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Sample records for 1h-1h coupling constants

  1. Simple Approaches for Estimating Vicinal 1H- 1H Coupling-Constants and for Obtaining Stereospecific Resonance Assignments in Leucine Side Chains

    NASA Astrophysics Data System (ADS)

    Constantine, K. L.; Friedrichs, M. S.; Mueller, L.

    An approach for deriving stereospecific δ-methyl assignments and χ 2 dihedral angle constraints for leucine residues, based on easily recognized patterns of 1H- 1H spin-spin coupling constants and intraresidue nuclear-Overhauser-effect spectroscopy (NOESY) cross-peak intensities, is described. The approach depends on resolved H γ and/or δ-methyl resonances and on initially obtaining stereospecific assignments for H β2 and H β3. As part of the overall strategy, a method is presented for obtaining qualitative or, in favorable cases, semiquantitative estimates of vicinal 1H- 1H coupling constants from peak intensities measured in a short-mixing-time 1H- 1H total correlation spectroscopy (TOCSY) experiment. This method of estimating 1H- 1H spin-spin coupling constants is generally applicable to all side-chain types. The approach is illustrated for several leucine residues within uniformly 15N-labeled and 15N/ 13C-double-labeled isolated light-chain variable domain of the anti-digoxin antibody 26-10. Estimates of 3Jαβ and 3Jβγ coupling constants are derived from a three-dimensional (3D) 13C-edited TOCSY-heteronuclear multiple-quantum coherence (HMQC) spectrum. These data are combined with information from 3D 15N-edited NOESY and 3D 13C-edited NOESY spectra to yield stereospecific H β2, H β3, and δ-methyl assignments, as well as constraints on χ (1) and χ 2 dihedral angles. Although the overall approach is illustrated using 3D 15N-edited and 13C-edited data, it is equally applicable to analysis of two-dimensional 1H- 1H NOESY and TOCSY spectra.

  2. Dynamics-based selective 2D 1H/1H chemical shift correlation spectroscopy under ultrafast MAS conditions

    PubMed Central

    Zhang, Rongchun; Ramamoorthy, Ayyalusamy

    2015-01-01

    Dynamics plays important roles in determining the physical, chemical, and functional properties of a variety of chemical and biological materials. However, a material (such as a polymer) generally has mobile and rigid regions in order to have high strength and toughness at the same time. Therefore, it is difficult to measure the role of mobile phase without being affected by the rigid components. Herein, we propose a highly sensitive solid-state NMR approach that utilizes a dipolar-coupling based filter (composed of 12 equally spaced 90° RF pulses) to selectively measure the correlation of 1H chemical shifts from the mobile regions of a material. It is interesting to find that the rotor-synchronized dipolar filter strength decreases with increasing inter-pulse delay between the 90° pulses, whereas the dipolar filter strength increases with increasing inter-pulse delay under static conditions. In this study, we also demonstrate the unique advantages of proton-detection under ultrafast magic-angle-spinning conditions to enhance the spectral resolution and sensitivity for studies on small molecules as well as multi-phase polymers. Our results further demonstrate the use of finite-pulse radio-frequency driven recoupling pulse sequence to efficiently recouple weak proton-proton dipolar couplings in the dynamic regions of a molecule and to facilitate the fast acquisition of 1H/1H correlation spectrum compared to the traditional 2D NOESY (Nuclear Overhauser effect spectroscopy) experiment. We believe that the proposed approach is beneficial to study mobile components in multi-phase systems, such as block copolymers, polymer blends, nanocomposites, heterogeneous amyloid mixture of oligomers and fibers, and other materials. PMID:26026440

  3. Finite-pulse radio frequency driven recoupling with phase cycling for 2D 1H/1H correlation at ultrafast MAS frequencies

    NASA Astrophysics Data System (ADS)

    Nishiyama, Yusuke; Zhang, Rongchun; Ramamoorthy, Ayyalusamy

    2014-06-01

    The first-order recoupling sequence radio frequency driven dipolar recoupling (RFDR) is commonly used in single-quantum/single-quantum homonuclear correlation 2D experiments under magic angle spinning (MAS) to determine homonuclear proximities. From previously reported analysis of the use of XY-based super-cycling schemes to enhance the efficiency of the finite-pulse-RFDR (fp-RFDR) pulse sequence, XY814 phase cycling was found to provide the optimum performance for 2D correlation experiments on low-γ nuclei. In this study, we analyze the efficiency of different phase cycling schemes for proton-based fp-RFDR experiments. We demonstrate the advantages of using a short phase cycle, XY4, and its super-cycle XY414 that only recouples the zero-quantum homonuclear dipolar coupling, for the fp-RFDR sequence in 2D 1H/1H correlation experiments at ultrafast MAS frequencies. The dipolar recoupling efficiencies of XY4, XY414 and XY814 phase cycling schemes are compared based on results obtained from 2D 1H/1H correlation experiments, utilizing the fp-RFDR pulse sequence, on powder samples of U-13C,15N-L-alanine, N-acetyl-15N-L-valyl-15N-L-leucine, and glycine. Experimental results and spin dynamics simulations show that XY414 performs the best when a high RF power is used for the 180° pulse, whereas XY4 renders the best performance when a low RF power is used. The effects of RF field inhomogeneity and chemical shift offsets are also examined. Overall, our results suggest that a combination of fp-RFDR-XY414 employed in the recycle delay with a large RF-field to decrease the recycle delay, and fp-RFDR-XY4 in the mixing period with a moderate RF-field, is a robust and efficient method for 2D single-quantum/single-quantum 1H/1H correlation experiments at ultrafast MAS frequencies.

  4. Three pion nucleon coupling constants

    NASA Astrophysics Data System (ADS)

    Ruiz Arriola, E.; Amaro, J. E.; Navarro Pérez, R.

    2016-08-01

    There exist four pion nucleon coupling constants, fπ0pp, - fπ0nn, fπ+pn/2 and fπ-np/2 which coincide when up and down quark masses are identical and the electron charge is zero. While there is no reason why the pion-nucleon-nucleon coupling constants should be identical in the real world, one expects that the small differences might be pinned down from a sufficiently large number of independent and mutually consistent data. Our discussion provides a rationale for our recent determination fp2 = 0.0759(4),f 02 = 0.079(1),f c2 = 0.0763(6), based on a partial wave analysis of the 3σ self-consistent nucleon-nucleon Granada-2013 database comprising 6713 published data in the period 1950-2013.

  5. Three pion nucleon coupling constants

    NASA Astrophysics Data System (ADS)

    Ruiz Arriola, E.; Amaro, J. E.; Navarro Pérez, R.

    2016-08-01

    There exist four pion nucleon coupling constants, fπ0pp, ‑ fπ0nn, fπ+pn/2 and fπ‑np/2 which coincide when up and down quark masses are identical and the electron charge is zero. While there is no reason why the pion-nucleon-nucleon coupling constants should be identical in the real world, one expects that the small differences might be pinned down from a sufficiently large number of independent and mutually consistent data. Our discussion provides a rationale for our recent determination fp2 = 0.0759(4),f 02 = 0.079(1),f c2 = 0.0763(6), based on a partial wave analysis of the 3σ self-consistent nucleon-nucleon Granada-2013 database comprising 6713 published data in the period 1950-2013.

  6. Crystal structure of 1H,1'H-[2,2'-biimid-azol]-3-ium hydrogen tartrate hemi-hydrate.

    PubMed

    Gao, Xiao-Li; Bian, Li-Fang; Guo, Shao-Wei

    2014-11-01

    In the crystal of the title hydrated salt, C6H7N4 (+)·C4H5O6 (-)·0.5H2O, the bi-imidazole monocation, 1H,1'H-[2,2'-biimidazol]-3-ium, is hydrogen bonded, via N-H⋯O, O-H⋯O and O-H⋯N hydrogen bonds, to the hydrogen tartrate anion and the water mol-ecule, which is located on a twofold rotation axis, forming sheets parallel to (001). The sheets are linked via C-H⋯O hydrogen bonds, forming a three-dimensional structure. There are also C=O⋯π inter-actions present [O⋯π distances are 3.00 (9) and 3.21 (7) Å], involving the carbonyl O atoms and the imidazolium ring, which may help to consolidate the structure. In the cation, the dihedral angle between the rings is 11.6 (2)°.

  7. Determination of relative orientation between (1)H CSA tensors from a 3D solid-state NMR experiment mediated through (1)H/(1)H RFDR mixing under ultrafast MAS.

