-dipole attraction as is revealed by calculated charge distributions. For reactions (1a)-(1d), the CCSD(T)/[5s4p3d2 f1g/4s3p2d] activation energies at 300 K are 1.1, 5.4, 10.8, and 12.7 kcal/mol which differ by just 0.1, 1.4, 2.3, and 1.8 kcal/mol, respectively, from the corresponding experimental values of 1±0.1, 4±0.5, 8.5±0.5, and 10.9±0.5 kcal/mol. For reactions (1), this is the best agreement between experiment and theory that has been obtained from ab initio calculations not including any empirically based corrections. Agreement is achieved after considering basis set effects, basis set superposition errors, spin contamination, tunneling effect and, in particular, zero-point energies as well as temperature corrections. Net corrections for the four activation energies are -1.05, -0.2, 1.25, and 0.89 kcal/mol, which shows that for high accuracy calculations a direct comparison of classical barriers and activation energies is misleading.

Theoretical studies of mechanisms of cycloaddition reaction between difluoromethylene carbene and acetone

NASA Astrophysics Data System (ADS)

Lu, Xiu Hui; Yu, Hai Bin; Wu, Wei Rong; Xu, Yue Hua

Mechanisms of the cycloaddition reaction between singlet difluoromethylene carbene and acetone have been investigated with the second-order Møller-Plesset (MP2)/6-31G* method, including geometry optimization and vibrational analysis. Energies for the involved stationary points on the potential energy surface (PES) are corrected by zero-point energy (ZPE) and CCSD(T)/6-31G* single-point calculations. From the PES obtained with the CCSD(T)//MP2/6-31G* method for the cycloaddition reaction between singlet difluoromethylene carbene and acetone, it can be predicted that path B of reactions 2 and 3 should be two competitive leading channels of the cycloaddition reaction between difluoromethylene carbene and acetone. The former consists of two steps: (i) the two reactants first form a four-membered ring intermediate, INT2, which is a barrier-free exothermic reaction of 97.8 kJ/mol; (ii) the intermediate INT2 isomerizes to a four-membered product P2b via a transition state TS2b with an energy barrier of 24.9 kJ/mol, which results from the methyl group transfer. The latter proceeds in three steps: (i) the two reactants first form an intermediate, INT1c, through a barrier-free exothermic reaction of 199.4 kJ/mol; (ii) the intermediate INT1c further reacts with acetone to form a polycyclic intermediate, INT3, which is also a barrier-free exothermic reaction of 27.4 kJ/mol; and (iii) INT3 isomerizes to a polycyclic product P3 via a transition state TS3 with an energy barrier of 25.8 kJ/mol.

The patient-zero problem with noisy observations

NASA Astrophysics Data System (ADS)

Altarelli, Fabrizio; Braunstein, Alfredo; Dall'Asta, Luca; Ingrosso, Alessandro; Zecchina, Riccardo

2014-10-01

A belief propagation approach has been recently proposed for the patient-zero problem in SIR epidemics. The patient-zero problem consists of finding the initial source of an epidemic outbreak given observations at a later time. In this work, we study a more difficult but related inference problem, in which observations are noisy and there is confusion between observed states. In addition to studying the patient-zero problem, we also tackle the problem of completing and correcting the observations to possibly find undiscovered infected individuals and false test results. Moreover, we devise a set of equations, based on the variational expression of the Bethe free energy, to find the patient-zero along with maximum-likelihood epidemic parameters. We show, by means of simulated epidemics, that this method is able to infer details on the past history of an epidemic outbreak based solely on the topology of the contact network and a single snapshot of partial and noisy observations.

A maximally particle-hole asymmetric spectrum emanating from a semi-Dirac point.

PubMed

Quan, Yundi; Pickett, Warren E

2018-02-21

Tight binding models have proven an effective means of revealing Dirac (massless) dispersion, flat bands (infinite mass), and intermediate cases such as the semi-Dirac (sD) dispersion. This approach is extended to a three band model that yields, with chosen parameters in a two-band limit, a closed line with maximally asymmetric particle-hole dispersion: infinite mass holes, zero mass particles. The model retains the sD points for a general set of parameters. Adjacent to this limiting case, hole Fermi surfaces are tiny and needle-like. A pair of large electron Fermi surfaces at low doping merge and collapse at half filling to a flat (zero energy) closed contour with infinite mass along the contour and enclosing no carriers on either side, while the hole Fermi surface has shrunk to a point at zero energy, also containing no carriers. The tight binding model is used to study several characteristics of the dispersion and density of states. The model inspired generalization of sD dispersion to a general  ±[Formula: see text] form, for which analysis reveals that both n and m must be odd to provide a diabolical point with topological character. Evolution of the Hofstadter spectrum of this three band system with interband coupling strength is presented and discussed.

A maximally particle-hole asymmetric spectrum emanating from a semi-Dirac point

NASA Astrophysics Data System (ADS)

Quan, Yundi; Pickett, Warren E.

2018-02-01

Tight binding models have proven an effective means of revealing Dirac (massless) dispersion, flat bands (infinite mass), and intermediate cases such as the semi-Dirac (sD) dispersion. This approach is extended to a three band model that yields, with chosen parameters in a two-band limit, a closed line with maximally asymmetric particle-hole dispersion: infinite mass holes, zero mass particles. The model retains the sD points for a general set of parameters. Adjacent to this limiting case, hole Fermi surfaces are tiny and needle-like. A pair of large electron Fermi surfaces at low doping merge and collapse at half filling to a flat (zero energy) closed contour with infinite mass along the contour and enclosing no carriers on either side, while the hole Fermi surface has shrunk to a point at zero energy, also containing no carriers. The tight binding model is used to study several characteristics of the dispersion and density of states. The model inspired generalization of sD dispersion to a general  ± \\sqrt{k_x2n +k_y2m} form, for which analysis reveals that both n and m must be odd to provide a diabolical point with topological character. Evolution of the Hofstadter spectrum of this three band system with interband coupling strength is presented and discussed.

Ariel 6 measurements of ultra-heavy cosmic ray fluxes in the region Z or = 48

NASA Technical Reports Server (NTRS)

Fowler, P. H.; Masheder, M. R. W.; Moses, R. T.; Walker, R. N. F.; Worley, A.; Gay, A. M.

1985-01-01

For this re-analysis of the Ariel VI data, the contribution of non Z square effects to the restricted energy loss and to Cerenkov radiation in the Bristol sphere has been evaluated using the Mott cross section ratios and the non-relativistic Bloch correction. Results obtained were similar in form to those derived for HEAO3 but with maximum deviations approximately 10% rather than 15% for the Mott term, corresponding to a thinner detector. Because of the large uncertainties in the parameters involved, no relativistic Bloch term was included. In addition the experiments on the HEAO detector make the application of a correction to the Cerenkov response of doubtful justification and none was applied in this analysis. An energy dependent correction was made using an effective energy calculated from the vertical cut-off for a given event. The maximum value of this correction was about 0.6% in Z for low cut-offs, declining to approximately zero by 10 GV.

Computing Wigner distributions and time correlation functions using the quantum thermal bath method: application to proton transfer spectroscopy.

PubMed

Basire, Marie; Borgis, Daniel; Vuilleumier, Rodolphe

2013-08-14

Langevin dynamics coupled to a quantum thermal bath (QTB) allows for the inclusion of vibrational quantum effects in molecular dynamics simulations at virtually no additional computer cost. We investigate here the ability of the QTB method to reproduce the quantum Wigner distribution of a variety of model potentials, designed to assess the performances and limits of the method. We further compute the infrared spectrum of a multidimensional model of proton transfer in the gas phase and in solution, using classical trajectories sampled initially from the Wigner distribution. It is shown that for this type of system involving large anharmonicities and strong nonlinear coupling to the environment, the quantum thermal bath is able to sample the Wigner distribution satisfactorily and to account for both zero point energy and tunneling effects. It leads to quantum time correlation functions having the correct short-time behavior, and the correct associated spectral frequencies, but that are slightly too overdamped. This is attributed to the classical propagation approximation rather than the generation of the quantized initial conditions themselves.

Improving Photometric Calibration of Meteor Video Camera Systems.

PubMed

Ehlert, Steven; Kingery, Aaron; Suggs, Robert

2017-09-01

We present the results of new calibration tests performed by the NASA Meteoroid Environment Office (MEO) designed to help quantify and minimize systematic uncertainties in meteor photometry from video camera observations. These systematic uncertainties can be categorized by two main sources: an imperfect understanding of the linearity correction for the MEO's Watec 902H2 Ultimate video cameras and uncertainties in meteor magnitudes arising from transformations between the Watec camera's Sony EX-View HAD bandpass and the bandpasses used to determine reference star magnitudes. To address the first point, we have measured the linearity response of the MEO's standard meteor video cameras using two independent laboratory tests on eight cameras. Our empirically determined linearity correction is critical for performing accurate photometry at low camera intensity levels. With regards to the second point, we have calculated synthetic magnitudes in the EX bandpass for reference stars. These synthetic magnitudes enable direct calculations of the meteor's photometric flux within the camera band pass without requiring any assumptions of its spectral energy distribution. Systematic uncertainties in the synthetic magnitudes of individual reference stars are estimated at ∼ 0.20 mag, and are limited by the available spectral information in the reference catalogs. These two improvements allow for zero-points accurate to ∼ 0.05 - 0.10 mag in both filtered and unfiltered camera observations with no evidence for lingering systematics. These improvements are essential to accurately measuring photometric masses of individual meteors and source mass indexes.

Improving Photometric Calibration of Meteor Video Camera Systems

NASA Technical Reports Server (NTRS)

Ehlert, Steven; Kingery, Aaron; Suggs, Robert

2017-01-01

We present the results of new calibration tests performed by the NASA Meteoroid Environment Office (MEO) designed to help quantify and minimize systematic uncertainties in meteor photometry from video camera observations. These systematic uncertainties can be categorized by two main sources: an imperfect understanding of the linearity correction for the MEO's Watec 902H2 Ultimate video cameras and uncertainties in meteor magnitudes arising from transformations between the Watec camera's Sony EX-View HAD bandpass and the bandpasses used to determine reference star magnitudes. To address the first point, we have measured the linearity response of the MEO's standard meteor video cameras using two independent laboratory tests on eight cameras. Our empirically determined linearity correction is critical for performing accurate photometry at low camera intensity levels. With regards to the second point, we have calculated synthetic magnitudes in the EX bandpass for reference stars. These synthetic magnitudes enable direct calculations of the meteor's photometric flux within the camera bandpass without requiring any assumptions of its spectral energy distribution. Systematic uncertainties in the synthetic magnitudes of individual reference stars are estimated at approx. 0.20 mag, and are limited by the available spectral information in the reference catalogs. These two improvements allow for zero-points accurate to 0.05 - 0.10 mag in both filtered and unfiltered camera observations with no evidence for lingering systematics. These improvements are essential to accurately measuring photometric masses of individual meteors and source mass indexes.

Tight-binding modeling and low-energy behavior of the semi-Dirac point.

PubMed

Banerjee, S; Singh, R R P; Pardo, V; Pickett, W E

2009-07-03

We develop a tight-binding model description of semi-Dirac electronic spectra, with highly anisotropic dispersion around point Fermi surfaces, recently discovered in electronic structure calculations of VO2-TiO2 nanoheterostructures. We contrast their spectral properties with the well-known Dirac points on the honeycomb lattice relevant to graphene layers and the spectra of bands touching each other in zero-gap semiconductors. We also consider the lowest order dispersion around one of the semi-Dirac points and calculate the resulting electronic energy levels in an external magnetic field. In spite of apparently similar electronic structures, Dirac and semi-Dirac systems support diverse low-energy physics.

Structural, electronic, elastic and thermodynamic properties of Li2ZrO3: A comprehensive study using DFT formalism

NASA Astrophysics Data System (ADS)

Chattaraj, D.

2017-12-01

Lithium zirconate is considered to be potential tritium breeder material for fusion reactors. Here I report a comprehensive study on structural, electronic, elastic, and thermodynamic properties of Li2ZrO3 using plane wave based density functional theory. While the electron-ion interaction term has been described by projected-augmented wave method, the exchange-correlation energy was taken care of through generalized gradient approximation scheme. The optimized lattice and internal parameters of Li2ZrO3 unit cell agree well within ±1-2% from the experimental values. From the electronic structure analysis it is seen that the Fermi energy has significant contribution from the 2s, 2p and 4d orbitals of Li, O and Zr atoms, respectively. Elastic property calculation of Li2ZrO3 showed mechanical stability and anisotropy at ambient pressure. The formation energy (ΔfH) of Li2ZrO3 at 0 K, after zero point energy correction, has been estimated to be -1550 kJ/mol. The temperature dependent thermodynamic functions of Li2ZrO3 have also been calculated from the Debye-Grüneisen quasi-harmonic approximation and reported here.

Structures, Energetics, and IR Spectra of Monohydrated Inorganic Acids: Ab initio and DFT Study.

PubMed

Kołaski, Maciej; Zakharenko, Aleksey A; Karthikeyan, S; Kim, Kwang S

2011-10-11

We carried out extensive calculations of diverse inorganic acids interacting with a single water molecule, through a detailed analysis of many possible conformations. The optimized structures were obtained by using density functional theory (DFT) and the second order Møller-Plesset perturbation theory (MP2). For the most stable conformers, we calculated the interaction energies at the complete basis set (CBS) limit using coupled cluster theory with single, double, and perturbative triple excitations [CCSD(T)]. The -OH stretching harmonic and anharmonic frequencies are provided as fingerprints of characteristic conformers. The zero-point energy (ZPE) uncorrected/corrected (ΔEe/ΔE0) interaction energies and the enthalpies/free energies (ΔHr/ΔGr at room temperature and 1 bar) are reported. Various comparisons are made between many diverse inorganic acids (HmXOn where X = B/N/P/Cl/Br/I, m = 1-3, and n = 0-4) as well as other simple inorganic acids. In many cases, we find that the dispersion-driven van der Waals interactions between X in inorganic acid molecules and O in water molecules as well as the X(+)···O(-) electrostatic interactions are important.

Tsallis entropy and decoherence of CsI quantum pseudo dot qubit

NASA Astrophysics Data System (ADS)

Tiotsop, M.; Fotue, A. J.; Fotsin, H. B.; Fai, L. C.

2017-05-01

Polaron in CsI quantum pseudo dot under an electromagnetic field was considered, and the ground and first excited state energies were derived by employing the combining Pekar variational and unitary transformation methods. With the two-level system obtained, single qubit was envisioned and the decoherence was studied using non-extensive entropy (Tsallis entropy). Numerical results showed: (i) the increase (decrease) of the energy levels (period of oscillation) with the increase of chemical potential, the zero point of pseudo dot, cyclotron frequency, and transverse and longitudinal confinements; (ii) the Tsallis entropy evolved as a wave envelop that increase with the increase of non-extenxive parameter and with the increase of electric field strength, zero point of pseudo dot and cyclotron frequency the wave envelop evolve periodically with reduction of period; (iii) The transition probability increases from the boundary to the centre of the dot where it has its maximum value. It was also noted that the probability density oscillate with period T0 = ℏ / Δ Ε with the tunnelling of the chemical potential and zero point of the pseudo dot. These results are helpful in the control of decoherence in quantum systems and may also be useful for the design of quantum computers.

A practical method to avoid zero-point leak in molecular dynamics calculations: application to the water dimer.

PubMed

Czakó, Gábor; Kaledin, Alexey L; Bowman, Joel M

2010-04-28

We report the implementation of a previously suggested method to constrain a molecular system to have mode-specific vibrational energy greater than or equal to the zero-point energy in quasiclassical trajectory calculations [J. M. Bowman et al., J. Chem. Phys. 91, 2859 (1989); W. H. Miller et al., J. Chem. Phys. 91, 2863 (1989)]. The implementation is made practical by using a technique described recently [G. Czako and J. M. Bowman, J. Chem. Phys. 131, 244302 (2009)], where a normal-mode analysis is performed during the course of a trajectory and which gives only real-valued frequencies. The method is applied to the water dimer, where its effectiveness is shown by computing mode energies as a function of integration time. Radial distribution functions are also calculated using constrained quasiclassical and standard classical molecular dynamics at low temperature and at 300 K and compared to rigorous quantum path integral calculations.

TOPICAL REVIEW: Experimental study of organic zero-gap conductor α-(BEDT-TTF)2I3

NASA Astrophysics Data System (ADS)

Tajima, Naoya; Kajita, Koji

2009-04-01

A zero-gap state with a Dirac cone type energy dispersion was discovered in the organic conductor α-(BEDT-TTF)2I3 under high hydrostatic pressures. This is the first two-dimensional (2D) zero-gap state discovered in bulk crystals with a layered structure. In contrast to the case of graphene, the Dirac cone in this system is highly anisotropic. The present system, therefore, provides a new type of massless Dirac fermion system with anisotropic Fermi velocity. This system exhibits remarkable transport phenomena characteristic to electrons on the Dirac cone type energy structure. The carrier density, written as n~T2, is a characteristic feature of the 2D zero-gap structure. On the other hand, the resistivity per layer (sheet resistance RS) is given as RS=h/e2 and is independent of temperature. The effect of a magnetic field on samples in the zero-gap system was examined. The difference between zero-gap conductors and conventional conductors is the appearance of a Landau level called the zero mode at the contact points when a magnetic field is applied normal to the conductive layer. Zero-mode Landau carriers give rise to strong negative out-of-plane magnetoresistance.

Pulsed-field ionization zero electron kinetic energy spectrum of the ground electronic state of BeOBe+.

PubMed

Antonov, Ivan O; Barker, Beau J; Heaven, Michael C

2011-01-28

The ground electronic state of BeOBe(+) was probed using the pulsed-field ionization zero electron kinetic energy photoelectron technique. Spectra were rotationally resolved and transitions to the zero-point level, the symmetric stretch fundamental and first two bending vibrational levels were observed. The rotational state symmetry selection rules confirm that the ground electronic state of the cation is (2)Σ(g)(+). Detachment of an electron from the HOMO of neutral BeOBe results in little change in the vibrational or rotational constants, indicating that this orbital is nonbonding in nature. The ionization energy of BeOBe [65480(4) cm(-1)] was refined over previous measurements. Results from recent theoretical calculations for BeOBe(+) (multireference configuration interaction) were found to be in good agreement with the experimental data.

Magnetic properties of graphene quantum dots

NASA Astrophysics Data System (ADS)

Espinosa-Ortega, T.; Luk'yanchuk, I. A.; Rubo, Y. G.

2013-05-01

Using the tight-binding approximation we calculated the diamagnetic susceptibility of graphene quantum dots (GQDs) of different geometrical shapes and characteristic sizes of 2-10 nm, when the magnetic properties are governed by the electron edge states. Two types of edge states can be discerned: the zero-energy states (ZESs), located exactly at the zero-energy Dirac point, and the dispersed edge states (DESs), with the energy close but not exactly equal to zero. DESs are responsible for a temperature-independent diamagnetic response, while ZESs provide a temperature-dependent spin paramagnetism. Hexagonal, circular, and randomly shaped GQDs contain mainly DESs, and, as a result, they are diamagnetic. The edge states of the triangular GQDs are of ZES type. These dots reveal the crossover between spin paramagnetism, dominating for small dots and at low temperatures, and orbital diamagnetism, dominating for large dots and at high temperatures.

On the zero-crossing of the three-gluon Green's function from lattice simulations

NASA Astrophysics Data System (ADS)

Athenodorou, Andreas; Boucaud, Philippe; de Soto, Feliciano; Rodríguez-Quintero, José; Zafeiropoulos, Savvas

2018-03-01

We report on some efforts recently made in order to gain a better understanding of some IR properties of the 3-point gluon Green's function by exploiting results from large-volume quenched lattice simulations. These lattice results have been obtained by using both tree-level Symanzik and the standard Wilson action, in the aim of assessing the possible impact of effects presumably resulting from a particular choice for the discretization of the action. The main resulting feature is the existence of a negative log-aritmic divergence at zero-momentum, which pulls the 3-gluon form factors down at low momenta and, consequently, yields a zero-crossing at a given deep IR momentum. The results can be correctly explained by analyzing the relevant Dyson-Schwinger equations and appropriate truncation schemes.

Magnification of signatures of a topological phase transition by quantum zero point motion

NASA Astrophysics Data System (ADS)

Lopes, Pedro L. e. S.; Ghaemi, Pouyan

2015-08-01

We show that the zero point motion of a vortex in superconducting doped topological insulators leads to significant changes in the electronic spectrum at the topological phase transition in this system. This topological phase transition is tuned by the doping level, and the corresponding effects are manifest in the density of states at energies which are on the order of the vortex fluctuation frequency. Although the electronic energy gap in the spectrum generated by a stationary vortex is but a small fraction of the bulk superconducting gap, the vortex fluctuation frequency may be much larger. As a result, this quantum zero point motion can induce a discontinuous change in the spectral features of the system at the topological vortex phase transition to energies which are well within the resolution of scanning tunneling microscopy. This discontinuous change is exclusive to superconducting systems in which we have a topological phase transition. Moreover, the phenomena studied in this paper present effects of Magnus forces on the vortex spectrum which are not present in the ordinary s -wave superconductors. Finally, we demonstrate explicitly that the vortex in this system is equivalent to a Kitaev chain. This allows for the mapping of the vortex fluctuating scenario in three dimensions into similar one-dimensional situations in which one may search for other novel signatures of topological phase transitions.

Reaction mechanism of guanidinoacetate methyltransferase, concerted or step-wise

PubMed Central

Zhang, Xiaodong; Bruice, Thomas C.

2006-01-01

We describe a quantum mechanics/molecular mechanics investigation of the guanidinoacetate methyltransferase catalyzed reaction, which shows that proton transfer from guanidinoacetate (GAA) to Asp-134 and methyl transfer from S-adenosyl-l-methionine (AdoMet) to GAA are concerted. By self-consistent-charge density functional tight binding/molecular mechanics, the bond lengths in the concerted mechanism's transition state are 1.26 Å for both the OD1 (Asp-134)–HE (GAA) and HE (GAA)–NE (GAA) bonds, and 2.47 and 2.03 Å for the S8 (AdoMet)–C9 (AdoMet) and C9 (AdoMet)–NE (GAA) bonds, respectively. The potential-energy barrier (ΔE‡) determined by single-point B3LYP/6–31+G*//MM is 18.9 kcal/mol. The contributions of the entropy (−TΔS‡) and zero-point energy corrections Δ(ZPE)‡ by normal mode analysis are 2.3 kcal/mol and −1.7 kcal/mol, respectively. Thus, the activation enthalpy of this concerted mechanism is predicted to be ΔH‡ = ΔE‡ + Δ(ZPE)‡ = 17.2 kcal/mol. The calculated free-energy barrier for the concerted mechanism is ΔG‡ = 19.5 kcal/mol, which is in excellent agreement with the value of 19.0 kcal/mol calculated from the experimental rate constant (3.8 ± 0.2·min−1). PMID:17053070

Direct dynamics trajectory study of the reaction of formaldehyde cation with D2: vibrational and zero-point energy effects on quasiclassical trajectories.

PubMed

Liu, Jianbo; Song, Kihyung; Hase, William L; Anderson, Scott L

2005-12-22

Quasiclassical, direct dynamics trajectories have been used to study the reaction of formaldehyde cation with molecular hydrogen, simulating the conditions in an experimental study of H2CO+ vibrational effects on this reaction. Effects of five different H2CO+ modes were probed, and we also examined different approaches to treating zero-point energy in quasiclassical trajectories. The calculated absolute cross-sections are in excellent agreement with experiments, and the results provide insight into the reaction mechanism, product scattering behavior, and energy disposal, and how they vary with impact parameter and reactant state. The reaction is sharply orientation-dependent, even at high collision energies, and both trajectories and experiment find that H2CO+ vibration inhibits reaction. On the other hand, the trajectories do not reproduce the anomalously strong effect of nu2(+) (the CO stretch). The origin of the discrepancy and approaches for minimizing such problems in quasiclassical trajectories are discussed.

Physical condition for elimination of ambiguity in conditionally convergent lattice sums

NASA Astrophysics Data System (ADS)

Young, K.

1987-02-01

The conditional convergence of the lattice sum defining the Madelung constant gives rise to an ambiguity in its value. It is shown that this ambiguity is related, through a simple and universal integral, to the average charge density on the crystal surface. The physically correct value is obtained by setting the charge density to zero. A simple and universally applicable formula for the Madelung constant is derived as a consequence. It consists of adding up dipole-dipole energies together with a nontrivial correction term.

Quasisaddles as relevant points of the potential energy surface in the dynamics of supercooled liquids

NASA Astrophysics Data System (ADS)

Angelani, L.; Di Leonardo, R.; Ruocco, G.; Scala, A.; Sciortino, F.

2002-06-01

The supercooled dynamics of a Lennard-Jones model liquid is numerically investigated studying relevant points of the potential energy surface, i.e., the minima of the square gradient of total potential energy V. The main findings are (i) the number of negative curvatures n of these sampled points appears to extrapolate to zero at the mode coupling critical temperature Tc; (ii) the temperature behavior of n(T) has a close relationship with the temperature behavior of the diffusivity; (iii) the potential energy landscape shows a high regularity in the distances among the relevant points and in their energy location. Finally we discuss a model of the landscape, previously introduced by Madan and Keyes [J. Chem. Phys. 98, 3342 (1993)], able to reproduce the previous findings.

Two-dimensional Dirac fermions in thin films of C d3A s2

NASA Astrophysics Data System (ADS)

Galletti, Luca; Schumann, Timo; Shoron, Omor F.; Goyal, Manik; Kealhofer, David A.; Kim, Honggyu; Stemmer, Susanne

2018-03-01

Two-dimensional states in confined thin films of the three-dimensional Dirac semimetal C d3A s2 are probed by transport and capacitance measurements under applied magnetic and electric fields. The results establish the two-dimensional Dirac electronic spectrum of these states. We observe signatures of p -type conduction in the two-dimensional states as the Fermi level is tuned across their charge neutrality point and the presence of a zero-energy Landau level, all of which indicate topologically nontrivial states. The resistance at the charge neutrality point is approximately h /e2 and increases rapidly under the application of a magnetic field. The results open many possibilities for gate-tunable topological devices and for the exploration of novel physics in the zero-energy Landau level.

Characterizing the potential energy surface of the water dimer with DFT: failures of some popular functionals for hydrogen bonding.

PubMed

Anderson, Julie A; Tschumper, Gregory S

2006-06-08

Ten stationary points on the water dimer potential energy surface have been examined with ten density functional methods (X3LYP, B3LYP, B971, B98, MPWLYP, PBE1PBE, PBE, MPW1K, B3P86, and BHandHLYP). Geometry optimizations and vibrational frequency calculations were carried out with the TZ2P(f,d)+dif basis set. All ten of the density functionals correctly describe the relative energies of the ten stationary points. However, correctly describing the curvature of the potential energy surface is far more difficult. Only one functional (BHandHLYP) reproduces the number of imaginary frequencies from CCSD(T) calculations. The other nine density functionals fail to correctly characterize the nature of at least one of the ten (H(2)O)(2) stationary points studied here.

Ab initio structures and polarizabilities of sodium clusters

NASA Astrophysics Data System (ADS)

Kronik, Leeor; Vasiliev, Igor; Jain, Manish; Chelikowsky, James R.

2001-09-01

We present quantitative ab initio calculations for Na cluster structures and polarizabilities, for all cluster sizes up to 20 atoms. Our calculations are performed by combining an ab initio core-corrected pseudopotential and a gradient-corrected density functional within a real space approach. We find the cluster bonding to be very floppy and catalog a host of low-energy quasi-degenerate isomers for all second-decade clusters. The existence of these isomers results in a band of polarizability values for each cluster size even at zero temperature. This eliminates any finer structure in the polarizability curve. We further show that the experimental polarizability values are consistently underestimated by calculations at zero temperature. By computing the effects of structure expansion and distortion due to a finite temperature we arrive at a quantitative agreement between theory and experiment.

Noncommutative Wilson lines in higher-spin theory and correlation functions of conserved currents for free conformal fields

NASA Astrophysics Data System (ADS)

Bonezzi, Roberto; Boulanger, Nicolas; De Filippi, David; Sundell, Per

2017-11-01

We first prove that, in Vasiliev’s theory, the zero-form charges studied in Sezgin E and Sundell P 2011 (arXiv:1103.2360 [hep-th]) and Colombo N and Sundell P 20 (arXiv:1208.3880 [hep-th]) are twisted open Wilson lines in the noncommutative Z space. This is shown by mapping Vasiliev’s higher-spin model on noncommutative Yang-Mills theory. We then prove that, prior to Bose-symmetrising, the cyclically-symmetric higher-spin invariants given by the leading order of these n-point zero-form charges are equal to corresponding cyclically-invariant building blocks of n-point correlation functions of bilinear operators in free conformal field theories (CFT) in three dimensions. On the higher spin gravity side, our computation reproduces the results of Didenko V and Skvortsov E 2013 J. High Energy Phys. JHEP04(2013)158 using an alternative method amenable to the computation of subleading corrections obtained by perturbation theory in normal order. On the free CFT side, our proof involves the explicit computation of the separate cyclic building blocks of the correlation functions of n conserved currents in arbitrary dimension d>2 using polarization vectors, which is an original result. It is shown to agree, for d=3 , with the results obtained in Gelfond O A and Vasiliev M A 2013 Nucl. Phys. B 876 871-917 in various dimensions and where polarization spinors were used.

Ground-state-entanglement bound for quantum energy teleportation of general spin-chain models

NASA Astrophysics Data System (ADS)

Hotta, Masahiro

2013-03-01

Many-body quantum systems in the ground states have zero-point energy due to the uncertainty relation. In many cases, the system in the ground state accompanies spatially entangled energy density fluctuation via the noncommutativity of the energy density operators, though the total energy takes a fixed value, i.e., the lowest eigenvalue of the Hamiltonian. Quantum energy teleportation (QET) is a protocol for the extraction of the zero-point energy out of one subsystem using information of a remote measurement of another subsystem. From an operational viewpoint of protocol users, QET can be regarded as an effective rapid energy transportation without breaking all physical laws, including causality and local energy conservation. In the protocol, the ground-state entanglement plays a crucial role. In this paper, we show analytically for a general class of spin-chain systems that the entanglement entropy is lower bounded by a positive quadratic function of the teleported energy between the regions of a QET protocol. This supports a general conjecture that ground-state entanglement is an evident physical resource for energy transportation in the context of QET. The result may also deepen our understanding of the energy density fluctuation in condensed-matter systems from a perspective of quantum information theory.

Theoretical predictions for hexagonal BN based nanomaterials as electrocatalysts for the oxygen reduction reaction.

PubMed

Lyalin, Andrey; Nakayama, Akira; Uosaki, Kohei; Taketsugu, Tetsuya

2013-02-28

The catalytic activity for the oxygen reduction reaction (ORR) of both the pristine and defect-possessing hexagonal boron nitride (h-BN) monolayer and H-terminated nanoribbon have been studied theoretically using density functional theory. It is demonstrated that an inert h-BN monolayer can be functionalized and become catalytically active by nitrogen doping. It is shown that the energetics of adsorption of O(2), O, OH, OOH, and H(2)O on N atom impurities in the h-BN monolayer (N(B)@h-BN) is quite similar to that known for a Pt(111) surface. The specific mechanism of destructive and cooperative adsorption of ORR intermediates on the surface point defects is discussed. It is demonstrated that accounting for entropy and zero-point energy (ZPE) corrections results in destabilization of the ORR intermediates adsorbed on N(B)@h-BN, while solvent effects lead to their stabilization. Therefore, entropy, ZPE and solvent effects partly cancel each other and have to be taken into account simultaneously. Analysis of the free energy changes along the ORR pathway allows us to suggest that a N-doped h-BN monolayer can demonstrate catalytic properties for the ORR under the condition that electron transport to the catalytically active center is provided.

Effects of phonon broadening on x-ray near-edge spectra in molecular crystals

NASA Astrophysics Data System (ADS)

Vinson, John; Jach, Terrence; Elam, Tim; Denlinger, Jonathon

2014-03-01

Calculations of near-edge x-ray spectra are often carried out using the average atomic coordinates from x-ray or neutron scattering experiments or from density functional theory (DFT) energy minimization. This neglects disorder from thermal and zero-point vibrations. Here we look at the nitrogen K-edge of ammonium chloride and ammonium nitrate, comparing Bethe-Salpeter calculations of absorption and fluorescence to experiment. We find that intra-molecular vibrational effects lead to significant, non-uniform broadening of the spectra, and that for some features zero-point motion is the primary source of the observed shape.

Chaos in a restricted problem of rotation of a rigid body with a fixed point

NASA Astrophysics Data System (ADS)

Borisov, A. V.; Kilin, A. A.; Mamaev, I. S.

2008-06-01

In this paper, we consider the transition to chaos in the phase portrait of a restricted problem of rotation of a rigid body with a fixed point. Two interrelated mechanisms responsible for chaotization are indicated: (1) the growth of the homoclinic structure and (2) the development of cascades of period doubling bifurcations. On the zero level of the area integral, an adiabatic behavior of the system (as the energy tends to zero) is noted. Meander tori induced by the break of the torsion property of the mapping are found.

Fission barriers at the end of the chart of the nuclides

DOE PAGES

Möller, Peter; Sierk, Arnold J.; Ichikawa, Takatoshi; ...

2015-02-12

We present calculated fission-barrier heights for 5239 nuclides for all nuclei between the proton and neutron drip lines with 171 ≤ A ≤ 330. The barriers are calculated in the macroscopic-microscopic finite-range liquid-drop (FRLDM) with a 2002 set of macroscopic-model parameters. The saddle-point energies are determined from potential-energy surfaces based on more than five million different shapes, defined by five deformation parameters in the three-quadratic-surface shape parametrization: elongation, neck diameter, left-fragment spheroidal deformation, right-fragment spheroidal deformation, and nascent-fragment mass asymmetry. The energy of the ground state is determined by calculating the lowest-energy configuration in both the Nilsson perturbed-spheroid (ϵ) andmore » the spherical-harmonic (β) parametrizations, including axially asymmetric deformations. The lower of the two results (correcting for zero-point motion) is defined as the ground-state energy. The effect of axial asymmetry on the inner barrier peak is calculated in the (ϵ,γ) parametrization. We have earlier benchmarked our calculated barrier heights to experimentally extracted barrier parameters and found average agreement to about one MeV for known data across the nuclear chart. Here we do additional benchmarks and investigate the qualitative and, when possible, quantitative agreement and/or consistency with data on β-delayed fission, isotope generation along prompt-neutron-capture chains in nuclear-weapons tests, and superheavy-element stability. In addition these studies all indicate that the model is realistic at considerable distances in Z and N from the region of nuclei where its parameters were determined.« less

Full-dimensional quantum calculations of the dissociation energy, zero-point, and 10 K properties of H7+/D7+ clusters using an ab initio potential energy surface.

PubMed

Barragán, Patricia; Pérez de Tudela, Ricardo; Qu, Chen; Prosmiti, Rita; Bowman, Joel M

2013-07-14

Diffusion Monte Carlo (DMC) and path-integral Monte Carlo computations of the vibrational ground state and 10 K equilibrium state properties of the H7 (+)/D7 (+) cations are presented, using an ab initio full-dimensional potential energy surface. The DMC zero-point energies of dissociated fragments H5 (+)(D5 (+))+H2(D2) are also calculated and from these results and the electronic dissociation energy, dissociation energies, D0, of 752 ± 15 and 980 ± 14 cm(-1) are reported for H7 (+) and D7 (+), respectively. Due to the known error in the electronic dissociation energy of the potential surface, these quantities are underestimated by roughly 65 cm(-1). These values are rigorously determined for first time, and compared with previous theoretical estimates from electronic structure calculations using standard harmonic analysis, and available experimental measurements. Probability density distributions are also computed for the ground vibrational and 10 K state of H7 (+) and D7 (+). These are qualitatively described as a central H3 (+)/D3 (+) core surrounded by "solvent" H2/D2 molecules that nearly freely rotate.

The role of large-amplitude motions in the spectroscopy and dynamics of H{sub 5}{sup +}

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

Lin, Zhou; McCoy, Anne B., E-mail: mccoy@chemistry.ohio-state.edu

2014-03-21

Protonated hydrogen dimer, H{sub 5}{sup +}, is the intermediate in the astrochemically important proton transfer reaction between H{sub 3}{sup +} and H{sub 2}. To understand the mechanism for this process, we focus on how large amplitude motions in H{sub 5}{sup +} result in scrambling of the five hydrogen atoms in the collision complex. To this end, the one-dimensional zero-point corrected potential surfaces were mapped out as functions of reaction coordinates for the H{sub 3}{sup +} + H{sub 2} collision using minimized energy path diffusion Monte Carlo [C. E. Hinkle and A. B. McCoy, J. Phys. Chem. Lett. 1, 562 (2010)].more » In this study, the previously developed approach was extended to allow for the investigation of selected excited states that are expected to be involved in the proton scrambling dynamics. Specifically, excited states in the shared proton motion between the two H{sub 2} groups, and in the outer H{sub 2} bending motions were investigated. Of particular interest is the minimum distance between H{sub 3}{sup +} and H{sub 2} at which all five hydrogen atoms become free to exchange. In addition, this diffusion Monte Carlo-based approach was used to determine the zero-point energy E{sub 0}, the dissociation energy D{sub 0}, and excitation energies associated with the vibrational motions that were investigated. The evolution of the wave functions was also studied, with a focus on how the intramolecular vibrations in H{sub 5}{sup +} evolve into motions of H{sub 3}{sup +} or H{sub 2}. In the case of the proton scrambling, we find that the relevant transition states become fully accessible at separations between H{sub 3}{sup +} and H{sub 2} of approximately 2.15 Å, a distance that is accessed by the excited states of H{sub 5}{sup +} with two or more quanta in the shared proton stretch. The implications of this finding on the vibrational spectroscopy of H{sub 5}{sup +} are also discussed.« less

Proposed Use of Zero Bias Diode Arrays as Thermal Electric Noise Rectifiers and Non-Thermal Energy Harvesters

NASA Astrophysics Data System (ADS)

Valone, Thomas F.

2009-03-01

The well known built-in voltage potential for some select semiconductor p-n junctions and various rectifying devices is proposed to be favorable for generating DC electricity at "zero bias" (with no DC bias voltage applied) in the presence of Johnson noise or 1/f noise which originates from the quantum vacuum (Koch et al., 1982). The 1982 Koch discovery that certain solid state devices exhibit measurable quantum noise has also recently been labeled a finding of dark energy in the lab (Beck and Mackey, 2004). Tunnel diodes are a class of rectifiers that are qualified and some have been credited with conducting only because of quantum fluctuations. Microwave diodes are also good choices since many are designed for zero bias operation. A completely passive, unamplified zero bias diode converter/detector for millimeter (GHz) waves was developed by HRL Labs in 2006 under a DARPA contract, utilizing a Sb-based "backward tunnel diode" (BTD). It is reported to be a "true zero-bias diode." It was developed for a "field radiometer" to "collect thermally radiated power" (in other words, 'night vision'). The diode array mounting allows a feed from horn antenna, which functions as a passive concentrating amplifier. An important clue is the "noise equivalent power" of 1.1 pW per root hertz and the "noise equivalent temperature difference" of 10° K, which indicate sensitivity to Johnson noise (Lynch, et al., 2006). There also have been other inventions such as "single electron transistors" that also have "the highest signal to noise ratio" near zero bias. Furthermore, "ultrasensitive" devices that convert radio frequencies have been invented that operate at outer space temperatures (3 degrees above zero point: 3° K). These devices are tiny nanotech devices which are suitable for assembly in parallel circuits (such as a 2-D array) to possibly produce zero point energy direct current electricity with significant power density (Brenning et al., 2006). Photovoltaic p-n junction cells are also considered for possible higher frequency ZPE transduction. Diode arrays of self-assembled molecular rectifiers or preferably, nano-sized cylindrical diodes are shown to reasonably provide for rectification of electron fluctuations from thermal and non-thermal ZPE sources to create an alternative energy DC electrical generator in the picowatt per diode range.

Zero-field magnetic response functions in Landau levels

PubMed Central

Gao, Yang; Niu, Qian

2017-01-01

We present a fresh perspective on the Landau level quantization rule; that is, by successively including zero-field magnetic response functions at zero temperature, such as zero-field magnetization and susceptibility, the Onsager’s rule can be corrected order by order. Such a perspective is further reinterpreted as a quantization of the semiclassical electron density in solids. Our theory not only reproduces Onsager’s rule at zeroth order and the Berry phase and magnetic moment correction at first order but also explains the nature of higher-order corrections in a universal way. In applications, those higher-order corrections are expected to curve the linear relation between the level index and the inverse of the magnetic field, as already observed in experiments. Our theory then provides a way to extract the correct value of Berry phase as well as the magnetic susceptibility at zero temperature from Landau level fan diagrams in experiments. Moreover, it can be used theoretically to calculate Landau levels up to second-order accuracy for realistic models. PMID:28655849

Theory of Raman scattering in coupled electron-phonon systems

NASA Astrophysics Data System (ADS)

Itai, K.

1992-01-01

The Raman spectrum is calculated for a coupled conduction-electron-phonon system in the zero-momentum-transfer limit. The Raman scattering is due to electron-hole excitations and phonons as well. The phonons of those branches that contribute to the electron self-energy and the correction of the electron-phonon vertex are assumed to have flat energy dispersion (the Einstein phonons). The effect of electron-impurity scattering is also incorporated. Both the electron-phonon interaction and the electron-impurity interaction cause the fluctuation of the electron distribution between different parts of the Fermi surface, which results in overdamped zero-sound modes of various symmetries. The scattering cross section is obtained by solving the Bethe-Salpeter equation. The spectrum shows a lower threshold at the smallest Einstein phonon energy when only the electron-phonon interaction is taken into consideration. When impurities are also taken into consideration, the threshold disappears.

On the zero-crossing of the three-gluon Green's function from lattice simulations

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

Athenodorou, Andreas; Boucaud, Philippe; de Soto, Feliciano

We report on some efforts recently made in order to gain a better understanding of some IR properties of the 3-point gluon Green’s function by exploiting results from large-volume quenched lattice simulations. These lattice results have been obtained by using both tree-level Symanzik and the standard Wilson action, in the aim of assessing the possible impact of effects presumably resulting from a particular choice for the discretization of the action. The main resulting feature is the existence of a negative log-aritmic divergence at zero-momentum, which pulls the 3-gluon form factors down at low momenta and, consequently, yields a zero-crossing atmore » a given deep IR momentum. The results can be correctly explained by analyzing the relevant Dyson-Schwinger equations and appropriate truncation schemes.« less

Topological order and memory time in marginally-self-correcting quantum memory

NASA Astrophysics Data System (ADS)

Siva, Karthik; Yoshida, Beni

2017-03-01

We examine two proposals for marginally-self-correcting quantum memory: the cubic code by Haah and the welded code by Michnicki. In particular, we prove explicitly that they are absent of topological order above zero temperature, as their Gibbs ensembles can be prepared via a short-depth quantum circuit from classical ensembles. Our proof technique naturally gives rise to the notion of free energy associated with excitations. Further, we develop a framework for an ergodic decomposition of Davies generators in CSS codes which enables formal reduction to simpler classical memory problems. We then show that memory time in the welded code is doubly exponential in inverse temperature via the Peierls argument. These results introduce further connections between thermal topological order and self-correction from the viewpoint of free energy and quantum circuit depth.

The Tip of the Red Giant Branch Distances to Type Ia Supernova Host Galaxies. IV. Color Dependence and Zero-point Calibration

NASA Astrophysics Data System (ADS)

Jang, In Sung; Lee, Myung Gyoon

2017-01-01

We present a revised Tip of the Red Giant Branch (TRGB) calibration, accurate to 2.7% of distance. A modified TRGB magnitude corrected for its color dependence, the QT magnitude, is introduced for better measurement of the TRGB. We determine the color-magnitude relation of the TRGB from photometry of deep images of HST/ACS fields around eight nearby galaxies. The zero-point of the TRGB at the fiducial metallicity ([Fe/H] = -1.6 ({(V-I)}0,{TRGB}=1.5)) is obtained from photometry of two distance anchors, NGC 4258 (M106) and the Large Magellanic Cloud (LMC), to which precise geometric distances are known: MQT,TRGB = -4.023 ± 0.073 mag from NGC 4258 and MQT,TRGB = -4.004 ± 0.096 mag from the LMC. A weighted mean of the two zero-points is MQT,TRGB = -4.016 ± 0.058 mag. Quoted uncertainty is ˜2× smaller than those of previous calibrations. We compare the empirical TRGB calibration derived in this study with theoretical stellar models, finding that there are significant discrepancies, especially for red color ({({{F}}606{{W}}-{{F}}814{{W}})}0≳ 2.5). We provide the revised TRGB calibration in several magnitude systems for future studies.