    PubMed

    Pandey, Manoj Kumar; Nishiyama, Yusuke

    2015-09-01

    To obtain piercing insights into inter and intramolecular H-bonding, and π-electron interactions measurement of (1)H chemical shift anisotropy (CSA) tensors is gradually becoming an obvious choice. While the magnitude of CSA tensors provides unique information about the local electronic environment surrounding the nucleus, the relative orientation between these tensors can offer further insights into the spatial arrangement of interacting nuclei in their respective three-dimensional (3D) space. In this regard, we present a 3D anisotropic/anisotropic/isotropic proton chemical shift (CSA/CSA/CS) correlation experiment mediated through (1)H/(1)H radio frequency-driven recoupling (RFDR) which enhances spin diffusion through recoupled (1)H-(1)H dipolar couplings under ultrafast magic angle spinning (MAS) frequency (70kHz). Relative orientation between two interacting 1H CSA tensors is obtained by fitting two-interacting (1)H CSA tensors by fitting two-dimensional (2D) (1)H/(1)H CSA/CSA spectral slices through extensive numerical simulations. To recouple (1)H CSAs in the indirect frequency dimensions of a 3D experiment we have employed γ-encoded radio frequency (RF) pulse sequence based on R-symmetry (R188(7)) with a series of phase-alternated 2700(°)-90180(°) composite-180° pulses on citric acid sample. Due to robustness of applied (1)H CSA recoupling sequence towards the presence of RF field inhomogeneity, we have successfully achieved an excellent (1)H/(1)H CSA/CSA cross-correlation efficiency between H-bonded sites of citric acid. PMID:26065628

  8. Proton zero-quantum 2D NMR of 2-propenenitrile aligned by an electric field. Determination of the 2H and 14N quadrupole coupling constants

    NASA Astrophysics Data System (ADS)

    Ruessink, B. H.; De Kanter, F. J. J.; MaClean, C.

    Zero-quantum NMR, selectively detected by 2D NMR, is applied to observe small 1H- 1H dipolar couplings in a polar liquid partially oriented by a strong electric field. The normal (single-quantum) 1H spectrum is severely broadened, which prevents the observation of small couplings. The results from the zero-quantum proton spectrum are used to calculate the 2H and 14N quadrupole coupling constants of 2-deutero-2-propenenitrile from the 2H and 14N NMR spectra.

  9. Selective excitation enables assignment of proton resonances and (1)H-(1)H distance measurement in ultrafast magic angle spinning solid state NMR spectroscopy.

    PubMed

    Zhang, Rongchun; Ramamoorthy, Ayyalusamy

    2015-07-21

    Remarkable developments in ultrafast magic angle spinning (MAS) solid-state NMR spectroscopy enabled proton-based high-resolution multidimensional experiments on solids. To fully utilize the benefits rendered by proton-based ultrafast MAS experiments, assignment of (1)H resonances becomes absolutely necessary. Herein, we propose an approach to identify different proton peaks by using dipolar-coupled heteronuclei such as (13)C or (15)N. In this method, after the initial preparation of proton magnetization and cross-polarization to (13)C nuclei, transverse magnetization of desired (13)C nuclei is selectively prepared by using DANTE (Delays Alternating with Nutations for Tailored Excitation) sequence and then, it is transferred to bonded protons with a short-contact-time cross polarization. Our experimental results demonstrate that protons bonded to specific (13)C atoms can be identified and overlapping proton peaks can also be assigned. In contrast to the regular 2D HETCOR experiment, only a few 1D experiments are required for the complete assignment of peaks in the proton spectrum. Furthermore, the finite-pulse radio frequency driven recoupling sequence could be incorporated right after the selection of specific proton signals to monitor the intensity buildup for other proton signals. This enables the extraction of (1)H-(1)H distances between different pairs of protons. Therefore, we believe that the proposed method will greatly aid in fast assignment of peaks in proton spectra and will be useful in the development of proton-based multi-dimensional solid-state NMR experiments to study atomic-level resolution structure and dynamics of solids. PMID:26203019

  10. Selective excitation enables assignment of proton resonances and (1)H-(1)H distance measurement in ultrafast magic angle spinning solid state NMR spectroscopy.

    PubMed

    Zhang, Rongchun; Ramamoorthy, Ayyalusamy

    2015-07-21

    Remarkable developments in ultrafast magic angle spinning (MAS) solid-state NMR spectroscopy enabled proton-based high-resolution multidimensional experiments on solids. To fully utilize the benefits rendered by proton-based ultrafast MAS experiments, assignment of (1)H resonances becomes absolutely necessary. Herein, we propose an approach to identify different proton peaks by using dipolar-coupled heteronuclei such as (13)C or (15)N. In this method, after the initial preparation of proton magnetization and cross-polarization to (13)C nuclei, transverse magnetization of desired (13)C nuclei is selectively prepared by using DANTE (Delays Alternating with Nutations for Tailored Excitation) sequence and then, it is transferred to bonded protons with a short-contact-time cross polarization. Our experimental results demonstrate that protons bonded to specific (13)C atoms can be identified and overlapping proton peaks can also be assigned. In contrast to the regular 2D HETCOR experiment, only a few 1D experiments are required for the complete assignment of peaks in the proton spectrum. Furthermore, the finite-pulse radio frequency driven recoupling sequence could be incorporated right after the selection of specific proton signals to monitor the intensity buildup for other proton signals. This enables the extraction of (1)H-(1)H distances between different pairs of protons. Therefore, we believe that the proposed method will greatly aid in fast assignment of peaks in proton spectra and will be useful in the development of proton-based multi-dimensional solid-state NMR experiments to study atomic-level resolution structure and dynamics of solids.

  11. Selective excitation enables assignment of proton resonances and 1H-1H distance measurement in ultrafast magic angle spinning solid state NMR spectroscopy

    NASA Astrophysics Data System (ADS)

    Zhang, Rongchun; Ramamoorthy, Ayyalusamy

    2015-07-01

    Remarkable developments in ultrafast magic angle spinning (MAS) solid-state NMR spectroscopy enabled proton-based high-resolution multidimensional experiments on solids. To fully utilize the benefits rendered by proton-based ultrafast MAS experiments, assignment of 1H resonances becomes absolutely necessary. Herein, we propose an approach to identify different proton peaks by using dipolar-coupled heteronuclei such as 13C or 15N. In this method, after the initial preparation of proton magnetization and cross-polarization to 13C nuclei, transverse magnetization of desired 13C nuclei is selectively prepared by using DANTE (Delays Alternating with Nutations for Tailored Excitation) sequence and then, it is transferred to bonded protons with a short-contact-time cross polarization. Our experimental results demonstrate that protons bonded to specific 13C atoms can be identified and overlapping proton peaks can also be assigned. In contrast to the regular 2D HETCOR experiment, only a few 1D experiments are required for the complete assignment of peaks in the proton spectrum. Furthermore, the finite-pulse radio frequency driven recoupling sequence could be incorporated right after the selection of specific proton signals to monitor the intensity buildup for other proton signals. This enables the extraction of 1H-1H distances between different pairs of protons. Therefore, we believe that the proposed method will greatly aid in fast assignment of peaks in proton spectra and will be useful in the development of proton-based multi-dimensional solid-state NMR experiments to study atomic-level resolution structure and dynamics of solids.

  12. Vicinal coupling constants and protein dynamics.

    PubMed

    Hoch, J C; Dobson, C M; Karplus, M

    1985-07-16

    The effects of motional averaging on the analysis of vicinal spin-spin coupling constants derived from proton NMR studies of proteins have been examined. Trajectories obtained from molecular dynamics simulations of bovine pancreatic trypsin inhibitor and of hen egg white lysozyme were used in conjunction with an expression for the dependence of the coupling constant on the intervening dihedral angle to calculate the time-dependent behavior of the coupling constants. Despite large fluctuations, the time-average values of the coupling constants are not far from those computed for the average structure in the cases where fluctuations occur about a single potential well. The calculated differences show a high correlation with the variation in the magnitude of the fluctuations of individual dihedral angles. For the cases where fluctuations involve multiple sites, large differences are found between the time-average values and the average structure values for the coupling constants. Comparison of the simulation results with the experimental trends suggests that side chains with more than one position are more common in proteins than is inferred from X-ray results. It is concluded that for the main chain, motional effects do not introduce significant errors where vicinal coupling constants are used in structure determinations; however, for side chains, the motional average can alter deductions about the structure. Accurately measured coupling constants are shown to provide information concerning the magnitude of dihedral angle fluctuations.