Empirically Calibrated Asteroseismic Masses and Radii for Red Giants in the Kepler Fields

NASA Astrophysics Data System (ADS)

Pinsonneault, Marc; Elsworth, Yvonne; Silva Aguirre, Victor; Chaplin, William J.; Garcia, Rafael A.; Hekker, Saskia; Holtzman, Jon; Huber, Daniel; Johnson, Jennifer; Kallinger, Thomas; Mosser, Benoit; Mathur, Savita; Serenelli, Aldo; Shetrone, Matthew; Stello, Dennis; Tayar, Jamie; Zinn, Joel; APOGEE Team, KASC Team, APOKASC Team

2018-01-01

We report on the joint asteroseismic and spectroscopic properties of a sample of 6048 evolved stars in the fields originally observed by the Kepler satellite. We use APOGEE spectroscopic data taken from Data Release 13 of the Sloan Digital Sky Survey, combined with asteroseismic data analyzed by members of the Kepler Asteroseismic Science Consortium. With high statistical significance, the different pipelines do not have relative zero points that are the same as the solar values, and red clump stars do not have the same empirical relative zero points as red giants. We employ theoretically motivated corrections to the scaling relation for the large frequency spacing, and adjust the zero point of the frequency of maximum power scaling relation to be consistent with masses and radii for members of star clusters. The scatter in calibrator masses is consistent with our error estimation. Systematic and random mass errors are explicitly separated and identified. The measurement scatter, and random uncertainties, are three times larger for red giants where one or more technique failed to return a value than for targets where all five methods could do so, and this is a substantial fraction of the sample (20% of red giants and 25% of red clump stars). Overall trends and future prospects are discussed.

A DFT study of permanganate oxidation of toluene and its ortho-nitroderivatives.

PubMed

Adamczyk, Paweł; Wijker, Reto S; Hofstetter, Thomas B; Paneth, Piotr

2014-02-01

Calculations of alternative oxidation pathways of toluene and its ortho-substituted nitro derivatives by permanganate anion have been performed. The competition between methyl group and ring oxidation has been addressed. Acceptable results have been obtained using IEFPCM/B3LYP/6-31+G(d,p) calculations with zero-point (ZPC) and thermal corrections, as validated by comparison with the experimental data. It has been shown that ring oxidation reactions proceed via relatively early transition states that become quite unsymmetrical for reactions involving ortho-nitrosubstituted derivatives. Transition states for the hydrogen atom abstraction reactions, on the other hand, are late. All favored reactions are characterized by the Gibbs free energy of activation, ΔG(≠), of about 25 kcal mol(-1). Methyl group oxidations are exothermic by about 20 kcal mol(-1) while ring oxidations are around thermoneutrality.

On the wall perturbation correction for a parallel-plate NACP-02 chamber in clinical electron beams.

PubMed

Zink, K; Wulff, J

2011-02-01

In recent years, several Monte Carlo studies have been published concerning the perturbation corrections of a parallel-plate chamber in clinical electron beams. In these studies, a strong depth dependence of the relevant correction factors (p(wall) and P(cav)) for depth beyond the reference depth is recognized and it has been shown that the variation with depth is sensitive to the choice of the chamber's effective point of measurement. Recommendations concerning the positioning of parallel-plate ionization chambers in clinical electron beams are not the same for all current dosimetry protocols. The IAEA TRS-398 as well as the IPEM protocol and the German protocol DIN 6800-2 interpret the depth of measurement within the phantom as the water equivalent depth, i.e., the nonwater equivalence of the entrance window has to be accounted for by shifting the chamber by an amount deltaz. This positioning should ensure that the primary electrons traveling from the surface of the water phantom through the entrance window to the chamber's reference point sustain the same energy loss as the primary electrons in the undisturbed phantom. The objective of the present study is the determination of the shift deltaz for a NACP-02 chamber and the calculation of the resulting wall perturbation correction as a function of depth. Moreover, the contributions of the different chamber walls to the wall perturbation correction are identified. The dose and fluence within the NACP-02 chamber and a wall-less air cavity is calculated using the Monte Carlo code EGSnrc in a water phantom at different depths for different clinical electron beams. In order to determine the necessary shift to account for the nonwater equivalence of the entrance window, the chamber is shifted in steps deltaz around the depth of measurement. The optimal shift deltaz is determined from a comparison of the spectral fluence within the chamber and the bare cavity. The wall perturbation correction is calculated as the ratio between doses for the complete chamber and a wall-less air cavity. The high energy part of the fluence spectra within the chamber strongly varies even with small chamber shifts, allowing the determination of deltaz within micrometers. For the NACP-02 chamber a shift deltaz = -0.058 cm results. This value is independent of the energy of the primary electrons as well as of the depth within the phantom and it is in good agreement with the value recommended in the German dosimetry protocol. Applying this shift, the calculated wall perturbation correction as a function of depth is varying less than 1% from zero up to the half value depth R50 for electron energies in the range of 6-21 MeV. The remaining depth dependence can mainly be attributed to the scatter properties of the entrance window. When neglecting the nonwater equivalence of the entrance window, the variation of p(wall) with depth is up to 10% and more, especially for low electron energies. The variation of the wall perturbation correction for the NACP-02 chamber in clinical electron beams strongly depends on the positioning of the chamber. Applying a shift deltaz = -0.058 cm toward the focus ensures that the primary electron spectrum within the chamber bears the largest resemblance to the fluence of a wall-less cavity. Hence, the influence of the chamber walls on the perturbation correction can be separated out and the residual variation of p(wall) with depth is minimized.

Water and energy link in the cities of the future - achieving net zero carbon and pollution emissions footprint.

PubMed

Novotny, V

2011-01-01

This article discusses the link between water conservation, reclamation, reuse and energy use as related to the goal of achieving the net zero carbon emission footprint in future sustainable cities. It defines sustainable ecocities and outlines quantitatively steps towards the reduction of energy use due to water and used water flows, management and limits in linear and closed loop water/stormwater/wastewater management systems. The three phase water energy nexus diagram may have a minimum inflection point beyond which reduction of water demand may not result in a reduction of energy and carbon emissions. Hence, water conservation is the best alternative solution to water shortages and minimizing the carbon footprint. A marginal water/energy chart is developed and proposed to assist planners in developing future ecocities and retrofitting older communities to achieve sustainability.

Pulsed, high-current, in-line reversal electron attachment detector

NASA Technical Reports Server (NTRS)

Bernius, Mark T.; Chutjian, Ara

1989-01-01

A new, pulsed, high-current, in-line reversal electron attachment ionizer/detector is described. The ionizer is capable of delivering a beam of electrons into an electrostatic mirror field to form a planar wall of electrons having zero kinetic energy. Electron attachment to a molecular target at the reversal point produces either parent or fragment negative ions through a zero-energy (s-wave) state. The atomic or molecular ion is pulsed out of the attachment region approximately 2 microsec after the electrons are pulsed off, and focused onto the entrance plane of a quadrupole mass analyzer. The sensitivity of the apparatus is preliminarily assessed, and its higher-energy behavior with regard to molecular attachment and ionization is described.

Atomistic properties of γ uranium.

PubMed

Beeler, Benjamin; Deo, Chaitanya; Baskes, Michael; Okuniewski, Maria

2012-02-22

The properties of the body-centered cubic γ phase of uranium (U) are calculated using atomistic simulations. First, a modified embedded-atom method interatomic potential is developed for the high temperature body-centered cubic (γ) phase of U. This phase is stable only at high temperatures and is thus relatively inaccessible to first principles calculations and room temperature experiments. Using this potential, equilibrium volume and elastic constants are calculated at 0 K and found to be in close agreement with previous first principles calculations. Further, the melting point, heat capacity, enthalpy of fusion, thermal expansion and volume change upon melting are calculated and found to be in reasonable agreement with experiment. The low temperature mechanical instability of γ U is correctly predicted and investigated as a function of pressure. The mechanical instability is suppressed at pressures greater than 17.2 GPa. The vacancy formation energy is analyzed as a function of pressure and shows a linear trend, allowing for the calculation of the extrapolated zero pressure vacancy formation energy. Finally, the self-defect formation energy is analyzed as a function of temperature. This is the first atomistic calculation of γ U properties above 0 K with interatomic potentials.

Atomistic properties of γ uranium

NASA Astrophysics Data System (ADS)

Beeler, Benjamin; Deo, Chaitanya; Baskes, Michael; Okuniewski, Maria

2012-02-01

The properties of the body-centered cubic γ phase of uranium (U) are calculated using atomistic simulations. First, a modified embedded-atom method interatomic potential is developed for the high temperature body-centered cubic (γ) phase of U. This phase is stable only at high temperatures and is thus relatively inaccessible to first principles calculations and room temperature experiments. Using this potential, equilibrium volume and elastic constants are calculated at 0 K and found to be in close agreement with previous first principles calculations. Further, the melting point, heat capacity, enthalpy of fusion, thermal expansion and volume change upon melting are calculated and found to be in reasonable agreement with experiment. The low temperature mechanical instability of γ U is correctly predicted and investigated as a function of pressure. The mechanical instability is suppressed at pressures greater than 17.2 GPa. The vacancy formation energy is analyzed as a function of pressure and shows a linear trend, allowing for the calculation of the extrapolated zero pressure vacancy formation energy. Finally, the self-defect formation energy is analyzed as a function of temperature. This is the first atomistic calculation of γ U properties above 0 K with interatomic potentials.

Breakdown of the Migdal approximation at Lifshitz transitions with giant zero-point motion in the H3S superconductor.

PubMed

Jarlborg, Thomas; Bianconi, Antonio

2016-04-20

While 203 K high temperature superconductivity in H3S has been interpreted by BCS theory in the dirty limit here we focus on the effects of hydrogen zero-point-motion and the multiband electronic structure relevant for multigap superconductivity near Lifshitz transitions. We describe how the topology of the Fermi surfaces evolves with pressure giving different Lifshitz-transitions. A neck-disrupting Lifshitz-transition (type 2) occurs where the van Hove singularity, vHs, crosses the chemical potential at 210 GPa and new small 2D Fermi surface portions appear with slow Fermi velocity where the Migdal-approximation becomes questionable. We show that the neglected hydrogen zero-point motion ZPM, plays a key role at Lifshitz transitions. It induces an energy shift of about 600 meV of the vHs. The other Lifshitz-transition (of type 1) for the appearing of a new Fermi surface occurs at 130 GPa where new Fermi surfaces appear at the Γ point of the Brillouin zone here the Migdal-approximation breaks down and the zero-point-motion induces large fluctuations. The maximum Tc = 203 K occurs at 160 GPa where EF/ω0 = 1 in the small Fermi surface pocket at Γ. A Feshbach-like resonance between a possible BEC-BCS condensate at Γ and the BCS condensate in different k-space spots is proposed.

Negative-ion formation in the explosives RDX, PETN, and TNT by using the reversal electron attachment detection technique

NASA Technical Reports Server (NTRS)

Boumsellek, S.; Alajajian, S. H.; Chutjian, A.

1992-01-01

First results of a beam-beam, single-collision study of negative-ion mass spectra produced by attachment of zero-energy electrons to the molecules of the explosives RDX, PETN, and TNT are presented. The technique used is reversal electron attachment detection (READ) wherein the zero-energy electrons are produced by focusing an intense electron beam into a shaped electrostatic field which reverses the trajectory of electrons. The target beam is introduced at the reversal point, and attachment occurs because the electrons have essentially zero longitudinal and radial velocity. The READ technique is used to obtain the 'signature' of molecular ion formation and/or fragmentation for each explosive. Present data are compared with results from atmospheric-pressure ionization and negative-ion chemical ionization methods.

Fragile surface zero-energy flat bands in three-dimensional chiral superconductors

NASA Astrophysics Data System (ADS)

Kobayashi, Shingo; Tanaka, Yukio; Sato, Masatoshi

2015-12-01

We study surface zero-energy flat bands in three-dimensional chiral superconductors with pz(px+i py) ν -wave pairing symmetry (ν is a nonzero integer), based on topological arguments and tunneling conductance. It is shown that the surface flat bands are fragile against (i) the surface misorientation and (ii) the surface Rashba spin-orbit interaction. The fragility of (i) is specific to chiral SCs, whereas that of (ii) happens for general odd-parity SCs. We demonstrate that these flat-band instabilities vanish or suppress a zero-bias conductance peak in a normal/insulator/superconductor junction, which behavior is clearly different from high-Tc cuprates and noncentrosymmetric superconductors. By calculating the angle-resolved conductance, we also discuss a topological surface state associated with the coexistence of line and point nodes.

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

NASA Astrophysics Data System (ADS)

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

1984-08-01

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

Gas phase hydrolysis of formaldehyde to form methanediol: impact of formic acid catalysis.

PubMed

Hazra, Montu K; Francisco, Joseph S; Sinha, Amitabha

2013-11-21

We find that formic acid (FA) is very effective at facilitating diol formation through its ability to reduce the barrier for the formaldehyde (HCHO) hydrolysis reaction. The rate limiting step in the mechanism involves the isomerization of a prereactive collision complex formed through either the HCHO···H2O + FA and/or HCHO + FA···H2O pathways. The present study finds that the effective barrier height, defined as the difference between the zero-point vibrational energy (ZPE) corrected energy of the transition state (TS) and the HCHO···H2O + FA and HCHO + FA···H2O starting reagents, are respectively only ∼1 and ∼4 kcal/mol. These barriers are substantially lower than the ∼17 kcal/mol barrier associated with the corresponding step in the hydrolysis of HCHO catalyzed by a single water molecule (HCHO + H2O + H2O). The significantly lower barrier heights for the formic acid catalyzed pathway reveal a new important role that organic acids play in the gas phase hydrolysis of atmospheric carbonyl compounds.

Mesoscopic structure formation in condensed matter due to vacuum fluctuations

NASA Astrophysics Data System (ADS)

Sen, Siddhartha; Gupta, Kumar S.; Coey, J. M. D.

2015-10-01

An observable influence of zero-point fluctuations of the vacuum electromagnetic field on bound electrons is well known in the hydrogen atom, where it produces the Lamb shift. Here, we adapt an approach used to explain the Lamb shift in terms of a slight expansion of the orbits due to interaction with the zero-point field and apply it to assemblies of N electrons that are modeled as independent atomically bound two-level systems. The effect is to stabilize a collective ground-state energy, which leads to a prediction of novel effects at room temperature for quasi-two-dimensional systems over a range of parameters in the model, namely, N , the two-level excitation energy ℏ ω and the ionization energy ℏ ω +ɛ . Some mesoscopic systems where these effects may be observable include water sheaths on protein or DNA, surfaces of gaseous nanobubbles, and the magnetic response of inhomogeneous, electronically dilute oxides. No such effects are envisaged for uniform three-dimensional systems.

Optimized point dose measurement for monitor unit verification in intensity modulated radiation therapy using 6 MV photons by three different methodologies with different detector-phantom combinations: A comparative study

PubMed Central

Sarkar, Biplab; Ghosh, Bhaswar; Sriramprasath; Mahendramohan, Sukumaran; Basu, Ayan; Goswami, Jyotirup; Ray, Amitabh

2010-01-01

The study was aimed to compare accuracy of monitor unit verification in intensity modulated radiation therapy (IMRT) using 6 MV photons by three different methodologies with different detector phantom combinations. Sixty patients were randomly chosen. Zero degree couch and gantry angle plans were generated in a plastic universal IMRT verification phantom and 30×30×30 cc water phantom and measured using 0.125 cc and 0.6 cc chambers, respectively. Actual gantry and couch angle plans were also measured in water phantom using 0.6 cc chamber. A suitable point of measurement was chosen from the beam profile for each field. When the zero-degree gantry, couch angle plans and actual gantry, couch angle plans were measured by 0.6 cc chamber in water phantom, the percentage mean difference (MD) was 1.35%, 2.94 % and Standard Deviation (SD) was 2.99%, 5.22%, respectively. The plastic phantom measurements with 0.125 cc chamber Semiflex ionisation chamber (SIC) showed an MD=4.21% and SD=2.73 %, but when corrected for chamber-medium response, they showed an improvement, with MD=3.38 % and SD=2.59 %. It was found that measurements with water phantom and 0.6cc chamber at gantry angle zero degree showed better conformity than other measurements of medium-detector combinations. Correction in plastic phantom measurement improved the result only marginally, and actual gantry angle measurement in a flat- water phantom showed higher deviation. PMID:20927221

Computational Chemistry Modeling of the Atmospheric Fate of Toxic Industrial Compounds (TICs)

DTIC Science & Technology

2007-06-01

1+G(3df,2p) number of atoms and number of basis functions) of the (LRG) compounds under study precludes the use of coupled 0 Zero Point Energy ( ZPE ...overlap (NDDO) The extrapolated energy = E(QCI) + E(LRG) - Hamiltonian that is reparameterized to accurately E(SML) + ZPE reproduce coupled cluster

An ab initio potential energy surface for the formic acid dimer: zero-point energy, selected anharmonic fundamental energies, and ground-state tunneling splitting calculated in relaxed 1-4-mode subspaces.

PubMed

Qu, Chen; Bowman, Joel M

2016-09-14

We report a full-dimensional, permutationally invariant potential energy surface (PES) for the cyclic formic acid dimer. This PES is a least-squares fit to 13475 CCSD(T)-F12a/haTZ (VTZ for H and aVTZ for C and O) energies. The energy-weighted, root-mean-square fitting error is 11 cm -1 and the barrier for the double-proton transfer on the PES is 2848 cm -1 , in good agreement with the directly-calculated ab initio value of 2853 cm -1 . The zero-point vibrational energy of 15 337 ± 7 cm -1 is obtained from diffusion Monte Carlo calculations. Energies of fundamentals of fifteen modes are calculated using the vibrational self-consistent field and virtual-state configuration interaction method. The ground-state tunneling splitting is computed using a reduced-dimensional Hamiltonian with relaxed potentials. The highest-level, four-mode coupled calculation gives a tunneling splitting of 0.037 cm -1 , which is roughly twice the experimental value. The tunneling splittings of (DCOOH) 2 and (DCOOD) 2 from one to three mode calculations are, as expected, smaller than that for (HCOOH) 2 and consistent with experiment.

Structure, stability, thermodynamic properties, and IR spectra of the protonated water decamer H+(H2O)10.

PubMed

Karthikeyan, S; Kim, Kwang S

2009-08-13

Protonated water clusters H+(H2O)n favor two-dimensional (2D) structures for n < or = 7 at low temperatures. At 0 K, the 2D and three-dimensional (3D) structures for n = 8 are almost isoenergetic, and the 3D structures for n > 9 tend to be more stable. However, for n = 9, the netlike structures are likely to be more stable above 150 K. In this regard, we investigate the case of n = 10 to find which structure is more stable between the 3D structure and the netlike structure around 150 and 250 K. We use density functional theory, Møller-Plesset second-order perturbation theory, and coupled cluster theory with single, double, and perturbative triple excitations (CCSD(T)). At the complete basis set limit for the CCSD(T) level of theory, three isomers of 3D cage structure are much more stable in zero point energy corrected binding energy and in free binding energies at 150 K than the lowest energy netlike structures, while the netlike structure would be more stable around approximately 250 K. The predicted vibrational spectra are in good agreement with the experiment. One of the three isomers explains the experimental IR observation of an acceptor (A) type peak of a dangling hydrogen atom.

Solution and diffusion of hydrogen isotopes in tungsten-rhenium alloy

NASA Astrophysics Data System (ADS)

Ren, Fei; Yin, Wen; Yu, Quanzhi; Jia, Xuejun; Zhao, Zongfang; Wang, Baotian

2017-08-01

Rhenium is one of the main transmutation elements forming in tungsten under neutron irradiation. Therefore, it is essential to understand the influence of rhenium impurity on hydrogen isotopes retention in tungsten. First-principle calculations were used to study the properties of hydrogen solution and diffusion in perfect tungsten-rhenium lattice. The interstitial hydrogen still prefers the tetrahedral site in presence of rhenium, and rhenium atom cannot act directly as a trapping site of hydrogen. The presence of rhenium in tungsten raises the solution energy and the real normal modes of vibration on the ground state and the transition state, compared to hydrogen in pure tungsten. Without zero point energy corrections, the presence of rhenium decreases slightly the migration barrier. It is found that although the solution energy would tend to increase slightly with the rising of the concentration of rhenium, but which does not influence noticeably the solution energy of hydrogen in tungsten-rhenium alloy. The solubility and diffusion coefficient of hydrogen in perfect tungsten and tungsten-rhenium alloy have been estimated, according to Sievert's law and harmonic transition state theory. The results show the solubility of hydrogen in tungsten agrees well the experimental data, and the presence of Re would decrease the solubility and increase the diffusivity for the perfect crystals.

Observable consequences of zero-point energy

NASA Astrophysics Data System (ADS)

Sen, Siddhartha; Gupta, Kumar S.

2017-12-01

Spectral line widths, the Lamb shift and the Casimir effect are generally accepted to be observable consequences of the zero-point electromagnetic (ZPEM) fields. A new class of observable consequences of ZPEM field at the mesoscopic scale were recently proposed and observed. Here, we extend this class of observable effects and predict that mesoscopic water layers should have a high value for its solid-liquid phase transition temperature, as illustrated by water inside a single-walled carbon nanotube (CNT). For this case, our analysis predicts that the phase transition temperature scales inversely with the square of the effective radius available for the water flow within the CNT.

Microscopic description of fission in odd-mass uranium and plutonium nuclei with the Gogny energy density functional

NASA Astrophysics Data System (ADS)

Rodrıguez-Guzmán, R.; Robledo, L. M.

2017-12-01

The parametrization D1M of the Gogny energy density functional is used to study fission in the odd-mass Uranium and Plutonium isotopes with A=233, \\ldots , 249 within the framework of the Hartree-Fock-Bogoliubov (HFB) Equal Filling Approximation (EFA). Ground state quantum numbers and deformations, pairing energies, one-neutron separation energies, barrier heights and fission isomer excitation energies are given. Fission paths, collective masses and zero point rotational and vibrational quantum corrections are used to compute the systematic of the spontaneous fission half-lives t_{SF}, the masses and charges of the fission fragments as well as their intrinsic shapes. Although there exits a strong variance of the predicted fission rates with respect to the details involved in their computation, it is shown that both the specialization energy and the pairing quenching effects, taken into account fully variationally within the HFB-EFA blocking scheme, lead to larger spontaneous fission half-lives in odd-mass U and Pu nuclei as compared with the corresponding even-even neighbors. It is shown that modifications of a few percent in the strengths of the neutron and proton pairing fields can have a significant impact on the collective masses leading to uncertainties of several orders of magnitude in the predicted t_{SF} values. Alpha-decay lifetimes have also been computed using a parametrization of the Viola-Seaborg formula.

Radiative corrections to the quark masses in the ferromagnetic Ising and Potts field theories

NASA Astrophysics Data System (ADS)

Rutkevich, Sergei B.

2017-10-01

We consider the Ising Field Theory (IFT), and the 3-state Potts Field Theory (PFT), which describe the scaling limits of the two-dimensional lattice q-state Potts model with q = 2, and q = 3, respectively. At zero magnetic field h = 0, both field theories are integrable away from the critical point, have q degenerate vacua in the ferromagnetic phase, and q (q - 1) particles of the same mass - the kinks interpolating between two different vacua. Application of a weak magnetic field induces confinement of kinks into bound states - the "mesons" (for q = 2 , 3) consisting predominantly of two kinks, and "baryons" (for q = 3), which are essentially the three-kink excitations. The kinks in the confinement regime are also called "the quarks". We review and refine the Form Factor Perturbation Theory (FFPT), adapting it to the analysis of the confinement problem in the limit of small h, and apply it to calculate the corrections to the kink (quark) masses induced by the multi-kink fluctuations caused by the weak magnetic field. It is shown that the subleading third-order ∼h3 correction to the kink mass vanishes in the IFT. The leading second order ∼h2 correction to the kink mass in the 3-state PFT is estimated by truncation the infinite form factor expansion at the first term representing contribution of the two-kink fluctuations into the kink self-energy.

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

NASA Technical Reports Server (NTRS)

Woon, D. E.

1996-01-01

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

Proton affinity and enthalpy of formation of formaldehyde

NASA Astrophysics Data System (ADS)

Czakó, Gábor; Nagy, Balázs; Tasi, Gyula; Somogyi, Árpád; Šimunek, Ján; Noga, Jozef; Braams, Bastiaan J.; Bowman, Joel M.; Császár; , Attila G.

The proton affinity and the enthalpy of formation of the prototypical carbonyl, formaldehyde, have been determined by the first-principles composite focal-point analysis (FPA) approach. The electronic structure computations employed the all-electron coupled-cluster method with up to single, double, triple, quadruple, and even pentuple excitations. In these computations the aug-cc-p(C)VXZ [X = 2(D), 3(T), 4(Q), 5, and 6] correlation-consistent Gaussian basis sets for C and O were used in conjunction with the corresponding aug-cc-pVXZ (X = 2-6) sets for H. The basis set limit values have been confirmed via explicitly correlated computations. Our FPA study supersedes previous computational work for the proton affinity and to some extent the enthalpy of formation of formaldehyde by accounting for (a) electron correlation beyond the "gold standard" CCSD(T) level; (b) the non-additivity of core electron correlation effects; (c) scalar relativity; (d) diagonal Born-Oppenheimer corrections computed at a correlated level; (e) anharmonicity of zero-point vibrational energies, based on global potential energy surfaces and variational vibrational computations; and (f) thermal corrections to enthalpies by direct summation over rovibrational energy levels. Our final proton affinities at 298.15 (0.0) K are ΔpaHo (H2CO) = 711.02 (704.98) ± 0.39 kJ mol-1. Our final enthalpies of formation at 298.15 (0.0) K are ΔfHo (H2CO) = -109.23 (-105.42) ± 0.33 kJ mol-1. The latter values are based on the enthalpy of the H2 + CO → H2CO reaction but supported by two further reaction schemes, H2O + C → H2CO and 2H + C + O → H2CO. These values, especially ΔpaHo (H2CO), have better accuracy and considerably lower uncertainty than the best previous recommendations and thus should be employed in future studies.

New mechanism for autocatalytic decomposition of H2CO3 in the vapor phase.

PubMed

Ghoshal, Sourav; Hazra, Montu K

2014-04-03

In this article, we present high level ab initio calculations investigating the energetics of a new autocatalytic decomposition mechanism for carbonic acid (H2CO3) in the vapor phase. The calculation have been performed at the MP2 level of theory in conjunction with aug-cc-pVDZ, aug-cc-pVTZ, and 6-311++G(3df,3pd) basis sets as well as at the CCSD(T)/aug-cc-pVTZ level. The present study suggests that this new decomposition mechanism is effectively a near-barrierless process at room temperature and makes vapor phase of H2CO3 unstable even in the absence of water molecules. Our calculation at the MP2/aug-cc-pVTZ level predicts that the effective barrier, defined as the difference between the zero-point vibrational energy (ZPE) corrected energy of the transition state and the total energy of the isolated starting reactants in terms of bimolecular encounters, is nearly zero for the autocatalytic decomposition mechanism. The results at the CCSD(T)/aug-cc-pVTZ level of calculations suggest that the effective barrier, as defined above, is sensitive to some extent to the levels of calculations used, nevertheless, we find that the effective barrier height predicted at the CCSD(T)/aug-cc-pVTZ level is very small or in other words the autocatalytic decomposition mechanism presented in this work is a near-barrierless process as mentioned above. Thus, we suggest that this new autocatalytic decomposition mechanism has to be considered as the primary mechanism for the decomposition of carbonic acid, especially at its source, where the vapor phase concentration of H2CO3 molecules reaches its highest levels.

Method and apparatus for digitally based high speed x-ray spectrometer for direct coupled use with continuous discharge preamplifiers

DOEpatents

Warburton, W.K.

1998-06-30

A high speed, digitally based, signal processing system is disclosed which accepts directly coupled input data from a detector with a continuous discharge type preamplifier and produces a spectral analysis of the x-rays illuminating the detector. The system`s principal elements are an analog signal conditioning section, a combinatorial logic section which implements digital triangular filtering and pileup inspection, and a microprocessor which accepts values captured by the logic section and uses them to compute x-ray energy values. Operating without pole-zero correction, the system achieves high resolution by capturing, in conjunction with each peak value from the digital filter, an associated value of the unfiltered signal, and using this latter signal to correct the former for errors which arise from its local slope terms. This correction greatly reduces both energy resolution degradation and peak centroid shifting in the output spectrum as a function of input count rate. When the noise of this correction is excessive, a modification allows two filtered averages of the signal to be captured and a corrected peak amplitude computed therefrom. 14 figs.

Method and apparatus for digitally based high speed x-ray spectrometer for direct coupled use with continuous discharge preamplifiers

DOEpatents

Warburton, William K.

1998-01-01

A high speed, digitally based, signal processing system which accepts directly coupled input data from a detector with a continuous discharge type preamplifier and produces a spectral analysis of the x-rays illuminating the detector. The system's principal elements are an analog signal conditioning section, a combinatorial logic section which implements digital triangular filtering and pileup inspection, and a microprocessor which accepts values captured by the logic section and uses them to compute x-ray energy values. Operating without pole-zero correction, the system achieves high resolution by capturing, in conjunction with each peak value from the digital filter, an associated value of the unfiltered signal, and using this latter signal to correct the former for errors which arise from its local slope terms. This correction greatly reduces both energy resolution degradation and peak centroid shifting in the output spectrum as a function of input count rate. When the noise of this correction is excessive, a modification allows two filtered averages of the signal to be captured and a corrected peak amplitude computed therefrom.

Zero-point energy effects in anion solvation shells.

PubMed

Habershon, Scott

2014-05-21

By comparing classical and quantum-mechanical (path-integral-based) molecular simulations of solvated halide anions X(-) [X = F, Cl, Br and I], we identify an ion-specific quantum contribution to anion-water hydrogen-bond dynamics; this effect has not been identified in previous simulation studies. For anions such as fluoride, which strongly bind water molecules in the first solvation shell, quantum simulations exhibit hydrogen-bond dynamics nearly 40% faster than the corresponding classical results, whereas those anions which form a weakly bound solvation shell, such as iodide, exhibit a quantum effect of around 10%. This observation can be rationalized by considering the different zero-point energy (ZPE) of the water vibrational modes in the first solvation shell; for strongly binding anions, the ZPE of bound water molecules is larger, giving rise to faster dynamics in quantum simulations. These results are consistent with experimental investigations of anion-bound water vibrational and reorientational motion.

Geometric constraints in semiclassical initial value representation calculations in Cartesian coordinates: accurate reduction in zero-point energy.

PubMed

Issack, Bilkiss B; Roy, Pierre-Nicholas

2005-08-22

An approach for the inclusion of geometric constraints in semiclassical initial value representation calculations is introduced. An important aspect of the approach is that Cartesian coordinates are used throughout. We devised an algorithm for the constrained sampling of initial conditions through the use of multivariate Gaussian distribution based on a projected Hessian. We also propose an approach for the constrained evaluation of the so-called Herman-Kluk prefactor in its exact log-derivative form. Sample calculations are performed for free and constrained rare-gas trimers. The results show that the proposed approach provides an accurate evaluation of the reduction in zero-point energy. Exact basis set calculations are used to assess the accuracy of the semiclassical results. Since Cartesian coordinates are used, the approach is general and applicable to a variety of molecular and atomic systems.

Impurity bound states in mesoscopic topological superconducting loops

NASA Astrophysics Data System (ADS)

Jin, Yan-Yan; Zha, Guo-Qiao; Zhou, Shi-Ping

2018-06-01

We study numerically the effect induced by magnetic impurities in topological s-wave superconducting loops with spin-orbit interaction based on spin-generalized Bogoliubov-de Gennes equations. In the case of a single magnetic impurity, it is found that the midgap bound states can cross the Fermi level at an appropriate impurity strength and the circulating spin current jumps at the crossing point. The evolution of the zero-energy mode can be effectively tuned by the located site of a single magnetic impurity. For the effect of many magnetic impurities, two independent midway or edge impurities cannot lead to the overlap of zero modes. The multiple zero-energy modes can be effectively realized by embedding a single Josephson junction with impurity scattering into the system, and the spin current displays oscillatory feature with increasing the layer thickness.

40 CFR 86.1333 - Transient test cycle generation.

Code of Federal Regulations, 2014 CFR

2014-07-01

... zero percent speeds, zero percent torque points, but may be engaged up to two points preceding a non-zero point, and may be engaged for time segments with zero percent speed and torque points of durations...

Quantum effects and anharmonicity in the H2-Li+-benzene complex: A model for hydrogen storage materials

NASA Astrophysics Data System (ADS)

Kolmann, Stephen J.; D'Arcy, Jordan H.; Jordan, Meredith J. T.

2013-12-01

Quantum and anharmonic effects are investigated in H2-Li+-benzene, a model for hydrogen adsorption in metal-organic frameworks and carbon-based materials. Three- and 8-dimensional quantum diffusion Monte Carlo (QDMC) and rigid-body diffusion Monte Carlo (RBDMC) simulations are performed on potential energy surfaces interpolated from electronic structure calculations at the M05-2X/6-31+G(d,p) and M05-2X/6-311+G(2df,p) levels of theory using a three-dimensional spline or a modified Shepard interpolation. These calculations investigate the intermolecular interactions in this system, with three- and 8-dimensional 0 K H2 binding enthalpy estimates, ΔHbind (0 K), being 16.5 kJ mol-1 and 12.4 kJ mol-1, respectively: 0.1 and 0.6 kJ mol-1 higher than harmonic values. Zero-point energy effects are 35% of the value of ΔHbind (0 K) at M05-2X/6-311+G(2df,p) and cannot be neglected; uncorrected electronic binding energies overestimate ΔHbind (0 K) by at least 6 kJ mol-1. Harmonic intermolecular binding enthalpies can be corrected by treating the H2 "helicopter" and "ferris wheel" rotations as free and hindered rotations, respectively. These simple corrections yield results within 2% of the 8-dimensional anharmonic calculations. Nuclear ground state probability density histograms obtained from the QDMC and RBDMC simulations indicate the H2 molecule is delocalized above the Li+-benzene system at 0 K.

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

Kolmann, Stephen J.; D'Arcy, Jordan H.; Jordan, Meredith J. T., E-mail: m.jordan@chem.usyd.edu.au

Quantum and anharmonic effects are investigated in H{sub 2}-Li{sup +}-benzene, a model for hydrogen adsorption in metal-organic frameworks and carbon-based materials. Three- and 8-dimensional quantum diffusion Monte Carlo (QDMC) and rigid-body diffusion Monte Carlo (RBDMC) simulations are performed on potential energy surfaces interpolated from electronic structure calculations at the M05-2X/6-31+G(d,p) and M05-2X/6-311+G(2df,p) levels of theory using a three-dimensional spline or a modified Shepard interpolation. These calculations investigate the intermolecular interactions in this system, with three- and 8-dimensional 0 K H{sub 2} binding enthalpy estimates, ΔH{sub bind} (0 K), being 16.5 kJ mol{sup −1} and 12.4 kJ mol{sup −1}, respectively: 0.1 and 0.6more » kJ mol{sup −1} higher than harmonic values. Zero-point energy effects are 35% of the value of ΔH{sub bind} (0 K) at M05-2X/6-311+G(2df,p) and cannot be neglected; uncorrected electronic binding energies overestimate ΔH{sub bind} (0 K) by at least 6 kJ mol{sup −1}. Harmonic intermolecular binding enthalpies can be corrected by treating the H{sub 2} “helicopter” and “ferris wheel” rotations as free and hindered rotations, respectively. These simple corrections yield results within 2% of the 8-dimensional anharmonic calculations. Nuclear ground state probability density histograms obtained from the QDMC and RBDMC simulations indicate the H{sub 2} molecule is delocalized above the Li{sup +}-benzene system at 0 K.« less

Dynamical approach to the cosmological constant.

PubMed

Mukohyama, Shinji; Randall, Lisa

2004-05-28

We consider a dynamical approach to the cosmological constant. There is a scalar field with a potential whose minimum occurs at a generic, but negative, value for the vacuum energy, and it has a nonstandard kinetic term whose coefficient diverges at zero curvature as well as the standard kinetic term. Because of the divergent coefficient of the kinetic term, the lowest energy state is never achieved. Instead, the cosmological constant automatically stalls at or near zero. The merit of this model is that it is stable under radiative corrections and leads to stable dynamics, despite the singular kinetic term. The model is not complete, however, in that some reheating is required. Nonetheless, our approach can at the very least reduce fine-tuning by 60 orders of magnitude or provide a new mechanism for sampling possible cosmological constants and implementing the anthropic principle.

Comment on "How the huge energy of quantum vacuum gravitates to drive the slow accelerating expansion of the Universe"

NASA Astrophysics Data System (ADS)

Mazzitelli, Francisco D.; Trombetta, Leonardo G.

2018-03-01

In a recent paper [Q. Wang, Z. Zhu, and W. G. Unruh, Phys. Rev. D 95, 103504 (2017), 10.1103/PhysRevD.95.103504] it was argued that, due to the fluctuations around its mean value, vacuum energy gravitates differently from what was previously assumed. As a consequence, the Universe would accelerate with a small Hubble expansion rate, solving the cosmological constant and dark energy problems. We point out here that the results depend on the type of cutoff used to evaluate the vacuum energy. In particular, they are not valid when one uses a covariant cutoff such that the zero-point energy density is positive definite.

Explicit hydration of ammonium ion by correlated methods employing molecular tailoring approach

NASA Astrophysics Data System (ADS)

Singh, Gurmeet; Verma, Rahul; Wagle, Swapnil; Gadre, Shridhar R.

2017-11-01

Explicit hydration studies of ions require accurate estimation of interaction energies. This work explores the explicit hydration of the ammonium ion (NH4+) employing Møller-Plesset second order (MP2) perturbation theory, an accurate yet relatively less expensive correlated method. Several initial geometries of NH4+(H2O)n (n = 4 to 13) clusters are subjected to MP2 level geometry optimisation with correlation consistent aug-cc-pVDZ (aVDZ) basis set. For large clusters (viz. n > 8), molecular tailoring approach (MTA) is used for single point energy evaluation at MP2/aVTZ level for the estimation of MP2 level binding energies (BEs) at complete basis set (CBS) limit. The minimal nature of the clusters upto n ≤ 8 is confirmed by performing vibrational frequency calculations at MP2/aVDZ level of theory, whereas for larger clusters (9 ≤ n ≤ 13) such calculations are effected via grafted MTA (GMTA) method. The zero point energy (ZPE) corrections are done for all the isomers lying within 1 kcal/mol of the lowest energy one. The resulting frequencies in N-H region (2900-3500 cm-1) and in O-H stretching region (3300-3900 cm-1) are in found to be in excellent agreement with the available experimental findings for 4 ≤ n ≤ 13. Furthermore, GMTA is also applied for calculating the BEs of these clusters at coupled cluster singles and doubles with perturbative triples (CCSD(T)) level of theory with aVDZ basis set. This work thus represents an art of the possible on contemporary multi-core computers for studying explicit molecular hydration at correlated level theories.

In Silico Prediction of Cytochrome P450-Mediated Biotransformations of Xenobiotics: A Case Study of Epoxidation.

PubMed

Zhang, Jing; Ji, Li; Liu, Weiping

2015-08-17

Predicting the biotransformation of xenobiotics is important in toxicology; however, as more compounds are synthesized than can be investigated experimentally, powerful computational methods are urgently needed to prescreen potentially useful candidates. Cytochrome P450 enzymes (P450s) are the major enzymes involved in xenobiotic metabolism, and many substances are bioactivated by P450s to form active compounds. An example is the conversion of olefinic substrates to epoxides, which are intermediates in the metabolic activation of many known or suspected carcinogens. We have calculated the activation energies for epoxidation by the active species of P450 enzymes (an iron-oxo porphyrin cation radical oxidant, compound I) for a diverse set of 36 olefinic substrates with state-of-the-art density functional theory (DFT) methods. Activation energies can be estimated by the computationally less demanding method of calculating the ionization potentials of the substrates, which provides a useful and simple predictive model based on the reaction mechanism; however, the preclassification of these diverse substrates into weakly polar and strongly polar groups is a prerequisite for the construction of specific predictive models with good predictability for P450 epoxidation. This approach has been supported by both internal and external validations. Furthermore, the relation between the activation energies for the regioselective epoxidation and hydroxylation reactions of P450s and experimental data has been investigated. The results show that the computational method used in this work, single-point energy calculations with the B3LYP functional including zero-point energy and solvation and dispersion corrections based on B3LYP-optimized geometries, performs well in reproducing the experimental trends of the epoxidation and hydroxylation reactions.

Towards zero-power ICT.

PubMed

Gammaitoni, Luca; Chiuchiú, D; Madami, M; Carlotti, G

2015-06-05

Is it possible to operate a computing device with zero energy expenditure? This question, once considered just an academic dilemma, has recently become strategic for the future of information and communication technology. In fact, in the last forty years the semiconductor industry has been driven by its ability to scale down the size of the complementary metal-oxide semiconductor-field-effect transistor, the building block of present computing devices, and to increase computing capability density up to a point where the power dissipated in heat during computation has become a serious limitation. To overcome such a limitation, since 2004 the Nanoelectronics Research Initiative has launched a grand challenge to address the fundamental limits of the physics of switches. In Europe, the European Commission has recently funded a set of projects with the aim of minimizing the energy consumption of computing. In this article we briefly review state-of-the-art zero-power computing, with special attention paid to the aspects of energy dissipation at the micro- and nanoscales.

Towards zero-power ICT

NASA Astrophysics Data System (ADS)

Gammaitoni, Luca; Chiuchiú, D.; Madami, M.; Carlotti, G.

2015-06-01

Is it possible to operate a computing device with zero energy expenditure? This question, once considered just an academic dilemma, has recently become strategic for the future of information and communication technology. In fact, in the last forty years the semiconductor industry has been driven by its ability to scale down the size of the complementary metal-oxide semiconductor-field-effect transistor, the building block of present computing devices, and to increase computing capability density up to a point where the power dissipated in heat during computation has become a serious limitation. To overcome such a limitation, since 2004 the Nanoelectronics Research Initiative has launched a grand challenge to address the fundamental limits of the physics of switches. In Europe, the European Commission has recently funded a set of projects with the aim of minimizing the energy consumption of computing. In this article we briefly review state-of-the-art zero-power computing, with special attention paid to the aspects of energy dissipation at the micro- and nanoscales.

Incorporating nuclear vibrational energies into the "atom in molecules" analysis: An analytical study

NASA Astrophysics Data System (ADS)

Gharabaghi, Masumeh; Shahbazian, Shant

2017-04-01

The quantum theory of atoms in molecules (QTAIM) is based on the clamped nucleus paradigm and solely working with the electronic wavefunctions, so does not include nuclear vibrations in the AIM analysis. On the other hand, the recently extended version of the QTAIM, called the multi-component QTAIM (MC-QTAIM), incorporates both electrons and quantum nuclei, i.e., those nuclei treated as quantum waves instead of clamped point charges, into the AIM analysis using non-adiabatic wavefunctions. Thus, the MC-QTAIM is the natural framework to incorporate the role of nuclear vibrations into the AIM analysis. In this study, within the context of the MC-QTAIM, the formalism of including nuclear vibrational energy in the atomic basin energy is developed in detail and its contribution is derived analytically using the recently proposed non-adiabatic Hartree product nuclear wavefunction. It is demonstrated that within the context of this wavefunction, the quantum nuclei may be conceived pseudo-adiabatically as quantum oscillators and both isotropic harmonic and anisotropic anharmonic oscillator models are used to compute the zero-point nuclear vibrational energy contribution to the basin energies explicitly. Inspired by the results gained within the context of the MC-QTAIM analysis, a heuristic approach is proposed within the context of the QTAIM to include nuclear vibrational energy in the basin energy from the vibrational wavefunction derived adiabatically. The explicit calculation of the basin contribution of the zero-point vibrational energy using the uncoupled harmonic oscillator model leads to results consistent with those derived from the MC-QTAIM.

Incorporating nuclear vibrational energies into the "atom in molecules" analysis: An analytical study.

PubMed

Gharabaghi, Masumeh; Shahbazian, Shant

2017-04-21

The quantum theory of atoms in molecules (QTAIM) is based on the clamped nucleus paradigm and solely working with the electronic wavefunctions, so does not include nuclear vibrations in the AIM analysis. On the other hand, the recently extended version of the QTAIM, called the multi-component QTAIM (MC-QTAIM), incorporates both electrons and quantum nuclei, i.e., those nuclei treated as quantum waves instead of clamped point charges, into the AIM analysis using non-adiabatic wavefunctions. Thus, the MC-QTAIM is the natural framework to incorporate the role of nuclear vibrations into the AIM analysis. In this study, within the context of the MC-QTAIM, the formalism of including nuclear vibrational energy in the atomic basin energy is developed in detail and its contribution is derived analytically using the recently proposed non-adiabatic Hartree product nuclear wavefunction. It is demonstrated that within the context of this wavefunction, the quantum nuclei may be conceived pseudo-adiabatically as quantum oscillators and both isotropic harmonic and anisotropic anharmonic oscillator models are used to compute the zero-point nuclear vibrational energy contribution to the basin energies explicitly. Inspired by the results gained within the context of the MC-QTAIM analysis, a heuristic approach is proposed within the context of the QTAIM to include nuclear vibrational energy in the basin energy from the vibrational wavefunction derived adiabatically. The explicit calculation of the basin contribution of the zero-point vibrational energy using the uncoupled harmonic oscillator model leads to results consistent with those derived from the MC-QTAIM.

Chiral zero energy modes in two-dimensional disordered Dirac semimetals

NASA Astrophysics Data System (ADS)

Liu, Lei; Yu, Yan; Wu, Hai-Bin; Zhang, Yan-Yang; Liu, Jian-Jun; Li, Shu-Shen

2018-04-01

The vacancy-induced chiral zero energy modes (CZEMs) of chiral-unitary-class (AIII) and chiral-symplectic-class (CII) two-dimensional (2 D ) disordered Dirac semimetals realized on a square bipartite lattice are investigated numerically by using the Kubo-Greenwood formula with the kernel polynomial method. The results show that, for both systems, the CZEMs exhibit the critical delocalization. The CZEM conductivity remains a robust constant (i.e., σ CZEM≈1.05 e2/h ), which is insensitive to the sample sizes, the vacancy concentrations, and the numbers of moments of Chebyshev polynomials, i.e., the dephasing strength. For both kinds of chiral systems, the CZEM conductivities are almost identical. However, they are not equal to that of graphene (i.e., 4 e2/π h ), which belongs to the chiral orthogonal class (BDI) semimetal on a 2 D hexagonal bipartite lattice. In addition, for the case that the vacancy concentrations are different in the two sublattices, the CZEM conductivity vanishes, and thus both systems exhibit localization at the Dirac point. Moreover, a band gap and a mobility gap open around zero energy. The widths of the energy gaps and mobility gaps are increasing with larger vacancy concentration difference. The width of the mobility gap is greater than that of the band gap, and a δ -function-like peak of density of states emerges at the Dirac point within the band gap, implying the existence of numerous localized states.

The GaOH-HGaO potential energy hypersurface and the necessity of correlating the 3d electrons

NASA Astrophysics Data System (ADS)

Richards, Claude A., Jr.; Yamaguchi, Yukio; Kim, Seung-Joon; Schaefer, Henry F., III

1996-06-01

The ground state potential energy hypersurface of the GaOH-HGaO system has been investigated using high level ab initio molecular electronic structure theory. The geometries and physical properties of two equilibrium structures, one isomerization transition state and one inversion transition state were determined at the self-consistent field (SCF), configuration interaction with single and double excitations (CISD), coupled cluster with single and double excitations (CCSD), and CCSD with perturbative triple excitations [CCSD(T)] levels of theory with four sets of basis functions. It has been found that freezing the 3d electrons of the Ga atom in the correlation procedures is not appropriate for this system. For the energy difference ΔE (GaOH-HGaO) the freezing of the 3d electrons results in an error of 25 kcal/mol! The dipole moments, harmonic vibrational frequencies, and infrared (IR) intensities are predicted for the four stationary points. At the highest level of theory employed in this study, CCSD(T) using triple zeta plus double polarization with higher angular momentum and diffuse functions [TZ2P(f,d)+diff] basis set, the bent GaOH was found to be 41.9 kcal/mol more stable than the linear HGaO species; with the zero-point vibrational energy (ZPVE) correction, the energy separation becomes 40.4 kcal/mol. The classical barrier height for the exothermic isomerization (1,2 hydrogen shift) reaction HGaO→GaOH is determined to be 44.5 kcal/mol and the barrier height with the ZPVE correction 42.3 kcal/mol. The classical barrier to linearity for the bent GaOH molecule is determined to be 1.7 kcal/mol and the barrier height with the ZPVE correction to be 1.2 kcal/mol. The predicted dipole moments of GaOH and HGaO are 1.41 and 4.45 Debye, respectively. The effects of electron correlation reduce the dipole moment of HGaO by the sizable amount of 1.2 Debye. The two equilibrium species may be suitable for microwave spectroscopic investigation. Furthermore, they may also be detectable by IR techniques due to the relatively large intensities of their vibrational modes. The geometrical and energetic features are compared with those of the valence isoelectronic HXO-XOH systems, where X is a group IIIA atom and the HXO+-XOH+ systems, where X is a group IVA atom.

Theory of First Order Chemical Kinetics at the Critical Point of Solution.

PubMed

Baird, James K; Lang, Joshua R

2017-10-26

Liquid mixtures, which have a phase diagram exhibiting a miscibility gap ending in a critical point of solution, have been used as solvents for chemical reactions. The reaction rate in the forward direction has often been observed to slow down as a function of temperature in the critical region. Theories based upon the Gibbs free energy of reaction as the driving force for chemical change have been invoked to explain this behavior. With the assumption that the reaction is proceeding under relaxation conditions, these theories expand the free energy in a Taylor series about the position of equilibrium. Since the free energy is zero at equilibrium, the leading term in the Taylor series is proportional to the first derivative of the free energy with respect to the extent of reaction. To analyze the critical behavior of this derivative, the theories exploit the principle of critical point isomorphism, which is thought to govern all critical phenomena. They find that the derivative goes to zero in the critical region, which accounts for the slowing down observed in the reaction rate. As has been pointed out, however, most experimental rate investigations have been carried out under irreversible conditions as opposed to relaxation conditions [Shen et al. J. Phys. Chem. A 2015, 119, 8784-8791]. Below, we consider a reaction governed by first order kinetics and invoke transition state theory to take into account the irreversible conditions. We express the apparent activation energy in terms of thermodynamic derivatives evaluated under standard conditions as well as the pseudoequilibrium conditions associated with the reactant and the activated complex. We show that these derivatives approach infinity in the critical region. The apparent activation energy follows this behavior, and its divergence accounts for the slowing down of the reaction rate.

Quantum-Fluctuation Effects in the Transport Properties of Ultrathin Films of Disordered Superconductors above the Paramagnetic Limit

NASA Astrophysics Data System (ADS)

Khodas, M.; Levchenko, A.; Catelani, G.

2012-06-01

We study the transport in ultrathin disordered film near the quantum critical point induced by the Zeeman field. We calculate corrections to the normal state conductivity due to quantum pairing fluctuations. The fluctuation-induced transport is mediated by virtual rather than real quasiparticle excitations. We find that at zero temperature, where the corrections come from purely quantum fluctuations, the Aslamazov-Larkin paraconductivity term, the Maki-Thompson interference contribution, and the density of states effects are all of the same order. The total correction leads to the negative magnetoresistance. This result is in qualitative agreement with the recent transport observations in the parallel magnetic field of the homogeneously disordered amorphous films and superconducting two-dimensional electron gas realized at the oxide interfaces.

Full dimensional (15-dimensional) quantum-dynamical simulation of the protonated water-dimer III: Mixed Jacobi-valence parametrization and benchmark results for the zero point energy, vibrationally excited states, and infrared spectrum.

PubMed

Vendrell, Oriol; Brill, Michael; Gatti, Fabien; Lauvergnat, David; Meyer, Hans-Dieter

2009-06-21

Quantum dynamical calculations are reported for the zero point energy, several low-lying vibrational states, and the infrared spectrum of the H(5)O(2)(+) cation. The calculations are performed by the multiconfiguration time-dependent Hartree (MCTDH) method. A new vector parametrization based on a mixed Jacobi-valence description of the system is presented. With this parametrization the potential energy surface coupling is reduced with respect to a full Jacobi description, providing a better convergence of the n-mode representation of the potential. However, new coupling terms appear in the kinetic energy operator. These terms are derived and discussed. A mode-combination scheme based on six combined coordinates is used, and the representation of the 15-dimensional potential in terms of a six-combined mode cluster expansion including up to some 7-dimensional grids is discussed. A statistical analysis of the accuracy of the n-mode representation of the potential at all orders is performed. Benchmark, fully converged results are reported for the zero point energy, which lie within the statistical uncertainty of the reference diffusion Monte Carlo result for this system. Some low-lying vibrationally excited eigenstates are computed by block improved relaxation, illustrating the applicability of the approach to large systems. Benchmark calculations of the linear infrared spectrum are provided, and convergence with increasing size of the time-dependent basis and as a function of the order of the n-mode representation is studied. The calculations presented here make use of recent developments in the parallel version of the MCTDH code, which are briefly discussed. We also show that the infrared spectrum can be computed, to a very good approximation, within D(2d) symmetry, instead of the G(16) symmetry used before, in which the complete rotation of one water molecule with respect to the other is allowed, thus simplifying the dynamical problem.

Thomas-Fermi approximation for a condensate with higher-order interactions

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

Thoegersen, M.; Jensen, A. S.; Zinner, N. T.

We consider the ground state of a harmonically trapped Bose-Einstein condensate within the Gross-Pitaevskii theory including the effective-range corrections for a two-body zero-range potential. The resulting nonlinear Schroedinger equation is solved analytically in the Thomas-Fermi approximation neglecting the kinetic-energy term. We present results for the chemical potential and the condensate profiles, discuss boundary conditions, and compare to the usual Thomas-Fermi approach. We discuss several ways to increase the influence of effective-range corrections in experiment with magnetically tunable interactions. The level of tuning required could be inside experimental reach in the near future.

Pulse-excited, auto-zeroing multiple channel data transmission system

NASA Astrophysics Data System (ADS)

Fasching, G. E.

1985-02-01

A multiple channel data transmission system is provided in which signals from a plurality of pulse operated transducers and a corresponding plurality of pulse operated signal processor channels are multiplexed for single channel FM transmission to a receiving station. The transducers and corresponding channel amplifiers are powered by pulsing the dc battery power to these devices to conserve energy and battery size for long-term data transmission from remote or inaccessible locations. Auto zeroing of the signal channel amplifiers to compensate for drift associated with temperature changes, battery decay, component aging, etc., in each channel is accomplished by means of a unique auto zero feature which between signal pulses holds a zero correction voltage on an integrating capacitor coupled to the corresponding channel amplifier output. Pseudo-continuous outputs for each channel are achieved by pulsed sample-and-hold circuits which are updated at the pulsed operation rate. The sample-and-hold outputs are multiplexed into an FM/FM transmitter for transmission to an FM receiver station for demultiplexing and storage in separate channel recorders.

Pulse-excited, auto-zeroing multiple channel data transmission system

DOEpatents

Fasching, G.E.

1985-02-22

A multiple channel data transmission system is provided in which signals from a plurality of pulse operated transducers and a corresponding plurality of pulse operated signal processor channels are multiplexed for single channel FM transmission to a receiving station. The transducers and corresponding channel amplifiers are powered by pulsing the dc battery power to these devices to conserve energy and battery size for long-term data transmission from remote or inaccessible locations. Auto zeroing of the signal channel amplifiers to compensate for drift associated with temperature changes, battery decay, component aging, etc., in each channel is accomplished by means of a unique auto zero feature which between signal pulses holds a zero correction voltage on an integrating capacitor coupled to the corresponding channel amplifier output. Pseudo-continuous outputs for each channel are achieved by pulsed sample-and-hold circuits which are updated at the pulsed operation rate. The sample-and-hold outputs are multiplexed into an FM/FM transmitter for transmission to an FM receiver station for demultiplexing and storage in separate channel recorders.

Pulse-excited, auto-zeroing multiple channel data transmission system

DOEpatents

Fasching, George E.

1987-01-01

A multiple channel data transmission system is provided in which signals from a plurality of pulse operated transducers and a corresponding plurality of pulse operated signal processor channels are multiplexed for single channel FM transmission to a receiving station. The transducers and corresponding channel amplifiers are powered by pulsing the dc battery power to these devices to conserve energy and battery size for long-term data transmission from remote or inaccessible locations. Auto zeroing of the signal channel amplifiers to compensate for drift associated with temperature changes, battery decay, component aging, etc., in each channel is accomplished by means of a unique auto zero feature which between signal pulses holds a zero correction voltage on an integrating capacitor coupled to the corresponding channel amplifier output. Pseudo-continuous outputs for each channel are achieved by pulsed sample-and-hold circuits which are updated at the pulsed operation rate. The sample-and-hold outputs are multiplexed into an FM/FM transmitter for transmission to an FM receiver station for demultiplexing and storage in separate channel recorders.

Cosmology, Cosmomicrophysics and Gravitation Properties of the Gravitational Lens Mapping in the Vicinity of a Cusp Caustic

NASA Astrophysics Data System (ADS)

Alexandrov, A. N.; Zhdanov, V. I.; Koval, S. M.

We derive approximate formulas for the coordinates and magnification of critical images of a point source in a vicinity of a cusp caustic arising in the gravitational lens mapping. In the lowest (zero-order) approximation, these formulas were obtained in the classical work by Schneider&Weiss (1992) and then studied by a number of authors; first-order corrections in powers of the proximity parameter were treated by Congdon, Keeton and Nordgren. We have shown that the first-order corrections are solely due to the asymmetry of the cusp. We found expressions for the second-order corrections in the case of general lens potential and for an arbitrary position of the source near a symmetric cusp. Applications to a lensing galaxy model represented by a singular isothermal sphere with an external shear y are studied and the role of the second-order corrections is demonstrated.

Implementation of a MFAC based position sensorless drive for high speed BLDC motors with nonideal back EMF.

PubMed

Li, Haitao; Ning, Xin; Li, Wenzhuo

2017-03-01

In order to improve the reliability and reduce power consumption of the high speed BLDC motor system, this paper presents a model free adaptive control (MFAC) based position sensorless drive with only a dc-link current sensor. The initial commutation points are obtained by detecting the phase of EMF zero-crossing point and then delaying 30 electrical degrees. According to the commutation error caused by the low pass filter (LPF) and other factors, the relationship between commutation error angle and dc-link current is analyzed, a corresponding MFAC based control method is proposed, and the commutation error can be corrected by the controller in real time. Both the simulation and experimental results show that the proposed correction method can achieve ideal commutation effect within the entire operating speed range. Copyright © 2016 ISA. Published by Elsevier Ltd. All rights reserved.

A direct potential fitting RKR method: Semiclassical vs. quantal comparisons

NASA Astrophysics Data System (ADS)

Tellinghuisen, Joel

2016-12-01

Quantal and semiclassical (SC) eigenvalues are compared for three diatomic molecular potential curves: the X state of CO, the X state of Rb2, and the A state of I2. The comparisons show higher levels of agreement than generally recognized, when the SC calculations incorporate a quantum defect correction to the vibrational quantum number, in keeping with the Kaiser modification. One particular aspect of this is better agreement between quantal and SC estimates of the zero-point vibrational energy, supporting the need for the Y00 correction in this context. The pursuit of a direct-potential-fitting (DPF) RKR method is motivated by the notion that some of the limitations of RKR potentials may be innate, from their generation by an exact inversion of approximate quantities: the vibrational energy Gυ and rotational constant Bυ from least-squares analysis of spectroscopic data. In contrast, the DPF RKR method resembles the quantal DPF methods now increasingly used to analyze diatomic spectral data, but with the eigenvalues obtained from SC phase integrals. Application of this method to the analysis of 9500 assigned lines in the I2A ← X spectrum fails to alter the quantal-SC disparities found for the A-state RKR curve from a previous analysis. On the other hand, the SC method can be much faster than the quantal method in exploratory work with different potential functions, where it is convenient to use finite-difference methods to evaluate the partial derivatives required in nonlinear fitting.

Stochastic many-body perturbation theory for anharmonic molecular vibrations

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

Hermes, Matthew R.; Hirata, So, E-mail: sohirata@illinois.edu; CREST, Japan Science and Technology Agency, 4-1-8 Honcho, Kawaguchi, Saitama 332-0012

2014-08-28

A new quantum Monte Carlo (QMC) method for anharmonic vibrational zero-point energies and transition frequencies is developed, which combines the diagrammatic vibrational many-body perturbation theory based on the Dyson equation with Monte Carlo integration. The infinite sums of the diagrammatic and thus size-consistent first- and second-order anharmonic corrections to the energy and self-energy are expressed as sums of a few m- or 2m-dimensional integrals of wave functions and a potential energy surface (PES) (m is the vibrational degrees of freedom). Each of these integrals is computed as the integrand (including the value of the PES) divided by the value ofmore » a judiciously chosen weight function evaluated on demand at geometries distributed randomly but according to the weight function via the Metropolis algorithm. In this way, the method completely avoids cumbersome evaluation and storage of high-order force constants necessary in the original formulation of the vibrational perturbation theory; it furthermore allows even higher-order force constants essentially up to an infinite order to be taken into account in a scalable, memory-efficient algorithm. The diagrammatic contributions to the frequency-dependent self-energies that are stochastically evaluated at discrete frequencies can be reliably interpolated, allowing the self-consistent solutions to the Dyson equation to be obtained. This method, therefore, can compute directly and stochastically the transition frequencies of fundamentals and overtones as well as their relative intensities as pole strengths, without fixed-node errors that plague some QMC. It is shown that, for an identical PES, the new method reproduces the correct deterministic values of the energies and frequencies within a few cm{sup −1} and pole strengths within a few thousandths. With the values of a PES evaluated on the fly at random geometries, the new method captures a noticeably greater proportion of anharmonic effects.« less

UVIS Photometric Zero Points

NASA Astrophysics Data System (ADS)

Kalirai, Jason

2009-07-01

This proposal obtains the photometric zero points in 53 of the 62 UVIS/WFC3 filters: the 18 broad-band filters, 8 medium-band filters, 16 narrow-band filters, and 11 of the 20 quad filters {those being used in cycle 17}. The observations will be primary obtained by observing the hot DA white dwarf standards GD153 and G191-B2B. A redder secondary standard, P330E, will be observed in a subset of the filters to provide color corrections. Repeat observations in 16 of the most widely used cycle 17 filters will be obtained once per month for the first three months, and then once every second month for the duration of cycle 17, alternating and depending on target availability. These observations will enable monitoring of the stability of the photometric system. Photometric transformation equations will be calculated by comparing the photometry of stars in two globular clusters, 47 Tuc and NGC 2419, to previous measurements with other telescopes/instruments.

Ignition of Ionic Liquids. Volume 2

DTIC Science & Technology

2010-09-01

TOFMS time-of-flight-mass-spectrometry TS transition state VUV vacuum ultraviolet ZPE zero-point energy Approved for public...energies ( ZPEs ) were scaled by a factor of 0.9613 and 0.9804, respectively, and when necessary intrinsic reaction coordinate (IRC) calculations were...oscillations in the PE reflect the vibration of the DNB molecule, including ZPE . The trajectory shows three dissociation steps, eliminating NO2 followed

Trajectory dynamics study of the Ar + CH4 dissociation reaction at high temperatures: the importance of zero-point-energy effects.

PubMed

Marques, J M C; Martínez-Núñez, E; Fernandez-Ramos, A; Vazquez, S A

2005-06-23

Large-scale classical trajectory calculations have been performed to study the reaction Ar + CH4--> CH3 +H + Ar in the temperature range 2500 < or = T/K < or = 4500. The potential energy surface used for ArCH4 is the sum of the nonbonding pairwise potentials of Hase and collaborators (J. Chem. Phys. 2001, 114, 535) that models the intermolecular interaction and the CH4 intramolecular potential of Duchovic et al. (J. Phys. Chem. 1984, 88, 1339), which has been modified to account for the H-H repulsion at small bending angles. The thermal rate coefficient has been calculated, and the zero-point energy (ZPE) of the CH3 product molecule has been taken into account in the analysis of the results; also, two approaches have been applied for discarding predissociative trajectories. In both cases, good agreement is observed between the experimental and trajectory results after imposing the ZPE of CH3. The energy-transfer parameters have also been obtained from trajectory calculations and compared with available values estimated from experiment using the master equation formalism; in general, the agreement is good.

Accurate thermochemistry and spectroscopy of the oxygen-protonated sulfur dioxide isomers.

PubMed

Puzzarini, Cristina

2011-12-28

Despite the promising relevance of protonated sulfur dioxide in astrophysical and atmospheric fields, its thermochemical and spectroscopic characterization is very limited. High-level quantum-chemical calculations have shown that the most stable isomer is the cis oxygen-protonated sulfur dioxide, HOSO(+), while the trans form is about 2 kcal mol(-1) less stable; even less stable (by about 42 kcal mol(-1)) is the S-protonated isomer [V. Lattanzi et al., J. Chem. Phys., 2010, 133, 194305]. The enthalpy of formation for the cis- and trans-HOSO(+) is presented, based on the well tested HEAT protocol [A. Tajti et al., J. Chem. Phys., 2004, 121, 11599]. Systematically extrapolated ab initio energies, accounting for electron correlation through coupled cluster theory, including up to single, double, triple and quadruple excitations, have been corrected for core-electron correlation, anharmonic zero-point vibrational energy, diagonal Born-Oppenheimer and scalar relativistic effects. As a byproduct, proton affinity of sulfur dioxide and atomization energies have also been obtained at the same levels of theory. Vibrational and rotational spectroscopic properties have been investigated by means of composite schemes that allow us to account for truncation of basis set as well as core correlation. Where available, for both thermochemistry and spectroscopy, very good agreement with experimental data has been observed.

Cost Benefit Analysis of a Utility Scale Waste-to-Energy/Concentrating Solar Power Hybrid Facility at Fort Bliss

DTIC Science & Technology

2012-06-01

installations for Energy, Waste, and Water. This means Fort Bliss will strive to become Net Zero Energy, Net Zero Waste , and Net Zero Water in the coming...years. Net Zero Energy requires Fort Bliss to produce as much energy on-installation as it consumes annually. Net Zero Waste aims to reduce, reuse...become Net Zero Energy and Net Zero Waste by 2020. A WtE facility actually goes well beyond Fort Bliss’ Net Zero Energy mission. That mission

The multichannel n-propyl + O2 reaction surface: Definitive theory on a model hydrocarbon oxidation mechanism

NASA Astrophysics Data System (ADS)

Bartlett, Marcus A.; Liang, Tao; Pu, Liang; Schaefer, Henry F.; Allen, Wesley D.

2018-03-01

The n-propyl + O2 reaction is an important model of chain branching reactions in larger combustion systems. In this work, focal point analyses (FPAs) extrapolating to the ab initio limit were performed on the n-propyl + O2 system based on explicit quantum chemical computations with electron correlation treatments through coupled cluster single, double, triple, and perturbative quadruple excitations [CCSDT(Q)] and basis sets up to cc-pV5Z. All reaction species and transition states were fully optimized at the rigorous CCSD(T)/cc-pVTZ level of theory, revealing some substantial differences in comparison to the density functional theory geometries existing in the literature. A mixed Hessian methodology was implemented and benchmarked that essentially makes the computations of CCSD(T)/cc-pVTZ vibrational frequencies feasible and thus provides critical improvements to zero-point vibrational energies for the n-propyl + O2 system. Two key stationary points, n-propylperoxy radical (MIN1) and its concerted elimination transition state (TS1), were located 32.7 kcal mol-1 and 2.4 kcal mol-1 below the reactants, respectively. Two competitive β-hydrogen transfer transition states (TS2 and TS2') were found separated by only 0.16 kcal mol-1, a fact unrecognized in the current combustion literature. Incorporating TS2' in master equation (ME) kinetic models might reduce the large discrepancy of 2.5 kcal mol-1 between FPA and ME barrier heights for TS2. TS2 exhibits an anomalously large diagonal Born-Oppenheimer correction (ΔDBOC = 1.71 kcal mol-1), which is indicative of a nearby surface crossing and possible nonadiabatic reaction dynamics. The first systematic conformational search of three hydroperoxypropyl (QOOH) intermediates was completed, uncovering a total of 32 rotamers lying within 1.6 kcal mol-1 of their respective lowest-energy minima. Our definitive energetics for stationary points on the n-propyl + O2 potential energy surface provide key benchmarks for future studies of hydrocarbon oxidation.

Verification of floating-point software

NASA Technical Reports Server (NTRS)

Hoover, Doug N.

1990-01-01

Floating point computation presents a number of problems for formal verification. Should one treat the actual details of floating point operations, or accept them as imprecisely defined, or should one ignore round-off error altogether and behave as if floating point operations are perfectly accurate. There is the further problem that a numerical algorithm usually only approximately computes some mathematical function, and we often do not know just how good the approximation is, even in the absence of round-off error. ORA has developed a theory of asymptotic correctness which allows one to verify floating point software with a minimum entanglement in these problems. This theory and its implementation in the Ariel C verification system are described. The theory is illustrated using a simple program which finds a zero of a given function by bisection. This paper is presented in viewgraph form.

Saddle point localization of molecular wavefunctions.

PubMed

Mellau, Georg Ch; Kyuberis, Alexandra A; Polyansky, Oleg L; Zobov, Nikolai; Field, Robert W

2016-09-15

The quantum mechanical description of isomerization is based on bound eigenstates of the molecular potential energy surface. For the near-minimum regions there is a textbook-based relationship between the potential and eigenenergies. Here we show how the saddle point region that connects the two minima is encoded in the eigenstates of the model quartic potential and in the energy levels of the [H, C, N] potential energy surface. We model the spacing of the eigenenergies with the energy dependent classical oscillation frequency decreasing to zero at the saddle point. The eigenstates with the smallest spacing are localized at the saddle point. The analysis of the HCN ↔ HNC isomerization states shows that the eigenstates with small energy spacing relative to the effective (v1, v3, ℓ) bending potentials are highly localized in the bending coordinate at the transition state. These spectroscopically detectable states represent a chemical marker of the transition state in the eigenenergy spectrum. The method developed here provides a basis for modeling characteristic patterns in the eigenenergy spectrum of bound states.

Detailed study of the water trimer potential energy surface

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

Fowler, J.E.; Schaefer, H.F. III

The potential energy surface of the water trimer has been studied through the use of ab initio quantum mechanical methods. Five stationary points were located, including one minimum and two transition states. All geometries were optimized at levels up to the double-[Zeta] plus polarization plus diffuse (DZP + diff) single and double excitation coupled cluster (CCSD) level of theory. CCSD single energy points were obtained for the minimum, two transition states, and the water monomer using the triple-[Zeta] plus double polarization plus diffuse (TZ2P + diff) basis at the geometries predicted by the DZP + diff CCSD method. Reported aremore » the following: geometrical parameters, total and relative energies, harmonic vibrational frequencies and infrared intensities for the minimum, and zero point vibrational energies for the minimum, two transition states, and three separated water molecules. 27 refs., 5 figs., 10 tabs.« less

Effect of chiral symmetry on chaotic scattering from Majorana zero modes.

PubMed

Schomerus, H; Marciani, M; Beenakker, C W J

2015-04-24

In many of the experimental systems that may host Majorana zero modes, a so-called chiral symmetry exists that protects overlapping zero modes from splitting up. This symmetry is operative in a superconducting nanowire that is narrower than the spin-orbit scattering length, and at the Dirac point of a superconductor-topological insulator heterostructure. Here we show that chiral symmetry strongly modifies the dynamical and spectral properties of a chaotic scatterer, even if it binds only a single zero mode. These properties are quantified by the Wigner-Smith time-delay matrix Q=-iℏS^{†}dS/dE, the Hermitian energy derivative of the scattering matrix, related to the density of states by ρ=(2πℏ)^{-1}TrQ. We compute the probability distribution of Q and ρ, dependent on the number ν of Majorana zero modes, in the chiral ensembles of random-matrix theory. Chiral symmetry is essential for a significant ν dependence.

Nonempirical Semilocal Free-Energy Density Functional for Matter under Extreme Conditions.

PubMed

Karasiev, Valentin V; Dufty, James W; Trickey, S B

2018-02-16

Realizing the potential for predictive density functional calculations of matter under extreme conditions depends crucially upon having an exchange-correlation (XC) free-energy functional accurate over a wide range of state conditions. Unlike the ground-state case, no such functional exists. We remedy that with systematic construction of a generalized gradient approximation XC free-energy functional based on rigorous constraints, including the free-energy gradient expansion. The new functional provides the correct temperature dependence in the slowly varying regime and the correct zero-T, high-T, and homogeneous electron gas limits. Its accuracy in the warm dense matter regime is attested by excellent agreement of the calculated deuterium equation of state with reference path integral Monte Carlo results at intermediate and elevated T. Pressure shifts for hot electrons in compressed static fcc Al and for low-density Al demonstrate the combined magnitude of thermal and gradient effects handled well by this functional over a wide T range.

Technically natural vacuum energy at the tip of a supersymmetric teardrop

NASA Astrophysics Data System (ADS)

Williams, Matthew

2014-04-01

A minimal supersymmetric braneworld model is presented which has (i) zero classical four-dimensional vacuum curvature, despite the large naive vacuum energy due to contributions from Standard Model particles and (ii) one-(bulk)-loop quantum corrections to the vacuum energy with a size set by the radius of the extra-dimensional spheroid. These corrections are technically natural because a Bogomol'nyi-Prasad-Sommerfield-like relation between the brane tension and R charge—which would have preserved (half of) the bulk supersymmetry—is violated by the requirement that the stabilizing R-symmetry gauge flux be quantized. The extra-dimensional geometry is similar to previous rugby-ball geometries, but is simpler in that there is only one brane and so fewer free parameters. Although the sign of the renormalized vacuum energy ends up being the unphysical one for this model (in the limit considered here, where the massive bulk loop is the leading contribution), it serves as an illustrative example of the relevant physics.

Nonempirical Semilocal Free-Energy Density Functional for Matter under Extreme Conditions

NASA Astrophysics Data System (ADS)

Karasiev, Valentin V.; Dufty, James W.; Trickey, S. B.

2018-02-01

Realizing the potential for predictive density functional calculations of matter under extreme conditions depends crucially upon having an exchange-correlation (X C ) free-energy functional accurate over a wide range of state conditions. Unlike the ground-state case, no such functional exists. We remedy that with systematic construction of a generalized gradient approximation X C free-energy functional based on rigorous constraints, including the free-energy gradient expansion. The new functional provides the correct temperature dependence in the slowly varying regime and the correct zero-T , high-T , and homogeneous electron gas limits. Its accuracy in the warm dense matter regime is attested by excellent agreement of the calculated deuterium equation of state with reference path integral Monte Carlo results at intermediate and elevated T . Pressure shifts for hot electrons in compressed static fcc Al and for low-density Al demonstrate the combined magnitude of thermal and gradient effects handled well by this functional over a wide T range.

Simultaneous quaternion estimation (QUEST) and bias determination

NASA Technical Reports Server (NTRS)

Markley, F. Landis

1989-01-01

Tests of a new method for the simultaneous estimation of spacecraft attitude and sensor biases, based on a quaternion estimation algorithm minimizing Wahba's loss function are presented. The new method is compared with a conventional batch least-squares differential correction algorithm. The estimates are based on data from strapdown gyros and star trackers, simulated with varying levels of Gaussian noise for both inertially-fixed and Earth-pointing reference attitudes. Both algorithms solve for the spacecraft attitude and the gyro drift rate biases. They converge to the same estimates at the same rate for inertially-fixed attitude, but the new algorithm converges more slowly than the differential correction for Earth-pointing attitude. The slower convergence of the new method for non-zero attitude rates is believed to be due to the use of an inadequate approximation for a partial derivative matrix. The new method requires about twice the computational effort of the differential correction. Improving the approximation for the partial derivative matrix in the new method is expected to improve its convergence at the cost of increased computational effort.

Quantum vacuum effects from boundaries of designer potentials

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

Konopka, Tomasz

2009-04-15

Vacuum energy in quantum field theory, being the sum of zero-point energies of all field modes, is formally infinite but yet, after regularization or renormalization, can give rise to finite observable effects. One way of understanding how these effects arise is to compute the vacuum energy in an idealized system such as a large cavity divided into disjoint regions by pistons. In this paper, this type of calculation is carried out for situations where the potential affecting a field is not the same in all regions of the cavity. It is shown that the observable parts of the vacuum energymore » in such potentials do not fall off to zero as the region where the potential is nontrivial becomes large. This unusual behavior might be interesting for tests involving quantum vacuum effects and for studies on the relation between vacuum energy in quantum field theory and geometry.« less

Implications of the (H2O)n + CO ↔ trans-HCOOH + (H2O)n-1 (n = 1, 2, and 3) reactions for primordial atmospheres of Venus and Earth

NASA Astrophysics Data System (ADS)

Vichietti, R. M.; Spada, R. F. K.; da Silva, A. B. F.; Machado, F. B. C.; Haiduke, R. L. A.

2018-04-01

The forward and backward (H2O)n + CO ↔ HCOOH + (H2O)n-1 (n = 1, 2, and 3) reactions were studied in order to furnish trustworthy thermochemical and kinetic data. Stationary point structures involved in these chemical processes were achieved at the B2PLYP/cc-pVTZ level so that the corresponding vibrational frequencies, zero-point energies, and thermal corrections were scaled to consider anharmonicity effects. A complete basis set extrapolation was also employed with the CCSD(T) method in order to improve electronic energy descriptions and providing therefore more accurate results for enthalpies, Gibbs energies, and rate constants. Forward and backward rate constants were encountered at the high-pressure limit between 200 and 4000 K. In turn, modified Arrhenius' equations were fitted from these rate constants (between 700 and 4000 K). Next, considering physical and chemical conditions that have supposedly prevailed on primitive atmospheres of Venus and Earth, our main results indicate that 85-88 per cent of all water forms on these atmospheres were monomers, whereas (H2O)2 and (H2O)3 complexes would represent 12-15 and ˜0 per cent, respectively. Besides, we estimate that Earth's and Venus' primitive atmospheres could have been composed by ˜0.001-0.003 per cent of HCOOH when their temperatures were around 1000-2000 K. Finally, the water loss process on Venus may have occurred by a mechanism that includes the formic acid as intermediate species.

Computational Thermochemistry: Scale Factor Databases and Scale Factors for Vibrational Frequencies Obtained from Electronic Model Chemistries.

PubMed

Alecu, I M; Zheng, Jingjing; Zhao, Yan; Truhlar, Donald G

2010-09-14

Optimized scale factors for calculating vibrational harmonic and fundamental frequencies and zero-point energies have been determined for 145 electronic model chemistries, including 119 based on approximate functionals depending on occupied orbitals, 19 based on single-level wave function theory, three based on the neglect-of-diatomic-differential-overlap, two based on doubly hybrid density functional theory, and two based on multicoefficient correlation methods. Forty of the scale factors are obtained from large databases, which are also used to derive two universal scale factor ratios that can be used to interconvert between scale factors optimized for various properties, enabling the derivation of three key scale factors at the effort of optimizing only one of them. A reduced scale factor optimization model is formulated in order to further reduce the cost of optimizing scale factors, and the reduced model is illustrated by using it to obtain 105 additional scale factors. Using root-mean-square errors from the values in the large databases, we find that scaling reduces errors in zero-point energies by a factor of 2.3 and errors in fundamental vibrational frequencies by a factor of 3.0, but it reduces errors in harmonic vibrational frequencies by only a factor of 1.3. It is shown that, upon scaling, the balanced multicoefficient correlation method based on coupled cluster theory with single and double excitations (BMC-CCSD) can lead to very accurate predictions of vibrational frequencies. With a polarized, minimally augmented basis set, the density functionals with zero-point energy scale factors closest to unity are MPWLYP1M (1.009), τHCTHhyb (0.989), BB95 (1.012), BLYP (1.013), BP86 (1.014), B3LYP (0.986), MPW3LYP (0.986), and VSXC (0.986).

Understanding the reaction between muonium atoms and hydrogen molecules: zero point energy, tunnelling, and vibrational adiabaticity

NASA Astrophysics Data System (ADS)

Aldegunde, J.; Jambrina, P. G.; García, E.; Herrero, V. J.; Sáez-Rábanos, V.; Aoiz, F. J.

2013-11-01

The advent of very precise measurements of rate coefficients in reactions of muonium (Mu), the lightest hydrogen isotope, with H2 in its ground and first vibrational state and of kinetic isotope effects with respect to heavier isotopes has triggered a renewed interests in the field of muonic chemistry. The aim of the present article is to review the most recent results about the dynamics and mechanism of the reaction Mu+H2 to shed light on the importance of quantum effects such as tunnelling, the preservation of the zero point energy, and the vibrational adiabaticity. In addition to accurate quantum mechanical (QM) calculations, quasiclassical trajectories (QCT) have been run in order to check the reliability of this method for this isotopic variant. It has been found that the reaction with H2(v=0) is dominated by the high zero point energy (ZPE) of the products and that tunnelling is largely irrelevant. Accordingly, both QCT calculations that preserve the products' ZPE as well as those based on the Ring Polymer Molecular Dynamics methodology can reproduce the QM rate coefficients. However, when the hydrogen molecule is vibrationally excited, QCT calculations fail completely in the prediction of the huge vibrational enhancement of the reactivity. This failure is attributed to tunnelling, which plays a decisive role breaking the vibrational adiabaticity when v=1. By means of the analysis of the results, it can be concluded that the tunnelling takes place through the ν1=1 collinear barrier. Somehow, the tunnelling that is missing in the Mu+H2(v=0) reaction is found in Mu+H2(v=1).

Tunneling splitting in double-proton transfer: direct diagonalization results for porphycene.

PubMed

Smedarchina, Zorka; Siebrand, Willem; Fernández-Ramos, Antonio

2014-11-07

Zero-point and excited level splittings due to double-proton tunneling are calculated for porphycene and the results are compared with experiment. The calculation makes use of a multidimensional imaginary-mode Hamiltonian, diagonalized directly by an effective reduction of its dimensionality. Porphycene has a complex potential energy surface with nine stationary configurations that allow a variety of tunneling paths, many of which include classically accessible regions. A symmetry-based approach is used to show that the zero-point level, although located above the cis minimum, corresponds to concerted tunneling along a direct trans - trans path; a corresponding cis - cis path is predicted at higher energy. This supports the conclusion of a previous paper [Z. Smedarchina, W. Siebrand, and A. Fernández-Ramos, J. Chem. Phys. 127, 174513 (2007)] based on the instanton approach to a model Hamiltonian of correlated double-proton transfer. A multidimensional tunneling Hamiltonian is then generated, based on a double-minimum potential along the coordinate of concerted proton motion, which is newly evaluated at the RI-CC2/cc-pVTZ level of theory. To make it suitable for diagonalization, its dimensionality is reduced by treating fast weakly coupled modes in the adiabatic approximation. This results in a coordinate-dependent mass of tunneling, which is included in a unique Hermitian form into the kinetic energy operator. The reduced Hamiltonian contains three symmetric and one antisymmetric mode coupled to the tunneling mode and is diagonalized by a modified Jacobi-Davidson algorithm implemented in the Jadamilu software for sparse matrices. The results are in satisfactory agreement with the observed splitting of the zero-point level and several vibrational fundamentals after a partial reassignment, imposed by recently derived selection rules. They also agree well with instanton calculations based on the same Hamiltonian.

Marcus Bell-Shaped Electron Transfer Kinetics Observed in an Arrhenius Plot.

PubMed

Waskasi, Morteza M; Kodis, Gerdenis; Moore, Ana L; Moore, Thomas A; Gust, Devens; Matyushov, Dmitry V

2016-07-27

The Marcus theory of electron transfer predicts a bell-shaped dependence of the reaction rate on the reaction free energy. The top of the "inverted parabola" corresponds to zero activation barrier when the electron-transfer reorganization energy and the reaction free energy add up to zero. Although this point has traditionally been reached by altering the chemical structures of donors and acceptors, the theory suggests that it can also be reached by varying other parameters of the system including temperature. We find here dramatic evidence of this phenomenon from experiments on a fullerene-porphyrin dyad. Following photoinduced electron transfer, the rate of charge recombination shows a bell-shaped dependence on the inverse temperature, first increasing with cooling and then decreasing at still lower temperatures. This non-Arrhenius rate law is a result of a strong, approximately hyperbolic temperature variation of the reorganization energy and the reaction free energy. Our results provide potentially the cleanest confirmation of the Marcus energy gap law so far since no modification of the chemical structure is involved.

Urban Renewable Building And Neighborhood Optimization

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

URBANopt is a user interface for creating and running district and city scale building energy simulations. The framework is built around the OpenStudio Urban Measures which are part of the OpenStudio project. Building footprints, building height, building type, and other data can be imported from public records or other sources. Footprints and locations for new buildings and district systems can also be specified. OpenStudio Measures are used to create starting point energy models and to model energy design features and efficiency measures for each building. URBANopt allows a user to pose several scenarios such as “what if 30% of themore » commercial retail buildings added roof top solar” or “what if all elementary schools converted to ground source heat pumps” and then visualize the impacts at a district or city scale. URBANopt is capable of modeling existing buildings, new construction, and district energy systems. URBANopt can be used to explore options for achieving Zero Energy across a collection of buildings (e.g., Zero Energy Districts).« less

A DFT+U investigation of hydrogen adsorption on the LaFeO3(010) surface.

PubMed

Boateng, Isaac W; Tia, Richard; Adei, Evans; Dzade, Nelson Y; Catlow, C Richard A; de Leeuw, Nora H

2017-03-08

The ABO 3 perovskite lanthanum ferrite (LaFeO 3 ) is a technologically important electrode material for nickel-metal hydride batteries, energy storage and catalysis. However, the electrochemical hydrogen adsorption mechanism on LaFeO 3 surfaces remains under debate. In the present study, we have employed spin-polarized density functional theory calculations, with the Hubbard U correction (DFT+U), to unravel the adsorption mechanism of H 2 on the LaFeO 3 (010) surface. We show from our calculated adsorption energies that the preferred site for H 2 adsorption is the Fe-O bridge site, with an adsorption energy of -1.18 eV (including the zero point energy), which resulted in the formation of FeOH and FeH surface species. H 2 adsorption at the surface oxygen resulted in the formation of a water molecule, which leaves the surface to create an oxygen vacancy. The H 2 molecule is found to interact weakly with the Fe and La sites, where it is only physisorbed. The electronic structures of the surface-adsorption systems are discussed via projected density of state and Löwdin population analyses. The implications of the calculated adsorption strengths and structures are discussed in terms of the improved design of nickel-metal hydride (Ni-MH) battery prototypes based on LaFeO 3 .

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

NASA Astrophysics Data System (ADS)

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

2004-07-01

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

`Dem DEMs: Comparing Methods of Digital Elevation Model Creation

NASA Astrophysics Data System (ADS)

Rezza, C.; Phillips, C. B.; Cable, M. L.

2017-12-01

Topographic details of Europa's surface yield implications for large-scale processes that occur on the moon, including surface strength, modification, composition, and formation mechanisms for geologic features. In addition, small scale details presented from this data are imperative for future exploration of Europa's surface, such as by a potential Europa Lander mission. A comparison of different methods of Digital Elevation Model (DEM) creation and variations between them can help us quantify the relative accuracy of each model and improve our understanding of Europa's surface. In this work, we used data provided by Phillips et al. (2013, AGU Fall meeting, abs. P34A-1846) and Schenk and Nimmo (2017, in prep.) to compare DEMs that were created using Ames Stereo Pipeline (ASP), SOCET SET, and Paul Schenk's own method. We began by locating areas of the surface with multiple overlapping DEMs, and our initial comparisons were performed near the craters Manannan, Pwyll, and Cilix. For each region, we used ArcGIS to draw profile lines across matching features to determine elevation. Some of the DEMs had vertical or skewed offsets, and thus had to be corrected. The vertical corrections were applied by adding or subtracting the global minimum of the data set to create a common zero-point. The skewed data sets were corrected by rotating the plot so that it had a global slope of zero and then subtracting for a zero-point vertical offset. Once corrections were made, we plotted the three methods on one graph for each profile of each region. Upon analysis, we found relatively good feature correlation between the three methods. The smoothness of a DEM depends on both the input set of images and the stereo processing methods used. In our comparison, the DEMs produced by SOCET SET were less smoothed than those from ASP or Schenk. Height comparisons show that ASP and Schenk's model appear similar, alternating in maximum height. SOCET SET has more topographic variability due to its decreased smoothing, which is borne out by preliminary offset calculations. In the future, we plan to expand upon this preliminary work with more regions of Europa, continue quantifying the height differences and relative accuracy of each method, and generate more DEMs to expand our available comparison regions.