  13. The Determination of the Strong Coupling Constant

    NASA Astrophysics Data System (ADS)

    Dissertori, Günther

    2016-10-01

    The strong coupling constant is one of the fundamental parameters of the Standard Theory of particle physics. In this review I will briefly summarise the theoretical framework, within which the strong coupling constant is defined and how it is connected to measurable observables. Then I will give an historical overview of its experimental determinations and discuss the current status and world average value. Among the many different techniques used to determine this coupling constant in the context of quantum chromodynamics, I will focus in particular on a number of measurements carried out at the Large Electron-Positron Collider (LEP) and the Large Hadron Collider (LHC) at CERN.

  14. A General Method for Extracting Individual Coupling Constants from Crowded (1)H NMR Spectra.

    PubMed

    Sinnaeve, Davy; Foroozandeh, Mohammadali; Nilsson, Mathias; Morris, Gareth A

    2016-01-18

    Couplings between protons, whether scalar or dipolar, provide a wealth of structural information. Unfortunately, the high number of (1)H-(1)H couplings gives rise to complex multiplets and severe overlap in crowded spectra, greatly complicating their measurement. Many different methods exist for disentangling couplings, but none approaches optimum resolution. Here, we present a general new 2D J-resolved method, PSYCHEDELIC, in which all homonuclear couplings are suppressed in F2, and only the couplings to chosen spins appear, as simple doublets, in F1. This approaches the theoretical limit for resolving (1)H-(1)H couplings, with close to natural linewidths and with only chemical shifts in F2. With the same high sensitivity and spectral purity as the parent PSYCHE pure shift experiment, PSYCHEDELIC offers a robust method for chemists seeking to exploit couplings for structural, conformational, or stereochemical analyses.

  15. RNA structure and scalar coupling constants

    SciTech Connect

    Tinoco, I. Jr.; Cai, Z.; Hines, J.V.; Landry, S.M.; SantaLucia, J. Jr.; Shen, L.X.; Varani, G.

    1994-12-01

    Signs and magnitudes of scalar coupling constants-spin-spin splittings-comprise a very large amount of data that can be used to establish the conformations of RNA molecules. Proton-proton and proton-phosphorus splittings have been used the most, but the availability of {sup 13}C-and {sup 15}N-labeled molecules allow many more coupling constants to be used for determining conformation. We will systematically consider the torsion angles that characterize a nucleotide unit and the coupling constants that depend on the values of these torsion angles. Karplus-type equations have been established relating many three-bond coupling constants to torsion angles. However, one- and two-bond coupling constants can also depend on conformation. Serianni and coworkers measured carbon-proton coupling constants in ribonucleosides and have calculated their values as a function of conformation. The signs of two-bond coupling can be very useful because it is easier to measure a sign than an accurate magnitude.

  16. Environmental dependence of masses and coupling constants

    SciTech Connect

    Olive, Keith A.; Pospelov, Maxim

    2008-02-15

    We construct a class of scalar field models coupled to matter that lead to the dependence of masses and coupling constants on the ambient matter density. Such models predict a deviation of couplings measured on the Earth from values determined in low-density astrophysical environments, but do not necessarily require the evolution of coupling constants with the redshift in the recent cosmological past. Additional laboratory and astrophysical tests of {delta}{alpha} and {delta}(m{sub p}/m{sub e}) as functions of the ambient matter density are warranted.

  17. Proton-detected 3D (15)N/(1)H/(1)H isotropic/anisotropic/isotropic chemical shift correlation solid-state NMR at 70kHz MAS.

    PubMed

    Pandey, Manoj Kumar; Yarava, Jayasubba Reddy; Zhang, Rongchun; Ramamoorthy, Ayyalusamy; Nishiyama, Yusuke

    2016-01-01

    Chemical shift anisotropy (CSA) tensors offer a wealth of information for structural and dynamics studies of a variety of chemical and biological systems. In particular, CSA of amide protons can provide piercing insights into hydrogen-bonding interactions that vary with the backbone conformation of a protein and dynamics. However, the narrow span of amide proton resonances makes it very difficult to measure (1)H CSAs of proteins even by using the recently proposed 2D (1)H/(1)H anisotropic/isotropic chemical shift (CSA/CS) correlation technique. Such difficulties due to overlapping proton resonances can in general be overcome by utilizing the broad span of isotropic chemical shifts of low-gamma nuclei like (15)N. In this context, we demonstrate a proton-detected 3D (15)N/(1)H/(1)H CS/CSA/CS correlation experiment at fast MAS frequency (70kHz) to measure (1)H CSA values of unresolved amide protons of N-acetyl-(15)N-l-valyl-(15)N-l-leucine (NAVL).

  18. Bioinspired, cysteamine-catalyzed co-silicification of (1H, 1H, 2H, 2HPerfluorooctyl) triethoxysilane and tetraethyl orthosilicate: formation of superhydrophobic surfaces.

    PubMed

    Park, Ji Hun; Kim, Ji Yup; Cho, Woo Kyung; Choi, Insung S

    2014-03-01

    Bioinspired silicification attracts a great deal of interest because of its physiologically relevant, mild conditions for hydrolysis and condensation of silica precursors, which makes the bioinspired approach superior to the conventional sol–gel process, particularly when dealing with biological entities. However, the morphological control of silica structures with incorporation of functional groups in the bioinspired silicilication has been unexplored. In this work, we co-silicificated (1H, 1H, 2H, 2H-perfluorooctyl)triethoxysilane and tetraethyl orthosilicate to investigate the morphological evolution of fluorinated silica structures in the cetyltrimethylammonium bromide-mediated, cysteamine-catalyzed silicification. The generated micrometer-long wormlike and spherical silica structures display superhydrophobicity after film formation. Interestingly, the measurement of dynamic water contact angles shows that the morphological difference leads to a different wetting state, either the self-cleaning or the pinning state of the superhydrophobic surface.

  19. Do Wormholes Fix the Coupling Constants?

    NASA Astrophysics Data System (ADS)

    Goradia, Shantilal

    2004-05-01

    If Newtonian gravitation is modified to use surface-to-surface separation between particles, it can have the strength of nuclear force between nucleons. This may be justified by possible existence of quantum wormholes in particles. All gravitational interactions would be between coupled wormholes, emitting 1/r graviton flux from their exit mouths as a function of the particle size, allowing the point-like treatment above. When the wormhole exit mouths are 1 Planck length apart, the resultant force is the known strong force coupling constant with an order of magnitude of 40 compared to the normal gravitational strength for nucleons. In addition to being mathematically simple, the above finding is consistent with observations of other coupling constants, Feynman's speculation of "transfusion" of two particles into spin 2 gravitons (published in 1962), Hawking radiation, big-bang theory abundance of quantum wormholes, wormhole theory fine-tuned by Kip S. Thorne and Matt Visser, and recent microscopic gravity measurements. It potentially leads to the holographic principle being promoted by Dr. G. t' Hooft, by naturally pointing out that the mass of the particles is proportional to their diameter squared.

  20. Relativistic Force Field: Parametrization of (13)C-(1)H Nuclear Spin-Spin Coupling Constants.

    PubMed

    Kutateladze, Andrei G; Mukhina, Olga A

    2015-11-01

    Previously, we reported a reliable DU8 method for natural bond orbital (NBO)-aided parametric scaling of Fermi contacts to achieve fast and accurate prediction of proton-proton spin-spin coupling constants (SSCC) in (1)H NMR. As sophisticated NMR experiments for precise measurements of carbon-proton SSCCs are becoming more user-friendly and broadly utilized by the organic chemistry community to guide and inform the process of structure determination of complex organic compounds, we have now developed a fast and accurate method for computing (13)C-(1)H SSCCs. Fermi contacts computed with the DU8 basis set are scaled using selected NBO parameters in conjunction with empirical scaling coefficients. The method is optimized for inexpensive B3LYP/6-31G(d) geometries. The parametric scaling is based on a carefully selected training set of 274 ((3)J), 193 ((2)J), and 143 ((1)J) experimental (13)C-(1)H spin-spin coupling constants reported in the literature. The DU8 basis set, optimized for computing Fermi contacts, which by design had evolved from optimization of a collection of inexpensive 3-21G*, 4-21G, and 6-31G(d) bases, offers very short computational (wall) times even for relatively large organic molecules containing 15-20 carbon atoms. The most informative SSCCs for structure determination, i.e., (3)J, were computed with an accuracy of 0.41 Hz (rmsd). The new unified approach for computing (1)H-(1)H and (13)C-(1)H SSCCs is termed "DU8c".