Multicomponent Density Functional Theory: Impact of Nuclear Quantum Effects on Proton Affinities and Geometries.

PubMed

Brorsen, Kurt R; Yang, Yang; Hammes-Schiffer, Sharon

2017-08-03

Nuclear quantum effects such as zero point energy play a critical role in computational chemistry and often are included as energetic corrections following geometry optimizations. The nuclear-electronic orbital (NEO) multicomponent density functional theory (DFT) method treats select nuclei, typically protons, quantum mechanically on the same level as the electrons. Electron-proton correlation is highly significant, and inadequate treatments lead to highly overlocalized nuclear densities. A recently developed electron-proton correlation functional, epc17, has been shown to provide accurate nuclear densities for molecular systems. Herein, the NEO-DFT/epc17 method is used to compute the proton affinities for a set of molecules and to examine the role of nuclear quantum effects on the equilibrium geometry of FHF - . The agreement of the computed results with experimental and benchmark values demonstrates the promise of this approach for including nuclear quantum effects in calculations of proton affinities, pK a 's, optimized geometries, and reaction paths.

Communication: rate coefficients from quasiclassical trajectory calculations from the reverse reaction: The Mu + H2 reaction re-visited.

PubMed

Homayoon, Zahra; Jambrina, Pablo G; Aoiz, F Javier; Bowman, Joel M

2012-07-14

In a previous paper [P. G. Jambrina et al., J. Chem. Phys. 135, 034310 (2011)] various calculations of the rate coefficient for the Mu + H(2) → MuH + H reaction were presented and compared to experiment. The widely used standard quasiclassical trajectory (QCT) method was shown to overestimate the rate coefficients by several orders of magnitude over the temperature range 200-1000 K. This was attributed to a major failure of that method to describe the correct threshold for the reaction owing to the large difference in zero-point energies (ZPE) of the reactant H(2) and product MuH (∼0.32 eV). In this Communication we show that by performing standard QCT calculations for the reverse reaction and then applying detailed balance, the resulting rate coefficient is in very good agreement with the other computational results that respect the ZPE, (as well as with the experiment) but which are more demanding computationally.

Communication: Rate coefficients from quasiclassical trajectory calculations from the reverse reaction: The Mu + H2 reaction re-visited

NASA Astrophysics Data System (ADS)

Homayoon, Zahra; Jambrina, Pablo G.; Aoiz, F. Javier; Bowman, Joel M.

2012-07-01

In a previous paper [P. G. Jambrina et al., J. Chem. Phys. 135, 034310 (2011), 10.1063/1.3611400] various calculations of the rate coefficient for the Mu + H2 → MuH + H reaction were presented and compared to experiment. The widely used standard quasiclassical trajectory (QCT) method was shown to overestimate the rate coefficients by several orders of magnitude over the temperature range 200-1000 K. This was attributed to a major failure of that method to describe the correct threshold for the reaction owing to the large difference in zero-point energies (ZPE) of the reactant H2 and product MuH (˜0.32 eV). In this Communication we show that by performing standard QCT calculations for the reverse reaction and then applying detailed balance, the resulting rate coefficient is in very good agreement with the other computational results that respect the ZPE, (as well as with the experiment) but which are more demanding computationally.

Simulation of the photodetachment spectrum of HHfO- using coupled-cluster calculations

NASA Astrophysics Data System (ADS)

Mok, Daniel K. W.; Dyke, John M.; Lee, Edmond P. F.

2016-12-01

The photodetachment spectrum of HHfO- was simulated using restricted-spin coupled-cluster single-double plus perturbative triple {RCCSD(T)} calculations performed on the ground electronic states of HHfO and HHfO-, employing basis sets of up to quintuple-zeta quality. The computed RCCSD(T) electron affinity of 1.67 ± 0.02 eV at the complete basis set limit, including Hf 5s25p6 core correlation and zero-point energy corrections, agrees well with the experimental value of 1.70 ± 0.05 eV from a recent photodetachment study [X. Li et al., J. Chem. Phys. 136, 154306 (2012)]. For the simulation, Franck-Condon factors were computed which included allowances for anharmonicity and Duschinsky rotation. Comparisons between simulated and experimental spectra confirm the assignments of the molecular carrier and electronic states involved but suggest that the experimental vibrational structure has suffered from poor signal-to-noise ratio. An alternative assignment of the vibrational structure to that suggested in the experimental work is presented.

Extended Tersoff potential for boron nitride: Energetics and elastic properties of pristine and defective h -BN

NASA Astrophysics Data System (ADS)

Los, J. H.; Kroes, J. M. H.; Albe, K.; Gordillo, R. M.; Katsnelson, M. I.; Fasolino, A.

2017-11-01

We present an extended Tersoff potential for boron nitride (BN-ExTeP) for application in large scale atomistic simulations. BN-ExTeP accurately describes the main low energy B, N, and BN structures and yields quantitatively correct trends in the bonding as a function of coordination. The proposed extension of the bond order, added to improve the dependence of bonding on the chemical environment, leads to an accurate description of point defects in hexagonal BN (h -BN) and cubic BN (c -BN). We have implemented this potential in the molecular dynamics LAMMPS code and used it to determine some basic properties of pristine 2D h -BN and the elastic properties of defective h -BN as a function of defect density at zero temperature. Our results show that there is a strong correlation between the size of the static corrugation induced by the defects and the weakening of the in-plane elastic moduli.

Integrated Heat Pump HVAC Systems for Near-Zero-Energy Homes - Business Case Assessment

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

Baxter, Van D

2007-05-01

The long range strategic goal of the Department of Energy's Building Technologies (DOE/BT) Program is to create, by 2020, technologies and design approaches that enable the construction of net-zero energy homes at low incremental cost (DOE/BT 2005). A net zero energy home (NZEH) is a residential building with greatly reduced needs for energy through efficiency gains, with the balance of energy needs supplied by renewable technologies. While initially focused on new construction, these technologies and design approaches are intended to have application to buildings constructed before 2020 as well resulting in substantial reduction in energy use for all building typesmore » and ages. DOE/BT's Emerging Technologies (ET) team is working to support this strategic goal by identifying and developing advanced heating, ventilating, air-conditioning, and water heating (HVAC/WH) technology options applicable to NZEHs. Although the energy efficiency of heating, ventilating, and air-conditioning (HVAC) equipment has increased substantially in recent years, new approaches are needed to continue this trend. Dramatic efficiency improvements are necessary to enable progress toward the NZEH goals, and will require a radical rethinking of opportunities to improve system performance. The large reductions in HVAC energy consumption necessary to support the NZEH goals require a systems-oriented analysis approach that characterizes each element of energy consumption, identifies alternatives, and determines the most cost-effective combination of options. In particular, HVAC equipment must be developed that addresses the range of special needs of NZEH applications in the areas of reduced HVAC and water heating energy use, humidity control, ventilation, uniform comfort, and ease of zoning. In FY05 ORNL conducted an initial Stage 1 (Applied Research) scoping assessment of HVAC/WH systems options for future NZEHs to help DOE/BT identify and prioritize alternative approaches for further development. Eleven system concepts with central air distribution ducting and nine multi-zone systems were selected and their annual and peak demand performance estimated for five locations: Atlanta (mixed-humid), Houston (hot-humid), Phoenix (hot-dry), San Francisco (marine), and Chicago (cold). Performance was estimated by simulating the systems using the TRNSYS simulation engine (Solar Energy Laboratory et al. 2006) in two 1800-ft{sup 2} houses--a Building America (BA) benchmark house and a prototype NZEH taken from BEopt results at the take-off (or crossover) point (i.e., a house incorporating those design features such that further progress towards ZEH is through the addition of photovoltaic power sources, as determined by current BEopt analyses conducted by NREL). Results were summarized in a project report, 'HVAC Equipment Design options for Near-Zero-Energy Homes--A Stage 2 Scoping Assessment', ORNL/TM-2005/194 (Baxter 2005). The 2005 study report describes the HVAC options considered, the ranking criteria used, and the system rankings by priority. Table 1 summarizes the energy savings potential of the highest scoring options from the 2005 study for all five locations. All system options were scored by the ORNL building equipment research team and by William Goetzler of Navigant Consulting. These scores were reviewed by DOE/BT's Residential Integration program leaders and Building America team members. Based on these results, the two centrally ducted integrated heat pump (IHP) systems (air source and ground source versions) were selected for advancement to Stage 2 (Exploratory Development) business case assessments in FY06. This report describes results of these business case assessments. It is a compilation of three separate reports describing the initial business case study (Baxter 2006a), an update to evaluate the impact of an economizer cooling option (Baxter 2006b), and a second update to evaluate the impact of a winter humidification option (Baxter 2007). In addition it reports some corrections made subsequent to release of the first two reports to correct some errors in the TRNSYS building model for Atlanta and in the refrigerant pressure drop calculation in the water-to-refrigerant evaporator module of the ORNL Heat Pump Design Model (HPDM) used for the IHP analyses. These changes resulted in some minor differences between IHP performance as reported in Baxter (2006a, b) and in this report.« less

Phonon dispersions, band structures, and dielectric functions of BeO and BeS polymorphs

NASA Astrophysics Data System (ADS)

Wang, Ke-Long; Gao, Shang-Peng

2018-07-01

Structures, phonon dispersions, electronic structures, and dielectric functions of beryllium oxide (BeO) and beryllium sulfide (BeS) polymorphs are investigated by density functional theory and many-body perturbation theory. Phonon calculations indicate that both wurtzite (w-) and zincblende (zb-) structures are dynamically stable for BeO and BeS, whereas rocksalt (rs-) structures for both BeO and BeS have imaginary phonon frequencies and thus are dynamically unstable at zero pressure. Band structures for the 4 dynamically stable phases show that only w-BeO has a direct band gap. Both the one-shot G0W0 and quasiparticle self-consistent GW methods are used to correct band energies at high symmetry k-points. Bethe-Salpeter equation (BSE), which considers Coulomb correlated electron-hole pairs, is employed to deal with the computation of macroscopic dielectric functions. It is shown that BSE calculation, employing scissors operator derived by self-consistent GW method, can give dielectric functions agreeing very well with experimental measurement of w-BeO. Weak anisotropic characters can be observed for w-BeO and w-BeS. Both zb-BeS and w-BeS show high optical transition probabilities within a narrow ultraviolet energy range.

Renormalized Energy Concentration in Random Matrices

NASA Astrophysics Data System (ADS)

Borodin, Alexei; Serfaty, Sylvia

2013-05-01

We define a "renormalized energy" as an explicit functional on arbitrary point configurations of constant average density in the plane and on the real line. The definition is inspired by ideas of Sandier and Serfaty (From the Ginzburg-Landau model to vortex lattice problems, 2012; 1D log-gases and the renormalized energy, 2013). Roughly speaking, it is obtained by subtracting two leading terms from the Coulomb potential on a growing number of charges. The functional is expected to be a good measure of disorder of a configuration of points. We give certain formulas for its expectation for general stationary random point processes. For the random matrix β-sine processes on the real line ( β = 1,2,4), and Ginibre point process and zeros of Gaussian analytic functions process in the plane, we compute the expectation explicitly. Moreover, we prove that for these processes the variance of the renormalized energy vanishes, which shows concentration near the expected value. We also prove that the β = 2 sine process minimizes the renormalized energy in the class of determinantal point processes with translation invariant correlation kernels.

Three-part joint modeling methods for complex functional data mixed with zero-and-one-inflated proportions and zero-inflated continuous outcomes with skewness.

PubMed

Li, Haocheng; Staudenmayer, John; Wang, Tianying; Keadle, Sarah Kozey; Carroll, Raymond J

2018-02-20

We take a functional data approach to longitudinal studies with complex bivariate outcomes. This work is motivated by data from a physical activity study that measured 2 responses over time in 5-minute intervals. One response is the proportion of time active in each interval, a continuous proportions with excess zeros and ones. The other response, energy expenditure rate in the interval, is a continuous variable with excess zeros and skewness. This outcome is complex because there are 3 possible activity patterns in each interval (inactive, partially active, and completely active), and those patterns, which are observed, induce both nonrandom and random associations between the responses. More specifically, the inactive pattern requires a zero value in both the proportion for active behavior and the energy expenditure rate; a partially active pattern means that the proportion of activity is strictly between zero and one and that the energy expenditure rate is greater than zero and likely to be moderate, and the completely active pattern means that the proportion of activity is exactly one, and the energy expenditure rate is greater than zero and likely to be higher. To address these challenges, we propose a 3-part functional data joint modeling approach. The first part is a continuation-ratio model to reorder the ordinal valued 3 activity patterns. The second part models the proportions when they are in interval (0,1). The last component specifies the skewed continuous energy expenditure rate with Box-Cox transformations when they are greater than zero. In this 3-part model, the regression structures are specified as smooth curves measured at various time points with random effects that have a correlation structure. The smoothed random curves for each variable are summarized using a few important principal components, and the association of the 3 longitudinal components is modeled through the association of the principal component scores. The difficulties in handling the ordinal and proportional variables are addressed using a quasi-likelihood type approximation. We develop an efficient algorithm to fit the model that also involves the selection of the number of principal components. The method is applied to physical activity data and is evaluated empirically by a simulation study. Copyright © 2017 John Wiley & Sons, Ltd.

A neural network potential energy surface for the NaH2 system and dynamics studies on the H(2S) + NaH(X1Σ+) → Na(2S) + H2(X1Σg+) reaction.

PubMed

Wang, Shufen; Yuan, Jiuchuang; Li, Huixing; Chen, Maodu

2017-08-02

In order to study the dynamics of the reaction H( 2 S) + NaH(X 1 Σ + ) → Na( 2 S) + H 2 (X 1 Σ g + ), a new potential energy surface (PES) for the ground state of the NaH 2 system is constructed based on 35 730 ab initio energy points. Using basis sets of quadruple zeta quality, multireference configuration interaction calculations with Davidson correction were carried out to obtain the ab initio energy points. The neural network method is used to fit the PES, and the root mean square error is very small (0.00639 eV). The bond lengths, dissociation energies, zero-point energies and spectroscopic constants of H 2 (X 1 Σ g + ) and NaH(X 1 Σ + ) obtained on the new NaH 2 PES are in good agreement with the experiment data. On the new PES, the reactant coordinate-based time-dependent wave packet method is applied to study the reaction dynamics of H( 2 S) + NaH(X 1 Σ + ) → Na( 2 S) + H 2 (X 1 Σ g + ), and the reaction probabilities, integral cross-sections (ICSs) and differential cross-sections (DCSs) are obtained. There is no threshold in the reaction due to the absence of an energy barrier on the minimum energy path. When the collision energy increases, the ICSs decrease from a high value at low collision energy. The DCS results show that the angular distribution of the product molecules tends to the forward direction. Compared with the LiH 2 system, the NaH 2 system has a larger mass and the PES has a larger well at the H-NaH configuration, which leads to a higher ICS value in the H( 2 S) + NaH(X 1 Σ + ) → Na( 2 S) + H 2 (X 1 Σ g + ) reaction. Because the H( 2 S) + NaH(X 1 Σ + ) → Na( 2 S) + H 2 (X 1 Σ g + ) reaction releases more energy, the product molecules can be excited to a higher vibrational state.

Zero-bias photocurrent in ferromagnetic topological insulator.

PubMed

Ogawa, N; Yoshimi, R; Yasuda, K; Tsukazaki, A; Kawasaki, M; Tokura, Y

2016-07-20

Magnetic interactions in topological insulators cause essential modifications in the originally mass-less surface states. They offer a mass gap at the Dirac point and/or largely deform the energy dispersion, providing a new path towards exotic physics and applications to realize dissipation-less electronics. The nonequilibrium electron dynamics at these modified Dirac states unveil additional functions, such as highly efficient photon to spin-current conversion. Here we demonstrate the generation of large zero-bias photocurrent in magnetic topological insulator thin films on mid-infrared photoexcitation, pointing to the controllable band asymmetry in the momentum space. The photocurrent spectra with a maximal response to the intra-Dirac-band excitations can be a sensitive measure for the correlation between Dirac electrons and magnetic moments.

Fine structural features of nanoscale zero-valent iron characterized by spherical aberration corrected scanning transmission electron microscopy (Cs-STEM).

PubMed

Liu, Airong; Zhang, Wei-xian

2014-09-21

An angstrom-resolution physical model of nanoscale zero-valent iron (nZVI) is generated with a combination of spherical aberration corrected scanning transmission electron microscopy (Cs-STEM), selected area electron diffraction (SAED), energy-dispersive X-ray spectroscopy (EDS) and electron energy-loss spectroscopy (EELS) on the Fe L-edge. Bright-field (BF), high-angle annular dark-field (HAADF) and secondary electron (SE) imaging of nZVI acquired by a Hitachi HD-2700 STEM show near atomic resolution images and detailed morphological and structural information of nZVI. The STEM-EDS technique confirms that the fresh nZVI comprises of a metallic iron core encapsulated with a thin layer of iron oxides or oxyhydroxides. SAED patterns of the Fe core suggest the polycrystalline structure in the metallic core and amorphous nature of the oxide layer. Furthermore, Fe L-edge of EELS shows varied structural features from the innermost Fe core to the outer oxide shell. A qualitative analysis of the Fe L(2,3) edge fine structures reveals that the shell of nZVI consists of a mixed Fe(II)/Fe(III) phase close to the Fe (0) interface and a predominantly Fe(III) at the outer surface of nZVI.

Aspects of the zero Λ limit in the AdS/CFT correspondence

NASA Astrophysics Data System (ADS)

Caldeira Costa, R. N.

2014-11-01

We examine the correspondence between QFT observables and bulk solutions in the context of AdS/CFT in the limit as the cosmological constant Λ →0 . We focus specifically on the spacetime metric and a nonbackreacting scalar in the bulk, compute the one-point functions of the dual operators, and determine the necessary conditions for the correspondence to admit a well-behaved zero-Λ limit. We discuss holographic renormalization in this limit and find that it requires schemes that partially break diffeomorphism invariance of the bulk theory. In the specific case of three bulk dimensions, we compute the zero-Λ limit of the holographic Weyl anomaly and reproduce the central charge that arises in the central extension of bms3 . We compute holographically the energy and momentum of those QFT states dual to flat cosmological solutions and to the Kerr solution and find an agreement with the bulk theory. We also compute holographically the renormalized two-point function of a scalar operator in the zero-Λ limit and find it to be consistent with that of a conformal operator in two dimensions fewer. Finally, our results can be used in a new definition of asymptotic Ricci flatness at null infinity based on the zero-Λ limit of asymptotically Einstein manifolds.

Theoretical and kinetic study of the hydrogen atom abstraction reactions of esters with H(O.)2 radicals.

PubMed

Mendes, Jorge; Zhou, Chong-Wen; Curran, Henry J

2013-12-27

This work details an ab initio and chemical kinetic study of the hydrogen atom abstraction reactions by the hydroperoxyl radical (HȮ2) on the following esters: methyl ethanoate, methyl propanoate, methyl butanoate, methyl pentanoate, methyl isobutyrate, ethyl ethanoate, propyl ethanoate, and isopropyl ethanoate. Geometry optimizations and frequency calculations of all of the species involved, as well as the hindrance potential descriptions for reactants and transition states, have been performed with the Møller-Plesset (MP2) method using the 6-311G(d,p) basis set. A validation of all of the connections between transition states and local minima was performed by intrinsic reaction coordinate calculations. Electronic energies for all of the species are reported at the CCSD(T)/cc-pVTZ level of theory in kcal mol(-1) with the zero-point energy corrections. The CCSD(T)/CBS (extrapolated from CCSD(T)/cc-pVXZ, in which X = D, T, Q) was used for the reactions of methyl ethanoate + HȮ2 radicals as a benchmark in the electronic energy calculations. High-pressure limit rate constants, in the temperature range 500-2000 K, have been calculated for all of the reaction channels using conventional transition state theory with asymmetric Eckart tunneling corrections. The 1-D hindered rotor approximation has been used for the low frequency torsional modes in both reactants and transition states. The calculated individual and total rate constants are reported for all of the reaction channels in each reaction system. A branching ratio analysis for each reaction site has also been investigated for all of the esters studied in this work.

Nanoscale zero-valent metals: a review of synthesis, characterization, and applications to environmental remediation.

PubMed

Li, Lingyun; Hu, Jiwei; Shi, Xuedan; Fan, Mingyi; Luo, Jin; Wei, Xionghui

2016-09-01

Engineered nanoscale zero-valent metals (NZVMs) representing the forefront of technologies have been considered as promising materials for environmental remediation and antimicrobial effect, due to their high reducibility and strong adsorption capability. This review is focused on the methodology for synthesis of bare NZVMs, supported NZVMs, modified NZVMs, and bimetallic systems with both traditional and green methods. Recent studies have demonstrated that self-assembly methods can play an important role for obtaining ordered, controllable, and tunable NZVMs. In addition to common characterization methods, the state-of-the-art methods have been developed to obtain the properties of NZVMs (e.g., granularity, size distribution, specific surface area, shape, crystal form, and chemical bond) with the resolution down to subnanometer scale. These methods include spherical aberration corrected scanning transmission electron microscopy (Cs-corrected STEM), electron energy-loss spectroscopy (EELS), and near edge X-ray absorption fine structure (NEXAFS). A growing body of experimental data has proven that nanoscale zero-valent iron (NZVI) is highly effective and versatile. This article discusses the applications of NZVMs to treatment of heavy metals, halogenated organic compounds, polycyclic aromatic hydrocarbons, nutrients, radioelements, and microorganisms, using both ex situ and in situ methods. Furthermore, this paper briefly describes the ecotoxicological effects for NZVMs and the research prospects related to their synthesis, modification, characterization, and applications.

Chemical Reaction Rates from Ring Polymer Molecular Dynamics: Zero Point Energy Conservation in Mu + H2 → MuH + H.

PubMed

Pérez de Tudela, Ricardo; Aoiz, F J; Suleimanov, Yury V; Manolopoulos, David E

2012-02-16

A fundamental issue in the field of reaction dynamics is the inclusion of the quantum mechanical (QM) effects such as zero point energy (ZPE) and tunneling in molecular dynamics simulations, and in particular in the calculation of chemical reaction rates. In this work we study the chemical reaction between a muonium atom and a hydrogen molecule. The recently developed ring polymer molecular dynamics (RPMD) technique is used, and the results are compared with those of other methods. For this reaction, the thermal rate coefficients calculated with RPMD are found to be in excellent agreement with the results of an accurate QM calculation. The very minor discrepancies are within the convergence error even at very low temperatures. This exceptionally good agreement can be attributed to the dominant role of ZPE in the reaction, which is accounted for extremely well by RPMD. Tunneling only plays a minor role in the reaction.

A Comparison of Density Functional Theory with Ab initio Approaches for Systems Involving First Transition Row Metals

NASA Technical Reports Server (NTRS)

Ricca, Alessandra; Bauschlicher, Charles W.; Langhoff, Stephen R. (Technical Monitor)

1994-01-01

Density functional theory (DFT) is found to give a better description of the geometries and vibrational frequencies of FeL and FeL(sup +) systems than second order Moller Plesset perturbation theory (MP2). Namely, the DFT correctly predicts the shift in the CO vibrational frequency between free CO and the Sigma(sup -) state of FeCO and yields a good result for the Fe-C distance in the quartet states of FeCH4(+) 4 These are properties where the MP2 results are unsatisfactory. Thus DFT appears to be an excellent approach for optimizing the geometries and computing the zero-point energies of systems containing first transition row atoms. Because the DFT approach is biased in favor of the 3d(exp 7) occupation, whereas the more traditional approaches are biased in favor of the 3d(exp 6) occupation, differences are found in the relative ordering of states. It is shown that if the dissociation is computed to the most appropriate atomic asymptote and corrected to the ground state asymptote using the experimental separations, the DFT results are in good agreement with high levels of theory. The energetics at the DFT level are much superior to the MP2 and in most cases in good agreement with high levels of theory.

Research on a high-precision calibration method for tunable lasers

NASA Astrophysics Data System (ADS)

Xiang, Na; Li, Zhengying; Gui, Xin; Wang, Fan; Hou, Yarong; Wang, Honghai

2018-03-01

Tunable lasers are widely used in the field of optical fiber sensing, but nonlinear tuning exists even for zero external disturbance and limits the accuracy of the demodulation. In this paper, a high-precision calibration method for tunable lasers is proposed. A comb filter is introduced and the real-time output wavelength and scanning rate of the laser are calibrated by linear fitting several time-frequency reference points obtained from it, while the beat signal generated by the auxiliary interferometer is interpolated and frequency multiplied to find more accurate zero crossing points, with these points being used as wavelength counters to resample the comb signal to correct the nonlinear effect, which ensures that the time-frequency reference points of the comb filter are linear. A stability experiment and a strain sensing experiment verify the calibration precision of this method. The experimental result shows that the stability and wavelength resolution of the FBG demodulation can reach 0.088 pm and 0.030 pm, respectively, using a tunable laser calibrated by the proposed method. We have also compared the demodulation accuracy in the presence or absence of the comb filter, with the result showing that the introduction of the comb filter results to a 15-fold wavelength resolution enhancement.

Influence of the starting temperature of calorimetric measurements on the accuracy of determined magnetocaloric effect

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

Moreno-Ramirez, L. M.; Franco, V.; Conde, A.

Availability of a restricted heat capacity data range has a clear influence on the accuracy of calculated magnetocaloric effect, as confirmed by both numerical simulations and experimental measurements. Simulations using the Bean-Rodbell model show that, in general, the approximated magnetocaloric effect curves calculated using a linear extrapolation of the data starting from a selected temperature point down to zero kelvin deviate in a non-monotonic way from those correctly calculated by fully integrating the data from near zero temperatures. However, we discovered that a particular temperature range exists where the approximated magnetocaloric calculation provides the same result as the fully integratedmore » one. These specific truncated intervals exist for both first and second order phase transitions and are the same for the adiabatic temperature change and magnetic entropy change curves. Here, the effect of this truncated integration in real samples was confirmed using heat capacity data of Gd metal and Gd 5Si 2Ge 2 compound measured from near zero temperatures.« less

Influence of the starting temperature of calorimetric measurements on the accuracy of determined magnetocaloric effect

DOE PAGES

Moreno-Ramirez, L. M.; Franco, V.; Conde, A.; ...

2018-02-27

Availability of a restricted heat capacity data range has a clear influence on the accuracy of calculated magnetocaloric effect, as confirmed by both numerical simulations and experimental measurements. Simulations using the Bean-Rodbell model show that, in general, the approximated magnetocaloric effect curves calculated using a linear extrapolation of the data starting from a selected temperature point down to zero kelvin deviate in a non-monotonic way from those correctly calculated by fully integrating the data from near zero temperatures. However, we discovered that a particular temperature range exists where the approximated magnetocaloric calculation provides the same result as the fully integratedmore » one. These specific truncated intervals exist for both first and second order phase transitions and are the same for the adiabatic temperature change and magnetic entropy change curves. Here, the effect of this truncated integration in real samples was confirmed using heat capacity data of Gd metal and Gd 5Si 2Ge 2 compound measured from near zero temperatures.« less

Vibrational energies for HFCO using a neural network sum of exponentials potential energy surface

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

Pradhan, Ekadashi; Brown, Alex, E-mail: alex.brown@ualberta.ca

2016-05-07

A six-dimensional potential energy surface (PES) for formyl fluoride (HFCO) is fit in a sum-of-products form using neural network exponential fitting functions. The ab initio data upon which the fit is based were computed at the explicitly correlated coupled cluster with single, double, and perturbative triple excitations [CCSD(T)-F12]/cc-pVTZ-F12 level of theory. The PES fit is accurate (RMSE = 10 cm{sup −1}) up to 10 000 cm{sup −1} above the zero point energy and covers most of the experimentally measured IR data. The PES is validated by computing vibrational energies for both HFCO and deuterated formyl fluoride (DFCO) using block improved relaxationmore » with the multi-configuration time dependent Hartree approach. The frequencies of the fundamental modes, and all other vibrational states up to 5000 cm{sup −1} above the zero-point energy, are more accurate than those obtained from the previous MP2-based PES. The vibrational frequencies obtained on the PES are compared to anharmonic frequencies at the MP2/aug-cc-pVTZ and CCSD(T)/aug-cc-pVTZ levels of theory obtained using second-order vibrational perturbation theory. The new PES will be useful for quantum dynamics simulations for both HFCO and DFCO, e.g., studies of intramolecular vibrational redistribution leading to unimolecular dissociation and its laser control.« less

Ground-state energies of simple metals

NASA Technical Reports Server (NTRS)

Hammerberg, J.; Ashcroft, N. W.

1974-01-01

A structural expansion for the static ground-state energy of a simple metal is derived. Two methods are presented, one an approach based on single-particle band structure which treats the electron gas as a nonlinear dielectric, the other a more general many-particle analysis using finite-temperature perturbation theory. The two methods are compared, and it is shown in detail how band-structure effects, Fermi-surface distortions, and chemical-potential shifts affect the total energy. These are of special interest in corrections to the total energy beyond third order in the electron-ion interaction and hence to systems where differences in energies for various crystal structures are exceptionally small. Preliminary calculations using these methods for the zero-temperature thermodynamic functions of atomic hydrogen are reported.

Structural expansions for the ground state energy of a simple metal

NASA Technical Reports Server (NTRS)

Hammerberg, J.; Ashcroft, N. W.

1973-01-01

A structural expansion for the static ground state energy of a simple metal is derived. An approach based on single particle band structure which treats the electron gas as a non-linear dielectric is presented, along with a more general many particle analysis using finite temperature perturbation theory. The two methods are compared, and it is shown in detail how band-structure effects, Fermi surface distortions, and chemical potential shifts affect the total energy. These are of special interest in corrections to the total energy beyond third order in the electron ion interaction, and hence to systems where differences in energies for various crystal structures are exceptionally small. Preliminary calculations using these methods for the zero temperature thermodynamic functions of atomic hydrogen are reported.

F+ and F⁻ affinities of simple N(x)F(y) and O(x)F(y) compounds.

PubMed

Grant, Daniel J; Wang, Tsang-Hsiu; Vasiliu, Monica; Dixon, David A; Christe, Karl O

2011-03-07

Atomization energies at 0 K and heats of formation at 0 and 298 K are predicted for the neutral and ionic N(x)F(y) and O(x)F(y) systems using coupled cluster theory with single and double excitations and including a perturbative triples correction (CCSD(T)) method with correlation consistent basis sets extrapolated to the complete basis set (CBS) limit. To achieve near chemical accuracy (±1 kcal/mol), three corrections to the electronic energy were added to the frozen core CCSD(T)/CBS binding energies: corrections for core-valence, scalar relativistic, and first order atomic spin-orbit effects. Vibrational zero point energies were computed at the CCSD(T) level of theory where possible. The calculated heats of formation are in good agreement with the available experimental values, except for FOOF because of the neglect of higher order correlation corrections. The F(+) affinity in the N(x)F(y) series increases from N(2) to N(2)F(4) by 63 kcal/mol, while that in the O(2)F(y) series decreases by 18 kcal/mol from O(2) to O(2)F(2). Neither N(2) nor N(2)F(4) is predicted to bind F(-), and N(2)F(2) is a very weak Lewis acid with an F(-) affinity of about 10 kcal/mol for either the cis or trans isomer. The low F(-) affinities of the nitrogen fluorides explain why, in spite of the fact that many stable nitrogen fluoride cations are known, no nitrogen fluoride anions have been isolated so far. For example, the F(-) affinity of NF is predicted to be only 12.5 kcal/mol which explains the numerous experimental failures to prepare NF(2)(-) salts from the well-known strong acid HNF(2). The F(-) affinity of O(2) is predicted to have a small positive value and increases for O(2)F(2) by 23 kcal/mol, indicating that the O(2)F(3)(-) anion might be marginally stable at subambient temperatures. The calculated adiabatic ionization potentials and electron affinities are in good agreement with experiment considering that many of the experimental values are for vertical processes. © 2011 American Chemical Society

40 CFR 503.44 - Operational standard-total hydrocarbons.

Code of Federal Regulations, 2012 CFR

2012-07-01

... incinerator shall be corrected for zero percent moisture by multiplying the measured total hydrocarbons... the percent moisture in the sewage sludge incinerator exit gas in hundredths. (b) The total... the exit gas from a sewage sludge incinerator stack, corrected for zero percent moisture using the...

40 CFR 503.44 - Operational standard-total hydrocarbons.

Code of Federal Regulations, 2014 CFR

2014-07-01

... incinerator shall be corrected for zero percent moisture by multiplying the measured total hydrocarbons... the percent moisture in the sewage sludge incinerator exit gas in hundredths. (b) The total... the exit gas from a sewage sludge incinerator stack, corrected for zero percent moisture using the...

40 CFR 503.44 - Operational standard-total hydrocarbons.

Code of Federal Regulations, 2013 CFR

2013-07-01

... incinerator shall be corrected for zero percent moisture by multiplying the measured total hydrocarbons... the percent moisture in the sewage sludge incinerator exit gas in hundredths. (b) The total... the exit gas from a sewage sludge incinerator stack, corrected for zero percent moisture using the...

Nonempirical Semilocal Free-Energy Density Functional for Matter under Extreme Conditions

DOE PAGES

Karasiev, Valentin V.; Dufty, James W.; Trickey, S. B.

2018-02-14

The potential for density functional calculations to predict the properties of matter under extreme conditions depends crucially upon having a non-empirical approximate free energy functional valid over a wide range of state conditions. Unlike the ground-state case, no such free-energy exchange- correlation (XC) functional exists. We remedy that with systematic construction of a generalized gradient approximation XC free-energy functional based on rigorous constraints, including the free energy gradient expansion. The new functional provides the correct temperature dependence in the slowly varying regime and the correct zero-T, high-T, and homogeneous electron gas limits. Application in Kohn-Sham calculations for hot electrons inmore » a static fcc Aluminum lattice demon- strates the combined magnitude of thermal and gradient effects handled by this functional. Its accuracy in the increasingly important warm dense matter regime is attested by excellent agreement of the calculated deuterium equation of state with reference path integral Monte Carlo results at intermediate and elevated temperatures and by low density Al calculations over a wide T range.« less

Nonempirical Semilocal Free-Energy Density Functional for Matter under Extreme Conditions

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

Karasiev, Valentin V.; Dufty, James W.; Trickey, S. B.

The potential for density functional calculations to predict the properties of matter under extreme conditions depends crucially upon having a non-empirical approximate free energy functional valid over a wide range of state conditions. Unlike the ground-state case, no such free-energy exchange- correlation (XC) functional exists. We remedy that with systematic construction of a generalized gradient approximation XC free-energy functional based on rigorous constraints, including the free energy gradient expansion. The new functional provides the correct temperature dependence in the slowly varying regime and the correct zero-T, high-T, and homogeneous electron gas limits. Application in Kohn-Sham calculations for hot electrons inmore » a static fcc Aluminum lattice demon- strates the combined magnitude of thermal and gradient effects handled by this functional. Its accuracy in the increasingly important warm dense matter regime is attested by excellent agreement of the calculated deuterium equation of state with reference path integral Monte Carlo results at intermediate and elevated temperatures and by low density Al calculations over a wide T range.« less

Research on fully distributed optical fiber sensing security system localization algorithm

NASA Astrophysics Data System (ADS)

Wu, Xu; Hou, Jiacheng; Liu, Kun; Liu, Tiegen

2013-12-01

A new fully distributed optical fiber sensing and location technology based on the Mach-Zehnder interferometers is studied. In this security system, a new climbing point locating algorithm based on short-time average zero-crossing rate is presented. By calculating the zero-crossing rates of the multiple grouped data separately, it not only utilizes the advantages of the frequency analysis method to determine the most effective data group more accurately, but also meets the requirement of the real-time monitoring system. Supplemented with short-term energy calculation group signal, the most effective data group can be quickly picked out. Finally, the accurate location of the climbing point can be effectively achieved through the cross-correlation localization algorithm. The experimental results show that the proposed algorithm can realize the accurate location of the climbing point and meanwhile the outside interference noise of the non-climbing behavior can be effectively filtered out.

Expanding space-time and variable vacuum energy

NASA Astrophysics Data System (ADS)

Parmeggiani, Claudio

2017-08-01

The paper describes a cosmological model which contemplates the presence of a vacuum energy varying, very slightly (now), with time. The constant part of the vacuum energy generated, some 6 Gyr ago, a deceleration/acceleration transition of the metric expansion; so now, in an aged Universe, the expansion is inexorably accelerating. The vacuum energy varying part is instead assumed to be eventually responsible of an acceleration/deceleration transition, which occurred about 14 Gyr ago; this transition has a dynamic origin: it is a consequence of the general relativistic Einstein-Friedmann equations. Moreover, the vacuum energy (constant and variable) is here related to the zero-point energy of some quantum fields (scalar, vector, or spinor); these fields are necessarily described in a general relativistic way: their structure depends on the space-time metric, typically non-flat. More precisely, the commutators of the (quantum field) creation/annihilation operators are here assumed to depend on the local value of the space-time metric tensor (and eventually of its curvature); furthermore, these commutators rapidly decrease for high momentum values and they reduce to the standard ones for a flat metric. In this way, the theory is ”gravitationally” regularized; in particular, the zero-point (vacuum) energy density has a well defined value and, for a non static metric, depends on the (cosmic) time. Note that this varying vacuum energy can be negative (Fermi fields) and that a change of its sign typically leads to a minimum for the metric expansion factor (a ”bounce”).

Zero-Point Spin-Fluctuations of Single Adatoms.

PubMed

Ibañez-Azpiroz, Julen; Dos Santos Dias, Manuel; Blügel, Stefan; Lounis, Samir

2016-07-13

Stabilizing the magnetic signal of single adatoms is a crucial step toward their successful usage in widespread technological applications such as high-density magnetic data storage devices. The quantum mechanical nature of these tiny objects, however, introduces intrinsic zero-point spin-fluctuations that tend to destabilize the local magnetic moment of interest by dwindling the magnetic anisotropy potential barrier even at absolute zero temperature. Here, we elucidate the origins and quantify the effect of the fundamental ingredients determining the magnitude of the fluctuations, namely, the (i) local magnetic moment, (ii) spin-orbit coupling, and (iii) electron-hole Stoner excitations. Based on a systematic first-principles study of 3d and 4d adatoms, we demonstrate that the transverse contribution of the fluctuations is comparable in size to the magnetic moment itself, leading to a remarkable ≳50% reduction of the magnetic anisotropy energy. Our analysis gives rise to a comprehensible diagram relating the fluctuation magnitude to characteristic features of adatoms, providing practical guidelines for designing magnetically stable nanomagnets with minimal quantum fluctuations.

Forcing Regression through a Given Point Using Any Familiar Computational Routine.

DTIC Science & Technology

1983-03-01

a linear model , Y =a + OX + e ( Model I) then adopt the principle of least squares; and use sample data to estimate the unknown parameters, a and 8...has an expected value of zero indicates that the "average" response is considered linear . If c varies widely, Model I, though conceptually correct, may...relationship is linear from the maximum observed x to x - a, then Model II should be used. To pro- ceed with the customary evaluation of Model I would be

The elimination of zero-order diffraction of 10.6 μm infrared digital holography

NASA Astrophysics Data System (ADS)

Liu, Ning; Yang, Chao

2017-05-01

A new method of eliminating the zero-order diffraction in infrared digital holography has been raised in this paper. Usually in the reconstruction of digital holography, the spatial frequency of the infrared thermal imager, such as microbolometer, cannot be compared to the common visible CCD or CMOS devices. The infrared imager suffers the problems of large pixel size and low spatial resolution, which cause the zero-order diffraction a severe influence of the reconstruction process of digital holograms. The zero-order diffraction has very large energy and occupies the central region in the spectrum domain. In this paper, we design a new filtering strategy to overcome this problem. This filtering strategy contains two kinds of filtering process which are the Gaussian low-frequency filter and the high-pass phase averaging filter. With the correct set of the calculating parameters, these filtering strategies can work effectively on the holograms and fully eliminate the zero-order diffraction, as well as the two crossover bars shown in the spectrum domain. Detailed explanation and discussion about the new method have been proposed in this paper, and the experiment results are also demonstrated to prove the performance of this method.

FIRST-ORDER COSMOLOGICAL PERTURBATIONS ENGENDERED BY POINT-LIKE MASSES

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

Eingorn, Maxim, E-mail: maxim.eingorn@gmail.com

2016-07-10

In the framework of the concordance cosmological model, the first-order scalar and vector perturbations of the homogeneous background are derived in the weak gravitational field limit without any supplementary approximations. The sources of these perturbations (inhomogeneities) are presented in the discrete form of a system of separate point-like gravitating masses. The expressions found for the metric corrections are valid at all (sub-horizon and super-horizon) scales and converge at all points except at the locations of the sources. The average values of these metric corrections are zero (thus, first-order backreaction effects are absent). Both the Minkowski background limit and the Newtonianmore » cosmological approximation are reached under certain well-defined conditions. An important feature of the velocity-independent part of the scalar perturbation is revealed: up to an additive constant, this part represents a sum of Yukawa potentials produced by inhomogeneities with the same finite time-dependent Yukawa interaction range. The suggested connection between this range and the homogeneity scale is briefly discussed along with other possible physical implications.« less

NASA Net Zero Energy Buildings Roadmap

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

Pless, S.; Scheib, J.; Torcellini, P.

In preparation for the time-phased net zero energy requirement for new federal buildings starting in 2020, set forth in Executive Order 13514, NASA requested that the National Renewable Energy Laboratory (NREL) to develop a roadmap for NASA's compliance. NASA detailed a Statement of Work that requested information on strategic, organizational, and tactical aspects of net zero energy buildings. In response, this document presents a high-level approach to net zero energy planning, design, construction, and operations, based on NREL's first-hand experience procuring net zero energy construction, and based on NREL and other industry research on net zero energy feasibility. The strategicmore » approach to net zero energy starts with an interpretation of the executive order language relating to net zero energy. Specifically, this roadmap defines a net zero energy acquisition process as one that sets an aggressive energy use intensity goal for the building in project planning, meets the reduced demand goal through energy efficiency strategies and technologies, then adds renewable energy in a prioritized manner, using building-associated, emission- free sources first, to offset the annual energy use required at the building; the net zero energy process extends through the life of the building, requiring a balance of energy use and production in each calendar year.« less

Explicit calculation of the two-loop corrections to the chiral magnetic effect with the NJL model

NASA Astrophysics Data System (ADS)

Chu, Kit-fai; Huang, Peng-hui; Liu, Hui

2018-05-01

The chiral magnetic effect (CME) is usually believed to not receive higher-order corrections due to the nonrenormalization of the AVV triangle diagram in the framework of quantum field theory. However, the CME-relevant triangle, which is obtained by expanding the current-current correlation, requires zero momentum on the axial vertex and is not equivalent to the general AVV triangle when taking the zero-momentum limit owing to the infrared problem on the axial vertex. Therefore, it is still significant to check if there exists perturbative higher-order corrections to the current-current correlation. In this paper, we explicitly calculate the two-loop corrections of CME within the Nambu-Jona-Lasinio model with a Chern-Simons term, which ensures a consistent μ5 . The result shows the two-loop corrections to the CME conductivity are zero, which confirms the nonrenomalization of CME conductivity.

Splitting of the zero-energy Landau level and universal dissipative conductivity at critical points in disordered graphene.