  1. Relativistic Force Field: Parametrization of (13)C-(1)H Nuclear Spin-Spin Coupling Constants.

    PubMed

    Kutateladze, Andrei G; Mukhina, Olga A

    2015-11-01

    Previously, we reported a reliable DU8 method for natural bond orbital (NBO)-aided parametric scaling of Fermi contacts to achieve fast and accurate prediction of proton-proton spin-spin coupling constants (SSCC) in (1)H NMR. As sophisticated NMR experiments for precise measurements of carbon-proton SSCCs are becoming more user-friendly and broadly utilized by the organic chemistry community to guide and inform the process of structure determination of complex organic compounds, we have now developed a fast and accurate method for computing (13)C-(1)H SSCCs. Fermi contacts computed with the DU8 basis set are scaled using selected NBO parameters in conjunction with empirical scaling coefficients. The method is optimized for inexpensive B3LYP/6-31G(d) geometries. The parametric scaling is based on a carefully selected training set of 274 ((3)J), 193 ((2)J), and 143 ((1)J) experimental (13)C-(1)H spin-spin coupling constants reported in the literature. The DU8 basis set, optimized for computing Fermi contacts, which by design had evolved from optimization of a collection of inexpensive 3-21G*, 4-21G, and 6-31G(d) bases, offers very short computational (wall) times even for relatively large organic molecules containing 15-20 carbon atoms. The most informative SSCCs for structure determination, i.e., (3)J, were computed with an accuracy of 0.41 Hz (rmsd). The new unified approach for computing (1)H-(1)H and (13)C-(1)H SSCCs is termed "DU8c". PMID:26414291

  2. Preparation and dielectric properties of core-shell structural composites of poly(1H,1H,2H,2H-perfluorooctyl methacrylate)@BaTiO3 nanoparticles

    NASA Astrophysics Data System (ADS)

    Zhang, Xianhong; Chen, Haochuan; Ma, Yuhong; Zhao, Changwen; Yang, Wantai

    2013-07-01

    Polymer nanocomposite films, poly(1H,1H,2H,2H-perfluorooctyl methacrylate)@BaTiO3 (PPFOMA@BaTiO3), with enhanced dielectric permittivity was fabricated via a two-step processes, consisting of BaTiO3 nanoparticle surface modification and surface initiated atom transfer radical grafting polymerization (SI-ATRP). At first, BaTiO3 nanoparticles were treated by hydroxylation, silylation and amidation to offer their SI-ATRP capability. Then PPFOMA chains were grafted from the modified BaTiO3 nanoparticles by SI-ATRP at 70 °C to form core-shell composites. The effects of polymer structure and polymer/BaTiO3 ratios on dielectric properties were measured over a broad frequency from 40 Hz to 30 MHz at room temperature. The results showed that the dielectric constant (k) increased and dielectric loss reduced significantly with the addition of BaTiO3. The k of the composite was up to 7.4 at 100 kHz at room temperature when the BaTiO3 loading was up to 70.70 wt% which is almost three time of pure PPFOMA (k = 2.6). While the dielectric loss (tan δ) of PPFOMA@BaTiO3 composite was about 0.01, which was much lower than that of the pure PPFOMA (tan δ = 0.04).

  3. Nuclear Magnetic Resonance Coupling Constants and Electronic Structure in Molecules.

    ERIC Educational Resources Information Center

    Venanzi, Thomas J.

    1982-01-01

    Theory of nuclear magnetic resonance spin-spin coupling constants and nature of the three types of coupling mechanisms contributing to the overall spin-spin coupling constant are reviewed, including carbon-carbon coupling (neither containing a lone pair of electrons) and carbon-nitrogen coupling (one containing a lone pair of electrons).…

  4. Electrochemical oxidation of 1H,1H,2H,2H-perfluorooctane sulfonic acid (6:2 FTS) on DSA electrode: operating parameters and mechanism.

    PubMed

    Zhuo, Qiongfang; Li, Xiang; Yan, Feng; Yang, Bo; Deng, Shubo; Huang, Jun; Yu, Gang

    2014-08-01

    The 6:2 FTS was the substitute for perfluorooctane sulfonate (PFOS) in the chrome plating industry in Japan. Electrochemical oxidation of 6:2 FTS was investigated in this study. The degradabilities of PFOS and 6:2 FTS were tested on the Ti/SnO₂-Sb₂O₅-Bi₂O₃ anode. The effects of current density, potential, and supporting electrolyte on the degradation of 6:2 FTS were evaluated. Experimental results showed that 6:2 FTS was more easily degraded than PFOS on the Ti/SnO₂-Sb₂O₅-Bi₂O₃ anode. At a low current density of 1.42 mA/cm², 6:2 FTS was not degraded on Ti/SnO₂-Sb₂O₅-Bi₂O₃, while the degradation ratio increased when the current density ranged from 4.25 to 6.80 mA/cm². The degradation of 6:2 FTS at current density of 6.80 mA/cm² followed pseudo first-order kinetics with the rate constant of 0.074 hr⁻¹. The anodic potential played an important role in the degradation of 6:2 FTS, and the pseudo first-order rate constants increased with the potential. The surface of Ti/SnO₂-Sb₂O₅-Bi₂O₃ was contaminated after electrolysis at constant potential of 3V, while the fouling phenomenon was not observed at 5V. The fouled anode could be regenerated by incinerating at 600°C. The intermediates detected by ultra-performance liquid chromatography coupled with a triple-stage quadrupole mass spectrometer (UPLC-MS/MS) were shorter chain perfluorocarboxylic acids. The 6:2 FTS was first attacked by hydroxyl radical, and then formed perfluorinated carboxylates, which decarboxylated and removed CF2 units to yield shorter-chain perfluorocarboxylic acids.

  5. Temporal variation of coupling constants and nucleosynthesis

    NASA Astrophysics Data System (ADS)

    Oberhummer, H.; Csótó, A.; Fairbairn, M.; Schlattl, H.; Sharma, M. M.

    2003-05-01

    We investigate the triple-alpha process and the Oklo phenomenon to obtain constraints on possible cosmological time variations of fundamental constants. Specifically we study cosmological temporal constraints for the fine structure constant and nucleon and meson masses.

  6. Scalar-tensor theory of gravitation with negative coupling constant

    NASA Technical Reports Server (NTRS)

    Smalley, L. L.; Eby, P. B.

    1976-01-01

    The possibility of a Brans-Dicke scalar-tensor gravitation theory with a negative coupling constant is considered. The admissibility of a negative-coupling theory is investigated, and a simplified cosmological solution is obtained which allows a negative derivative of the gravitation constant. It is concluded that a Brans-Dicke theory with a negative coupling constant can be a viable alternative to general relativity and that a large negative value for the coupling constant seems to bring the original scalar-tensor theory into close agreement with perihelion-precession results in view of recent observations of small solar oblateness.

  7. Constants and Pseudo-Constants of Coupled Beam Motion in the PEP-II Rings

    SciTech Connect

    Decker, F.J.; Colocho, W.S.; Wang, M.H.; Yan, Y.T.; Yocky, G.; /SLAC

    2011-11-01

    Constants of beam motion help as cross checks to analyze beam diagnostics and the modeling procedure. Pseudo-constants, like the betatron mismatch parameter or the coupling parameter det C, are constant till certain elements in the beam line change them. This can be used to visually find the non-desired changes, pinpointing errors compared with the model.

  8. Gluons and the NJL coupling constant

    SciTech Connect

    Braghin, Fábio L.; Barros Jr, Ednaldo; Paulo Jr, Ademar

    2014-11-11

    The QCD origin of the NJL model is re-analysed by considering the gluon condensate of order two . The key point is the treatment of the gluon interactions. To linearize the action the auxiliary variable method is employed to introduce a scalar variable φ(x) that yield such condensate by means of its value in the vacuum, and then another auxiliary variable that corresponds to an antisymmetric gluon configuration φ(x). For that, besides that, two different possible limits of the fourth order non local quark interaction that may contribute to the NJL coupling are compared.

  9. Constant field gradient planar coupled cavity structure

    DOEpatents

    Kang, Yoon W.; Kustom, Robert L.

    1999-01-01

    A cavity structure having at least two opposing planar housing members spaced apart to accommodate the passage of a particle beam through the structure between the members. Each of the housing members have a plurality of serially aligned hollows defined therein, and also passages, formed in the members, which interconnect serially adjacent hollows to provide communication between the hollows. The opposing planar housing members are spaced and aligned such that the hollows in one member cooperate with corresponding hollows in the other member to form a plurality of resonant cavities aligned along the particle beam within the cavity structure. To facilitate the obtaining of a constant field gradient within the cavity structure, the passages are configured so as to be incrementally narrower in the direction of travel of the particle beam. In addition, the spacing distance between the opposing housing members is configured to be incrementally smaller in the direction of travel of the beam.

  10. Constant field gradient planar coupled cavity structure

    DOEpatents

    Kang, Y.W.; Kustom, R.L.

    1999-07-27

    A cavity structure is disclosed having at least two opposing planar housing members spaced apart to accommodate the passage of a particle beam through the structure between the members. Each of the housing members have a plurality of serially aligned hollows defined therein, and also passages, formed in the members, which interconnect serially adjacent hollows to provide communication between the hollows. The opposing planar housing members are spaced and aligned such that the hollows in one member cooperate with corresponding hollows in the other member to form a plurality of resonant cavities aligned along the particle beam within the cavity structure. To facilitate the obtaining of a constant field gradient within the cavity structure, the passages are configured so as to be incrementally narrower in the direction of travel of the particle beam. In addition, the spacing distance between the opposing housing members is configured to be incrementally smaller in the direction of travel of the beam. 16 figs.

  11. Experimental determination of the effective strong coupling constant

    SciTech Connect

    Alexandre Deur; Volker Burkert; Jian-Ping Chen; Wolfgang Korsch

    2007-07-01

    We extract an effective strong coupling constant from low Q{sup 2} data on the Bjorken sum. Using sum rules, we establish its Q{sup 2}-behavior over the complete Q{sup 2}-range. The result is compared to effective coupling constants extracted from different processes and to calculations based on Schwinger-Dyson equations, hadron spectroscopy or lattice QCD. Although the connection between the experimentally extracted effective coupling constant and the calculations is not clear, the results agree surprisingly well.

  12. Measurement of Small One-Bond Proton-Carbon Residual Dipolar Coupling Constants in Partially Oriented 13C Natural Abundance Oligosaccharide Samples: Analysis of Heteronuclear 1JCH-Modulated Spectra with the BIRD Inversion Pulse

    NASA Astrophysics Data System (ADS)

    Pham, Tran Nghia; Liptaj, Tibor; Bromek, Krystyna; Uhrín, Dušan

    2002-08-01

    Two 2D J-modulated HSQC-based experiments were designed for precise determination of small residual dipolar one-bond carbon-proton coupling constants in 13C natural abundance carbohydrates. Crucial to the precision of a few hundredths of Hz achieved by these methods was the use of long modulation intervals and BIRD pulses, which acted as semiselective inversion pulses. The BIRD pulses eliminated effective evolution of all but 1JCH couplings, resulting in signal modulation that can be described by simple modulation functions. A thorough analysis of such modulation functions for a typical four-spin carbohydrate spin system was performed for both experiments. The results showed that the evolution of the 1H- 1H and long-range 1H- 13C couplings during the BIRD pulses did not necessitate the introduction of more complicated modulation functions. The effects of pulse imperfections were also inspected. While weakly coupled spin systems can be analyzed by simple fitting of cross peak intensities, in strongly coupled spin systems the evolution of the density matrix needs to be considered in order to analyse data accurately. However, if strong coupling effects are modest the errors in coupling constants determined by the "weak coupling" analysis are of similar magnitudes in oriented and isotropic samples and are partially cancelled during dipolar coupling calculation. Simple criteria have been established as to when the strong coupling treatment needs to be invoked.

  13. Exponential tuning of the coupling constant of coupled microcantilevers by modifying their separation

    SciTech Connect

    Gil-Santos, Eduardo; Ramos, Daniel; Pini, Valerio; Calleja, Montserrat; Tamayo, Javier

    2011-03-21

    Vibration localization in coupled nanomechanical resonators has emerged as a promising concept for ultrasensitive mass sensing. It possesses intrinsic common mode rejection and the mass sensitivity can be enhanced with no need of extreme miniaturization of the devices. In this work, we have experimentally studied the role of the separation between cantilevers that are elastically coupled by an overhang. The results show that the coupling constant exponentially decays with the separation. In consistency with the theoretical expectations, the mass sensitivity is inversely proportional to the coupling constant. Finite element simulations show that the coupling constant can be exponentially reduced by increasing the ratio of the cantilever separation to the overhang length.

  14. Higgs coupling constants as a probe of new physics

    NASA Astrophysics Data System (ADS)

    Kanemura, Shinya; Okada, Yasuhiro; Senaha, Eibun; Yuan, C.-P.

    2004-12-01

    We study new physics effects on the couplings of weak gauge bosons with the lightest CP-even Higgs boson (h), hZZ, and the trilinear coupling of the lightest Higgs boson, hhh, at the one-loop order, as predicted by the two Higgs doublet model. Those renormalized coupling constants can deviate from the standard model (SM) predictions due to two distinct origins: the tree level mixing effect of Higgs bosons and the quantum effect of additional particles in loop diagrams. The latter can be enhanced in the renormalized hhh coupling constant when the additional particles show the nondecoupling property. Therefore, even in the case where the hZZ coupling is close to the SM value, deviation in the hhh coupling from the SM value can become as large as plus 100%, while that in the hZZ coupling is at most minus 1% level. Such large quantum effect on the Higgs trilinear coupling is distinguishable from the tree level mixing effect, and is expected to be detectable at a future linear collider.

  15. Spectra of magnetic chain graphs: coupling constant perturbations

    NASA Astrophysics Data System (ADS)

    Exner, Pavel; Manko, Stepan S.

    2015-03-01

    We analyze spectral properties of a quantum graph in the form of a ring chain with a δ coupling in the vertices exposed to a homogeneous magnetic field perpendicular to the graph plane. We find the band spectrum in the case when the chain exhibits a translational symmetry and study the discrete spectrum in the gaps resulting from changing a finite number of vertex coupling constants. In particular, we discuss in detail some examples such as perturbations of one or two vertices, weak perturbation asymptotics, and a pair of distant perturbations.

  16. Direct Determinations of the πNN Coupling Constants

    NASA Astrophysics Data System (ADS)

    Ericson, T. E. O.; Loiseau, B.

    1998-11-01

    A novel extrapolation method has been used to deduce directly the charged πN N coupling constant from backward np differential scattering cross sections. The extracted value, g2c = 14.52(0.26) is higher than the indirectly deduced values obtained in nucleon-nucleon energy-dependent partial-wave analyses. Our preliminary direct value from a reanalysis of the GMO sum-rule points to an intermediate value of g2c about 13.97(30).

  17. Non-minimally coupled varying constants quantum cosmologies

    SciTech Connect

    Balcerzak, Adam

    2015-04-01

    We consider gravity theory with varying speed of light and varying gravitational constant. Both constants are represented by non-minimally coupled scalar fields. We examine the cosmological evolution in the near curvature singularity regime. We find that at the curvature singularity the speed of light goes to infinity while the gravitational constant vanishes. This corresponds to the Newton's Mechanics limit represented by one of the vertex of the Bronshtein-Zelmanov-Okun cube [1,2]. The cosmological evolution includes both the pre-big-bang and post-big-bang phases separated by the curvature singularity. We also investigate the quantum counterpart of the considered theory and find the probability of transition of the universe from the collapsing pre-big-bang phase to the expanding post-big-bang phase.

  18. Responsive Copolymer Brushes of Poly[(2-(Methacryloyloxy)Ethyl) Trimethylammonium Chloride] (PMETAC) and Poly((1)H,(1)H,(2)H,(2)H-Perfluorodecyl acrylate) (PPFDA) to Modulate Surface Wetting Properties.

    PubMed

    Politakos, Nikolaos; Azinas, Stavros; Moya, Sergio Enrique

    2016-04-01

    Polymer brushes have a large potential for controlling properties such as surface lubrication or wetting through facile functionalization. Polymer chemistry, chain density, and length impact on the wetting properties of brushes. This study explores the use of diblock copolymer brushes with different block length and spatial arrangement of the blocks to tune surface wettability. Block copolymer brushes of the polyelectrolyte [2-(methacryloyloxy)ethyl] trimethylammonium chloride (PMETAC) with a contact angle of 17° and a hydrophobic block of (1)H, (1)H, (2)H, (2)H-perfluorodecyl Acrylate (PPFDA) with a contact angle of 130° are synthesized by RAFT polymerization. By changing the sequence of polymerization either block is synthesized as top or bottom block. By varying the concentration of initiator the length of the blocks is varied. Contact angle values with intermediate values between 17° and 130° are measured. In addition, by changing solvent pH and in presence of a different salt the contact angle of the copolymer brushes can be fine tuned. Brushes are characterized by atomic force microscopy, Raman confocal microscopy, and X-ray photoelectron spectroscopy.