PubMed

Ortmann, Frank; Roche, Stephan

2013-02-22

We report on robust features of the longitudinal conductivity (σ(xx)) of the graphene zero-energy Landau level in the presence of disorder and varying magnetic fields. By mixing an Anderson disorder potential with a low density of sublattice impurities, the transition from metallic to insulating states is theoretically explored as a function of Landau-level splitting, using highly efficient real-space methods to compute the Kubo conductivities (both σ(xx) and Hall σ(xy)). As long as valley degeneracy is maintained, the obtained critical conductivity σ(xx) =/~ 1.4e(2)/h is robust upon an increase in disorder (by almost 1 order of magnitude) and magnetic fields ranging from about 2 to 200 T. When the sublattice symmetry is broken, σ(xx) eventually vanishes at the Dirac point owing to localization effects, whereas the critical conductivities of pseudospin-split states (dictating the width of a σ(xy) = 0 plateau) change to σ(xx) =/~ e(2)/h, regardless of the splitting strength, superimposed disorder, or magnetic strength. These findings point towards the nondissipative nature of the quantum Hall effect in disordered graphene in the presence of Landau level splitting.

Energy conversion modeling of the intrinsic persistent luminescence of solids via energy transfer paths between transition levels.

PubMed

Huang, Bolong; Sun, Mingzi

2017-04-05

An energy conversion model has been established for the intrinsic persistent luminescence in solids related to the native point defect levels, formations, and transitions. In this study, we showed how the recombination of charge carriers between different defect levels along the zero phonon line (ZPL) can lead to energy conversions supporting the intrinsic persistent phosphorescence in solids. This suggests that the key driving force for this optical phenomenon is the pair of electrons hopping between different charged defects with negative-U eff . Such a negative correlation energy will provide a sustainable energy source for electron-holes to further recombine in a new cycle with a specific quantum yield. This will help us to understand the intrinsic persistent luminescence with respect to native point defect levels as well as the correlations of electronics and energetics.

Estimating the intrinsic limit of the Feller-Peterson-Dixon composite approach when applied to adiabatic ionization potentials in atoms and small molecules

NASA Astrophysics Data System (ADS)

Feller, David

2017-07-01

Benchmark adiabatic ionization potentials were obtained with the Feller-Peterson-Dixon (FPD) theoretical method for a collection of 48 atoms and small molecules. In previous studies, the FPD method demonstrated an ability to predict atomization energies (heats of formation) and electron affinities well within a 95% confidence level of ±1 kcal/mol. Large 1-particle expansions involving correlation consistent basis sets (up to aug-cc-pV8Z in many cases and aug-cc-pV9Z for some atoms) were chosen for the valence CCSD(T) starting point calculations. Despite their cost, these large basis sets were chosen in order to help minimize the residual basis set truncation error and reduce dependence on approximate basis set limit extrapolation formulas. The complementary n-particle expansion included higher order CCSDT, CCSDTQ, or CCSDTQ5 (coupled cluster theory with iterative triple, quadruple, and quintuple excitations) corrections. For all of the chemical systems examined here, it was also possible to either perform explicit full configuration interaction (CI) calculations or to otherwise estimate the full CI limit. Additionally, corrections associated with core/valence correlation, scalar relativity, anharmonic zero point vibrational energies, non-adiabatic effects, and other minor factors were considered. The root mean square deviation with respect to experiment for the ionization potentials was 0.21 kcal/mol (0.009 eV). The corresponding level of agreement for molecular enthalpies of formation was 0.37 kcal/mol and for electron affinities 0.20 kcal/mol. Similar good agreement with experiment was found in the case of molecular structures and harmonic frequencies. Overall, the combination of energetic, structural, and vibrational data (655 comparisons) reflects the consistent ability of the FPD method to achieve close agreement with experiment for small molecules using the level of theory applied in this study.

Fixing Stellarator Magnetic Surfaces

NASA Astrophysics Data System (ADS)

Hanson, James D.

1999-11-01

Magnetic surfaces are a perennial issue for stellarators. The design heuristic of finding a magnetic field with zero perpendicular component on a specified outer surface often yields inner magnetic surfaces with very small resonant islands. However, magnetic fields in the laboratory are not design fields. Island-causing errors can arise from coil placement errors, stray external fields, and design inadequacies such as ignoring coil leads and incomplete characterization of current distributions within the coil pack. The problem addressed is how to eliminate such error-caused islands. I take a perturbation approach, where the zero order field is assumed to have good magnetic surfaces, and comes from a VMEC equilibrium. The perturbation field consists of error and correction pieces. The error correction method is to determine the correction field so that the sum of the error and correction fields gives zero island size at specified rational surfaces. It is particularly important to correctly calculate the island size for a given perturbation field. The method works well with many correction knobs, and a Singular Value Decomposition (SVD) technique is used to determine minimal corrections necessary to eliminate islands.

Phase stability of TiO 2 polymorphs from diffusion Quantum Monte Carlo

DOE PAGES

Luo, Ye; Benali, Anouar; Shulenburger, Luke; ...

2016-11-24

Titanium dioxide, TiO 2, has multiple applications in catalysis, energy conversion and memristive devices because of its electronic structure. Most of applications utilize the naturally existing phases: rutile, anatase and brookite. In spite of the simple form of TiO 2 and its wide uses, there is long- standing disagreement between theory and experiment on the energetic ordering of these phases that has never been resolved. We present the first analysis of phase stability at zero temperature using the highly accurate many-body fixed node diffusion Quantum Monte Carlo (QMC) method. We include temperature effects by calculating the Helmholtz free energy includingmore » both internal energy corrected by QMC and vibrational contributions from phonon calculations within the quasi harmonic approximation via density functional perturbation theory. Our QMC calculations find that anatase is the most stable phase at zero temperature, consistent with many previous mean- field calculations. Furthermore, at elevated temperatures, rutile becomes the most stable phase. For all finite temperatures, brookite is always the least stable phase.« less

An abbreviated Reynolds stress turbulence model for airfoil flows

NASA Technical Reports Server (NTRS)

Gaffney, R. L., Jr.; Hassan, H. A.; Salas, M. D.

1990-01-01

An abbreviated Reynolds stress turbulence model is presented for solving turbulent flow over airfoils. The model consists of two partial differential equations, one for the Reynolds shear stress and the other for the turbulent kinetic energy. The normal stresses and the dissipation rate of turbulent kinetic energy are computed from algebraic relationships having the correct asymptotic near wall behavior. This allows the model to be integrated all the way to the wall without the use of wall functions. Results for a flat plate at zero angle of attack, a NACA 0012 airfoil and a RAE 2822 airfoil are presented.

Quantification of the Relationship between Surrogate Fuel Structure and Performance

DTIC Science & Technology

2012-07-31

order to account for know deficiencies [18]. The frequencies are then used to calculate the zero point energy ( ZPE ). In the G3 theory HF/6-31G* was used...for the ZPE and the new procedure is likely to be more reliable. Also in contrast to previous G series composite methods, the Hartree–Fock energy...The total energy is obtained by adding the previously calculated ZPE . Durant and Rohlfing [38] reported that B3LYP density functional methods provide

Characterization of the HSiN HNSi system in its electronic ground state

NASA Astrophysics Data System (ADS)

Lind, Maria C.; Pickard, Frank C.; Ingels, Justin B.; Paul, Ankan; Yamaguchi, Yukio; Schaefer, Henry F.

2009-03-01

The electronic ground states (X˜Σ+1) of HSiN, HNSi, and the transition state connecting the two isomers were systematically studied using configuration interaction with single and double (CISD) excitations, coupled cluster with single and double (CCSD) excitations, CCSD with perturbative triple corrections [CCSD(T)], multireference complete active space self-consistent field (CASSCF), and internally contracted multireference configuration interaction (ICMRCI) methods. The correlation-consistent polarized valence (cc-pVXZ), augmented correlation-consistent polarized valence (aug-cc-pVXZ) (X=T,Q,5), correlation-consistent polarized core-valence (cc-pCVYZ), and augmented correlation-consistent polarized core-valence (aug-cc-pCVYZ) (Y=T,Q) basis sets were used. Via focal point analyses, we confirmed the HNSi isomer as the global minimum on the ground state HSiN HNSi zero-point vibrational energy corrected surface and is predicted to lie 64.7kcalmol-1 (22640cm-1, 2.81eV) below the HSiN isomer. The barrier height for the forward isomerization reaction (HSiN→HNSi) is predicted to be 9.7kcalmol-1, while the barrier height for the reverse process (HNSi→HSiN) is determined to be 74.4kcalmol-1. The dipole moments of the HSiN and HNSi isomers are predicted to be 4.36 and 0.26D, respectively. The theoretical vibrational isotopic shifts for the HSiN/DSiN and HNSi/DNSi isotopomers are in strong agreement with the available experimental values. The dissociation energy for HSiN [HSiN(X˜Σ+1)→H(S2)+SiN(XΣ+2)] is predicted to be D0=59.6kcalmol-1, whereas the dissociation energy for HNSi [HNSi(X˜Σ+1)→H(S2)+NSi(XΣ+2)] is predicted to be D0=125.0kcalmol-1 at the CCSD(T)/aug-cc-pCVQZ level of theory. Anharmonic vibrational frequencies computed using second order vibrational perturbation theory are in good agreement with available matrix isolation experimental data for both HSiN and HNSi isomers root mean squared derivation (RMSD=9cm-1).

Distorting general relativity: gravity's rainbow and f(R) theories at work

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

Garattini, Remo, E-mail: Remo.Garattini@unibg.it

2013-06-01

We compute the Zero Point Energy in a spherically symmetric background combining the high energy distortion of Gravity's Rainbow with the modification induced by a f(R) theory. Here f(R) is a generic analytic function of the Ricci curvature scalar R in 4D and in 3D. The explicit calculation is performed for a Schwarzschild metric. Due to the spherically symmetric property of the Schwarzschild metric we can compare the effects of the modification induced by a f(R) theory in 4D and in 3D. We find that the final effect of the combined theory is to have finite quantities that shift themore » Zero Point Energy. In this context we setup a Sturm-Liouville problem with the cosmological constant considered as the associated eigenvalue. The eigenvalue equation is a reformulation of the Wheeler-DeWitt equation which is analyzed by means of a variational approach based on gaussian trial functionals. With the help of a canonical decomposition, we find that the relevant contribution to one loop is given by the graviton quantum fluctuations around the given background. A final discussion on the connection of our result with the observed cosmological constant is also reported.« less

Many-body effects and ultraviolet renormalization in three-dimensional Dirac materials

NASA Astrophysics Data System (ADS)

Throckmorton, Robert; Hofmann, Johannes; Barnes, Edwin

We develop a theory for electron-electron interaction-induced many-body effects in three dimensional (3D) Weyl or Dirac semimetals, including interaction corrections to the polarizability, electron self-energy, and vertex function, up to second order in the effective fine structure constant of the Dirac material. These results are used to derive the higher-order ultraviolet renormalization of the Fermi velocity, effective coupling, and quasiparticle residue, revealing that the corrections to the renormalization group (RG) flows of both the velocity and coupling counteract the leading-order tendencies of velocity enhancement and coupling suppression at low energies. This in turn leads to the emergence of a critical coupling above which the interaction strength grows with decreasing energy scale. In addition, we identify a range of coupling strengths below the critical point in which the Fermi velocity varies non-monotonically as the low-energy, non-interacting fixed point is approached. Furthermore, we find that while the higher-order correction to the flow of the coupling is generally small compared to the leading order, the corresponding correction to the velocity flow carries an additional factor of the Dirac cone flavor number relative to the leading-order result. Supported by LPS-MPO-CMTC.

Thermodynamic stability of boron: the role of defects and zero point motion.

PubMed

van Setten, Michiel J; Uijttewaal, Matthé A; de Wijs, Gilles A; de Groot, Robert A

2007-03-07

Its low weight, high melting point, and large degree of hardness make elemental boron a technologically interesting material. The large number of allotropes, mostly containing over a hundred atoms in the unit cell, and their difficult characterization challenge both experimentalists and theoreticians. Even the ground state of this element is still under discussion. For over 30 years, scientists have attempted to determine the relative stability of alpha- and beta-rhombohedral boron. We use density functional calculations in the generalized gradient approximation to study a broad range of possible beta-rhombohedral structures containing interstitial atoms and partially occupied sites within a 105 atoms framework. The two most stable structures are practically degenerate in energy and semiconducting. One contains the experimental 320 atoms in the hexagonal unit cell, and the other contains 106 atoms in the triclinic unit cell. When populated with the experimental 320 electrons, the 106 atom structure exhibits a band gap of 1.4 eV and an in-gap hole trap at 0.35 eV above the valence band, consistent with known experiments. The total energy of these two structures is 23 meV/B lower than the original 105 atom framework, but it is still 1 meV/B above the alpha phase. Adding zero point energies finally makes the beta phase the ground state of elemental boron by 3 meV/B. At finite temperatures, the difference becomes even larger.

Branch-point energies and the band-structure lineup at Schottky contacts and heterostrucures

NASA Astrophysics Data System (ADS)

Mönch, Winfried

2011-06-01

Empirical branch-point energies of Si, the group-III nitrides AlN, GaN, and InN, and the group-II and group-III oxides MgO, ZnO, Al2O3 and In2O3 are determined from experimental valance-band offsets of their heterostructures. For Si, GaN, and MgO, these values agree with the branch-point energies obtained from the barrier heights of their Schottky contacts. The empirical branch-point energies of Si and the group-III nitrides are in very good agreement with results of previously published calculations using quite different approaches such as the empirical tight-binding approximation and modern electronic-structure theory. In contrast, the empirical branch-point energies of the group-II and group-III oxides do not confirm the respective theoretical results. As at Schottky contacts, the band-structure lineup at heterostructures is also made up of a zero-charge-transfer term and an intrinsic electric-dipole contribution. Hence, valence-band offsets are not equal to the difference of the branch-point energies of the two semiconductors forming the heterostructure. The electric-dipole term may be described by the electronegativity difference of the two solids in contact. A detailed analysis of experimental Si Schottky barrier heights and heterostructure valence-band offsets explains and proves these conclusions.

Thermodynamic variables of first-order entropy corrected Lovelock-AdS black holes: P{-}V criticality analysis

NASA Astrophysics Data System (ADS)

Haldar, Amritendu; Biswas, Ritabrata

2018-06-01

We investigate the effect of thermal fluctuations on the thermodynamics of a Lovelock-AdS black hole. Taking the first order logarithmic correction term in entropy we analyze the thermodynamic potentials like Helmholtz free energy, enthalpy and Gibbs free energy. We find that all the thermodynamic potentials are decreasing functions of correction coefficient α . We also examined this correction coefficient must be positive by analysing P{-}V diagram. Further we study the P{-}V criticality and stability and find that presence of logarithmic correction in it is necessary to have critical points and stable phases. When P{-}V criticality appears, we calculate the critical volume V_c, critical pressure P_c and critical temperature T_c using different equations and show that there is no critical point for this black hole without thermal fluctuations. We also study the geometrothermodynamics of this kind of black holes. The Ricci scalar of the Ruppeiner metric is graphically analysed.

The Atomization Energy of Mg4

NASA Technical Reports Server (NTRS)

Bauschlicher, Charles W., Jr.; Arnold, James O. (Technical Monitor)

1999-01-01

The atomization energy of Mg4 is determined using the MP2 and CCSD(T) levels of theory. Basis set incompleteness, basis set extrapolation, and core-valence effects are discussed. Our best atomization energy, including the zero-point energy and scalar relativistic effects, is 24.6+/-1.6 kcal per mol. Our computed and extrapolated values are compared with previous results, where it is observed that our extrapolated MP2 value is good agreement with the MP2-R12 value. The CCSD(T) and MP2 core effects are found to have the opposite signs.

Fixing the reference frame for PPMXL proper motions using extragalactic sources

DOE PAGES

Grabowski, Kathleen; Carlin, Jeffrey L.; Newberg, Heidi Jo; ...

2015-05-27

In this study, we quantify and correct systematic errors in PPMXL proper motions using extragalactic sources from the first two LAMOST data releases and the Vèron-Cetty & Vèron Catalog of Quasars. Although the majority of the sources are from the Vèron catalog, LAMOST makes important contributions in regions that are not well-sampled by previous catalogs, particularly at low Galactic latitudes and in the south Galactic cap. We show that quasars in PPMXL have measurable and significant proper motions, which reflect the systematic zero-point offsets present in the catalog. We confirm the global proper motion shifts seen by Wu et al.,more » and additionally find smaller-scale fluctuations of the QSO-derived corrections to an absolute frame. Finally, we average the proper motions of 158 106 extragalactic objects in bins of 3° × 3° and present a table of proper motion corrections.« less

Practical Application Limits of Fuel Cells and Batteries for Zero Emission Vessels

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

Minnehan, John J.; Pratt, Joseph William

Batteries and hydrogen fuel cells provide zero emission power at the point of use. They are studied as an alternative powerplant for maritime vessels by considering 14 case studies of various ship sizes and routes varying from small passenger vessels to the largest cargo ships. The method used was to compare the mass and volume of the required zero emission solution to the available mass and volume on an existing vessel considering its current engine and fuel storage systems. The results show that it is practically feasible to consider these zero emission technologies for most vessels in the world's fleet.more » Hydrogen fuel cells proved to be the most capable while battery systems showed an advantage for high power, short duration missions. The results provide a guide to ship designers to determine the most suitable types of zero emission powerplants to fit a ship based on its size and energy requirements.« less

Casimir free energy of dielectric films: classical limit, low-temperature behavior and control.

PubMed

Klimchitskaya, G L; Mostepanenko, V M

2017-07-12

The Casimir free energy of dielectric films, both free-standing in vacuum and deposited on metallic or dielectric plates, is investigated. It is shown that the values of the free energy depend considerably on whether the calculation approach used neglects or takes into account the dc conductivity of film material. We demonstrate that there are material-dependent and universal classical limits in the former and latter cases, respectively. The analytic behavior of the Casimir free energy and entropy for a free-standing dielectric film at low temperature is found. According to our results, the Casimir entropy goes to zero when the temperature vanishes if the calculation approach with neglected dc conductivity of a film is employed. If the dc conductivity is taken into account, the Casimir entropy takes the positive value at zero temperature, depending on the parameters of a film, i.e. the Nernst heat theorem is violated. By considering the Casimir free energy of SiO 2 and Al 2 O 3 films deposited on a Au plate in the framework of two calculation approaches, we argue that physically correct values are obtained by disregarding the role of dc conductivity. A comparison with the well known results for the configuration of two parallel plates is made. Finally, we compute the Casimir free energy of SiO 2 , Al 2 O 3 and Ge films deposited on high-resistivity Si plates of different thicknesses and demonstrate that it can be positive, negative and equal to zero. The effect of illumination of a Si plate with laser light is considered. Possible applications of the obtained results to thin films used in microelectronics are discussed.

Casimir free energy of dielectric films: classical limit, low-temperature behavior and control

NASA Astrophysics Data System (ADS)

Klimchitskaya, G. L.; Mostepanenko, V. M.

2017-07-01

The Casimir free energy of dielectric films, both free-standing in vacuum and deposited on metallic or dielectric plates, is investigated. It is shown that the values of the free energy depend considerably on whether the calculation approach used neglects or takes into account the dc conductivity of film material. We demonstrate that there are material-dependent and universal classical limits in the former and latter cases, respectively. The analytic behavior of the Casimir free energy and entropy for a free-standing dielectric film at low temperature is found. According to our results, the Casimir entropy goes to zero when the temperature vanishes if the calculation approach with neglected dc conductivity of a film is employed. If the dc conductivity is taken into account, the Casimir entropy takes the positive value at zero temperature, depending on the parameters of a film, i.e. the Nernst heat theorem is violated. By considering the Casimir free energy of SiO2 and Al2O3 films deposited on a Au plate in the framework of two calculation approaches, we argue that physically correct values are obtained by disregarding the role of dc conductivity. A comparison with the well known results for the configuration of two parallel plates is made. Finally, we compute the Casimir free energy of SiO2, Al2O3 and Ge films deposited on high-resistivity Si plates of different thicknesses and demonstrate that it can be positive, negative and equal to zero. The effect of illumination of a Si plate with laser light is considered. Possible applications of the obtained results to thin films used in microelectronics are discussed.

Spherical nanoindentation stress-strain analysis, Version 1

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

Weaver, Jordan S.; Turner, David; Miller, Calvin

Nanoindentation is a tool that allows the mechanical response of a variety of materials at the nano to micron length scale to be measured. Recent advances in spherical nanoindentation techniques have allowed for a more reliable and meaningful characterization of the mechanical response from nanoindentation experiments in the form on an indentation stress-strain curve. This code base, Spin, is written in MATLAB (The Mathworks, Inc.) and based on the analysis protocols developed by S.R. Kalidindi and S. Pathak [1, 2]. The inputs include the displacement, load, harmonic contact stiffness, harmonic displacement, and harmonic load from spherical nanoindentation tests in themore » form of an Excel (Microsoft) spreadsheet. The outputs include indentation stress-strain curves and indentation properties as well their variance due to the uncertainty of the zero-point correction in the form of MATLAB data (.mat) and figures (.png). [1] S. Pathak, S.R. Kalidindi. Spherical nanoindentation stress–strain curves, Mater. Sci. Eng R-Rep 91 (2015). [2] S.R. Kalidindi, S. Pathak. Determination of the effective zero-point and the extraction of spherical nanoindentation stress-strain curves, Acta Materialia 56 (2008) 3523-3532.« less

Majorana bound states from exceptional points in non-topological superconductors

PubMed Central

San-Jose, Pablo; Cayao, Jorge; Prada, Elsa; Aguado, Ramón

2016-01-01

Recent experimental efforts towards the detection of Majorana bound states have focused on creating the conditions for topological superconductivity. Here we demonstrate an alternative route, which achieves fully localised zero-energy Majorana bound states when a topologically trivial superconductor is strongly coupled to a helical normal region. Such a junction can be experimentally realised by e.g. proximitizing a finite section of a nanowire with spin-orbit coupling, and combining electrostatic depletion and a Zeeman field to drive the non-proximitized (normal) portion into a helical phase. Majorana zero modes emerge in such an open system without fine-tuning as a result of charge-conjugation symmetry, and can be ultimately linked to the existence of ‘exceptional points’ (EPs) in parameter space, where two quasibound Andreev levels bifurcate into two quasibound Majorana zero modes. After the EP, one of the latter becomes non-decaying as the junction approaches perfect Andreev reflection, thus resulting in a Majorana dark state (MDS) localised at the NS junction. We show that MDSs exhibit the full range of properties associated to conventional closed-system Majorana bound states (zero-energy, self-conjugation, 4π-Josephson effect and non-Abelian braiding statistics), while not requiring topological superconductivity. PMID:26865011

Effects of zero point vibration on the reaction dynamics of water dimer cations following ionization.

PubMed

Tachikawa, Hiroto

2017-06-30

Reactions of water dimer cation (H2O)2+ following ionization have been investigated by means of a direct ab initio molecular dynamics method. In particular, the effects of zero point vibration and zero point energy (ZPE) on the reaction mechanism were considered in this work. Trajectories were run on two electronic potential energy surfaces (PESs) of (H2O)2+: ground state ( 2 A″-like state) and the first excited state ( 2 A'-like state). All trajectories on the ground-state PES lead to the proton-transferred product: H 2 O + (Wd)-H 2 O(Wa) → OH(Wd)-H 3 O + (Wa), where Wd and Wa refer to the proton donor and acceptor water molecules, respectively. Time of proton transfer (PT) varied widely from 15 to 40 fs (average time of PT = 30.9 fs). The trajectories on the excited-state PES gave two products: an intermediate complex with a face-to-face structure (H 2 O-OH 2 ) + and a PT product. However, the proton was transferred to the opposite direction, and the reverse PT was found on the excited-state PES: H 2 O(Wd)-H 2 O + (Wa) → H 3 O + (Wd)-OH(Wa). This difference occurred because the ionizing water molecule in the dimer switched between the ground and excited states. The reaction mechanism of (H2O)2+ and the effects of ZPE are discussed on the basis of the results. © 2017 Wiley Periodicals, Inc. © 2017 Wiley Periodicals, Inc.

Correcting the initialization of models with fractional derivatives via history-dependent conditions

NASA Astrophysics Data System (ADS)

Du, Maolin; Wang, Zaihua

2016-04-01

Fractional differential equations are more and more used in modeling memory (history-dependent, non-local, or hereditary) phenomena. Conventional initial values of fractional differential equations are defined at a point, while recent works define initial conditions over histories. We prove that the conventional initialization of fractional differential equations with a Riemann-Liouville derivative is wrong with a simple counter-example. The initial values were assumed to be arbitrarily given for a typical fractional differential equation, but we find one of these values can only be zero. We show that fractional differential equations are of infinite dimensions, and the initial conditions, initial histories, are defined as functions over intervals. We obtain the equivalent integral equation for Caputo case. With a simple fractional model of materials, we illustrate that the recovery behavior is correct with the initial creep history, but is wrong with initial values at the starting point of the recovery. We demonstrate the application of initial history by solving a forced fractional Lorenz system numerically.

Computing approximate random Delta v magnitude probability densities. [for spacecraft trajectory correction

NASA Technical Reports Server (NTRS)

Chadwick, C.

1984-01-01

This paper describes the development and use of an algorithm to compute approximate statistics of the magnitude of a single random trajectory correction maneuver (TCM) Delta v vector. The TCM Delta v vector is modeled as a three component Cartesian vector each of whose components is a random variable having a normal (Gaussian) distribution with zero mean and possibly unequal standard deviations. The algorithm uses these standard deviations as input to produce approximations to (1) the mean and standard deviation of the magnitude of Delta v, (2) points of the probability density function of the magnitude of Delta v, and (3) points of the cumulative and inverse cumulative distribution functions of Delta v. The approximates are based on Monte Carlo techniques developed in a previous paper by the author and extended here. The algorithm described is expected to be useful in both pre-flight planning and in-flight analysis of maneuver propellant requirements for space missions.

Chiral anomaly and anomalous finite-size conductivity in graphene

NASA Astrophysics Data System (ADS)

Shen, Shun-Qing; Li, Chang-An; Niu, Qian

2017-09-01

Graphene is a monolayer of carbon atoms packed into a hexagon lattice to host two spin degenerate pairs of massless two-dimensional Dirac fermions with different chirality. It is known that the existence of non-zero electric polarization in reduced momentum space which is associated with a hidden chiral symmetry will lead to the zero-energy flat band of a zigzag nanoribbon and some anomalous transport properties. Here it is proposed that the Adler-Bell-Jackiw chiral anomaly or non-conservation of chiral charges of Dirac fermions at different valleys can be realized in a confined ribbon of finite width, even in the absence of a magnetic field. In the laterally diffusive regime, the finite-size correction to conductivity is always positive and is inversely proportional to the square of the lateral dimension W, which is different from the finite-size correction inversely proportional to W from the boundary modes. This anomalous finite-size conductivity reveals the signature of the chiral anomaly in graphene, and it is measurable experimentally. This finding provides an alternative platform to explore the purely quantum mechanical effect in graphene.

Aberrations in stimulated emission depletion (STED) microscopy

NASA Astrophysics Data System (ADS)

Antonello, Jacopo; Burke, Daniel; Booth, Martin J.

2017-12-01

Like all methods of super-resolution microscopy, stimulated emission depletion (STED) microscopy can suffer from the effects of aberrations. The most important aspect of a STED microscope is that the depletion focus maintains a minimum, ideally zero, intensity point that is surrounded by a region of higher intensity. It follows that aberrations that cause a non-zero value of this minimum intensity are the most detrimental, as they inhibit fluorescence emission even at the centre of the depletion focus. We present analysis that elucidates the nature of these effects in terms of the different polarisation components at the focus for two-dimensional and three-dimensional STED resolution enhancement. It is found that only certain low-order aberration modes can affect the minimum intensity at the Gaussian focus. This has important consequences for the design of adaptive optics aberration correction systems.

Vacuum ultraviolet photoionization mass spectrometric study of cyclohexene.

PubMed

Chen, Jun; Cao, Maoqi; Wei, Bin; Ding, Mengmeng; Shan, Xiaobin; Liu, Fuyi; Sheng, Liusi

2016-02-01

In this work, photoionization and dissociation of cyclohexene have been studied by means of coupling a reflectron time-of-flight mass spectrometer with the tunable vacuum ultraviolet (VUV) synchrotron radiation. The adiabatic ionization energy of cyclohexene as well as the appearance energies of its fragment ions C6 H9 (+) , C6 H7 (+) , C5 H7 (+) , C5 H5 (+) , C4 H6 (+) , C4 H5 (+) , C3 H5 (+) and C3 H3 (+) were derived from the onset of the photoionization efficiency (PIE) curves. The optimized structures for the transition states and intermediates on the ground state potential energy surfaces related to photodissociation of cyclohexene were characterized at the ωB97X-D/6-31+g(d,p) level. The coupled cluster method, CCSD(T)/cc-pVTZ, was employed to calculate the corresponding energies with the zero-point energy corrections by the ωB97X-D/6-31+g(d,p) approach. Combining experimental and theoretical results, possible formation pathways of the fragment ions were proposed and discussed in detail. The retro-Cope rearrangement was found to play a crucial role in the formation of C4 H6 (+) , C4 H5 (+) and C3 H5 (+) . Intramolecular hydrogen migrations were observed as dominant processes in most of the fragmentation pathways of cyclohexene. The present research provides a clear picture of the photoionization and dissociation processes of cyclohexene in the 8- to 15.5-eV photon energy region. Copyright © 2016 John Wiley & Sons, Ltd.

40 CFR 86.1322-84 - Carbon monoxide analyzer calibration.

Code of Federal Regulations, 2010 CFR

2010-07-01

... be used. (2) Zero the carbon monoxide analyzer with either zero-grade air or zero-grade nitrogen. (3... columns is one form of corrective action which may be taken.) (b) Initial and periodic calibration. Prior... calibrated. (1) Adjust the analyzer to optimize performance. (2) Zero the carbon monoxide analyzer with...

Initial Business Case Analysis of Two Integrated Heat Pump HVAC Systems for Near-Zero-Energy Homes - Update to Include Evaluation of Impact of Including a Humidifier Option

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

Baxter, Van D

2007-02-01

The long range strategic goal of the Department of Energy's Building Technologies (DOE/BT) Program is to create, by 2020, technologies and design approaches that enable the construction of net-zero energy homes at low incremental cost (DOE/BT 2005). A net zero energy home (NZEH) is a residential building with greatly reduced needs for energy through efficiency gains, with the balance of energy needs supplied by renewable technologies. While initially focused on new construction, these technologies and design approaches are intended to have application to buildings constructed before 2020 as well resulting in substantial reduction in energy use for all building typesmore » and ages. DOE/BT's Emerging Technologies (ET) team is working to support this strategic goal by identifying and developing advanced heating, ventilating, air-conditioning, and water heating (HVAC/WH) technology options applicable to NZEHs. In FY05 ORNL conducted an initial Stage 1 (Applied Research) scoping assessment of HVAC/WH systems options for future NZEHs to help DOE/BT identify and prioritize alternative approaches for further development. Eleven system concepts with central air distribution ducting and nine multi-zone systems were selected and their annual and peak demand performance estimated for five locations: Atlanta (mixed-humid), Houston (hot-humid), Phoenix (hot-dry), San Francisco (marine), and Chicago (cold). Performance was estimated by simulating the systems using the TRNSYS simulation engine (Solar Energy Laboratory et al. 2006) in two 1800-ft{sup 2} houses--a Building America (BA) benchmark house and a prototype NZEH taken from BEopt results at the take-off (or crossover) point (i.e., a house incorporating those design features such that further progress towards ZEH is through the addition of photovoltaic power sources, as determined by current BEopt analyses conducted by NREL). Results were summarized in a project report, HVAC Equipment Design options for Near-Zero-Energy Homes--A Stage 2 Scoping Assessment, ORNL/TM-2005/194 (Baxter 2005). The 2005 study report describes the HVAC options considered, the ranking criteria used, and the system rankings by priority. In 2006, the two top-ranked options from the 2005 study, air-source and ground-source versions of a centrally ducted integrated heat pump (IHP) system, were subjected to an initial business case study. The IHPs were subjected to a more rigorous hourly-based assessment of their performance potential compared to a baseline suite of equipment of legally minimum efficiency that provided the same heating, cooling, water heating, demand dehumidification, and ventilation services as the IHPs. Results were summarized in a project report, Initial Business Case Analysis of Two Integrated Heat Pump HVAC Systems for Near-Zero-Energy Homes, ORNL/TM-2006/130 (Baxter 2006a). The present report is an update to that document which summarizes results of an analysis of the impact of adding a humidifier to the HVAC system to maintain minimum levels of space relative humidity (RH) in winter. The space RH in winter has direct impact on occupant comfort and on control of dust mites, many types of disease bacteria, and 'dry air' electric shocks. Chapter 8 in ASHRAE's 2005 Handbook of Fundamentals (HOF) suggests a 30% lower limit on RH for indoor temperatures in the range of {approx}68-69F based on comfort (ASHRAE 2005). Table 3 in chapter 9 of the same reference suggests a 30-55% RH range for winter as established by a Canadian study of exposure limits for residential indoor environments (EHD 1987). Harriman, et al (2001) note that for RH levels of 35% or higher, electrostatic shocks are minimized and that dust mites cannot live at RH levels below 40%. They also indicate that many disease bacteria life spans are minimized when space RH is held within a 30-60% range. From the foregoing it is reasonable to assume that a winter space RH range of 30-40% would be an acceptable compromise between comfort considerations and limitation of growth rates for dust mites and many bacteria. In addition it reports some corrections made to the simulation models used in order to correct some errors in the TRNSYS building model for Atlanta and in the refrigerant pressure drop calculation in the water-to-refrigerant evaporator module of the ORNL Heat Pump Design Model (HPDM) used for the IHP analyses. These changes resulted in some minor differences between IHP performance as reported in Baxter (2006) and in this report.« less

Manifestations of the rotation and gravity of the Earth in high-energy physics experiments

NASA Astrophysics Data System (ADS)

Obukhov, Yuri N.; Silenko, Alexander J.; Teryaev, Oleg V.

2016-08-01

The inertial (due to rotation) and gravitational fields of the Earth affect the motion of an elementary particle and its spin dynamics. This influence is not negligible and should be taken into account in high-energy physics experiments. Earth's influence is manifest in perturbations in the particle motion, in an additional precession of the spin, and in a change of the constitutive tensor of the Maxwell electrodynamics. Bigger corrections are oscillatory, and their contributions average to zero. Other corrections due to the inhomogeneity of the inertial field are not oscillatory but they are very small and may be important only for the storage ring electric dipole moment experiments. Earth's gravity causes the Newton-like force, the reaction force provided by a focusing system, and additional torques acting on the spin. However, there are no observable indications of the electromagnetic effects due to Earth's gravity.

Statistical distribution of the vacuum energy density in racetrack Kähler uplift models in string theory

NASA Astrophysics Data System (ADS)

Sumitomo, Yoske; Tye, S.-H. Henry; Wong, Sam S. C.

2013-07-01

We study a racetrack model in the presence of the leading α'-correction in flux compactification in Type IIB string theory, for the purpose of getting conceivable de-Sitter vacua in the large compactified volume approximation. Unlike the Kähler Uplift model studied previously, the α'-correction is more controllable for the meta-stable de-Sitter vacua in the racetrack case since the constraint on the compactified volume size is very much relaxed. We find that the vacuum energy density Λ for de-Sitter vacua approaches zero exponentially as the volume grows. We also analyze properties of the probability distribution of Λ in this class of models. As in other cases studied earlier, the probability distribution again peaks sharply at Λ = 0. We also study the Racetrack Kähler Uplift model in the Swiss-Cheese type model.

A model-dependent approach to the non-relativistic Lamb shift

NASA Astrophysics Data System (ADS)

Diaz-Valdes, J. F.; Bruce, S. A.

2018-02-01

The precise observation of the Lamb shift, between the 2s_{1/2} and 2p_{1/2} levels in hydrogen, was a genuine motivation for the development of modern quantum electrodynamics. According to Dirac theory, the 2s_{1/2} and 2p_{1/2} levels should have equal energies. However, "radiative corrections" due to the interaction between the atomic electron and the vacuum, shift the 2s_{1/2} level higher in energy by around 4.37493× 10^{-6} eV or 2π\\hbar× 1057.85 MHz relative to the 2p_{1/2} level. The measurement of Lamb and Retherford provided the stimulus for renormalization theory which has been so successful in handling troublesome divergences. The Lamb shift is still a central theme in atomic physics. W.E. Lamb was the first to see that this tiny shift, so elusive and hard to measure, would clarify in a fundamental way our thinking about particles and fields. In this article, the Lamb shift for the 2 s energy level in hydrogen is assessed for three different electron models by using the variational principle. It is then verified that this shift arises mostly from the interaction of a bound electron with the zero-point fluctuations of the free electromagnetic field (Welton's interpretation). We briefly comment on the construct validity of the proposed electron models.

Concerted hydrogen atom exchange between three HF molecules

NASA Technical Reports Server (NTRS)

Komornicki, Andrew; Dixon, David A.; Taylor, Peter R.

1992-01-01

We have investigated the termolecular reaction involving concerted hydrogen exchange between three HF molecules, with particular emphasis on the effects of correlation at the various stationary points along the reaction. Using an extended basis, we have located the geometries of the stable hydrogen-bonded trimer, which is of C(sub 3h) symmetry, and the transition state for hydrogen exchange, which is of D(sub 3h) symmetry. The energies of the exchange reation were then evaluated at the correlated level, using a large atomic natural orbital basis and correlating all valence electrons. Several correlation treatments were used, namely, configration interaction with single and double excitations, coupled-pair functional, and coupled-cluster methods. We are thus able to measure the effect of accounting for size-extensivity. Zero-point corrections to the correlated level energetics were determined using analytic second derivative techniques at the SCF level. Our best calculations, which include the effects of connected triple excitations in the coupled-cluster procedure, indicate that the trimer is bound by 9 +/- 1 kcal/mol relative to three separate monomers, in excellent agreement with previous estimates. The barrier to concerted hydrogen exchange is 15 kcal/mol above the trimer, or only 4.7 kcal/mol above three separated monomers. Thus the barrier to hydrogen exchange between HF molecules via this termolecular process is very low.

ISICS2011, an updated version of ISICS: A program for calculation K-, L-, and M-shell cross sections from PWBA and ECPSSR theories using a personal computer

NASA Astrophysics Data System (ADS)

Cipolla, Sam J.

2011-11-01

In this new version of ISICS, called ISICS2011, a few omissions and incorrect entries in the built-in file of electron binding energies have been corrected; operational situations leading to un-physical behavior have been identified and flagged. New version program summaryProgram title: ISICS2011 Catalogue identifier: ADDS_v5_0 Program summary URL:http://cpc.cs.qub.ac.uk/summaries/ADDS_v5_0.html Program obtainable from: CPC Program Library, Queen's University, Belfast, N. Ireland Licensing provisions: Standard CPC licence, http://cpc.cs.qub.ac.uk/licence/licence.html No. of lines in distributed program, including test data, etc.: 6011 No. of bytes in distributed program, including test data, etc.: 130 587 Distribution format: tar.gz Programming language: C Computer: 80486 or higher-level PCs Operating system: WINDOWS XP and all earlier operating systems Classification: 16.7 Catalogue identifier of previous version: ADDS_v4_0 Journal reference of previous version: Comput. Phys. Commun. 180 (2009) 1716. Does the new version supersede the previous version?: Yes Nature of problem: Ionization and X-ray production cross section calculations for ion-atom collisions. Solution method: Numerical integration of form factor using a logarithmic transform and Gaussian quadrature, plus exact integration limits. Reasons for new version: General need for higher precision in output format for projectile energies; some built-in binding energies needed correcting; some anomalous results occur due to faulty read-in data or calculated parameters becoming un-physical; erroneous calculations could result for the L and M shells when restricted K-shell options are inadvertently chosen; to achieve general compatibility with ISICSoo, a companion C++ version that is portable to Linux and MacOS platforms, has been submitted for publication in the CPC Program Library approximately at the same time as this present new standalone version of ISICS [1]. Summary of revisions: The format field for projectile energies in the output has been expanded from two to four decimal places in order to distinguish between closely spaced energy values. There were a few entries in the executable binding energy file that needed correcting; K shell of Eu, M shells of Zn, M1 shell of Kr. The corrected values were also entered in the ENERGY.DAT file. In addition, an alternate data file of binding energies is included, called ENERGY_GW.DAT, which is more up-to-date [2]. Likewise, an alternate atomic parameters data file is now included, called FLOURE_JC.DAT, which is more up-to-date [3] fluorescence yields for the K and L shells and Coster-Kronig parameters for the L shell. Both data files can be read in using the -f usage option. To do this, the original energy file should be renamed and saved (e.g., ENERGY_BB.DAT) and the new file (ENERGY_GW.DAT ) should be duplicated as ENERGY.DAT to be read in using the -f option. Similarly for reading in an alternate FLOURE.DAT file. As with previous versions, the user can also simply input different values of any input quantity by invoking the "specify your own parameters" option from the main menu. You can also use this option to simply check the values of the built-in values of the parameters. If it still happens that a zero binding energy for a particular sub-shell is read in, the program will not completely abort, but will calculate results for the other sub-shells while setting the affected sub-shell output to zero. In calculating the Coulomb deflection factor, if the quantity inside the radical sign of the parameter z z=√{(1} becomes zero or negative, to prevent the program from aborting, the PWBA cross sections are still calculated while the ECPSSR cross sections are set to zero. This situation can happen for very low energy collisions, such as were noticed for helium ions on copper at energies of E⩽11.2 keV. It was observed during the engineering of ISICSoo [1] that erroneous calculations could result for the L- and M-shell cases when restricted K-shell R or HSR scaling options were inappropriately chosen. The program has now been fixed so that these inappropriate options are ignored for the L and M shells. In the previous versions, the usage for inputting a batch data file was incorrectly stated in the Users Manual as -Bxxx; the correct designation is -Fxxx, or alternatively, -Ixxx, as indicated on the usage screen in running the program. A revised Users Manual is also available. Restrictions: The consumed CPU time increases with the atomic shell (K, L, M), but execution is still very fast. Running time: This depends on which shell and the number of different energies to be used in the calculation. The running time is not significantly changed from the previous version.

Zero Thermal Noise in Resistors at Zero Temperature

NASA Astrophysics Data System (ADS)

Kish, Laszlo B.; Niklasson, Gunnar A.; Granqvist, Claes-Göran

2016-06-01

The bandwidth of transistors in logic devices approaches the quantum limit, where Johnson noise and associated error rates are supposed to be strongly enhanced. However, the related theory — asserting a temperature-independent quantum zero-point (ZP) contribution to Johnson noise, which dominates the quantum regime — is controversial and resolution of the controversy is essential to determine the real error rate and fundamental energy dissipation limits of logic gates in the quantum limit. The Callen-Welton formula (fluctuation-dissipation theorem) of voltage and current noise for a resistance is the sum of Nyquist’s classical Johnson noise equation and a quantum ZP term with a power density spectrum proportional to frequency and independent of temperature. The classical Johnson-Nyquist formula vanishes at the approach of zero temperature, but the quantum ZP term still predicts non-zero noise voltage and current. Here, we show that this noise cannot be reconciled with the Fermi-Dirac distribution, which defines the thermodynamics of electrons according to quantum-statistical physics. Consequently, Johnson noise must be nil at zero temperature, and non-zero noise found for certain experimental arrangements may be a measurement artifact, such as the one mentioned in Kleen’s uncertainty relation argument.

Coexistence Curve of Perfluoromethylcyclohexane-Isopropyl Alcohol

NASA Technical Reports Server (NTRS)

Jacobs, D. T.; Kuhl, D. E.; Selby, C. E.

1996-01-01

The coexistence curve of the binary fluid mixture perfluoromethylcyclohexane-isopropyl alcohol was determined by precisely measuring the refractive index both above and below its upper critical consolute point. Sixty-seven two-phase data points were obtained over a wide range of reduced temperatures, 10(exp -5) less than t less than 2.5 x 10(exp -1), to determine the location of the critical point: critical temperature=89.901 C, and critical composition = 62.2% by volume perfluoromethylcyclohexane. These data were analyzed to determine the critical exponent 8 close to the critical point, the amplitude B, and the anomaly in the diameter. The volume-fraction coexistence curve is found to be as symmetric as any composition like variable. Correction to scaling is investigated as well as the need for a crossover theory. A model is proposed that describes the asymptotic approach to zero of the effective exponent Beta, which allows an estimation of the temperature regime free of crossover effects.