  19. Inflation from cosmological constant and nonminimally coupled scalar

    NASA Astrophysics Data System (ADS)

    Glavan, Dražen; Marunović, Anja; Prokopec, Tomislav

    2015-08-01

    We consider inflation in a universe with a positive cosmological constant and a nonminimally coupled scalar field, in which the field couples both quadratically and quartically to the Ricci scalar. When considered in the Einstein frame and when the nonminimal couplings are negative, the field starts in slow roll and inflation ends with an asymptotic value of the principal slow-roll parameter, ɛE=4 /3 . Graceful exit can be achieved by suitably (tightly) coupling the scalar field to matter, such that at late time the total energy density reaches the scaling of matter, ɛE=ɛm . Quite generically the model produces a red spectrum of scalar cosmological perturbations and a small amount of gravitational radiation. With a suitable choice of the nonminimal couplings, the spectral slope can be as large as ns≃0.955 , which is about one standard deviation away from the central value measured by the Planck satellite. The model can be ruled out by future measurements if any of the following is observed: (a) the spectral index of scalar perturbations is ns>0.960 ; (b) the amplitude of tensor perturbations is above about r ˜10-2 ; (c) the running of the spectral index of scalar perturbations is positive.

  20. Calculation of hyperfine coupling constant by symmetry adapted cluster expansion configuration interaction theory. II. Anisotropic constants

    NASA Astrophysics Data System (ADS)

    Momose, Takamasa; Yamaguchi, Makoto; Shida, Tadamasa

    1990-11-01

    Following the previous work on the isotropic hyperfine coupling constants (HFCCs) of polyatomic radicals the symmetry adapted cluster expansion-configuration interaction (SAC-CI) theory is applied to calculate anisotropic HFCCs also. The results are compared with available experimental data from diatomic to polyatomic radicals such as the vinoxy. For radicals consisting of only the first row atoms Dunning's double zeta (DZ) basis set is shown to be adequate, but for those containing the second row atoms inclusion of polarization functions is required. Compared with the isotropic HFCC the calculation of the anisotropic HFCC is less formidable. However, ignorance of electron correlation causes serious disagreements with experimental data.

  1. Scalar decay constant and Yukawa coupling in walking gauge theories

    SciTech Connect

    Hashimoto, Michio

    2011-05-01

    We propose an approach for the calculation of the Yukawa coupling through the scalar decay constant and the chiral condensate in the context of the extended technicolor . We perform the nonperturbative computation of the Yukawa coupling based on the improved ladder Schwinger-Dyson equation. It turns out that the Yukawa coupling can be larger or smaller than the standard model value, depending on the number N{sub D} of the weak doublets for each technicolor (TC) index. It is thus nontrivial whether or not the huge enhancement of the production of the scalar via the gluon fusion takes place even for a walking TC model with a colored techni-fermion. For the typical one-family TC model near conformality, it is found that the Yukawa coupling is slightly larger than the standard model one, where the expected mass of the scalar bound state is around 500 GeV. In this case, the production cross section via the gluon fusion is considerably enhanced, as naively expected, and hence such a scalar can be discovered/excluded at the early stage of the LHC.

  2. Assessment of DFT functionals with fluorine-fluorine coupling constants

    NASA Astrophysics Data System (ADS)

    García de la Vega, J. M.; San Fabián, J.

    2015-07-01

    Density functional theory (DFT) calculations of nuclear magnetic resonance (NMR) spin-spin coupling constants (SSCCs) provide an important contribution for understanding experimentally observed values. It is known that calculated SSCCs using DFT methods correlate well with those experimentally measured. Unlike most of SSCCs, in fluorine compounds, fluorine-fluorine SSCC JFF shows that the Fermi contact (FC) term is not dominant, particularly for JFF in polyfluorinated organic molecules. In order to devise a DFT approach that would correctly reproduce the variation of SSCCs within a series of fluorine compounds, we test several DFT-based approaches, using different exchange and correlation functionals. Isotropic contributions to NMR fluorine-fluorine coupling constants (FC, spin-dipolar, SD, paramagnetic spin-orbit, PSO, and diamagnetic spin-orbit, DSO) have been calculated. Results show that DFT methods give appropriate values for nJFF (n = 4 to 7), while for geminal and vicinal JFF present large deviations from experimental values. For the latter SSCCs (2JFF and 3JFF), the four contributions (FC, SD, PSO and DSO) are analysed as a function of the local and nonlocal exchange in 1,1- and 1,2-difluoroethylene. Although FC term is not dominant for these SSCCs, the variation of this contribution with exchange is remarkable. On the other hand, SD and PSO contributions can be suitably computed without and with exact exchange, respectively. This article is dedicated to the memory of Prof. N. C. Handy, whose contributions to the development of Theoretical Chemistry have been widely recognized.

  3. Coupling constant metamorphosis, the Staeckel transform and superintegrability

    SciTech Connect

    Post, Sarah

    2010-12-23

    This paper is dedicated to the memory of Marcos Moshinsky. In this paper, we discuss the important role that coupling constant metamorphosis (CCM) and the Staeckel transform have played in the analysis of superintegrable systems. We explain the relation between the two and in particular show that they coincide when transforming between second-order superintegrable systems. Unlike in the case of second-order superintegrability, the quantum analog of CCM has only been proven for a subclass of systems with integrals of a specific form. We give the proof and as an application show the mapping of a family of superintegrable deformations of the simple harmonic oscillator to an associated family of superintegrable deformations of the Kepler-Coulomb potential.

  4. The GMO Sumrule and the πNN Coupling Constant

    NASA Astrophysics Data System (ADS)

    Ericson, T. E. O.; Loiseau, B.; Thomas, A. W.

    The isovector GMO sumrule for forward πN scattering is critically evaluated using the precise π-p and π-d scattering lengths obtained recently from pionic atom measurements. The charged πNN coupling constant is then deduced with careful analysis of systematic and statistical sources of uncertainties. This determination gives directly from data gc2(GMO)/4π = 14.17±0.09 (statistic) ±0.17 (systematic) or fc2/ 4π=0.078(11). This value is half-way between that of indirect methods (phase-shift analyses) and the direct evaluation from from backward np differential scattering cross sections (extrapolation to pion pole). From the π-p and π-d scattering lengths our analysis leads also to accurate values for (1/2)(aπ-p+aπ-n) and (1/2) (aπ-p-aπ-n).

  5. Hyperfine Coupling Constants from Internally Contracted Multireference Perturbation Theory.

    PubMed

    Shiozaki, Toru; Yanai, Takeshi

    2016-09-13

    We present an accurate method for calculating hyperfine coupling constants (HFCCs) based on the complete active space second-order perturbation theory (CASPT2) with full internal contraction. The HFCCs are computed as a first-order property using the relaxed CASPT2 spin-density matrix that takes into account orbital and configurational relaxation due to dynamical electron correlation. The first-order unrelaxed spin-density matrix is calculated from one- and two-body spin-free counterparts that are readily available in the CASPT2 nuclear gradient program [M. K. MacLeod and T. Shiozaki, J. Chem. Phys. 142, 051103 (2015)], whereas the second-order part is computed directly using the newly extended automatic code generator. The relaxation contribution is then calculated from the so-called Z-vectors that are available in the CASPT2 nuclear gradient program. Numerical results are presented for the CN and AlO radicals, for which the CASPT2 values are comparable (or, even superior in some cases) to the ones computed by the coupled-cluster and density matrix renormalization group methods. The HFCCs for the hexaaqua complexes with V(II), Cr(III), and Mn(II) are also presented to demonstrate the accuracy and efficiency of our code. PMID:27479148

  6. Strong coupling constant from Adler function in lattice QCD

    NASA Astrophysics Data System (ADS)

    Hudspith, Renwick J.; Lewis, Randy; Maltman, Kim; Shintani, Eigo

    2016-09-01

    We compute the QCD coupling constant, αs, from the Adler function with vector hadronic vacuum polarization (HVP) function. On the lattice, Adler function can be measured by the differential of HVP at two different momentum scales. HVP is measured from the conserved-local vector current correlator using nf = 2 + 1 flavor Domain Wall lattice data with three different lattice cutoffs, up to a‑1 ≈ 3.14 GeV. To avoid the lattice artifact due to O(4) symmetry breaking, we set the cylinder cut on the lattice momentum with reflection projection onto vector current correlator, and it then provides smooth function of momentum scale for extracted HVP. We present a global fit of the lattice data at a justified momentum scale with three lattice cutoffs using continuum perturbation theory at 𝒪(αs4) to obtain the coupling in the continuum limit at arbitrary scale. We take the running to Z boson mass through the appropriate thresholds, and obtain αs(5)(MZ) = 0.1191(24)(37) where the first is statistical error and the second is systematic one.

  7. Hyperfine Coupling Constants from Internally Contracted Multireference Perturbation Theory.

    PubMed

    Shiozaki, Toru; Yanai, Takeshi

    2016-09-13

    We present an accurate method for calculating hyperfine coupling constants (HFCCs) based on the complete active space second-order perturbation theory (CASPT2) with full internal contraction. The HFCCs are computed as a first-order property using the relaxed CASPT2 spin-density matrix that takes into account orbital and configurational relaxation due to dynamical electron correlation. The first-order unrelaxed spin-density matrix is calculated from one- and two-body spin-free counterparts that are readily available in the CASPT2 nuclear gradient program [M. K. MacLeod and T. Shiozaki, J. Chem. Phys. 142, 051103 (2015)], whereas the second-order part is computed directly using the newly extended automatic code generator. The relaxation contribution is then calculated from the so-called Z-vectors that are available in the CASPT2 nuclear gradient program. Numerical results are presented for the CN and AlO radicals, for which the CASPT2 values are comparable (or, even superior in some cases) to the ones computed by the coupled-cluster and density matrix renormalization group methods. The HFCCs for the hexaaqua complexes with V(II), Cr(III), and Mn(II) are also presented to demonstrate the accuracy and efficiency of our code.

  8. Running couplings and operator mixing in the gravitational corrections to coupling constants

    SciTech Connect

    Anber, Mohamed M.; Donoghue, John F.; El-Houssieny, Mohamed

    2011-06-15

    The use of a running coupling constant in renormalizable theories is well known, but the implementation of this idea for effective field theories with a dimensional coupling constant is, in general, less useful. Nevertheless, there are multiple attempts to define running couplings, including the effects of gravity, with varying conclusions. We sort through many of the issues involved, most particularly the idea of operator mixing and also the kinematics of crossing, using calculations in Yukawa and {lambda}{phi}{sup 4} theories as illustrative examples. We remain in the perturbative regime. In some theories with a high permutation symmetry, such as {lambda}{phi}{sup 4}, a reasonable running coupling can be defined. However, in most cases, such as Yukawa and gauge theories, a running coupling fails to correctly account for the energy dependence of the interaction strength. As a by-product we also contrast on-shell and off-shell renormalization schemes and show that operators which are normally discarded, such as those that vanish by the equations of motion, are required for off-shell renormalization of effective field theories. Our results suggest that the inclusion of gravity in the running of couplings is not useful or universal in the description of physical processes.

  9. Density functional theory predictions of isotropic hyperfine coupling constants.

    PubMed

    Hermosilla, L; Calle, P; García de la Vega, J M; Sieiro, C

    2005-02-17

    The reliability of density functional theory (DFT) in the determination of the isotropic hyperfine coupling constants (hfccs) of the ground electronic states of organic and inorganic radicals is examined. Predictions using several DFT methods and 6-31G, TZVP, EPR-III and cc-pVQZ basis sets are made and compared to experimental values. The set of 75 radicals here studied was selected using a wide range of criteria. The systems studied are neutral, cationic, anionic; doublet, triplet, quartet; localized, and conjugated radicals, containing 1H, 9Be, 11B, 13C, 14N, 17O, 19F, 23Na, 25Mg, 27Al, 29Si, 31P, 33S, and 35Cl nuclei. The considered radicals provide 241 theoretical hfcc values, which are compared with 174 available experimental ones. The geometries of the studied systems are obtained by theoretical optimization using the same functional and basis set with which the hfccs were calculated. Regression analysis is used as a basic and appropriate methodology for this kind of comparative study. From this analysis, we conclude that DFT predictions of the hfccs are reliable for B3LYP/TZVP and B3LYP/EPR-III combinations. Both functional/basis set scheme are the more useful theoretical tools for predicting hfccs if compared to other much more expensive methods.

  10. Quantum-chemical simulation of 1H NMR spectra. 2. Comparison of DFT-based procedures for computing proton-proton coupling constants in organic molecules.

    PubMed

    Bally, Thomas; Rablen, Paul R

    2011-06-17

    The performance of 250 different computational protocols (combinations of density functionals, basis sets and methods) was assessed on a set of 165 well-established experimental (1)H-(1)H nuclear coupling constants (J(H-H)) from 65 molecules spanning a wide range of "chemical space". Thereby we found that, if one uses core-augmented basis sets and allows for linear scaling of the raw results, calculations of only the Fermi contact term yield more accurate predictions than calculations where all four terms that contribute to J(H-H) are evaluated. It turns out that B3LYP/6-31G(d,p)u+1s is the best (and, in addition, one of the most economical) of all tested methods, yielding predictions of J(H-H) with a root-mean-square deviation from experiment of less than 0.5 Hz for our test set. Another method that does similarly well, without the need for additional 1s basis functions, is B3LYP/cc-pVTZ, which is, however, ca. 8 times more "expensive" in terms of CPU time. A selection of the better methods was tested on a probe set comprising 61 J(H-H) values from 37 molecules. In this set we also included five molecules where conformational averaging is required. The rms deviations were better than or equal to those with the training set, which indicates that the method we recommend is generally applicable for organic molecules. We give instructions on how to carry out calculations of (1)H chemical shifts and J(H-H) most economically and provide scripts to extract the relevant information from the outputs of calculations with the Gaussian program in clearly arranged form, e.g., to feed them into programs for simulating entire (1)H NMR spectra.

  11. Theoretical calculations of hyperfine coupling constants for muoniated butyl radicals.

    PubMed

    Chen, Ya Kun; Fleming, Donald G; Wang, Yan Alexander

    2011-04-01

    The hyperfine coupling constants (HFCCs) of all the butyl radicals that can be produced by muonium (Mu) addition to butene isomers (1- and 2-butene and isobutene) have been calculated, to compare with the experimental results for the muon and proton HFFCs for these radicals reported in paper II (Fleming, D. G.; et al. J. Phys. Chem. A 2011, 10.1021/jp109676b) that follows. The equilibrium geometries and HFCCs of these muoniated butyl radicals as well as their unsubstituted isotopomers were treated at both the spin-unrestricted MP2/EPR-III and B3LYP/EPR-III levels of theory. Comparisons with calculations carried out for the EPR-II basis set have also been made. All calculations were carried out in vacuo at 0 K only. A C-Mu bond elongation scheme that lengthens the equilibrium C-H bond by a factor of 1.076, on the basis of recent quantum calculations of the muon HFCCs of the ethyl radical, has been exploited to determine the vibrationally corrected muon HFCCs. The sensitivity of the results to small variations around this scale factor was also investigated. The computational methodology employed was "benchmarked" in comparisons with the ethyl radical, both with higher level calculations and with experiment. For the β-HFCCs of interest, compared to B3LYP, the MP2 calculations agree better with higher level theories and with experiment in the case of the eclipsed C-Mu bond and are generally deemed to be more reliable in predicting the equilibrium conformations and muon HFCCs near 0 K, in the absence of environmental effects. In some cases though, the experimental results in paper II demonstrate that environmental effects enhance the muon HFCC in the solid phase, where much better agreement with the experimental muon HFCCs near 0 K is found from B3LYP than from MP2. This seemingly better level of agreement is probably fortuitous, due to error cancellations in the DFT calculations, which appear to mimic these environmental effects. For the staggered proton HFCCs of the

  12. Non-empirical calculations of NMR indirect carbon-carbon coupling constants. Part 6: propellanes.

    PubMed

    Krivdin, Leonid B

    2004-01-01

    A full set of carbon-carbon coupling constants have been calculated at the SOPPA level in the series of six most representative propellanes. Special attention was focused on spin-spin couplings involving both bridgehead carbons, and these data were rationalized in terms of the multipath coupling mechanism and hybridization effects. Many unknown couplings in the propellane frameworks were predicted with high reliability.