Electron teleportation and statistical transmutation in multiterminal Majorana islands

NASA Astrophysics Data System (ADS)

Michaeli, Karen; Landau, L. Aviad; Sela, Eran; Fu, Liang

2017-11-01

We study a topological superconductor island with spatially separated Majorana modes coupled to multiple normal-metal leads by single-electron tunneling in the Coulomb blockade regime. We show that low-temperature transport in such a Majorana island is carried by an emergent charge-e boson composed of a Majorana mode and an electronic excitation in leads. This transmutation from Fermi to Bose statistics has remarkable consequences. For noninteracting leads, the system flows to a non-Fermi-liquid fixed point, which is stable against tunnel couplings anisotropy or detuning away from the charge-degeneracy point. As a result, the system exhibits a universal conductance at zero temperature, which is a fraction of the conductance quantum, and low-temperature corrections with a universal power-law exponent. In addition, we consider Majorana islands connected to interacting one-dimensional leads, and find different stable fixed points near and far from the charge-degeneracy point.

Modelling Phase Transition Phenomena in Fluids

DTIC Science & Technology

2015-07-01

Sublimation line r @@I Triple point ? Vapourisation liner @@I Critical point -Fusion line Solid Liquid Gas Figure 1: Schematic of a phase diagram means that the...velocity field can be set zero, and only the balance of energy constitutes the Stefan model. In contrast to this the liquid - gas phase transitions...defined by requiring that the phase-transition line is crossed in a direction from solid to liquid or from liquid to gas (vapour) phases. The term T∗ δs is

Racemization of the Succinimide Intermediate Formed in Proteins and Peptides: A Computational Study of the Mechanism Catalyzed by Dihydrogen Phosphate Ion.

PubMed

Takahashi, Ohgi; Kirikoshi, Ryota; Manabe, Noriyoshi

2016-10-10

In proteins and peptides, d-aspartic acid (d-Asp) and d-β-Asp residues can be spontaneously formed via racemization of the succinimide intermediate formed from l-Asp and l-asparagine (l-Asn) residues. These biologically uncommon amino acid residues are known to have relevance to aging and pathologies. Although nonenzymatic, the succinimide racemization will not occur without a catalyst at room or biological temperature. In the present study, we computationally investigated the mechanism of succinimide racemization catalyzed by dihydrogen phosphate ion, H₂PO₄ - , by B3LYP/6-31+G(d,p) density functional theory calculations, using a model compound in which an aminosuccinyl (Asu) residue is capped with acetyl (Ace) and NCH₃ (Nme) groups on the N- and C-termini, respectively (Ace-Asu-Nme). It was shown that an H₂PO₄ - ion can catalyze the enolization of the H α -C α -C=O portion of the Asu residue by acting as a proton-transfer mediator. The resulting complex between the enol form and H₂PO₄ - corresponds to a very flat intermediate region on the potential energy surface lying between the initial reactant complex and its mirror-image geometry. The calculated activation barrier (18.8 kcal·mol -1 after corrections for the zero-point energy and the Gibbs energy of hydration) for the enolization was consistent with the experimental activation energies of Asp racemization.

Coupled-cluster and density functional theory studies of the electronic 0-0 transitions of the DNA bases.

PubMed

Ovchinnikov, Vasily A; Sundholm, Dage

2014-04-21

The 0-0 transitions of the electronic excitation spectra of the lowest tautomers of the four nucleotide (DNA) bases have been studied using linear-response approximate coupled-cluster singles and doubles (CC2) calculations. Excitation energies have also been calculated at the linear-response time-dependent density functional theory (TDDFT) level using the B3LYP functional. Large basis sets have been employed for ensuring that the obtained excitation energies are close to the basis-set limit. Zero-point vibrational energy corrections have been calculated at the B3LYP and CC2 levels for the ground and excited states rendering direct comparisons with high-precision spectroscopy measurements feasible. The obtained excitation energies for the 0-0 transitions of the first excited states of guanine tautomers are in good agreement with experimental values confirming the experimental assignment of the energetic order of the tautomers of the DNA bases. For the experimentally detected guanine tautomers, the first excited state corresponds to a π→π* transition, whereas for the tautomers of adenine, thymine, and the lowest tautomer of cytosine the transition to the first excited state has n →π* character. The calculations suggest that the 0-0 transitions of adenine, thymine, and cytosine are not observed in the absorption spectrum due to the weak oscillator strength of the formally symmetry-forbidden transitions, while 0-0 transitions of thymine have been detected in fluorescence excitation spectra.

Criticality in third order lovelock gravity and butterfly effect

NASA Astrophysics Data System (ADS)

Qaemmaqami, Mohammad M.

2018-01-01

We study third order Lovelock Gravity in D=7 at the critical point which three (A)dS vacua degenerate into one. We see there is not propagating graviton at the critical point. And also we compute the butterfly velocity for this theory at the critical point by considering the shock wave solutions near horizon, this is important to note that although there is no propagating graviton at the critical point, due to boundary gravitons the butterfly velocity is non-zero. Finally we observe that the butterfly velocity for third order Lovelock Gravity at the critical point in D=7 is less than the butterfly velocity for Einstein-Gauss-Bonnet Gravity at the critical point in D=7 which is less than the butterfly velocity in D = 7 for Einstein Gravity, vB^{E.H}>vB^{E.G.B}>vB^{3rd Lovelock} . Maybe we can conclude that by adding higher order curvature corrections to Einstein Gravity the butterfly velocity decreases.

Zero curvature-surface driven small objects

NASA Astrophysics Data System (ADS)

Dou, Xiaoxiao; Li, Shanpeng; Liu, Jianlin

2017-08-01

In this study, we investigate the spontaneous migration of small objects driven by surface tension on a catenoid, formed by a layer of soap constrained by two rings. Although the average curvature of the catenoid is zero at each point, the small objects always migrate to the position near the ring. The force and energy analyses have been performed to uncover the mechanism, and it is found that the small objects distort the local shape of the liquid film, thus making the whole system energetically favorable. These findings provide some inspiration to design microfluidics, aquatic robotics, and miniature boats.

Computational thermochemistry: Automated generation of scale factors for vibrational frequencies calculated by electronic structure model chemistries

NASA Astrophysics Data System (ADS)

Yu, Haoyu S.; Fiedler, Lucas J.; Alecu, I. M.; Truhlar, Donald G.

2017-01-01

We present a Python program, FREQ, for calculating the optimal scale factors for calculating harmonic vibrational frequencies, fundamental vibrational frequencies, and zero-point vibrational energies from electronic structure calculations. The program utilizes a previously published scale factor optimization model (Alecu et al., 2010) to efficiently obtain all three scale factors from a set of computed vibrational harmonic frequencies. In order to obtain the three scale factors, the user only needs to provide zero-point energies of 15 or 6 selected molecules. If the user has access to the Gaussian 09 or Gaussian 03 program, we provide the option for the user to run the program by entering the keywords for a certain method and basis set in the Gaussian 09 or Gaussian 03 program. Four other Python programs, input.py, input6, pbs.py, and pbs6.py, are also provided for generating Gaussian 09 or Gaussian 03 input and PBS files. The program can also be used with data from any other electronic structure package. A manual of how to use this program is included in the code package.

Uncertainties in scaling factors for ab initio vibrational zero-point energies

NASA Astrophysics Data System (ADS)

Irikura, Karl K.; Johnson, Russell D.; Kacker, Raghu N.; Kessel, Rüdiger

2009-03-01

Vibrational zero-point energies (ZPEs) determined from ab initio calculations are often scaled by empirical factors. An empirical scaling factor partially compensates for the effects arising from vibrational anharmonicity and incomplete treatment of electron correlation. These effects are not random but are systematic. We report scaling factors for 32 combinations of theory and basis set, intended for predicting ZPEs from computed harmonic frequencies. An empirical scaling factor carries uncertainty. We quantify and report, for the first time, the uncertainties associated with scaling factors for ZPE. The uncertainties are larger than generally acknowledged; the scaling factors have only two significant digits. For example, the scaling factor for B3LYP/6-31G(d) is 0.9757±0.0224 (standard uncertainty). The uncertainties in the scaling factors lead to corresponding uncertainties in predicted ZPEs. The proposed method for quantifying the uncertainties associated with scaling factors is based upon the Guide to the Expression of Uncertainty in Measurement, published by the International Organization for Standardization. We also present a new reference set of 60 diatomic and 15 polyatomic "experimental" ZPEs that includes estimated uncertainties.

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

PubMed

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

2015-03-05

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

Statistical methods for meta-analyses including information from studies without any events-add nothing to nothing and succeed nevertheless.

PubMed

Kuss, O

2015-03-30

Meta-analyses with rare events, especially those that include studies with no event in one ('single-zero') or even both ('double-zero') treatment arms, are still a statistical challenge. In the case of double-zero studies, researchers in general delete these studies or use continuity corrections to avoid them. A number of arguments against both options has been given, and statistical methods that use the information from double-zero studies without using continuity corrections have been proposed. In this paper, we collect them and compare them by simulation. This simulation study tries to mirror real-life situations as completely as possible by deriving true underlying parameters from empirical data on actually performed meta-analyses. It is shown that for each of the commonly encountered effect estimators valid statistical methods are available that use the information from double-zero studies without using continuity corrections. Interestingly, all of them are truly random effects models, and so also the current standard method for very sparse data as recommended from the Cochrane collaboration, the Yusuf-Peto odds ratio, can be improved on. For actual analysis, we recommend to use beta-binomial regression methods to arrive at summary estimates for the odds ratio, the relative risk, or the risk difference. Methods that ignore information from double-zero studies or use continuity corrections should no longer be used. We illustrate the situation with an example where the original analysis ignores 35 double-zero studies, and a superior analysis discovers a clinically relevant advantage of off-pump surgery in coronary artery bypass grafting. Copyright © 2014 John Wiley & Sons, Ltd.

Molecular dynamics simulations of the melting curve of NiAl alloy under pressure

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

Zhang, Wenjin; Peng, Yufeng; Liu, Zhongli, E-mail: zhongliliu@yeah.net

2014-05-15

The melting curve of B2-NiAl alloy under pressure has been investigated using molecular dynamics technique and the embedded atom method (EAM) potential. The melting temperatures were determined with two approaches, the one-phase and the two-phase methods. The first one simulates a homogeneous melting, while the second one involves a heterogeneous melting of materials. Both approaches reduce the superheating effectively and their results are close to each other at the applied pressures. By fitting the well-known Simon equation to our melting data, we yielded the melting curves for NiAl: 1783(1 + P/9.801){sup 0.298} (one-phase approach), 1850(1 + P/12.806){sup 0.357} (two-phase approach).more » The good agreement of the resulting equation of states and the zero-pressure melting point (calc., 1850 ± 25 K, exp., 1911 K) with experiment proved the correctness of these results. These melting data complemented the absence of experimental high-pressure melting of NiAl. To check the transferability of this EAM potential, we have also predicted the melting curves of pure nickel and pure aluminum. Results show the calculated melting point of Nickel agrees well with experiment at zero pressure, while the melting point of aluminum is slightly higher than experiment.« less

40 CFR 86.122-78 - Carbon monoxide analyzer calibration.

Code of Federal Regulations, 2010 CFR

2010-07-01

... sensitive range to be used. (2) Zero the carbon monoxide analyzer with either zero-grade air or zero-grade... conditioning columns is one form of corrective action which may be taken.) (b) Initial and periodic calibration... calibrated. (1) Adjust the analyzer to optimize performance. (2) Zero the carbon monoxide analyzer with...

Zero Income Basic Grant Applicants. Phase II Report.

ERIC Educational Resources Information Center

Applied Management Sciences, Inc., Silver Spring, MD.

The nature and extent of corrections made to their records by zero/low income applicants to the Basic Educational Opportunity Grant (BEOG) program was investigated. Behaviors of zero/low income applicants and the total pool of applicants were also compared. It was found that zero/low income applicants and all applicants who were rejected displayed…

An asymptotic solution to a passive biped walker model

NASA Astrophysics Data System (ADS)

Yudaev, Sergey A.; Rachinskii, Dmitrii; Sobolev, Vladimir A.

2017-02-01

We consider a simple model of a passive dynamic biped robot walker with point feet and legs without knee. The model is a switched system, which includes an inverted double pendulum. Robot’s gait and its stability depend on parameters such as the slope of the ramp, the length of robot’s legs, and the mass distribution along the legs. We present an asymptotic solution of the model. The first correction to the zero order approximation is shown to agree with the numerical solution for a limited parameter range.

Superconductivity versus quantum criticality: Effects of thermal fluctuations

NASA Astrophysics Data System (ADS)

Wang, Huajia; Wang, Yuxuan; Torroba, Gonzalo

2018-02-01

We study the interplay between superconductivity and non-Fermi liquid behavior of a Fermi surface coupled to a massless SU(N ) matrix boson near the quantum critical point. The presence of thermal infrared singularities in both the fermionic self-energy and the gap equation invalidates the Eliashberg approximation, and makes the quantum-critical pairing problem qualitatively different from that at zero temperature. Taking the large N limit, we solve the gap equation beyond the Eliashberg approximation, and obtain the superconducting temperature Tc as a function of N . Our results show an anomalous scaling between the zero-temperature gap and Tc. For N greater than a critical value, we find that Tc vanishes with a Berezinskii-Kosterlitz-Thouless scaling behavior, and the system retains non-Fermi liquid behavior down to zero temperature. This confirms and extends previous renormalization-group analyses done at T =0 , and provides a controlled example of a naked quantum critical point. We discuss the crucial role of thermal fluctuations in relating our results with earlier work where superconductivity always develops due to the special role of the first Matsubara frequency.

Acoustic power of a moving point source in a moving medium

NASA Technical Reports Server (NTRS)

Cole, J. E., III; Sarris, I. I.

1976-01-01

The acoustic power output of a moving point-mass source in an acoustic medium which is in uniform motion and infinite in extent is examined. The acoustic medium is considered to be a homogeneous fluid having both zero viscosity and zero thermal conductivity. Two expressions for the acoustic power output are obtained based on a different definition cited in the literature for the average energy-flux vector in an acoustic medium in uniform motion. The acoustic power output of the source is found by integrating the component of acoustic intensity vector in the radial direction over the surface of an infinitely long cylinder which is within the medium and encloses the line of motion of the source. One of the power expressions is found to give unreasonable results even though the flow is uniform.

Simple vertex correction improves G W band energies of bulk and two-dimensional crystals

NASA Astrophysics Data System (ADS)

Schmidt, Per S.; Patrick, Christopher E.; Thygesen, Kristian S.

2017-11-01

The G W self-energy method has long been recognized as the gold standard for quasiparticle (QP) calculations of solids in spite of the fact that the neglect of vertex corrections and the use of a density-functional theory starting point lack rigorous justification. In this work we remedy this situation by including a simple vertex correction that is consistent with a local-density approximation starting point. We analyze the effect of the self-energy by splitting it into short-range and long-range terms which are shown to govern, respectively, the center and size of the band gap. The vertex mainly improves the short-range correlations and therefore has a small effect on the band gap, while it shifts the band gap center up in energy by around 0.5 eV, in good agreement with experiments. Our analysis also explains how the relative importance of short- and long-range interactions in structures of different dimensionality is reflected in their QP energies. Inclusion of the vertex comes at practically no extra computational cost and even improves the basis set convergence compared to G W . Taken together, the method provides an efficient and rigorous improvement over the G W approximation.

An optically stimulated luminescence system to measure dose profiles in x-ray computed tomography

NASA Astrophysics Data System (ADS)

Yukihara, E. G.; Ruan, C.; Gasparian, P. B. R.; Clouse, W. J.; Kalavagunta, C.; Ahmad, S.

2009-10-01

This paper describes an LED-based optically stimulated luminescence (OSL) system for dose profile measurements using OSL detector strips and investigates its performance in x-ray computed tomography (CT) dosimetry. To compensate for the energy response of the Al2O3:C OSL detectors, which have an effective atomic number of 11.28, field-specific energy correction factors were determined using two methods: (a) comparing the OSL profiles with ionization chamber point measurements (0.3 cm3 ionization chamber) and (b) comparing the OSL profiles integrated over a 100 mm length with 100 mm long pencil ionization chamber measurements. These correction factors were obtained for the CT body and head phantoms, central and peripheral positions and three x-ray tube potential differences (100 kVp, 120 kVp and 140 kVp). The OSL dose profiles corrected by the energy dependence agreed with the ionization chamber point measurements over the entire length of the phantom (300 mm). For 120 kVp x-ray tube potential difference, the CTDI100 values calculated using the OSL dose profiles corrected for the energy dependence and those obtained from an independent measurement with a 100 mm long pencil ionization chamber also agreed within ±5%.

Kinetics of the Strain-Promoted Oxidation-Controlled Cycloalkyne-1,2-quinone Cycloaddition: Experimental and Theoretical Studies.

PubMed

Escorihuela, Jorge; Das, Anita; Looijen, Wilhelmus J E; van Delft, Floris L; Aquino, Adelia J A; Lischka, Hans; Zuilhof, Han

2018-01-05

Stimulated by its success in both bioconjugation and surface modification, we studied the strain-promoted oxidation-controlled cycloalkyne-1,2-quinone cycloaddition (SPOCQ) in three ways. First, the second-order rate constants and activation parameters (ΔH ⧧ ) were determined of various cyclooctynes reacting with 4-tert-butyl-1,2-quinone in a SPOCQ reaction, yielding values for ΔH ⧧ of 4.5, 7.3, and 12.1 kcal/mol, for bicyclo[6.1.0]non-4-yne (BCN), cyclooctyne (OCT), and dibenzoazacyclooctyne (DIBAC), respectively. Second, their reaction paths were investigated in detail by a range of quantum mechanical calculations. Single-configuration theoretical methods, like various DFT and a range of MP2-based methods, typically overestimate this barrier by 3-8 kcal/mol (after inclusion of zero-point energy, thermal, and solvation corrections), whereas MP2 itself underestimates the barrier significantly. Only dispersion-corrected DFT methods like B97D (yielding 4.9, 6.4, and 12.1 kcal/mol for these three reactions) and high-level CCSD(T) and multireference multiconfiguration AQCC ab initio approaches (both yielding 8.2 kcal/mol for BCN) give good approximations of experimental data. Finally, the multireference methods show that the radical character in the TS is rather small, thus rationalizing the use of single-reference methods like B97D and SCS-MP2 as intrinsically valid approaches.

Kinetics of the Strain-Promoted Oxidation-Controlled Cycloalkyne-1,2-quinone Cycloaddition: Experimental and Theoretical Studies

PubMed Central

2017-01-01

Stimulated by its success in both bioconjugation and surface modification, we studied the strain-promoted oxidation-controlled cycloalkyne–1,2-quinone cycloaddition (SPOCQ) in three ways. First, the second-order rate constants and activation parameters (ΔH⧧) were determined of various cyclooctynes reacting with 4-tert-butyl-1,2-quinone in a SPOCQ reaction, yielding values for ΔH⧧ of 4.5, 7.3, and 12.1 kcal/mol, for bicyclo[6.1.0]non-4-yne (BCN), cyclooctyne (OCT), and dibenzoazacyclooctyne (DIBAC), respectively. Second, their reaction paths were investigated in detail by a range of quantum mechanical calculations. Single-configuration theoretical methods, like various DFT and a range of MP2-based methods, typically overestimate this barrier by 3–8 kcal/mol (after inclusion of zero-point energy, thermal, and solvation corrections), whereas MP2 itself underestimates the barrier significantly. Only dispersion-corrected DFT methods like B97D (yielding 4.9, 6.4, and 12.1 kcal/mol for these three reactions) and high-level CCSD(T) and multireference multiconfiguration AQCC ab initio approaches (both yielding 8.2 kcal/mol for BCN) give good approximations of experimental data. Finally, the multireference methods show that the radical character in the TS is rather small, thus rationalizing the use of single-reference methods like B97D and SCS-MP2 as intrinsically valid approaches. PMID:29260879

The Calculation of Accurate Metal-Ligand Bond Energies

NASA Technical Reports Server (NTRS)

Bauschlicher, Charles W.; Partridge, Harry, III; Ricca, Alessandra; Arnold, James O. (Technical Monitor)

1997-01-01

The optimization of the geometry and calculation of zero-point energies are carried out at the B3LYP level of theory. The bond energies are determined at this level, as well as at the CCSD(T) level using very large basis sets. The successive OH bond energies to the first row transition metal cations are reported. For most systems there has been an experimental determination of the first OH. In general, the CCSD(T) values are in good agreement with experiment. The bonding changes from mostly covalent for the early metals to mostly electrostatic for the late transition metal systems.

Flying Off a Frictionless Curved Ramp

DTIC Science & Technology

2015-06-01

mechanical energy . The object is assumed to start from rest at a point on the curve of zero slope. The launch speed and angle are calculated for the...Conservation of mechanical energy . Resumen Una ecuación general se deriva para un punto a lo largo de una trayectoria curvada descendente, de una partícula...porque no puede alcanzar la velocidad de un objeto en caída libre que coincide superficialmente con una trayectoria de este tipo. Palabras clave

Quantum corrections in thermal states of fermions on anti-de Sitter space-time

NASA Astrophysics Data System (ADS)

Ambruş, Victor E.; Winstanley, Elizabeth

2017-12-01

We study the energy density and pressure of a relativistic thermal gas of massless fermions on four-dimensional Minkowski and anti-de Sitter space-times using relativistic kinetic theory. The corresponding quantum field theory quantities are given by components of the renormalized expectation value of the stress-energy tensor operator acting on a thermal state. On Minkowski space-time, the renormalized vacuum expectation value of the stress-energy tensor is by definition zero, while on anti-de Sitter space-time the vacuum contribution to this expectation value is in general nonzero. We compare the properties of the vacuum and thermal expectation values of the energy density and pressure for massless fermions and discuss the circumstances in which the thermal contribution dominates over the vacuum one.

From Zero Energy Buildings to Zero Energy Districts

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

Polly, Ben; Kutscher, Chuck; Macumber, Dan

Some U.S. cities are planning advanced districts that have goals for zero energy, water, waste, and/or greenhouse gas emissions. From an energy perspective, zero energy districts present unique opportunities to cost-effectively achieve high levels of energy efficiency and renewable energy penetration across a collection of buildings that may be infeasible at the individual building scale. These high levels of performance are accomplished through district energy systems that harness renewable and wasted energy at large scales and flexible building loads that coordinate with variable renewable energy supply. Unfortunately, stakeholders face a lack of documented processes, tools, and best practices to assistmore » them in achieving zero energy districts. The National Renewable Energy Laboratory (NREL) is partnering on two new district projects in Denver: the National Western Center and the Sun Valley Neighborhood. We are working closely with project stakeholders in their zero energy master planning efforts to develop the resources needed to resolve barriers and create replicable processes to support future zero energy district efforts across the United States. Initial results of these efforts include the identification and description of key zero energy district design principles (maximizing building efficiency, solar potential, renewable thermal energy, and load control), economic drivers, and master planning principles. The work has also resulted in NREL making initial enhancements to the U.S. Department of Energy's open source building energy modeling platform (OpenStudio and EnergyPlus) with the long-term goal of supporting the design and optimization of energy districts.« less

Vibrational effects in x-ray absorption and resonant inelastic x-ray scattering using a semiclassical scheme

NASA Astrophysics Data System (ADS)

Ljungberg, Mathias P.

2017-12-01

A method is presented for describing vibrational effects in x-ray absorption spectroscopy and resonant inelastic x-ray scattering (RIXS) using a combination of the classical Franck-Condon (FC) approximation and classical trajectories run on the core-excited state. The formulation of RIXS is an extension of the semiclassical Kramers-Heisenberg formalism of Ljungberg et al. [Phys. Rev. B 82, 245115 (2010), 10.1103/PhysRevB.82.245115] to the resonant case, retaining approximately the same computational cost. To overcome difficulties with connecting the absorption and emission processes in RIXS, the classical FC approximation is used for the absorption, which is seen to work well provided that a zero-point-energy correction is included. In the case of core-excited states with dissociative character, the method is capable of closely reproducing the main features for one-dimensional test systems, compared to the quantum-mechanical formulation. Due to the good accuracy combined with the relatively low computational cost, the method has great potential of being used for complex systems with many degrees of freedom, such as liquids and surface adsorbates.

Spectral Function and Quasiparticle Damping of Interacting Bosons in Two Dimensions

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

Sinner, Andreas; Kopietz, Peter; Hasselmann, Nils

2009-03-27

We employ the functional renormalization group to study dynamical properties of the two-dimensional Bose gas. Our approach is free of infrared divergences, which plague the usual diagrammatic approaches, and is consistent with the exact Nepomnyashchy identity, which states that the anomalous self-energy vanishes at zero frequency and momentum. We recover the correct infrared behavior of the propagators and present explicit results for the spectral line shape, from which we extract the quasiparticle dispersion and dampi0008.

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

PubMed

Kolmann, Stephen J; Jordan, Meredith J T

2010-02-07

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

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

NASA Astrophysics Data System (ADS)

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

2010-02-01

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

Zero-Point Energy Leakage in Quantum Thermal Bath Molecular Dynamics Simulations.

PubMed

Brieuc, Fabien; Bronstein, Yael; Dammak, Hichem; Depondt, Philippe; Finocchi, Fabio; Hayoun, Marc

2016-12-13

The quantum thermal bath (QTB) has been presented as an alternative to path-integral-based methods to introduce nuclear quantum effects in molecular dynamics simulations. The method has proved to be efficient, yielding accurate results for various systems. However, the QTB method is prone to zero-point energy leakage (ZPEL) in highly anharmonic systems. This is a well-known problem in methods based on classical trajectories where part of the energy of the high-frequency modes is transferred to the low-frequency modes leading to a wrong energy distribution. In some cases, the ZPEL can have dramatic consequences on the properties of the system. Thus, we investigate the ZPEL by testing the QTB method on selected systems with increasing complexity in order to study the conditions and the parameters that influence the leakage. We also analyze the consequences of the ZPEL on the structural and vibrational properties of the system. We find that the leakage is particularly dependent on the damping coefficient and that increasing its value can reduce and, in some cases, completely remove the ZPEL. When using sufficiently high values for the damping coefficient, the expected energy distribution among the vibrational modes is ensured. In this case, the QTB method gives very encouraging results. In particular, the structural properties are well-reproduced. The dynamical properties should be regarded with caution although valuable information can still be extracted from the vibrational spectrum, even for large values of the damping term.

Rare-Region-Induced Avoided Quantum Criticality in Disordered Three-Dimensional Dirac and Weyl Semimetals

NASA Astrophysics Data System (ADS)

Pixley, J. H.; Huse, David A.; Das Sarma, S.

2016-04-01

We numerically study the effect of short-ranged potential disorder on massless noninteracting three-dimensional Dirac and Weyl fermions, with a focus on the question of the proposed (and extensively theoretically studied) quantum critical point separating semimetal and diffusive-metal phases. We determine the properties of the eigenstates of the disordered Dirac Hamiltonian (H ) and exactly calculate the density of states (DOS) near zero energy, using a combination of Lanczos on H2 and the kernel polynomial method on H . We establish the existence of two distinct types of low-energy eigenstates contributing to the disordered density of states in the weak-disorder semimetal regime. These are (i) typical eigenstates that are well described by linearly dispersing perturbatively dressed Dirac states and (ii) nonperturbative rare eigenstates that are weakly dispersive and quasilocalized in the real-space regions with the largest (and rarest) local random potential. Using twisted boundary conditions, we are able to systematically find and study these two (essentially independent) types of eigenstates. We find that the Dirac states contribute low-energy peaks in the finite-size DOS that arise from the clean eigenstates which shift and broaden in the presence of disorder. On the other hand, we establish that the rare quasilocalized eigenstates contribute a nonzero background DOS which is only weakly energy dependent near zero energy and is exponentially small at weak disorder. We also find that the expected semimetal to diffusive-metal quantum critical point is converted to an avoided quantum criticality that is "rounded out" by nonperturbative effects, with no signs of any singular behavior in the DOS at the energy of the clean Dirac point. However, the crossover effects of the avoided (or hidden) criticality manifest themselves in a so-called quantum critical fan region away from the Dirac energy. We discuss the implications of our results for disordered Dirac and Weyl semimetals, and reconcile the large body of existing numerical work showing quantum criticality with the existence of these nonperturbative effects.

Phase transition behaviours near the triple point for Pb-free (1 - x)Ba(Zr0.2Ti0.8)O3-x(Ba0.7Ca0.3)TiO3 piezoceramics

NASA Astrophysics Data System (ADS)

Gao, Jinghui; Dai, Ye; Hu, Xinghao; Ke, Xiaoqin; Zhong, Lisheng; Li, Shengtao; Zhang, Lixue; Wang, Yu; Wang, Dong; Wang, Yan; Liu, Yongbin; Xiao, Hu; Ren, Xiaobing

2016-08-01

The reason for the large electromechanical response in Pb-free piezoceramic Ba(Zr0.2Ti0.8)O3-(Ba0.7Ca0.3)TiO3 (BZT-BCT) still remains controversial, and a central issue is whether or not the multi-phase-coexisting point (triple point) in the phase diagram is a thermodynamic tricritical point. In this letter, we study the phase transition behaviour for the ferro-para transitions of BZT-BCT specimens in the vicinity of a triple point. Our results show that latent heat and thermal hysteresis approach zero, while the permittivity peak value is maximized close to the triple-point composition, which suggests that the triple point exhibits nearly tricritical transition behaviours in the BZT-BCT system. Further, the TEM result shows that the domain width is minimized with composition approaching the triple point, which indicates a reduction of the domain wall energy possibly relevant to the tricriticality of the triple point. A sixth-order Landau energy modeling shows that the triple tricritical point provides a free-energy state of near-vanishing polarization anisotropy and thus enhances the piezoelectric response for such a material system.

The melting point of lithium: an orbital-free first-principles molecular dynamics study

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

Chen, Mohan; Hung, Linda; Huang, Chen

2013-08-25

The melting point of liquid lithium near zero pressure is studied with large-scale orbital-free first-principles molecular dynamics (OF-FPMD) in the isobaric-isothermal ensemble. Here, we adopt the Wang-Govind-Carter (WGC) functional as our kinetic energy density functional (KEDF) and construct a bulk-derived local pseudopotential (BLPS) for Li. Our simulations employ both the ‘heat-until-melts’ method and the coexistence method. We predict 465 K as an upper bound of the melting point of Li from the ‘heat-until-melts’ method, while we predict 434 K as the melting point of Li from the coexistence method. These values compare well with an experimental melting point of 453more » K at zero pressure. Furthermore, we calculate a few important properties of liquid Li including the diffusion coefficients, pair distribution functions, static structure factors, and compressibilities of Li at 470 K and 725 K in the canonical ensemble. This theoretically-obtained results show good agreement with known experimental results, suggesting that OF-FPMD using a non-local KEDF and a BLPS is capable of accurately describing liquid metals.« less

Corrected Implicit Monte Carlo

DOE PAGES

Cleveland, Mathew Allen; Wollaber, Allan Benton

2018-01-02

Here in this work we develop a set of nonlinear correction equations to enforce a consistent time-implicit emission temperature for the original semi-implicit IMC equations. We present two possible forms of correction equations: one results in a set of non-linear, zero-dimensional, non-negative, explicit correction equations, and the other results in a non-linear, non-negative, Boltzman transport correction equation. The zero-dimensional correction equations adheres to the maximum principle for the material temperature, regardless of frequency-dependence, but does not prevent maximum principle violation in the photon intensity, eventually leading to material overheating. The Boltzman transport correction guarantees adherence to the maximum principle formore » frequency-independent simulations, at the cost of evaluating a reduced source non-linear Boltzman equation. Finally, we present numerical evidence suggesting that the Boltzman transport correction, in its current form, significantly improves time step limitations but does not guarantee adherence to the maximum principle for frequency-dependent simulations.« less

Corrected implicit Monte Carlo

NASA Astrophysics Data System (ADS)

Cleveland, M. A.; Wollaber, A. B.

2018-04-01

In this work we develop a set of nonlinear correction equations to enforce a consistent time-implicit emission temperature for the original semi-implicit IMC equations. We present two possible forms of correction equations: one results in a set of non-linear, zero-dimensional, non-negative, explicit correction equations, and the other results in a non-linear, non-negative, Boltzman transport correction equation. The zero-dimensional correction equations adheres to the maximum principle for the material temperature, regardless of frequency-dependence, but does not prevent maximum principle violation in the photon intensity, eventually leading to material overheating. The Boltzman transport correction guarantees adherence to the maximum principle for frequency-independent simulations, at the cost of evaluating a reduced source non-linear Boltzman equation. We present numerical evidence suggesting that the Boltzman transport correction, in its current form, significantly improves time step limitations but does not guarantee adherence to the maximum principle for frequency-dependent simulations.

A New Reddening Law for M4

NASA Astrophysics Data System (ADS)

Hendricks, Benjamin; Stetson, Peter B.; VandenBerg, Don A.; Dall'Ora, Massimo

2012-07-01

We have used a combination of broadband near-infrared and optical Johnson-Cousins photometry to study the dust properties in the line of sight to the Galactic globular cluster M4. We have investigated the reddening effects in terms of absolute strength and variation across the cluster field, as well as the shape of the reddening law defined by the type of dust. All three aspects had been poorly defined for this system and, consequently, there has been controversy about the absolute distance to this globular cluster, which is closest to the Sun. Here, we determine the ratio of absolute to selective extinction (RV ) in the line of sight toward M4, which is known to be a useful indicator for the type of dust and therefore characterizes the applicable reddening law. Our method is independent of age assumptions and appears to be significantly more precise and accurate than previous approaches. We obtain AV /E(B - V) = 3.76 ± 0.07 (random error) for the dust in the line of sight to M4 for our set of filters. That corresponds to a dust-type parameter RV = 3.62 ± 0.07 in the Cardelli et al. reddening law. With this value, the distance to M4 is found to be 1.80 ± 0.05 kpc, corresponding to a true distance modulus of (m - M)0 = 11.28 ± 0.06 (random error). A reddening map for M4 has been created, which reveals a spatial differential reddening of δE(B - V) >= 0.2 mag across the field within 10' around the cluster center; this is about 50% of the total mean reddening, which we have determined to be E(B - V) = 0.37 ± 0.01. In order to provide accurate zero points for the extinction coefficients of our photometric filters, we investigated the impact of stellar parameters such as temperature, surface gravity, and metallicity on the extinction properties and the necessary corrections in different bandpasses. Using both synthetic ATLAS9 spectra and observed spectral energy distributions, we found similarly sized effects for the range of temperature and surface gravity typical of globular cluster stars: each causes a change of about 3% in the necessary correction factor for each filter combination. Interestingly, variations in the metallicity cause effects of the same order when the assumed value is changed from the solar metallicity ([Fe/H] = 0.0) to [Fe/H] = -2.5. The systematic differences between the reddening corrections for a typical main-sequence turnoff star in a metal poor globular cluster and a Vega-like star are even stronger (~5%). We compared the results from synthetic spectra to those obtained with observed spectral energy distributions and found significant differences for temperatures lower than ~5000 K. We have attributed these discrepancies to the inadequate treatment of some molecular bands in the B filter within the ATLAS9 models. Fortunately, these differences do not affect the principal astrophysical conclusions in this study, which are based on stars hotter than 5000 K. From our calculations, we provide extinction zero points for Johnson-Cousins and Two Micron All Sky Survey filters, spanning a wide range of stellar parameters and dust types. These extinction tables are suited for accurate, object-specific extinction corrections.

Targeting Net Zero Energy for Military Installations (Presentation)

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

Burman, K.

2012-05-01

Targeting Net Zero Energy for Military Installations in Kaneohe Bay, Hawaii. A net zero energy installation (NZEI) is one that produces as much energy from on-site renewable sources as it consumes. NZEI assessment provides a systematic approach to energy projects.

Initial Business Case Analysis of Two Integrated Heat Pump HVAC Systems for Near-Zero-Energy Homes -- Update to Include Analyses of an Economizer Option and Alternative Winter Water Heating Control Option

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

Baxter, Van D

2006-12-01

The long range strategic goal of the Department of Energy's Building Technologies (DOE/BT) Program is to create, by 2020, technologies and design approaches that enable the construction of net-zero energy homes at low incremental cost (DOE/BT 2005). A net zero energy home (NZEH) is a residential building with greatly reduced needs for energy through efficiency gains, with the balance of energy needs supplied by renewable technologies. While initially focused on new construction, these technologies and design approaches are intended to have application to buildings constructed before 2020 as well resulting in substantial reduction in energy use for all building typesmore » and ages. DOE/BT's Emerging Technologies (ET) team is working to support this strategic goal by identifying and developing advanced heating, ventilating, air-conditioning, and water heating (HVAC/WH) technology options applicable to NZEHs. Although the energy efficiency of heating, ventilating, and air-conditioning (HVAC) equipment has increased substantially in recent years, new approaches are needed to continue this trend. Dramatic efficiency improvements are necessary to enable progress toward the NZEH goals, and will require a radical rethinking of opportunities to improve system performance. The large reductions in HVAC energy consumption necessary to support the NZEH goals require a systems-oriented analysis approach that characterizes each element of energy consumption, identifies alternatives, and determines the most cost-effective combination of options. In particular, HVAC equipment must be developed that addresses the range of special needs of NZEH applications in the areas of reduced HVAC and water heating energy use, humidity control, ventilation, uniform comfort, and ease of zoning. In FY05 ORNL conducted an initial Stage 1 (Applied Research) scoping assessment of HVAC/WH systems options for future NZEHs to help DOE/BT identify and prioritize alternative approaches for further development. Eleven system concepts with central air distribution ducting and nine multi-zone systems were selected and their annual and peak demand performance estimated for five locations: Atlanta (mixed-humid), Houston (hot-humid), Phoenix (hot-dry), San Francisco (marine), and Chicago (cold). Performance was estimated by simulating the systems using the TRNSYS simulation engine (Solar Energy Laboratory et al. 2006) in two 1800-ft{sup 2} houses--a Building America (BA) benchmark house and a prototype NZEH taken from BEopt results at the take-off (or crossover) point (i.e., a house incorporating those design features such that further progress towards ZEH is through the addition of photovoltaic power sources, as determined by current BEopt analyses conducted by NREL). Results were summarized in a project report, HVAC Equipment Design options for Near-Zero-Energy Homes--A Stage 2 Scoping Assessment, ORNL/TM-2005/194 (Baxter 2005). The 2005 study report describes the HVAC options considered, the ranking criteria used, and the system rankings by priority. In 2006, the two top-ranked options from the 2005 study, air-source and ground-source versions of an integrated heat pump (IHP) system, were subjected to an initial business case study. The IHPs were subjected to a more rigorous hourly-based assessment of their performance potential compared to a baseline suite of equipment of legally minimum efficiency that provided the same heating, cooling, water heating, demand dehumidification, and ventilation services as the IHPs. Results were summarized in a project report, Initial Business Case Analysis of Two Integrated Heat Pump HVAC Systems for Near-Zero-Energy Homes, ORNL/TM-2006/130 (Baxter 2006). The present report is an update to that document. Its primary purpose is to summarize results of an analysis of the potential of adding an outdoor air economizer operating mode to the IHPs to take advantage of free cooling (using outdoor air to cool the house) whenever possible. In addition it provides some additional detail for an alternative winter water heating/space heating (WH/SH) control strategy briefly described in the original report and corrects some minor errors.« less

Exploring the importance of quantum effects in nucleation: The archetypical Nen case

NASA Astrophysics Data System (ADS)

Unn-Toc, Wesley; Halberstadt, Nadine; Meier, Christoph; Mella, Massimo

2012-07-01

The effect of quantum mechanics (QM) on the details of the nucleation process is explored employing Ne clusters as test cases due to their semi-quantal nature. In particular, we investigate the impact of quantum mechanics on both condensation and dissociation rates in the framework of the microcanonical ensemble. Using both classical trajectories and two semi-quantal approaches (zero point averaged dynamics, ZPAD, and Gaussian-based time dependent Hartree, G-TDH) to model cluster and collision dynamics, we simulate the dissociation and monomer capture for Ne8 as a function of the cluster internal energy, impact parameter and collision speed. The results for the capture probability Ps(b) as a function of the impact parameter suggest that classical trajectories always underestimate capture probabilities with respect to ZPAD, albeit at most by 15%-20% in the cases we studied. They also do so in some important situations when using G-TDH. More interestingly, dissociation rates kdiss are grossly overestimated by classical mechanics, at least by one order of magnitude. We interpret both behaviours as mainly due to the reduced amount of kinetic energy available to a quantum cluster for a chosen total internal energy. We also find that the decrease in monomer dissociation energy due to zero point energy effects plays a key role in defining dissociation rates. In fact, semi-quantal and classical results for kdiss seem to follow a common "corresponding states" behaviour when the proper definition of internal and dissociation energies are used in a transition state model estimation of the evaporation rate constants.

Methanol clusters (CH3OH)n: putative global minimum-energy structures from model potentials and dispersion-corrected density functional theory.

PubMed

Kazachenko, Sergey; Bulusu, Satya; Thakkar, Ajit J

2013-06-14

Putative global minima are reported for methanol clusters (CH3OH)n with n ≤ 15. The predictions are based on global optimization of three intermolecular potential energy models followed by local optimization and single-point energy calculations using two variants of dispersion-corrected density functional theory. Recurring structural motifs include folded and/or twisted rings, folded rings with a short branch, and stacked rings. Many of the larger structures are stabilized by weak C-H···O bonds.

Is HO3 minimum cis or trans? An analytic full-dimensional ab initio isomerization path.

PubMed

Varandas, A J C

2011-05-28

The minimum energy path for isomerization of HO(3) has been explored in detail using accurate high-level ab initio methods and techniques for extrapolation to the complete basis set limit. In agreement with other reports, the best estimates from both valence-only and all-electron single-reference methods here utilized predict the minimum of the cis-HO(3) isomer to be deeper than the trans-HO(3) one. They also show that the energy varies by less than 1 kcal mol(-1) or so over the full isomerization path. A similar result is found from valence-only multireference configuration interaction calculations with the size-extensive Davidson correction and a correlation consistent triple-zeta basis, which predict the energy difference between the two isomers to be of only Δ = -0.1 kcal mol(-1). However, single-point multireference calculations carried out at the optimum triple-zeta geometry with basis sets of the correlation consistent family but cardinal numbers up to X = 6 lead upon a dual-level extrapolation to the complete basis set limit of Δ = (0.12 ± 0.05) kcal mol(-1). In turn, extrapolations with the all-electron single-reference coupled-cluster method including the perturbative triples correction yield values of Δ = -0.19 and -0.03 kcal mol(-1) when done from triple-quadruple and quadruple-quintuple zeta pairs with two basis sets of increasing quality, namely cc-cpVXZ and aug-cc-pVXZ. Yet, if added a value of 0.25 kcal mol(-1) that accounts for the effect of triple and perturbative quadruple excitations with the VTZ basis set, one obtains a coupled cluster estimate of Δ = (0.14 ± 0.08) kcal mol(-1). It is then shown for the first time from systematic ab initio calculations that the trans-HO(3) isomer is more stable than the cis one, in agreement with the available experimental evidence. Inclusion of the best reported zero-point energy difference (0.382 kcal mol(-1)) from multireference configuration interaction calculations enhances further the relative stability to ΔE(ZPE) = (0.51 ± 0.08) kcal mol(-1). A scheme is also suggested to model the full-dimensional isomerization potential-energy surface using a quadratic expansion that is parametrically represented by a Fourier analysis in the torsion angle. The method illustrated at the raw and complete basis-set limit coupled-cluster levels can provide a valuable tool for a future analysis of the available (incomplete thus far) experimental rovibrational data. This journal is © the Owner Societies 2011

Gravitational Self-Energy as the Litmus of Reality

NASA Astrophysics Data System (ADS)

Jones, K. R. W.

It is argued that the correct physical treatment of self-energy in Newtonian quantum gravity offers a constrained and predictive discriminator for the interpretation of ψ, and thus a clear point of departure for the unification of modern physics.

Efficiency at maximum power of a chemical engine.

PubMed

Hooyberghs, Hans; Cleuren, Bart; Salazar, Alberto; Indekeu, Joseph O; Van den Broeck, Christian

2013-10-07

A cyclically operating chemical engine is considered that converts chemical energy into mechanical work. The working fluid is a gas of finite-sized spherical particles interacting through elastic hard collisions. For a generic transport law for particle uptake and release, the efficiency at maximum power η(mp) [corrected] takes the form 1/2+cΔμ+O(Δμ(2)), with 1∕2 a universal constant and Δμ the chemical potential difference between the particle reservoirs. The linear coefficient c is zero for engines featuring a so-called left/right symmetry or particle fluxes that are antisymmetric in the applied chemical potential difference. Remarkably, the leading constant in η(mp) [corrected] is non-universal with respect to an exceptional modification of the transport law. For a nonlinear transport model, we obtain η(mp) = 1/(θ + 1) [corrected], with θ > 0 the power of Δμ in the transport equation.

Zero Gravity Cryogenic Vent System Concepts for Upper Stages

NASA Technical Reports Server (NTRS)

Flachbart, Robin H.; Holt, James B.; Hastings, Leon J.

1999-01-01

The capability to vent in zero gravity without resettling is a technology need that involves practically all uses of sub-critical cryogenics in space. Venting without resettling would extend cryogenic orbital transfer vehicle capabilities. However, the lack of definition regarding liquid/ullage orientation coupled with the somewhat random nature of the thermal stratification and resulting pressure rise rates, lead to significant technical challenges. Typically a zero gravity vent concept, termed a thermodynamic vent system (TVS), consists of a tank mixer to destratify the propellant, combined with a Joule-Thomson (J-T) valve to extract thermal energy from the propellant. Marshall Space Flight Center's (MSFC's) Multipurpose Hydrogen Test Bed (MHTB) was used to test both spray bar and axial jet TVS concepts. The axial jet system consists of a recirculation pump heat exchanger unit. The spray bar system consists of a recirculation pump, a parallel flow concentric tube, heat exchanger, and a spray bar positioned close to the longitudinal axis of the tank. The operation of both concepts is similar. In the mixing mode, the recirculation pump withdraws liquid from the tank and sprays it into the tank liquid, ullage, and exposed tank surfaces. When energy is required. a small portion of the recirculated liquid is passed sequentially through the J-T expansion valve, the heat exchanger, and is vented overboard. The vented vapor cools the circulated bulk fluid, thereby removing thermal energy and reducing tank pressure. The pump operates alone, cycling on and off, to destratify the tank liquid and ullage until the liquid vapor pressure reaches the lower set point. At that point. the J-T valve begins to cycle on and off with the pump. Thus, for short duration missions, only the mixer may operate, thus minimizing or even eliminating, boil-off losses.

Zero Gravity Cryogenic Vent System Concepts for Upper Stages

NASA Technical Reports Server (NTRS)

Flachbart, Robin H.; Holt, James B.; Hastings, Leon J.

2001-01-01

The capability to vent in zero gravity without resettling is a technology need that involves practically all uses of sub-critical cryogenics in space, and would extend cryogenic orbital transfer vehicle capabilities. However, the lack of definition regarding liquid/ullage orientation coupled with the somewhat random nature of the thermal stratification and resulting pressure rise rates, lead to significant technical challenges. Typically a zero gravity vent concept, termed a thermodynamic vent system (TVS), consists of a tank mixer to destratify the propellant, combined with a Joule-Thomson (J-T) valve to extract thermal energy from the propellant. Marshall Space Flight Center's (MSFC's) Multipurpose Hydrogen Test Bed (MHTB) was used to test both spray-bar and axial jet TVS concepts. The axial jet system consists of a recirculation pump heat exchanger unit. The spray-bar system consists of a recirculation pump, a parallel flow concentric tube heat exchanger, and a spray-bar positioned close to the longitudinal axis of the tank. The operation of both concepts is similar. In the mixing mode, the recirculation pump withdraws liquid from the tank and sprays it into the tank liquid, ullage, and exposed tank surfaces. When energy extraction is required, a small portion of the recirculated liquid is passed sequentially through the J-T expansion valve, the heat exchanger, and is vented overboard. The vented vapor cools the circulated bulk fluid, thereby removing thermal energy and reducing tank pressure. The pump operates alone, cycling on and off, to destratify the tank liquid and ullage until the liquid vapor pressure reaches the lower set point. At that point, the J-T valve begins to cycle on and off with the pump. Thus, for short duration missions, only the mixer may operate, thus minimizing or even eliminating boil-off losses.

Robustness of predator-prey models for confinement regime transitions in fusion plasmas

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

Zhu, H.; Chapman, S. C.; Department of Mathematics and Statistics, University of Tromso

2013-04-15

Energy transport and confinement in tokamak fusion plasmas is usually determined by the coupled nonlinear interactions of small-scale drift turbulence and larger scale coherent nonlinear structures, such as zonal flows, together with free energy sources such as temperature gradients. Zero-dimensional models, designed to embody plausible physical narratives for these interactions, can help to identify the origin of enhanced energy confinement and of transitions between confinement regimes. A prime zero-dimensional paradigm is predator-prey or Lotka-Volterra. Here, we extend a successful three-variable (temperature gradient; microturbulence level; one class of coherent structure) model in this genre [M. A. Malkov and P. H. Diamond,more » Phys. Plasmas 16, 012504 (2009)], by adding a fourth variable representing a second class of coherent structure. This requires a fourth coupled nonlinear ordinary differential equation. We investigate the degree of invariance of the phenomenology generated by the model of Malkov and Diamond, given this additional physics. We study and compare the long-time behaviour of the three-equation and four-equation systems, their evolution towards the final state, and their attractive fixed points and limit cycles. We explore the sensitivity of paths to attractors. It is found that, for example, an attractive fixed point of the three-equation system can become a limit cycle of the four-equation system. Addressing these questions which we together refer to as 'robustness' for convenience is particularly important for models which, as here, generate sharp transitions in the values of system variables which may replicate some key features of confinement transitions. Our results help to establish the robustness of the zero-dimensional model approach to capturing observed confinement phenomenology in tokamak fusion plasmas.« less

Isometric immersions, energy minimization and self-similar buckling in non-Euclidean elastic sheets

NASA Astrophysics Data System (ADS)

Gemmer, John; Sharon, Eran; Shearman, Toby; Venkataramani, Shankar C.

2016-04-01

The edges of torn plastic sheets and growing leaves often display hierarchical buckling patterns. We show that this complex morphology i) emerges even in zero strain configurations, and ii) is driven by a competition between the two principal curvatures, rather than between bending and stretching. We identify the key role of branch point (or “monkey saddle”) singularities in generating complex wrinkling patterns in isometric immersions, and show how they arise naturally from minimizing the elastic energy.

CoFFEE: Corrections For Formation Energy and Eigenvalues for charged defect simulations

NASA Astrophysics Data System (ADS)

Naik, Mit H.; Jain, Manish

2018-05-01

Charged point defects in materials are widely studied using Density Functional Theory (DFT) packages with periodic boundary conditions. The formation energy and defect level computed from these simulations need to be corrected to remove the contributions from the spurious long-range interaction between the defect and its periodic images. To this effect, the CoFFEE code implements the Freysoldt-Neugebauer-Van de Walle (FNV) correction scheme. The corrections can be applied to charged defects in a complete range of material shapes and size: bulk, slab (or two-dimensional), wires and nanoribbons. The code is written in Python and features MPI parallelization and optimizations using the Cython package for slow steps.

Improving xylem hydraulic conductivity measurements by correcting the error caused by passive water uptake.

PubMed

Torres-Ruiz, José M; Sperry, John S; Fernández, José E

2012-10-01

Xylem hydraulic conductivity (K) is typically defined as K = F/(P/L), where F is the flow rate through a xylem segment associated with an applied pressure gradient (P/L) along the segment. This definition assumes a linear flow-pressure relationship with a flow intercept (F(0)) of zero. While linearity is typically the case, there is often a non-zero F(0) that persists in the absence of leaks or evaporation and is caused by passive uptake of water by the sample. In this study, we determined the consequences of failing to account for non-zero F(0) for both K measurements and the use of K to estimate the vulnerability to xylem cavitation. We generated vulnerability curves for olive root samples (Olea europaea) by the centrifuge technique, measuring a maximally accurate reference K(ref) as the slope of a four-point F vs P/L relationship. The K(ref) was compared with three more rapid ways of estimating K. When F(0) was assumed to be zero, K was significantly under-estimated (average of -81.4 ± 4.7%), especially when K(ref) was low. Vulnerability curves derived from these under-estimated K values overestimated the vulnerability to cavitation. When non-zero F(0) was taken into account, whether it was measured or estimated, more accurate K values (relative to K(ref)) were obtained, and vulnerability curves indicated greater resistance to cavitation. We recommend accounting for non-zero F(0) for obtaining accurate estimates of K and cavitation resistance in hydraulic studies. Copyright © Physiologia Plantarum 2012.

Creation of quasi-Dirac points in the Floquet band structure of bilayer graphene.

PubMed

Cheung, W M; Chan, K S

2017-06-01

We study the Floquet quasi-energy band structure of bilayer graphene when it is illuminated by two laser lights with frequencies [Formula: see text] and [Formula: see text] using Floquet theory. We focus on the dynamical gap formed by the conduction band with Floquet index  =  -1 and the valence band with Floquet index  =  +1 to understand how Dirac points can be formed. It is found that the dynamical gap does not have rotation symmetry in the momentum space, and quasi-Dirac points, where the conduction and valence bands almost touch, can be created when the dynamical gap closes along some directions with suitably chosen radiation parameters. We derive analytical expressions for the direction dependence of the dynamical gaps using Lowdin perturbation theory to gain a better understanding of the formation of quasi-Dirac points. When both radiations are circularly polarized, the gap can be exactly zero along some directions, when only the first and second order perturbations are considered. Higher order perturbations can open a very small gap in this case. When both radiations are linearly polarized, the gap can be exactly zero up to the fourth order perturbation and more than one quasi-Dirac point is formed. We also study the electron velocity around a dynamical gap and show that the magnitude of the velocity drops to values close to zero when the k vector is near to the gap minimum. The direction of the velocity also changes around the gap minimum, and when the gap is larger in value the change in the velocity direction is more gradual. The warping effect does not affect the formation of a Dirac point along the k x axis, while it prevents its formation when there is phase shift between the two radiations.

Binding-affinity predictions of HSP90 in the D3R Grand Challenge 2015 with docking, MM/GBSA, QM/MM, and free-energy simulations

NASA Astrophysics Data System (ADS)

Misini Ignjatović, Majda; Caldararu, Octav; Dong, Geng; Muñoz-Gutierrez, Camila; Adasme-Carreño, Francisco; Ryde, Ulf

2016-09-01

We have estimated the binding affinity of three sets of ligands of the heat-shock protein 90 in the D3R grand challenge blind test competition. We have employed four different methods, based on five different crystal structures: first, we docked the ligands to the proteins with induced-fit docking with the Glide software and calculated binding affinities with three energy functions. Second, the docked structures were minimised in a continuum solvent and binding affinities were calculated with the MM/GBSA method (molecular mechanics combined with generalised Born and solvent-accessible surface area solvation). Third, the docked structures were re-optimised by combined quantum mechanics and molecular mechanics (QM/MM) calculations. Then, interaction energies were calculated with quantum mechanical calculations employing 970-1160 atoms in a continuum solvent, combined with energy corrections for dispersion, zero-point energy and entropy, ligand distortion, ligand solvation, and an increase of the basis set to quadruple-zeta quality. Fourth, relative binding affinities were estimated by free-energy simulations, using the multi-state Bennett acceptance-ratio approach. Unfortunately, the results were varying and rather poor, with only one calculation giving a correlation to the experimental affinities larger than 0.7, and with no consistent difference in the quality of the predictions from the various methods. For one set of ligands, the results could be strongly improved (after experimental data were revealed) if it was recognised that one of the ligands displaced one or two water molecules. For the other two sets, the problem is probably that the ligands bind in different modes than in the crystal structures employed or that the conformation of the ligand-binding site or the whole protein changes.

Binding-affinity predictions of HSP90 in the D3R Grand Challenge 2015 with docking, MM/GBSA, QM/MM, and free-energy simulations.

PubMed

Misini Ignjatović, Majda; Caldararu, Octav; Dong, Geng; Muñoz-Gutierrez, Camila; Adasme-Carreño, Francisco; Ryde, Ulf

2016-09-01

We have estimated the binding affinity of three sets of ligands of the heat-shock protein 90 in the D3R grand challenge blind test competition. We have employed four different methods, based on five different crystal structures: first, we docked the ligands to the proteins with induced-fit docking with the Glide software and calculated binding affinities with three energy functions. Second, the docked structures were minimised in a continuum solvent and binding affinities were calculated with the MM/GBSA method (molecular mechanics combined with generalised Born and solvent-accessible surface area solvation). Third, the docked structures were re-optimised by combined quantum mechanics and molecular mechanics (QM/MM) calculations. Then, interaction energies were calculated with quantum mechanical calculations employing 970-1160 atoms in a continuum solvent, combined with energy corrections for dispersion, zero-point energy and entropy, ligand distortion, ligand solvation, and an increase of the basis set to quadruple-zeta quality. Fourth, relative binding affinities were estimated by free-energy simulations, using the multi-state Bennett acceptance-ratio approach. Unfortunately, the results were varying and rather poor, with only one calculation giving a correlation to the experimental affinities larger than 0.7, and with no consistent difference in the quality of the predictions from the various methods. For one set of ligands, the results could be strongly improved (after experimental data were revealed) if it was recognised that one of the ligands displaced one or two water molecules. For the other two sets, the problem is probably that the ligands bind in different modes than in the crystal structures employed or that the conformation of the ligand-binding site or the whole protein changes.

Understanding of assembly phenomena by aromatic-aromatic interactions: benzene dimer and the substituted systems.

PubMed

Lee, Eun Cheol; Kim, Dongwook; Jurecka, Petr; Tarakeshwar, P; Hobza, Pavel; Kim, Kwang S

2007-05-10

Interactions involving aromatic rings are important in molecular/biomolecular assembly and engineering. As a consequence, there have been a number of investigations on dimers involving benzene or other substituted pi systems. In this Feature Article, we examine the relevance of the magnitudes of their attractive and repulsive interaction energy components in governing the geometries of several pi-pi systems. The geometries and the associated binding energies were evaluated at the complete basis set (CBS) limit of coupled cluster theory with singles, doubles, and perturbative triples excitations [CCSD(T)] using a least biased scheme for the given data set. The results for the benzene dimer indicate that the floppy T-shaped structure (center-to-center distance: 4.96 A, with an axial benzene off-centered above the facial benzene) is isoenergetic in zero-point-energy (ZPE) corrected binding energy (D0) to the displaced-stacked structure (vertical interplanar distance: 3.54 A). However, the T-shaped structure is likely to be slightly more stable (D0 approximately equal to 2.4-2.5 kcal/mol) if quadruple excitations are included in the coupled cluster calculations. The presence of substituents on the aromatic ring, irrespective of their electron withdrawing or donating nature, leads to an increase in the binding energy, and the displaced-stacked conformations are more stabilized than the T-shaped conformers. This explains the wide prevalence of displaced stacked structures in organic crystals. Despite that the dispersion energy is dominating, the substituent as well as the conformational effects are correlated to the electrostatic interaction. This electrostatic origin implies that the substituent effect would be reduced in polar solution, but important in apolar media, in particular, for assembling processes.

Zero point and zero suffix methods with robust ranking for solving fully fuzzy transportation problems

NASA Astrophysics Data System (ADS)

Ngastiti, P. T. B.; Surarso, Bayu; Sutimin

2018-05-01

Transportation issue of the distribution problem such as the commodity or goods from the supply tothe demmand is to minimize the transportation costs. Fuzzy transportation problem is an issue in which the transport costs, supply and demand are in the form of fuzzy quantities. Inthe case study at CV. Bintang Anugerah Elektrik, a company engages in the manufacture of gensets that has more than one distributors. We use the methods of zero point and zero suffix to investigate the transportation minimum cost. In implementing both methods, we use robust ranking techniques for the defuzzification process. The studyresult show that the iteration of zero suffix method is less than that of zero point method.

75 FR 24997 - FPL Energy Point Beach, LLC; Point Beach Nuclear Plant, Units 1 and 2; Environmental Assessment...

Federal Register 2010, 2011, 2012, 2013, 2014

2010-05-06

... proposed action is necessary to correct a typographical error in Appendix C which incorrectly labels the... day of April 2010. For the Nuclear Regulatory Commission. Peter S. Tam, Senior Project Manager, Plant...

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

Cleveland, Mathew Allen; Wollaber, Allan Benton

Here in this work we develop a set of nonlinear correction equations to enforce a consistent time-implicit emission temperature for the original semi-implicit IMC equations. We present two possible forms of correction equations: one results in a set of non-linear, zero-dimensional, non-negative, explicit correction equations, and the other results in a non-linear, non-negative, Boltzman transport correction equation. The zero-dimensional correction equations adheres to the maximum principle for the material temperature, regardless of frequency-dependence, but does not prevent maximum principle violation in the photon intensity, eventually leading to material overheating. The Boltzman transport correction guarantees adherence to the maximum principle formore » frequency-independent simulations, at the cost of evaluating a reduced source non-linear Boltzman equation. Finally, we present numerical evidence suggesting that the Boltzman transport correction, in its current form, significantly improves time step limitations but does not guarantee adherence to the maximum principle for frequency-dependent simulations.« less

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

NASA Astrophysics Data System (ADS)

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

2013-12-01

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

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

PubMed

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

2013-12-28

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

Theories and applications of second-order correlation of longitudinal velocity increments at three points in isotropic turbulence

NASA Astrophysics Data System (ADS)

Wu, J. Z.; Fang, L.; Shao, L.; Lu, L. P.

2018-06-01

In order to introduce new physics to traditional two-point correlations, we define the second-order correlation of longitudinal velocity increments at three points and obtain the analytical expressions in isotropic turbulence. By introducing the Kolmogorov 4/5 law, this three-point correlation explicitly contains velocity second- and third-order moments, which correspond to energy and energy transfer respectively. The combination of them then shows additional information of non-equilibrium turbulence by comparing to two-point correlations. Moreover, this three-point correlation shows the underlying inconsistency between numerical interpolation and three-point scaling law in numerical calculations, and inspires a preliminary model to correct this problem in isotropic turbulence.

Quantum corrections for the phase diagram of systems with competing order.

PubMed

Silva, N L; Continentino, Mucio A; Barci, Daniel G

2018-06-06

We use the effective potential method of quantum field theory to obtain the quantum corrections to the zero temperature phase diagram of systems with competing order parameters. We are particularly interested in two different scenarios: regions of the phase diagram where there is a bicritical point, at which both phases vanish continuously, and the case where both phases coexist homogeneously. We consider different types of couplings between the order parameters, including a bilinear one. This kind of coupling breaks time-reversal symmetry and it is only allowed if both order parameters transform according to the same irreducible representation. This occurs in many physical systems of actual interest like competing spin density waves, different types of orbital antiferromagnetism, elastic instabilities of crystal lattices, vortices in a multigap SC and also applies to describe the unusual magnetism of the heavy fermion compound URu 2 Si 2 . Our results show that quantum corrections have an important effect on the phase diagram of systems with competing orders.

Quantum corrections for the phase diagram of systems with competing order

NASA Astrophysics Data System (ADS)

Silva, N. L., Jr.; Continentino, Mucio A.; Barci, Daniel G.

2018-06-01

We use the effective potential method of quantum field theory to obtain the quantum corrections to the zero temperature phase diagram of systems with competing order parameters. We are particularly interested in two different scenarios: regions of the phase diagram where there is a bicritical point, at which both phases vanish continuously, and the case where both phases coexist homogeneously. We consider different types of couplings between the order parameters, including a bilinear one. This kind of coupling breaks time-reversal symmetry and it is only allowed if both order parameters transform according to the same irreducible representation. This occurs in many physical systems of actual interest like competing spin density waves, different types of orbital antiferromagnetism, elastic instabilities of crystal lattices, vortices in a multigap SC and also applies to describe the unusual magnetism of the heavy fermion compound URu2Si2. Our results show that quantum corrections have an important effect on the phase diagram of systems with competing orders.

16 CFR Figure 5 to Subpart A of... - Zero Reference Point Related to Detecting Plane

Code of Federal Regulations, 2013 CFR

2013-01-01

... 16 Commercial Practices 2 2013-01-01 2013-01-01 false Zero Reference Point Related to Detecting Plane 5 Figure 5 to Subpart A of Part 1209 Commercial Practices CONSUMER PRODUCT SAFETY COMMISSION.... 1209, Subpt. A, Fig. 5 Figure 5 to Subpart A of Part 1209—Zero Reference Point Related to Detecting...

16 CFR Figure 5 to Subpart A of... - Zero Reference Point Related to Detecting Plane

Code of Federal Regulations, 2012 CFR

2012-01-01

... 16 Commercial Practices 2 2012-01-01 2012-01-01 false Zero Reference Point Related to Detecting Plane 5 Figure 5 to Subpart A of Part 1209 Commercial Practices CONSUMER PRODUCT SAFETY COMMISSION.... 1209, Subpt. A, Fig. 5 Figure 5 to Subpart A of Part 1209—Zero Reference Point Related to Detecting...

16 CFR Figure 5 to Subpart A of... - Zero Reference Point Related to Detecting Plane

Code of Federal Regulations, 2014 CFR

2014-01-01

... 16 Commercial Practices 2 2014-01-01 2014-01-01 false Zero Reference Point Related to Detecting Plane 5 Figure 5 to Subpart A of Part 1209 Commercial Practices CONSUMER PRODUCT SAFETY COMMISSION.... 1209, Subpt. A, Fig. 5 Figure 5 to Subpart A of Part 1209—Zero Reference Point Related to Detecting...

NREL and Army Validate Energy Savings for Net Zero Energy Installations |

Science.gov Websites

News | NREL and Army Validate Energy Savings for Net Zero Energy Installations News Release : NREL and Army Validate Energy Savings for Net Zero Energy Installations October 27, 2014 The U.S. Army (Army) has partnered with the Energy Department's National Renewable Energy Laboratory (NREL) to

Hexagonalization of correlation functions II: two-particle contributions

NASA Astrophysics Data System (ADS)

Fleury, Thiago; Komatsu, Shota

2018-02-01

In this work, we compute one-loop planar five-point functions in N=4 super-Yang-Mills using integrability. As in the previous work, we decompose the correlation functions into hexagon form factors and glue them using the weight factors which depend on the cross-ratios. The main new ingredient in the computation, as compared to the four-point functions studied in the previous paper, is the two-particle mirror contribution. We develop techniques to evaluate it and find agreement with the perturbative results in all the cases we analyzed. In addition, we consider next-to-extremal four-point functions, which are known to be protected, and show that the sum of one-particle and two-particle contributions at one loop adds up to zero as expected. The tools developed in this work would be useful for computing higher-particle contributions which would be relevant for more complicated quantities such as higher-loop corrections and non-planar correlators.

The motion near L{sub 4} equilibrium point under non-point mass primaries

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

Huda, I. N., E-mail: ibnu.nurul@students.itb.ac.id; Utama, J. A.; Madley, D.

2015-09-30

The Circular Restricted Three-Body Problem (CRTBP) possesses five equilibrium points, that comprise three collinear (L{sub 1}, L{sub 2}, and L{sub 3}) and two triangular points (L{sub 4} and L{sub 5}). The classical study (with the primaries are point mass) suggests that the equilibrium points may cause the velocity of infinitesimal object relatively becomes zero and reveals the zero velocity curve. We study the motion of infinitesimal object near triangular equilibrium point (L{sub 4}) and determine its zero velocity curve. We extend the study by taking into account the effects of radiation of the bigger primary (q{sub 1} ≠ 1, q{submore » 2} = 1) and oblateness of the smaller primary (A{sub 1} = 0, A{sub 2} ≠ 0). The location of L{sub 4} is analytically derived then the stability of L{sub 4} and its zero velocity curves are studied numerically. Our study suggests that the oblateness and the radiation of primaries may affect the stability and zero velocity curve around L{sub 4}.« less

Precision zero-home locator

DOEpatents

Stone, William J.

1986-01-01

A zero-home locator includes a fixed phototransistor switch and a moveable actuator including two symmetrical, opposed wedges, each wedge defining a point at which switching occurs. The zero-home location is the average of the positions of the points defined by the wedges.

Precision zero-home locator

DOEpatents

Stone, W.J.

1983-10-31

A zero-home locator includes a fixed phototransistor switch and a moveable actuator including two symmetrical, opposed wedges, each wedge defining a point at which switching occurs. The zero-home location is the average of the positions of the points defined by the wedges.

Building America Case Study: New Town Builders' Power of Zero Energy Center, Denver, Colorado (Brochure)

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

Not Available

New Town Builders, a builder of energy efficient homes in Denver, Colorado, offers a zero energy option for all the homes it builds. To attract a wide range of potential homebuyers to its energy efficient homes, New Town Builders created a 'Power of Zero Energy Center' linked to its model home in the Stapleton community of Denver. This case study presents New Town Builders' marketing approach, which is targeted to appeal to homebuyers' emotions rather than overwhelming homebuyers with scientific details about the technology. The exhibits in the Power of Zero Energy Center focus on reduced energy expenses for themore » homeowner, improved occupant comfort, the reputation of the builder, and the lack of sacrificing the homebuyers' desired design features to achieve zero net energy in the home. The case study also contains customer and realtor testimonials related to the effectiveness of the Center in influencing homebuyers to purchase a zero energy home.« less

New Whole-House Solutions Case Study: New Town Builders' Power of Zero Energy Center - Denver, Colorado

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

None

New Town Builders, a builder of energy efficient homes in Denver, Colorado, offers a zero energy option for all the homes it builds. To attract a wide range of potential homebuyers to its energy efficient homes, New Town Builders created a "Power of Zero Energy Center" linked to its model home in the Stapleton community. This case study presents New Town Builders' marketing approach, which is targeted to appeal to homebuyers' emotions rather than overwhelming homebuyers with scientific details about the technology. The exhibits in the Power of Zero Energy Center focus on reduced energy expenses for the homeowner, improvedmore » occupant comfort, the reputation of the builder, and the lack of sacrificing the homebuyers' desired design features to achieve zero net energy in the home. This case study also contains customer and realtor testimonials related to the effectiveness of the Center in influencing homebuyers to purchase a zero energy home.« less

The propagator of stochastic electrodynamics

NASA Astrophysics Data System (ADS)

Cavalleri, G.

1981-01-01

The "elementary propagator" for the position of a free charged particle subject to the zero-point electromagnetic field with Lorentz-invariant spectral density ~ω3 is obtained. The nonstationary process for the position is solved by the stationary process for the acceleration. The dispersion of the position elementary propagator is compared with that of quantum electrodynamics. Finally, the evolution of the probability density is obtained starting from an initial distribution confined in a small volume and with a Gaussian distribution in the velocities. The resulting probability density for the position turns out to be equal, to within radiative corrections, to ψψ* where ψ is the Kennard wave packet. If the radiative corrections are retained, the present result is new since the corresponding expression in quantum electrodynamics has not yet been found. Besides preceding quantum electrodynamics for this problem, no renormalization is required in stochastic electrodynamics.

High-level ab initio predictions for the ionization energy, bond dissociation energies, and heats of formations of iron carbide (FeC) and its cation (FeC+).

PubMed

Lau, Kai-Chung; Chang, Yih-Chung; Lam, Chow-Shing; Ng, C Y

2009-12-31

The ionization energy (IE) of FeC and the 0 K bond dissociation energies (D(0)) and the heats of formation at 0 K (DeltaH(o)(f0)) and 298 K (DeltaH(o)(f298)) for FeC and FeC(+) are predicted by the single-reference wave function based CCSDTQ(Full)/CBS approach, which involves the approximation to the complete basis set (CBS) limit at the coupled cluster level up to full quadruple excitations. The zero-point vibrational energy (ZPVE) correction, the core-valence electronic corrections (up to CCSDT level), spin-orbit couplings, and relativistic effects (up to CCSDTQ level) are included in the calculations. The present calculations provide the correct symmetry predictions for the ground states of FeC and FeC(+) to be (3)Delta and (2)Delta, respectively. We have also examined the theoretical harmonic vibrational frequencies of FeC/FeC(+) at the ROHF-UCCSD(T) and UHF-UCCSD(T) levels. While the UHF-UCCSD(T) harmonic frequencies are in good agreement with the experimental measurements, the ROHF-UCCSD(T) yields significantly higher harmonic frequency predictions for FeC/FeC(+). The CCSDTQ(Full)/CBS IE(FeC) = 7.565 eV is found to compare favorably with the experimental IE value of 7.59318 +/- 0.00006 eV, suggesting that the single-reference-based coupled cluster theory is capable of providing reliable IE prediction for FeC, despite its multireference character. The CCSDTQ(Full)/CBS D(0)(Fe(+)-C) and D(0)(Fe-C) give the prediction of D(0)(Fe(+)-C) - D(0)(Fe-C) = 0.334 eV, which is consistent with the experimental determination of 0.3094 +/- 0.0001 eV. The D(0) calculations also support the experimental D(0)(Fe(+)-C) = 4.1 +/- 0.3 eV and D(0)(Fe-C) = 3.8 +/- 0.3 eV determined by the previous ion photodissociation study. The present calculations also provide the DeltaH(o)(f0)(DeltaH(o)(f298)) predictions for FeC/FeC(+). The analysis of the correction terms in these calculations shows that the core-valence and valence-valence electronic correlations beyond CCSD(T) wave function and the relativistic effects make significant contributions to the calculated thermochemical properties of FeC/FeC(+). For the experimental D(0) and DeltaH(o)(f0) values of FeC/FeC(+), which are not known to high precision, we recommend the CCSDTQ(Full)/CBS predictions [D(0)(Fe-C) = 3.778 eV, D(0)(Fe(+)-C) = 4.112 eV, DeltaH(o)(f0)(FeC) = 760.8 kJ/mol and DeltaH(o)(f0)(FeC(+)) = 1490.6 kJ/mol] based on the ZPVE corrections using the experimental vibrational frequencies of FeC and FeC(+).

Technical Feasibility Study for Zero Energy K-12 Schools

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

Pless, Shanti D.; Torcellini, Paul A.; Bonnema, Eric

A simulation-based technical feasibility study was completed to show the types of technologies required to achieve ZEB status with this building type. These technologies are prioritized across the building's subsystem such that design teams can readily integrate the ideas. Energy use intensity (EUI) targets were established for U.S. climate zones such that K-12 schools can be zero-ready or can procure solar panels or other renewable energy production sources to meet the zero energy building definition. Results showed that it is possible for K-12 schools to achieve zero energy when the EUI is between 20 and 26 kBtu/ft2/yr. Temperate climates requiredmore » a smaller percentage of solar panel coverage than very hot or very cold climates. The paper provides a foundation for technically achieving zero energy schools with a vision of transforming the school construction market to mainstream zero energy buildings within typical construction budgets.« less

Observation of Dihalide Elimination Upon Electron Attachment to Oxalyl Chloride and Oxalyl Bromide, 300-550 K

DTIC Science & Technology

2006-05-10

fragment CC120 and bromine The positive ion chemistry of oxalyl chloride has been analog CBrO. Total energies, enthalpies, and zero-point energy ( ZPE ...that Ar+ reacting with oxalyl bromide produced System G3a G2 b 70% CBrO+ and 30% Br+. trants-C2C1202(C2h, Ag) ZPE 0.019 93 0.019 93 COMPUTATIONAL...secondary ZPE 0.01708 0.01708 ions were carried out using the G3 compound method, pri- Total energy (0 K) -1146.717 00 -1145.904 66 marily in order to

Scaling in the vicinity of the four-state Potts fixed point

NASA Astrophysics Data System (ADS)

Blöte, H. W. J.; Guo, Wenan; Nightingale, M. P.

2017-08-01

We study a self-dual generalization of the Baxter-Wu model, employing results obtained by transfer matrix calculations of the magnetic scaling dimension and the free energy. While the pure critical Baxter-Wu model displays the critical behavior of the four-state Potts fixed point in two dimensions, in the sense that logarithmic corrections are absent, the introduction of different couplings in the up- and down triangles moves the model away from this fixed point, so that logarithmic corrections appear. Real couplings move the model into the first-order range, away from the behavior displayed by the nearest-neighbor, four-state Potts model. We also use complex couplings, which bring the model in the opposite direction characterized by the same type of logarithmic corrections as present in the four-state Potts model. Our finite-size analysis confirms in detail the existing renormalization theory describing the immediate vicinity of the four-state Potts fixed point.

Determination of efficiency of an aged HPGe detector for gaseous sources by self absorption correction and point source methods

NASA Astrophysics Data System (ADS)

Sarangapani, R.; Jose, M. T.; Srinivasan, T. K.; Venkatraman, B.

2017-07-01

Methods for the determination of efficiency of an aged high purity germanium (HPGe) detector for gaseous sources have been presented in the paper. X-ray radiography of the detector has been performed to get detector dimensions for computational purposes. The dead layer thickness of HPGe detector has been ascertained from experiments and Monte Carlo computations. Experimental work with standard point and liquid sources in several cylindrical geometries has been undertaken for obtaining energy dependant efficiency. Monte Carlo simulations have been performed for computing efficiencies for point, liquid and gaseous sources. Self absorption correction factors have been obtained using mathematical equations for volume sources and MCNP simulations. Self-absorption correction and point source methods have been used to estimate the efficiency for gaseous sources. The efficiencies determined from the present work have been used to estimate activity of cover gas sample of a fast reactor.

Influence of nitrogen doping in sumanene framework toward hydrogen storage: A computational study.

PubMed

Reisi-Vanani, Adel; Shamsali, Fatemeh

2017-09-01

Two conditions are important to obtain appropriate substances for hydrogen storage; high surface area and fitting binding energy (BE). Doping is a key strategy that improves BE. We investigated hydrogen adsorption onto twenty six nitrogen disubstituted isomers of sumanene (C 19 N 2 H 12 ) by MP2/6-311++G(d,p)//B3LYP/6-31+G(d) and M06-2X/6-31+G(d) levels of theory. Effect of nitrogen doping in different positions of sumanene was checked. To obtain better BE, basis set superposition error (BSSE) and zero point energy (ZPE) corrections were used. Anticipating of adsorption sites and extra details about adsorption process was done by molecular electrostatic potential (MEP) surfaces. Various types of density of state (DOS) diagrams such as total DOS (TDOS), projected DOS (PDOS) and overlap population DOS (OPDOS) and natural bond orbital (NBO) analysis were used to find better insight on the adsorption properties. In addition of temperature depending of the BE, HOMO-LUMO gap (HLG), dipole moment, reactivity and stability, bowl depth and natural population analysis (NPA) of the isomers were studied. A physisorption mechanism for adsorption was proposed and a trivial change was seen. Place of nitrogen atoms in sumanene frame causes to binding energy increases or decreases compared with pristine sumanene. The best and the worst isomers and category of isomers were suggested. Copyright © 2017 Elsevier Inc. All rights reserved.

Solvent effects on the excited-state double proton transfer mechanism in the 7-azaindole dimer: a TDDFT study with the polarizable continuum model.

PubMed

Yu, Xue-Fang; Yamazaki, Shohei; Taketsugu, Tetsuya

2017-08-30

Solvent effects on the excited-state double proton transfer (ESDPT) mechanism in the 7-azaindole (7AI) dimer were investigated using the time-dependent density functional theory (TDDFT) method. Excited-state potential energy profiles along the reaction paths in a locally excited (LE) state and a charge transfer (CT) state were calculated using the polarizable continuum model (PCM) to include the solvent effect. A series of non-polar and polar solvents with different dielectric constants were used to examine the polarity effect on the ESDPT mechanism. The present results suggest that in a non-polar solvent and a polar solvent with a small dielectric constant, ESDPT follows a concerted mechanism, similar to the case in the gas phase. In a polar solvent with a relatively large dielectric constant, however, ESDPT is likely to follow a stepwise mechanism via a stable zwitterionic intermediate in the LE state on the adiabatic potential energy surface, although inclusion of zero-point vibrational energy (ZPE) corrections again suggests the concerted mechanism. In the meantime, the stepwise reaction path involving the CT state with neutral intermediates is also examined, and is found to be less competitive than the concerted or stepwise path in the LE state in both non-polar and polar solvents. The present study provides a new insight into the experimental controversy of the ESDPT mechanism of the 7AI dimer in a solution.

A Computational Framework for Automation of Point Defect Calculations

NASA Astrophysics Data System (ADS)

Goyal, Anuj; Gorai, Prashun; Peng, Haowei; Lany, Stephan; Stevanovic, Vladan; National Renewable Energy Laboratory, Golden, Colorado 80401 Collaboration

A complete and rigorously validated open-source Python framework to automate point defect calculations using density functional theory has been developed. The framework provides an effective and efficient method for defect structure generation, and creation of simple yet customizable workflows to analyze defect calculations. The package provides the capability to compute widely accepted correction schemes to overcome finite-size effects, including (1) potential alignment, (2) image-charge correction, and (3) band filling correction to shallow defects. Using Si, ZnO and In2O3as test examples, we demonstrate the package capabilities and validate the methodology. We believe that a robust automated tool like this will enable the materials by design community to assess the impact of point defects on materials performance. National Renewable Energy Laboratory, Golden, Colorado 80401.

Surface Impact Simulations of Helium Nanodroplets

DTIC Science & Technology

2015-06-30

mechanical delocalization of the individual helium atoms in the droplet and the quan- tum statistical effects that accompany the interchange of identical...incorporates the effects of atomic delocaliza- tion by treating individual atoms as smeared-out probability distributions that move along classical...probability density distributions to give effec- tive interatomic potential energy curves that have zero-point averaging effects built into them [25

Study on improved Ip-iq APF control algorithm and its application in micro grid

NASA Astrophysics Data System (ADS)

Xie, Xifeng; Shi, Hua; Deng, Haiyingv

2018-01-01

In order to enhance the tracking velocity and accuracy of harmonic detection by ip-iq algorithm, a novel ip-iq control algorithm based on the Instantaneous reactive power theory is presented, the improved algorithm adds the lead correction link to adjust the zero point of the detection system, the Fuzzy Self-Tuning Adaptive PI control is introduced to dynamically adjust the DC-link Voltage, which meets the requirement of the harmonic compensation of the micro grid. Simulation and experimental results verify the proposed method is feasible and effective in micro grid.

Highly Adjustable Systems: An Architecture for Future Space Observatories

NASA Astrophysics Data System (ADS)

Arenberg, Jonathan; Conti, Alberto; Redding, David; Lawrence, Charles R.; Hachkowski, Roman; Laskin, Robert; Steeves, John

2017-06-01

Mission costs for ground breaking space astronomical observatories are increasing to the point of unsustainability. We are investigating the use of adjustable or correctable systems as a means to reduce development and therefore mission costs. The poster introduces the promise and possibility of realizing a “net zero CTE” system for the general problem of observatory design and introduces the basic systems architecture we are considering. This poster concludes with an overview of our planned study and demonstrations for proving the value and worth of highly adjustable telescopes and systems ahead of the upcoming decadal survey.

Dark Energy Survey Year 1 Results: The Photometric Data Set for Cosmology

NASA Astrophysics Data System (ADS)

Drlica-Wagner, A.; Sevilla-Noarbe, I.; Rykoff, E. S.; Gruendl, R. A.; Yanny, B.; Tucker, D. L.; Hoyle, B.; Carnero Rosell, A.; Bernstein, G. M.; Bechtol, K.; Becker, M. R.; Benoit-Lévy, A.; Bertin, E.; Carrasco Kind, M.; Davis, C.; de Vicente, J.; Diehl, H. T.; Gruen, D.; Hartley, W. G.; Leistedt, B.; Li, T. S.; Marshall, J. L.; Neilsen, E.; Rau, M. M.; Sheldon, E.; Smith, J.; Troxel, M. A.; Wyatt, S.; Zhang, Y.; Abbott, T. M. C.; Abdalla, F. B.; Allam, S.; Banerji, M.; Brooks, D.; Buckley-Geer, E.; Burke, D. L.; Capozzi, D.; Carretero, J.; Cunha, C. E.; D’Andrea, C. B.; da Costa, L. N.; DePoy, D. L.; Desai, S.; Dietrich, J. P.; Doel, P.; Evrard, A. E.; Fausti Neto, A.; Flaugher, B.; Fosalba, P.; Frieman, J.; García-Bellido, J.; Gerdes, D. W.; Giannantonio, T.; Gschwend, J.; Gutierrez, G.; Honscheid, K.; James, D. J.; Jeltema, T.; Kuehn, K.; Kuhlmann, S.; Kuropatkin, N.; Lahav, O.; Lima, M.; Lin, H.; Maia, M. A. G.; Martini, P.; McMahon, R. G.; Melchior, P.; Menanteau, F.; Miquel, R.; Nichol, R. C.; Ogando, R. L. C.; Plazas, A. A.; Romer, A. K.; Roodman, A.; Sanchez, E.; Scarpine, V.; Schindler, R.; Schubnell, M.; Smith, M.; Smith, R. C.; Soares-Santos, M.; Sobreira, F.; Suchyta, E.; Tarle, G.; Vikram, V.; Walker, A. R.; Wechsler, R. H.; Zuntz, J.; DES Collaboration

2018-04-01

We describe the creation, content, and validation of the Dark Energy Survey (DES) internal year-one cosmology data set, Y1A1 GOLD, in support of upcoming cosmological analyses. The Y1A1 GOLD data set is assembled from multiple epochs of DES imaging and consists of calibrated photometric zero-points, object catalogs, and ancillary data products—e.g., maps of survey depth and observing conditions, star–galaxy classification, and photometric redshift estimates—that are necessary for accurate cosmological analyses. The Y1A1 GOLD wide-area object catalog consists of ∼ 137 million objects detected in co-added images covering ∼ 1800 {\\deg }2 in the DES grizY filters. The 10σ limiting magnitude for galaxies is g=23.4, r=23.2, i=22.5, z=21.8, and Y=20.1. Photometric calibration of Y1A1 GOLD was performed by combining nightly zero-point solutions with stellar locus regression, and the absolute calibration accuracy is better than 2% over the survey area. DES Y1A1 GOLD is the largest photometric data set at the achieved depth to date, enabling precise measurements of cosmic acceleration at z ≲ 1.

Energy theorem for (2+1)-dimensional gravity.

NASA Astrophysics Data System (ADS)

Menotti, P.; Seminara, D.

1995-05-01

We prove a positive energy theorem in (2+1)-dimensional gravity for open universes and any matter energy-momentum tensor satisfying the dominant energy condition. We consider on the space-like initial value surface a family of widening Wilson loops and show that the energy-momentum of the enclosed subsystem is a future directed time-like vector whose mass is an increasing function of the loop, until it reaches the value 1/4G corresponding to a deficit angle of 2π. At this point the energy-momentum of the system evolves, depending on the nature of a zero norm vector appearing in the evolution equations, either into a time-like vector of a universe which closes kinematically or into a Gott-like universe whose energy momentum vector, as first recognized by Deser, Jackiw, and 't Hooft (1984) is space-like. This treatment generalizes results obtained by Carroll, Fahri, Guth, and Olum (1994) for a system of point-like spinless particle, to the most general form of matter whose energy-momentum tensor satisfies the dominant energy condition. The treatment is also given for the anti-de Sitter (2+1)-dimensional gravity.

Advanced Energy Design Guide K-12: Next Generation of School Design and Operation

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

Torcellini, Paul A; Pless, Shanti

Driven by energy efficiency advances and renewable energy cost reductions, zero energy buildings are popping up all around the country. Although zero energy represents a bold paradigm shift - from buildings that consume energy to buildings that produce enough energy to meet their energy needs on an annual basis - it isn't a sudden shift. Zero energy buildings are the result of steady, incremental progress by researchers and building professionals working together to improve building energy performance. ASHRAE is taking the lead by publishing - in partnership with the American Institute of Architects (AIA), the Illuminating Engineering Society (IES), themore » U.S. Green Building Council (USGBC), and the U.S. Department of Energy (DOE) - a new series of advanced energy design guides (AEDGs) focused on zero energy buildings. The recently completed Advanced Energy Design Guide for K-12 School Buildings: Achieving Zero Energy (K-12 ZE AEDG) is the first in this series.« less

The paradoxical zero reflection at zero energy

NASA Astrophysics Data System (ADS)

Ahmed, Zafar; Sharma, Vibhu; Sharma, Mayank; Singhal, Ankush; Kaiwart, Rahul; Priyadarshini, Pallavi

2017-03-01

Usually, the reflection probability R(E) of a particle of zero energy incident on a potential which converges to zero asymptotically is found to be 1: R(0)=1. But earlier, a paradoxical phenomenon of zero reflection at zero energy (R(0)=0) has been revealed as a threshold anomaly. Extending the concept of half-bound state (HBS) of 3D, here we show that in 1D when a symmetric (asymmetric) attractive potential well possesses a zero-energy HBS, R(0)=0 (R(0)\\ll 1). This can happen only at some critical values q c of an effective parameter q of the potential well in the limit E\\to {0}+. We demonstrate this critical phenomenon in two simple analytically solvable models: square and exponential wells. However, in numerical calculations, even for these two models R(0)=0 is observed only as extrapolation to zero energy from low energies, close to a precise critical value q c. By numerical investigation of a variety of potential wells, we conclude that for a given potential well (symmetric or asymmetric), we can adjust the effective parameter q to have a low reflection at a low energy.

An automatic P‐Phase arrival‐time picker

USGS Publications Warehouse

Kalkan, Erol

2016-01-01

Presented is a new approach for picking P‐phase arrival time in single‐component acceleration or broadband velocity records without requiring detection interval or threshold settings. The algorithm PPHASEPICKER transforms the signal into a response domain of a single‐degree‐of‐freedom (SDOF) oscillator with viscous damping and then tracks the rate of change of dissipated damping energy to pick P‐wave phases. The SDOF oscillator has a short natural period and a correspondingly high resonant frequency, which is higher than most frequencies in a seismic wave. It also has a high damping ratio (60% of critical). At this damping level, the frequency response approaches the Butterworth maximally flat magnitude filter, and phase angles are preserved. The relative input energy imparted to the oscillator by the input signal is converted to elastic strain energy and then dissipated by the damping element as damping energy. The damping energy yields a smooth envelope over time; it is zero in the beginning of the signal, zero or near zero before theP‐phase arrival, and builds up rapidly with the P wave. Because the damping energy function changes considerably at the onset of the P wave, it is used as a metric to track and pick the P‐phase arrival time. The PPHASEPICKER detects P‐phase onset using the histogram method. Its performance is compared with picking techniques using short‐term‐average to long‐term‐average ratio, and a picking method that finds the first P‐phase arrival time using the Akaike information criterion. A large set of records with various intensities and signal‐to‐noise ratios is used for testing the PPHASEPICKER, and it is demonstrated thatPPHASEPICKER is able to more accurately pick the onset of genuine signals against the background noise and to correctly distinguish between whether the first arrival is a P wave (emergent or impulsive) or whether the signal is from a faulty sensor.

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

NASA Technical Reports Server (NTRS)

Boese, A. Daniel; Scuseria, Gustavo E.

1998-01-01

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

The Dissociation Energies of CH4 and C2H2 Revisited

NASA Technical Reports Server (NTRS)

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

1995-01-01

The bond dissociation energies of CH4 and C2H2 and their fragments are investigated using basis set extrapolations and high levels of correlation. The computed bond dissociation energies (D(sub e)) are accurate to within 0.2 kcal/mol. The agreement with the experimental (D(sub 0)) values is excellent if we assume that the zero-point energy of C2H is 9.18 kcal/mol. The effect of core (1s) correlation on the bond dissociation energies of C-H bonds is shown to vary from 0.2 to 0.7 kcal/mol and that for C-C bonds varies from 0.4 to 2.2 kcal/mol.

DRIFT COMPENSATED DIRECT COUPLED AMPLIFIER

DOEpatents

Windsor, A.A.

1959-05-01

An improved direct-coupled amplifier having zerolevel drift correction is described. The need for an auxiliary corrective-potential amplifier is eliminated thereby giving protection against overload saturation of the zero- level drift correcting circuit. (T.R.H.)

Trajectory phase transitions and dynamical Lee-Yang zeros of the Glauber-Ising chain.

PubMed

Hickey, James M; Flindt, Christian; Garrahan, Juan P

2013-07-01

We examine the generating function of the time-integrated energy for the one-dimensional Glauber-Ising model. At long times, the generating function takes on a large-deviation form and the associated cumulant generating function has singularities corresponding to continuous trajectory (or "space-time") phase transitions between paramagnetic trajectories and ferromagnetically or antiferromagnetically ordered trajectories. In the thermodynamic limit, the singularities make up a whole curve of critical points in the complex plane of the counting field. We evaluate analytically the generating function by mapping the generator of the biased dynamics to a non-Hermitian Hamiltonian of an associated quantum spin chain. We relate the trajectory phase transitions to the high-order cumulants of the time-integrated energy which we use to extract the dynamical Lee-Yang zeros of the generating function. This approach offers the possibility to detect continuous trajectory phase transitions from the finite-time behavior of measurable quantities.

Temperature and magnetic field effects on electron transport through DNA molecules in a two-dimensional four-channel system.

PubMed

Joe, Yong S; Lee, Sun H; Hedin, Eric R; Kim, Young D

2013-06-01

We utilize a two-dimensional four-channel DNA model, with a tight-binding (TB) Hamiltonian, and investigate the temperature and the magnetic field dependence of the transport behavior of a short DNA molecule. Random variation of the hopping integrals due to the thermal structural disorder, which partially destroy phase coherence of electrons and reduce quantum interference, leads to a reduction of the localization length and causes suppressed overall transmission. We also incorporate a variation of magnetic field flux density into the hopping integrals as a phase factor and observe Aharonov-Bohm (AB) oscillations in the transmission. It is shown that for non-zero magnetic flux, the transmission zero leaves the real-energy axis and moves up into the complex-energy plane. We also point out that the hydrogen bonds between the base pair with flux variations play a role to determine the periodicity of AB oscillations in the transmission.

Step-to-Step Ankle Inversion/Eversion Torque Modulation Can Reduce Effort Associated with Balance.

PubMed

Kim, Myunghee; Collins, Steven H

2017-01-01

Below-knee amputation is associated with higher energy expenditure during walking, partially due to difficulty maintaining balance. We previously found that once-per-step push-off work control can reduce balance-related effort, both in simulation and in experiments with human participants. Simulations also suggested that changing ankle inversion/eversion torque on each step, in response to changes in body state, could assist with balance. In this study, we investigated the effects of ankle inversion/eversion torque modulation on balance-related effort among amputees ( N = 5) using a multi-actuated ankle-foot prosthesis emulator. In stabilizing conditions, changes in ankle inversion/eversion torque were applied so as to counteract deviations in side-to-side center-of-mass acceleration at the moment of intact-limb toe off; higher acceleration toward the prosthetic limb resulted in a corrective ankle inversion torque during the ensuing stance phase. Destabilizing controllers had the opposite effect, and a zero gain controller made no changes to the nominal inversion/eversion torque. To separate the balance-related effects of step-to-step control from the potential effects of changes in average mechanics, average ankle inversion/eversion torque and prosthesis work were held constant across conditions. High-gain stabilizing control lowered metabolic cost by 13% compared to the zero gain controller ( p = 0.05). We then investigated individual responses to subject-specific stabilizing controllers following an enforced exploration period. Four of five participants experienced reduced metabolic rate compared to the zero gain controller (-15, -14, -11, -6, and +4%) an average reduction of 9% ( p = 0.05). Average prosthesis mechanics were unchanged across all conditions, suggesting that improvements in energy economy might have come from changes in step-to-step corrections related to balance. Step-to-step modulation of inversion/eversion torque could be used in new, active ankle-foot prostheses to reduce walking effort associated with maintaining balance.

Development and Evaluation of A Novel and Cost-Effective Approach for Low-Cost NO₂ Sensor Drift Correction.

PubMed

Sun, Li; Westerdahl, Dane; Ning, Zhi

2017-08-19

Emerging low-cost gas sensor technologies have received increasing attention in recent years for air quality measurements due to their small size and convenient deployment. However, in the diverse applications these sensors face many technological challenges, including sensor drift over long-term deployment that cannot be easily addressed using mathematical correction algorithms or machine learning methods. This study aims to develop a novel approach to auto-correct the drift of commonly used electrochemical nitrogen dioxide (NO₂) sensor with comprehensive evaluation of its application. The impact of environmental factors on the NO₂ electrochemical sensor in low-ppb concentration level measurement was evaluated in laboratory and the temperature and relative humidity correction algorithm was evaluated. An automated zeroing protocol was developed and assessed using a chemical absorbent to remove NO₂ as a means to perform zero correction in varying ambient conditions. The sensor system was operated in three different environments in which data were compared to a reference NO₂ analyzer. The results showed that the zero-calibration protocol effectively corrected the observed drift of the sensor output. This technique offers the ability to enhance the performance of low-cost sensor based systems and these findings suggest extension of the approach to improve data quality from sensors measuring other gaseous pollutants in urban air.

Spectroscopy of the UO+2 cation and the delayed ionization of UO2.

PubMed

Merritt, Jeremy M; Han, Jiande; Heaven, Michael C

2008-02-28

Vibronically resolved spectra for the UO+2 cation have been recorded using the pulsed field ionization zero electron kinetic energy (PFI-ZEKE) technique. For the ground state, long progressions in both the bending and symmetric stretch vibrations were observed. Bend and stretch progressions of the first electronically excited state were also observed, and the origin was found at an energy of 2678 cm(-1) above the ground state zero-point level. This observation is consistent with a recent theoretical prediction [Infante et al., J. Chem. Phys. 127, 124308 (2007)]. The ionization energy for UO2, derived from the PFI-ZEKE spectrum, namely, 6.127(1) eV, is in excellent agreement with the value obtained from an earlier photoionization efficiency measurement. Delayed ionization of UO2 in the gas phase has been reported previously [Han et al., J. Chem. Phys. 120, 5155 (2004)]. Here, we extend the characterization of the delayed ionization process by performing a quantitative study of the ionization rate as a function of the energy above the ionization threshold. The ionization rate was found to be 5 x 10(6) s(-1) at threshold, and increased linearly with increasing energy in the range investigated (0-1200 cm(-1)).

Many-body perturbation theory using the density-functional concept: beyond the GW approximation.

PubMed

Bruneval, Fabien; Sottile, Francesco; Olevano, Valerio; Del Sole, Rodolfo; Reining, Lucia

2005-05-13

We propose an alternative formulation of many-body perturbation theory that uses the density-functional concept. Instead of the usual four-point integral equation for the polarizability, we obtain a two-point one, which leads to excellent optical absorption and energy-loss spectra. The corresponding three-point vertex function and self-energy are then simply calculated via an integration, for any level of approximation. Moreover, we show the direct impact of this formulation on the time-dependent density-functional theory. Numerical results for the band gap of bulk silicon and solid argon illustrate corrections beyond the GW approximation for the self-energy.

Step free energies at faceted solid surfaces: Theory and atomistic calculations for steps on the Cu(111) surface

NASA Astrophysics Data System (ADS)

Freitas, Rodrigo; Frolov, Timofey; Asta, Mark

2017-04-01

A theory for the thermodynamic properties of steps on faceted crystalline surfaces is presented. The formalism leads to the definition of step excess quantities, including an excess step stress that is the step analogy of surface stress. The approach is used to develop a relationship between the temperature dependence of the step free energy (γst) and step excess quantities for energy and stress that can be readily calculated by atomistic simulations. We demonstrate the application of this formalism in thermodynamic-integration (TI) calculations of the step free energy, based on molecular-dynamics simulations, considering <110 > steps on the {111 } surface of a classical potential model for elemental Cu. In this application we employ the Frenkel-Ladd approach to compute the reference value of γst for the TI calculations. Calculated results for excess energy and stress show relatively weak temperature dependencies up to a homologous temperature of approximately 0.6, above which these quantities increase strongly and the step stress becomes more isotropic. From the calculated excess quantities we compute γst over the temperature range from zero up to the melting point (Tm). We find that γst remains finite up to Tm, indicating the absence of a roughening temperature for this {111 } surface facet, but decreases by roughly fifty percent from the zero-temperature value. The strongest temperature dependence occurs above homologous temperatures of approximately 0.6, where the step becomes configurationally disordered due to the formation of point defects and appreciable capillary fluctuations.

GRIS observations of Al-26 gamma-ray line emission from two points in the Galactic plane

NASA Technical Reports Server (NTRS)

Teegarden, B. J.; Barthelmy, S. D.; Gehrels, N.; Tueller, J.; Leventhal, M.

1991-01-01

Both of the Gamma-Ray Imaging Spectrometer (GRIS) experiment's two observations of the Galactic center region, at l = zero and 335 deg respectively, detected Al-26 gamma-ray line emission. While these observations are consistent with the assumed high-energy gamma-ray distribution, they are consistent with other distributions as well. The data suggest that the Al-26 emission is distributed over Galactic longitude rather than being confined to a point source. The GRIS data also indicate that the 1809 keV line is broadened.

Quantum-Fluctuation-Initiated Coherence in Multioctave Raman Optical Frequency Combs

NASA Astrophysics Data System (ADS)

Wang, Y. Y.; Wu, Chunbai; Couny, F.; Raymer, M. G.; Benabid, F.

2010-09-01

We show experimentally and theoretically that the spectral components of a multioctave frequency comb spontaneously created by stimulated Raman scattering in a hydrogen-filled hollow-core photonic crystal fiber exhibit strong self-coherence and mutual coherence within each 12 ns driving laser pulse. This coherence arises in spite of the field’s initiation being from quantum zero-point fluctuations, which causes each spectral component to show large phase and energy fluctuations. This points to the possibility of an optical frequency comb with nonclassical correlations between all comb lines.

Computer Analysis of 400 HZ Aircraft Electrical Generator Test Data.

DTIC Science & Technology

1980-06-01

Data Acquisition System. ............ 6 3 Voltage Waveform with Data Points. ....... 19 14 Zero Crossover Interpolation. ........ 20 5 Numerical...difference between successive positive-sloped zero crossovers of the waveform. However, the exact time of zero crossover is not known. This is because...data sampling and the generator output are not synchronized. This unsynchronization means that data points which correspond with an exact zero crossover

Numerical Field Model Simulation of Fire and Heat Transfer in a Rectangular Compartment

DTIC Science & Technology

1992-09-01

zero . However, due to the approximation inherent in the numerical scheme, we will be satisfied if S,, tends toward zero as determined by comparison... zero , the appropriate coefficient (A) corresponding to that boundary is also set equal to zero . After the local pressure correction (P’) is determined...chamber just prior to starting the fire. It is assumed that the air is uni- formly at rest, thus all components of velocity are set equal to zero

Net Zero Ft. Carson: making a greener Army base

EPA Science Inventory

The US Army Net Zero program seeks to reduce the energy, water, and waste footprint of bases. Seventeen pilot bases aim to achieve 100% renewable energy, zero depletion of water resources, and/or zero waste to landfill by 2020. Some bases are pursuing Net Zero in a single secto...

Intrinsic time quantum geometrodynamics

NASA Astrophysics Data System (ADS)

Ita, Eyo Eyo; Soo, Chopin; Yu, Hoi-Lai

2015-08-01

Quantum geometrodynamics with intrinsic time development and momentric variables is presented. An underlying SU(3) group structure at each spatial point regulates the theory. The intrinsic time behavior of the theory is analyzed, together with its ground state and primordial quantum fluctuations. Cotton-York potential dominates at early times when the universe was small; the ground state naturally resolves Penrose's Weyl curvature hypothesis, and thermodynamic and gravitational "arrows of time" point in the same direction. Ricci scalar potential corresponding to Einstein's general relativity emerges as a zero-point energy contribution. A new set of fundamental commutation relations without Planck's constant emerges from the unification of gravitation and quantum mechanics.

Calculation of binary magnetic properties and potential energy curve in xenon dimer: second virial coefficient of (129)Xe nuclear shielding.

PubMed

Hanni, Matti; Lantto, Perttu; Runeberg, Nino; Jokisaari, Jukka; Vaara, Juha

2004-09-22

Quantum chemical calculations of the nuclear shielding tensor, the nuclear quadrupole coupling tensor, and the spin-rotation tensor are reported for the Xe dimer using ab initio quantum chemical methods. The binary chemical shift delta, the anisotropy of the shielding tensor Delta sigma, the nuclear quadrupole coupling tensor component along the internuclear axis chi( parallel ), and the spin-rotation constant C( perpendicular ) are presented as a function of internuclear distance. The basis set superposition error is approximately corrected for by using the counterpoise correction (CP) method. Electron correlation effects are systematically studied via the Hartree-Fock, complete active space self-consistent field, second-order Møller-Plesset many-body perturbation, and coupled-cluster singles and doubles (CCSD) theories, the last one without and with noniterative triples, at the nonrelativistic all-electron level. We also report a high-quality theoretical interatomic potential for the Xe dimer, gained using the relativistic effective potential/core polarization potential scheme. These calculations used valence basis set of cc-pVQZ quality supplemented with a set of midbond functions. The second virial coefficient of Xe nuclear shielding, which is probably the experimentally best-characterized intermolecular interaction effect in nuclear magnetic resonance spectroscopy, is computed as a function of temperature, and compared to experiment and earlier theoretical results. The best results for the second virial coefficient, obtained using the CCSD(CP) binary chemical shift curve and either our best theoretical potential or the empirical potentials from the literature, are in good agreement with experiment. Zero-point vibrational corrections of delta, Delta sigma, chi (parallel), and C (perpendicular) in the nu=0, J=0 rovibrational ground state of the xenon dimer are also reported.

Conformal amplitude hierarchy and the Poincaré disk

NASA Astrophysics Data System (ADS)

Shimada, Hirohiko

2018-02-01

The amplitude for the singlet channels in the 4-point function of the fundamental field in the conformal field theory of the 2d O(n) model is studied as a function of n. For a generic value of n, the 4-point function has infinitely many amplitudes, whose landscape can be very spiky as the higher amplitude changes its sign many times at the simple poles, which generalize the unique pole of the energy operator amplitude at n = 0. In the stadard parameterization of n by angle in unit of π, we find that the zeros and poles happen at the rational angles, forming a hierarchical tree structure inherent in the Poincaré disk. Some relation between the amplitude and the Farey path, a piecewise geodesic that visits these zeros and poles, is suggested. In this hierarchy, the symmetry of the congruence subgroup Γ(2) of SL(2, ℤ) naturally arises from the two clearly distinct even/odd classes of the rational angles, in which one respectively gets the truncated operator algebras and the logarithmic 4-point functions.

Zero Energy Use School.

ERIC Educational Resources Information Center

Nelson, Brian, Ed.; And Others

The economic and physical realities of an energy shortage have caused many educators to consider alternative sources of energy when constructing their schools. This book contains studies and designs by fifth-year architecture students concerning the proposed construction of a zero energy-use elementary school in Albany, Oregon. "Zero energy…

A new phase correction method in NMR imaging based on autocorrelation and histogram analysis.

PubMed

Ahn, C B; Cho, Z H

1987-01-01

A new statistical approach to phase correction in NMR imaging is proposed. The proposed scheme consists of first-and zero-order phase corrections each by the inverse multiplication of estimated phase error. The first-order error is estimated by the phase of autocorrelation calculated from the complex valued phase distorted image while the zero-order correction factor is extracted from the histogram of phase distribution of the first-order corrected image. Since all the correction procedures are performed on the spatial domain after completion of data acquisition, no prior adjustments or additional measurements are required. The algorithm can be applicable to most of the phase-involved NMR imaging techniques including inversion recovery imaging, quadrature modulated imaging, spectroscopic imaging, and flow imaging, etc. Some experimental results with inversion recovery imaging as well as quadrature spectroscopic imaging are shown to demonstrate the usefulness of the algorithm.

Aspinall Courthouse: GSA's Historic Preservation and Net-Zero Renovation Case Study

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

Chang, R.; Hayter, S.; Hotchkiss, E.

2014-10-01

The federal government is mandated with improving efficiency of buildings, incorporating renewable energy, and achieving net-zero energy operations where possible. These challenges led GSA to consider aligning historic preservation renovations with net-zero energy goals. The Wayne N. Aspinall Federal Building and U.S. Courthouse (Aspinall Courthouse), in Grand Junction, Colorado, is an example of a renovation project that aimed to accomplish both historic preservation and net-zero energy goals.

Ab initio studies of the Rg–NO{sup +}(X{sup 1}Σ{sup +}) van der Waals complexes (Rg = He, Ne, Ar, Kr, and Xe)

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

Orek, Cahit; Bulut, Niyazi, E-mail: jklos@umd.edu, E-mail: francois.lique@univ-lehavre.fr, E-mail: bulut-niyazi@yahoo.com; Kłos, Jacek, E-mail: jklos@umd.edu, E-mail: francois.lique@univ-lehavre.fr, E-mail: bulut-niyazi@yahoo.com

2016-05-28

We used the explicitly correlated variant of the coupled clusters method with single, double, and noniterative triple excitations [CCSD(T)-F12] to compute two-dimensional potential energy surfaces of van der Waals complexes formed by rare gas atoms (Rg) and NO{sup +}(X{sup 1}Σ{sup +}) cations. We used the correlation-consistent, triple-zeta (cc-pVTZ-F12) atomic basis sets, and for Kr and Xe rare gases, we employed corresponding pseudopotential cc-pVTZ-PP-F12 atomic basis sets. These basis sets were additionally augmented with mid-bond functions. The complexes are all of skewed T-shape type with Rg atom being closer to the N-side. Using analytical representation of the potentials, we have estimatedmore » zero-point energy corrected dissociation energies from anharmonic calculations with BOUND program and also from the harmonic approximation. The binding energies increase with the polarization of the Rg atom in series from He to Xe and are 196 cm{sup −1}, 360 cm{sup −1}, 1024 cm{sup −1}, 1434 cm{sup −1}, and 2141 cm{sup −1}, respectively. Their corresponding dissociation energies are 132 cm{sup −1}, 300 cm{sup −1}, 927 cm{sup −1}, 1320 cm{sup −1}, and 1994 cm{sup −1} for the complexes with He to Xe, respectively. We find good agreement with previous theoretical and experimental results. The harmonic vibrational frequencies were calculated for the bending and stretching modes of the Rg–NO{sup +} complexes.« less

A Calibration of NICMOS Camera 2 for Low Count Rates

NASA Astrophysics Data System (ADS)

Rubin, D.; Aldering, G.; Amanullah, R.; Barbary, K.; Dawson, K. S.; Deustua, S.; Faccioli, L.; Fadeyev, V.; Fakhouri, H. K.; Fruchter, A. S.; Gladders, M. D.; de Jong, R. S.; Koekemoer, A.; Krechmer, E.; Lidman, C.; Meyers, J.; Nordin, J.; Perlmutter, S.; Ripoche, P.; Schlegel, D. J.; Spadafora, A.; Suzuki, N.

2015-05-01

NICMOS 2 observations are crucial for constraining distances to most of the existing sample of z\\gt 1 SNe Ia. Unlike conventional calibration programs, these observations involve long exposure times and low count rates. Reciprocity failure is known to exist in HgCdTe devices and a correction for this effect has already been implemented for high and medium count rates. However, observations at faint count rates rely on extrapolations. Here instead, we provide a new zero-point calibration directly applicable to faint sources. This is obtained via inter-calibration of NIC2 F110W/F160W with the Wide Field Camera 3 (WFC3) in the low count-rate regime using z∼ 1 elliptical galaxies as tertiary calibrators. These objects have relatively simple near-IR spectral energy distributions, uniform colors, and their extended nature gives a superior signal-to-noise ratio at the same count rate than would stars. The use of extended objects also allows greater tolerances on point-spread function profiles. We find space telescope magnitude zero points (after the installation of the NICMOS cooling system, NCS) of 25.296\\+/- 0.022 for F110W and 25.803\\+/- 0.023 for F160W, both in agreement with the calibration extrapolated from count rates ≳1000 times larger (25.262 and 25.799). Before the installation of the NCS, we find 24.843\\+/- 0.025 for F110W and 25.498\\+/- 0.021 for F160W, also in agreement with the high-count-rate calibration (24.815 and 25.470). We also check the standard bandpasses of WFC3 and NICMOS 2 using a range of stars and galaxies at different colors and find mild tension for WFC3, limiting the accuracy of the zero points. To avoid human bias, our cross-calibration was “blinded” in that the fitted zero-point differences were hidden until the analysis was finalized. Based on observations with the NASA/ESA Hubble Space Telescope, obtained at the Space Telescope Science Institute, which is operated by AURA, Inc., under NASA contract NAS 5-26555, under programs SM2/NIC-7049, SM2/NIC-7152, CAL/NIC-7607, CAL/NIC-7691, CAL/NIC-7693, GO-7887, CAL/NIC-7902, CAL/NIC-7904, GO/DD-7941, SM3/NIC-8983, SM3/NIC-8986, GTO/ACS-9290, ENG/NIC-9324, CAL/NIC-9325, GO-9352, GO-9375, SNAP-9485, CAL/NIC-9639, GO-9717, GO-9834, GO-9856, CAL/NIC-9995, CAL/NIC-9997, GO-10189, GO-10258, CAL/NIC-10381, CAL/NIC-10454, GO-10496, CAL/NIC-10725, CAL/NIC-10726, GO-10886, CAL/NIC-11060, CAL/NIC-11061, GO-11135, GO-11143, GO-11202, CAL/NIC-11319, GO/DD-11359, SM4/WFC3-11439, SM4/WFC3-11451, GO-11557, GO-11591, GO-11600, GO/DD-11799, CAL/WFC3-11921, CAL/WFC3-11926, GO/DD-12051, GO-12061, GO-12062, GO-12177, CAL/WFC3-12333, CAL/WFC3-12334, CAL/WFC3-12341, GO-12443, GO-12444, GO-12445, CAL/WFC3-12698, CAL/WFC3-12699, GO-12874, CAL/WFC3-13088, and CAL/WFC3-13089.

Knotted optical vortices in exact solutions to Maxwell's equations

NASA Astrophysics Data System (ADS)

de Klerk, Albertus J. J. M.; van der Veen, Roland I.; Dalhuisen, Jan Willem; Bouwmeester, Dirk

2017-05-01

We construct a family of exact solutions to Maxwell's equations in which the points of zero intensity form knotted lines topologically equivalent to a given but arbitrary algebraic link. These lines of zero intensity, more commonly referred to as optical vortices, and their topology are preserved as time evolves and the fields have finite energy. To derive explicit expressions for these new electromagnetic fields that satisfy the nullness property, we make use of the Bateman variables for the Hopf field as well as complex polynomials in two variables whose zero sets give rise to algebraic links. The class of algebraic links includes not only all torus knots and links thereof, but also more intricate cable knots. While the unknot has been considered before, the solutions presented here show that more general knotted structures can also arise as optical vortices in exact solutions to Maxwell's equations.

Kondo physics from quasiparticle poisoning in Majorana devices

DOE PAGES

Plugge, S.; Tsvelik, A. M.; Zazunov, A.; ...

2016-03-24

Here, we present a theoretical analysis of quasiparticle poisoning in Coulomb-blockaded Majorana fermion systems tunnel-coupled to normal-conducting leads. Taking into account finite-energy quasiparticles, we derive the effective low-energy theory and present a renormalization group analysis. We find qualitatively new effects when a quasiparticle state with very low energy is localized near a tunnel contact. For M = 2 attached leads, such “dangerous” quasiparticle poisoning processes cause a spin S = 1/2 single-channel Kondo effect, which can be detected through a characteristic zero-bias anomaly conductance peak in all Coulomb blockade valleys. For more than two attached leads, the topological Kondo effectmore » of the unpoisoned system becomes unstable. A strong-coupling bosonization analysis indicates that at low energy the poisoned lead is effectively decoupled and hence, for M > 3, the topological Kondo fixed point re-emerges, though now it involves only M–1 leads. As a consequence, for M = 3, the low-energy fixed point becomes trivial corresponding to decoupled leads.« less

Dynamic ductile fracture of a central crack

NASA Technical Reports Server (NTRS)

Tsai, Y. M.

1976-01-01

A central crack, symmetrically growing at a constant speed in a two dimensional ductile material subject to uniform tension at infinity, is investigated using the integral transform methods. The crack is assumed to be the Dugdale crack, and the finite stress condition at the crack tip is satisfied during the propagation of the crack. Exact expressions of solution are obtained for the finite stress condition at the crack tip, the crack shape, the crack opening displacement, and the energy release rate. All those expressions are written as the product of explicit dimensional quantities and a nondimensional dynamic correction function. The expressions reduce to the associated static results when the crack speed tends to zero, and the nondimensional dynamic correction functions were calculated for various values of the parameter involved.

Targeting Net Zero Energy at Marine Corps Base Hawaii, Kaneohe Bay: Preprint

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

Burman, K.; Kandt, A.; Lisell, L.

2012-05-01

This paper summarizes the results of an NREL assessment of Marine Corps Base Hawaii (MCBH), Kaneohe Bay to appraise the potential of achieving net zero energy status through energy efficiency, renewable energy, and hydrogen vehicle integration. In 2008, the U.S. Department of Defense's U.S. Pacific Command partnered with the U.S. Department of Energy's (DOE's) National Renewable Energy Laboratory (NREL) to assess opportunities for increasing energy security through renewable energy and energy efficiency at Hawaii military installations. DOE selected Marine Corps Base Hawaii (MCBH), Kaneohe Bay, to receive technical support for net zero energy assessment and planning funded through the Hawaiimore » Clean Energy Initiative (HCEI). NREL performed a comprehensive assessment to appraise the potential of MCBH Kaneohe Bay to achieve net zero energy status through energy efficiency, renewable energy, and hydrogen vehicle integration. This paper summarizes the results of the assessment and provides energy recommendations. The analysis shows that MCBH Kaneohe Bay has the potential to make significant progress toward becoming a net zero installation. Wind, solar photovoltaics, solar hot water, and hydrogen production were assessed, as well as energy efficiency technologies. Deploying wind turbines is the most cost-effective energy production measure. If the identified energy projects and savings measures are implemented, the base will achieve a 96% site Btu reduction and a 99% source Btu reduction. Using excess wind and solar energy to produce hydrogen for a fleet and fuel cells could significantly reduce energy use and potentially bring MCBH Kaneohe Bay to net zero. Further analysis with an environmental impact and interconnection study will need to be completed. By achieving net zero status, the base will set an example for other military installations, provide environmental benefits, reduce costs, increase energy security, and exceed its energy goals and mandates.« less

Selected topics on dynamical symmetry breaking

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

Veldhuis, W.T.A.

1993-12-31

In chapter 2 the fermion number induced by nontrivial topological configurations in the O(3) nonlinear {sigma} model in 2 + 1 dimensions is studied in the presence of a parity breaking fermion mass term. We consider a scalar background configuration that adiabatically evolves from the normal vacuum to a soliton of winding number unity. The appearance of zero energy modes is analyzed as a function of the relative magnitudes of the explicit, odd parity, fermion mass, m{sub odd}, the fermion mass induced by the Yukawa coupling, m{sub Y}, and the inverse soliton width, 1/{rho}{sub s}. We find {rho}{sub c}, themore » maximum value of {rho} = {rho}{sub s}m{sub Y} for which a fermion zero energy level crossing occurs during the adiabatical evolution. We obtain that whenever the ratio M{sub f} = m{sub odd}/m{sub Y} < 1 and {rho} > {rho}{sub c}(M{sub f}) the ground state charge of the soliton is wholly determined by its topological charge. Otherwise, it vanishes. In chapter 3 the top quark mass prediction in supersymmetric top condensate models is found to be insensitive to the inclusion of the effects of higher dimensional operators. For associated coefficients of characteristically moderate strength, the supersymmetric renormalization group trajectories are strongly focused to the infrared quasi-fixed point of the top Yukawa coupling constant. In chapter 4 the sensitivity of the top quark and Higgs boson masses in the top condensate model to two loop radiative corrections is studied. Both the top quark and the Higgs boson masses vary by a few GeV with respect to their values in the one loop calculation. Finally, in chapter 5 an upper bound on the mass of the lightest neutral scalar Higgs boson is calculated in an extended version of the minimal supersymmetric standard model that contains an additional Higgs singlet.« less

Energy in a String Wave

NASA Astrophysics Data System (ADS)

Ng, Chiu-king

2010-01-01

When one end of a taut horizontal elastic string is shaken repeatedly up and down, a transverse wave (assume sine waveform) will be produced and travel along it. College students know this type of wave motion well. They know when the wave passes by, each element of the string will perform an oscillating up-down motion, which in mechanics is termed simple harmonic2. They also know elements of the string at the highest and the lowest positions—the crests and the troughs—are momentarily at rest, while those at the centerline (zero displacement) have the greatest speed, as shown in Fig. 1. Irrespective of this, they are less familiar with the energy associated with the wave. They may fail to answer a question such as, "In a traveling string wave, which elements have respectively the greatest kinetic energy (KE) and the greatest potential energy (PE)?" The answer to the former is not difficult; elements at zero position have the fastest speed and hence their KE, being proportional to the square of speed, is the greatest. To the PE, what immediately comes to their mind may be the simple harmonic motion (SHM), in which the PE is the greatest and the KE is zero at the two turning points. It may thus lead them to think elements at crests or troughs have the greatest PE. Unfortunately, this association is wrong. Thinking that the crests or troughs have the greatest PE is a misconception.3

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

Sun, Zhigang, E-mail: zsun@dicp.ac.cn; Yu, Dequan; Xie, Wenbo

The O + O{sub 2} isotope exchange reactions play an important role in determining the oxygen isotopic composition of a number of trace gases in the atmosphere, and their temperature dependence and kinetic isotope effects (KIEs) provide important constraints on our understanding of the origin and mechanism of these and other unusual oxygen KIEs important in the atmosphere. This work reports a quantum dynamics study of the title reactions on the newly constructed Dawes-Lolur-Li-Jiang-Guo (DLLJG) potential energy surface (PES). The thermal reaction rate coefficients of both the {sup 18}O + {sup 32}O{sub 2} and {sup 16}O + {sup 36}O{sub 2}more » reactions obtained using the DLLJG PES exhibit a clear negative temperature dependence, in sharp contrast with the positive temperature dependence obtained using the earlier modified Siebert-Schinke-Bittererova (mSSB) PES. In addition, the calculated KIE shows an improved agreement with the experiment. These results strongly support the absence of the “reef” structure in the entrance/exit channels of the DLLJG PES, which is present in the mSSB PES. The quantum dynamics results on both PESs attribute the marked KIE to strong near-threshold reactive resonances, presumably stemming from the mass differences and/or zero point energy difference between the diatomic reactant and product. The accurate characterization of the reactivity for these near-thermoneutral reactions immediately above the reaction threshold is important for correct characterization of the thermal reaction rate coefficients.« less

Structure, stability, thermodynamic properties, and infrared spectra of the protonated water octamer H(+)(H2O)8.

PubMed

Karthikeyan, S; Park, Mina; Shin, Ilgyou; Kim, Kwang S

2008-10-16

We investigated various two-dimensional (2D) and three-dimensional (3D) structures of H (+)(H 2O) 8, using density functional theory (DFT), Moller-Plesset second-order perturbation theory (MP2), and coupled cluster theory with single, double, and perturbative triple excitations (CCSD(T)). The 3D structure is more stable than the 2D structure at all levels of theory on the Born-Oppenheimer surface. With the zero-point energy (ZPE) correction, the predicted structure varies depending on the level of theory. The DFT employing Becke's three parameters with Lee-Yang-Parr functionals (B3LYP) favors the 2D structure. At the complete basis set (CBS) limit, the MP2 calculation favors the 3D structure by 0.29 kcal/mol, and the CCSD(T) calculation favors the 3D structure by 0.27 kcal/mol. It is thus expected that both 2D and 3D structures are nearly isoenergetic near 0 K. At 100 K, all the calculations show that the 2D structure is much more stable in free binding energy than the 3D structure. The DFT and MP2 vibrational spectra of the 2D structure are consistent with the experimental spectra. First-principles Car-Parrinello molecular dynamics (CPMD) simulations show that the 2D Zundel-type vibrational spectra are in good agreement with the experiment.

Preliminary analysis toward GOSAT-2 new products, proxy-based XCH4 and SIF, using GOSAT data

NASA Astrophysics Data System (ADS)

Oshio, H.; Yoshida, Y.; Matsunaga, T.

2017-12-01

The Greenhouse gases Observing SATellite (GOSAT) has been operating for more than eight years. As a successor mission to the GOSAT, GOSAT-2 is planned to be launched in FY2018. In addition to the full-physics based dry air mole fractions of carbon dioxide, methane, water vapor, and carbon monoxide (XCO2, XCH4, XH2O, and XCO) products, we are planning to provide the proxy-based XCH4 and solar induced chlorophyll fluorescence (SIF) as a new product. XCH4 and XCO2 are retrieved from GOSAT CH4 1.67 μm band and CO2 1.6 μm band, respectively, under the clear-sky assumption, and their ratio is compared with TCCON data. As expected, most of the cloud and aerosol related errors are counteracted. During this retrieval, XH2O is simultaneously retrieved with XCO2. XCO2 and XH2O are also retrieved from CO2 2.08 μm band under the clear-sky assumption. Difference between Xgas retrieved from different wavelength domains is expected to be useful as cloud and aerosol information because the difference reflects the degree of optical path variation caused by clouds and aerosols. XCO2 ratio and XH2O ratio are compared to the cloud and aerosol information derived by Cloud and Aerosol Imager (CAI) onboarded GOSAT. SIF is retrieved using Fraunhofer lines near O2 A-band by the same method as Frankenberg et al. (2011). For GOSAT, correction of artifact signal (zero-level offset caused by non-linearity of the analog circuit in the spectrometer) is required to obtain SIF (retrieved signal = SIF + zero-level offset). The zero-level offset can be evaluated from the retrieved signal over the areas where the value of SIF is expected to be zero. Although it is currently unknown that such correction is required for GOSAT-2 SIF retrieval, SIF was retrieved from GOSAT data and zero-level offset correction was tested. We investigated the zero-level offset for clouds and bare soils and confirmed its applicability to the offset correction. Zero-level offset correction was then conducted while considering its temporal change and dependence on the observed radiance. Validity of the derived SIF was investigated through comparison with SIF derived by numerical model.

Insights and possible resolution to the information loss paradox via the tunneling picture

NASA Astrophysics Data System (ADS)

Singleton, Douglas; Vagenas, Elias C.; Zhu, Tao; Ren, Ji-Rong

2010-08-01

This paper investigates the information loss paradox in the WKB/tunneling picture of Hawking radiation. In the tunneling picture one can obtain the tunneling amplitude to all orders in ℏ. However all terms beyond the lowest, semi-classical term involve unknown constants. Despite this we find that one can still arrive at interesting restrictions on Hawking radiation to all orders in ℏ: (i) Taking into account only quantum corrections the spectrum remains thermal to all orders. Thus quantum corrections by themselves will not resolve the information loss paradox. (ii) The quantum corrections do imply that the temperature of the radiation goes to zero as the mass of the black hole goes to zero. This is in contrast to the lowest order result where the radiation temperature diverges as the mass of the black hole goes to zero. (iii) Finally we show that by taking both quantum corrections and back reaction into account it is possible under specific conditions to solve the information paradox by having the black hole evaporate completely with the information carried away by the correlations of the outgoing radiation.

New Precision Limit on the Strange Vector Form Factors of the Proton

DOE PAGES

Ahmed, Z.; Allada, K.; Aniol, K. A.; ...

2012-03-01

The parity-violating cross-section asymmetry in the elastic scattering of polarized electrons from unpolarized protons has been measured at a four-momentum transfer squared Q 2 = 0.624 GeV 2 and beam energy E b = 3.48 GeV to be A PV = -23.80 ± 0.78 (stat) ± 0.36 (syst) parts per million. This result is consistent with zero contribution of strange quarks to the combination of electric and magnetic form factors G E s + 0.517 G M s = 0.003 ± 0.010 (stat) ± 0.004 (syst) ± 0.009 (ff), where the third error is due to the limits of precisionmore » on the electromagnetic form factors and radiative corrections. With this measurement, the world data on strange contributions to nucleon form factors are seen to be consistent with zero and not more than a few percent of the proton form factors.« less

Cation-Cation pi-pi Stacking in Small Ionic Clusters of 1,2,4-Triazolium (Preprint)

DTIC Science & Technology

2007-07-12

Figure 1 is 1.5 kcal/mol lower than that of the neutral one. Including zero point energies ( ZPE ) obtained with MP2/aug-cc-pVDZ harmonic vibrational...the ionic tetramer is lower than that of the neutral tetramer by 6.0, 7.6 and 8.0 kcal/mol, respectively. Including ZPE , these three values become

Toward spectroscopically accurate global ab initio potential energy surface for the acetylene-vinylidene isomerization

NASA Astrophysics Data System (ADS)

Han, Huixian; Li, Anyang; Guo, Hua

2014-12-01

A new full-dimensional global potential energy surface (PES) for the acetylene-vinylidene isomerization on the ground (S0) electronic state has been constructed by fitting ˜37 000 high-level ab initio points using the permutation invariant polynomial-neural network method with a root mean square error of 9.54 cm-1. The geometries and harmonic vibrational frequencies of acetylene, vinylidene, and all other stationary points (two distinct transition states and one secondary minimum in between) have been determined on this PES. Furthermore, acetylene vibrational energy levels have been calculated using the Lanczos algorithm with an exact (J = 0) Hamiltonian. The vibrational energies up to 12 700 cm-1 above the zero-point energy are in excellent agreement with the experimentally derived effective Hamiltonians, suggesting that the PES is approaching spectroscopic accuracy. In addition, analyses of the wavefunctions confirm the experimentally observed emergence of the local bending and counter-rotational modes in the highly excited bending vibrational states. The reproduction of the experimentally derived effective Hamiltonians for highly excited bending states signals the coming of age for the ab initio based PES, which can now be trusted for studying the isomerization reaction.

High-resolution monochromated electron energy-loss spectroscopy of organic photovoltaic materials.

PubMed

Alexander, Jessica A; Scheltens, Frank J; Drummy, Lawrence F; Durstock, Michael F; Hage, Fredrik S; Ramasse, Quentin M; McComb, David W

2017-09-01

Advances in electron monochromator technology are providing opportunities for high energy resolution (10 - 200meV) electron energy-loss spectroscopy (EELS) to be performed in the scanning transmission electron microscope (STEM). The energy-loss near-edge structure in core-loss spectroscopy is often limited by core-hole lifetimes rather than the energy spread of the incident illumination. However, in the valence-loss region, the reduced width of the zero loss peak makes it possible to resolve clearly and unambiguously spectral features at very low energy-losses (<3eV). In this contribution, high-resolution EELS was used to investigate four materials commonly used in organic photovoltaics (OPVs): poly(3-hexlythiophene) (P3HT), [6,6] phenyl-C 61 butyric acid methyl ester (PCBM), copper phthalocyanine (CuPc), and fullerene (C 60 ). Data was collected on two different monochromated instruments - a Nion UltraSTEM 100 MC 'HERMES' and a FEI Titan 3 60-300 Image-Corrected S/TEM - using energy resolutions (as defined by the zero loss peak full-width at half-maximum) of 35meV and 175meV, respectively. The data was acquired to allow deconvolution of plural scattering, and Kramers-Kronig analysis was utilized to extract the complex dielectric functions. The real and imaginary parts of the complex dielectric functions obtained from the two instruments were compared to evaluate if the enhanced resolution in the Nion provides new opto-electronic information for these organic materials. The differences between the spectra are discussed, and the implications for STEM-EELS studies of advanced materials are considered. Copyright © 2017 Elsevier B.V. All rights reserved.

40 CFR 86.522-78 - Carbon monoxide analyzer calibration.

Code of Federal Regulations, 2010 CFR

2010-07-01

... performance on the most sensitive range. (2) Zero the carbon monoxide analyzer with either zero grade air or zero grade nitrogen. (3) Bubble a mixture of 3 percent CO2 in N2 through water at room temperature and... action. (Use of conditioning columns is one form of corrective action which may be taken.) (b) Initial...

76 FR 16234 - Prompt Corrective Action; Amended Definition of Low-Risk Assets

Federal Register 2010, 2011, 2012, 2013, 2014

2011-03-23

... guaranteed by NCUA. Assets in this category receive a risk-weighting of zero for regulatory capital purposes... not apply a risk-weighting of zero even when an investment carries no credit risk. The ``Low-risk assets'' risk portfolio, in contrast, does apply a risk- weighting of zero, but the NGNs did not fall...

Technical Feasibility Study for Zero Energy K-12 Schools

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

Bonnema, Eric; Goldwasser, David; Torcellini, Paul

This technical feasibility study provides documentation and research results supporting a possible set of strategies to achieve source zero energy K-12 school buildings as defined by the U.S. Department of Energy (DOE) zero energy building (ZEB) definition (DOE 2015a). Under this definition, a ZEB is an energy-efficient building in which, on a source energy basis, the actual annual delivered energy is less than or equal to the on-site renewable exported energy.