  13. Analyzing and Interpreting NMR Spin-Spin Coupling Constants Using Molecular Orbital Calculations

    ERIC Educational Resources Information Center

    Autschbach, Jochen; Le Guennic, Boris

    2007-01-01

    Molecular orbital plots are used to analyze and interpret NMR spin-spin coupling constants, also known as J coupling constants. Students have accepted the concept of contributions to molecular properties from individual orbitals without the requirement to provide explicit equations.

  14. Low energy determination of the QCD strong coupling constant on the lattice

    NASA Astrophysics Data System (ADS)

    Maezawa, Yu; Petreczky, Peter

    2016-09-01

    We present a determination of the strong coupling constant from lattice quantum chromodynamics (QCD) using the moments of pseudo-scalar charmonium correlators calculated using highly improved staggered quark action. We obtain a value αs(μ = mc) = 0.3397(56), which is the lowest energy determination of the strong coupling constant so far.

  15. Realization of power law inflation & variants via variation of the strong coupling constant

    NASA Astrophysics Data System (ADS)

    AlHallak, M.; Chamoun, N.

    2016-09-01

    We present a model of power law inflation generated by variation of the strong coupling constant. We then extend the model to two varying coupling constants which leads to a potential consisting of a linear combination of exponential terms. Some variants of the latter may be self-consistent and can accommodate the experimental data of the Planck 2015 and other recent experiments.

  16. Determination of unresolved heteronuclear scalar coupling constants by J(up)-HSQMBC

    NASA Astrophysics Data System (ADS)

    Glanzer, Simon; Kunert, Olaf; Zangger, Klaus

    2016-07-01

    Long-range heteronuclear scalar coupling constants provide important structural information, which is necessary for obtaining stereospecific assignment or dihedral angle information. The measurement of small proton-carbon splittings is particularly difficult due to the low natural abundance of carbon-13 and the presence of homonuclear couplings of similar size. Here we present a real-time J-upscaled HSQMBC, which allows the measurement of heteronuclear coupling constants even if they are hidden in the signal linewidth of a regular spectrum.

  17. Ro-vibrational averaging of the isotropic hyperfine coupling constant for the methyl radical.

    PubMed

    Adam, Ahmad Y; Yachmenev, Andrey; Yurchenko, Sergei N; Jensen, Per

    2015-12-28

    We present the first variational calculation of the isotropic hyperfine coupling constant of the carbon-13 atom in the CH3 radical for temperatures T = 0, 96, and 300 K. It is based on a newly calculated high level ab initio potential energy surface and hyperfine coupling constant surface of CH3 in the ground electronic state. The ro-vibrational energy levels, expectation values for the coupling constant, and its temperature dependence were calculated variationally by using the methods implemented in the computer program TROVE. Vibrational energies and vibrational and temperature effects for coupling constant are found to be in very good agreement with the available experimental data. We found, in agreement with previous studies, that the vibrational effects constitute about 44% of the constant's equilibrium value, originating mainly from the large amplitude out-of-plane bending motion and that the temperature effects play a minor role. PMID:26723670

  18. Ro-vibrational averaging of the isotropic hyperfine coupling constant for the methyl radical

    SciTech Connect

    Adam, Ahmad Y.; Jensen, Per; Yachmenev, Andrey; Yurchenko, Sergei N.

    2015-12-28

    We present the first variational calculation of the isotropic hyperfine coupling constant of the carbon-13 atom in the CH{sub 3} radical for temperatures T = 0, 96, and 300 K. It is based on a newly calculated high level ab initio potential energy surface and hyperfine coupling constant surface of CH{sub 3} in the ground electronic state. The ro-vibrational energy levels, expectation values for the coupling constant, and its temperature dependence were calculated variationally by using the methods implemented in the computer program TROVE. Vibrational energies and vibrational and temperature effects for coupling constant are found to be in very good agreement with the available experimental data. We found, in agreement with previous studies, that the vibrational effects constitute about 44% of the constant’s equilibrium value, originating mainly from the large amplitude out-of-plane bending motion and that the temperature effects play a minor role.

  19. Determination of unresolved heteronuclear scalar coupling constants by J(up)-HSQMBC.

    PubMed

    Glanzer, Simon; Kunert, Olaf; Zangger, Klaus

    2016-07-01

    Long-range heteronuclear scalar coupling constants provide important structural information, which is necessary for obtaining stereospecific assignment or dihedral angle information. The measurement of small proton-carbon splittings is particularly difficult due to the low natural abundance of carbon-13 and the presence of homonuclear couplings of similar size. Here we present a real-time J-upscaled HSQMBC, which allows the measurement of heteronuclear coupling constants even if they are hidden in the signal linewidth of a regular spectrum. PMID:27183090

  20. Relativistic force field: parametric computations of proton-proton coupling constants in (1)H NMR spectra.

    PubMed

    Kutateladze, Andrei G; Mukhina, Olga A

    2014-09-01

    Spin-spin coupling constants in (1)H NMR carry a wealth of structural information and offer a powerful tool for deciphering molecular structures. However, accurate ab initio or DFT calculations of spin-spin coupling constants have been very challenging and expensive. Scaling of (easy) Fermi contacts, fc, especially in the context of recent findings by Bally and Rablen (Bally, T.; Rablen, P. R. J. Org. Chem. 2011, 76, 4818), offers a framework for achieving practical evaluation of spin-spin coupling constants. We report a faster and more precise parametrization approach utilizing a new basis set for hydrogen atoms optimized in conjunction with (i) inexpensive B3LYP/6-31G(d) molecular geometries, (ii) inexpensive 4-31G basis set for carbon atoms in fc calculations, and (iii) individual parametrization for different atom types/hybridizations, not unlike a force field in molecular mechanics, but designed for the fc's. With the training set of 608 experimental constants we achieved rmsd <0.19 Hz. The methodology performs very well as we illustrate with a set of complex organic natural products, including strychnine (rmsd 0.19 Hz), morphine (rmsd 0.24 Hz), etc. This precision is achieved with much shorter computational times: accurate spin-spin coupling constants for the two conformers of strychnine were computed in parallel on two 16-core nodes of a Linux cluster within 10 min.

  1. Relativistic force field: parametric computations of proton-proton coupling constants in (1)H NMR spectra.

    PubMed

    Kutateladze, Andrei G; Mukhina, Olga A

    2014-09-01

    Spin-spin coupling constants in (1)H NMR carry a wealth of structural information and offer a powerful tool for deciphering molecular structures. However, accurate ab initio or DFT calculations of spin-spin coupling constants have been very challenging and expensive. Scaling of (easy) Fermi contacts, fc, especially in the context of recent findings by Bally and Rablen (Bally, T.; Rablen, P. R. J. Org. Chem. 2011, 76, 4818), offers a framework for achieving practical evaluation of spin-spin coupling constants. We report a faster and more precise parametrization approach utilizing a new basis set for hydrogen atoms optimized in conjunction with (i) inexpensive B3LYP/6-31G(d) molecular geometries, (ii) inexpensive 4-31G basis set for carbon atoms in fc calculations, and (iii) individual parametrization for different atom types/hybridizations, not unlike a force field in molecular mechanics, but designed for the fc's. With the training set of 608 experimental constants we achieved rmsd <0.19 Hz. The methodology performs very well as we illustrate with a set of complex organic natural products, including strychnine (rmsd 0.19 Hz), morphine (rmsd 0.24 Hz), etc. This precision is achieved with much shorter computational times: accurate spin-spin coupling constants for the two conformers of strychnine were computed in parallel on two 16-core nodes of a Linux cluster within 10 min. PMID:25158224

  2. Nuclear Quadrupole Coupling Constants in Niobium Pentachloride and Related Compounds (II) Transition Metal Nuclei

    NASA Astrophysics Data System (ADS)

    Okubo, Noriaki

    1982-02-01

    93Nb NQR spectrum in NbCl5 has been investigated from 4.2 K to 480 K. The coupling constant shows an unusual positive temperature dependence at low temperatures. The EFG tensor is calculated with the d2sp3 octahedral bond functions. The experimental data are analysed in terms of the contributions from the σ- and π-bonds. It is shown that the positive temperature dependence can be explained by the pπ-dπ bond mechanism. The theory is also applied to the related compounds and the consistency with the analysis of the halogen coupling constants is shown.

  3. More line narrowing in TROSY by decoupling of long-range couplings: shift correlation and 1JNC‧ coupling constant measurements

    NASA Astrophysics Data System (ADS)

    Kövér, Katalin E.; Batta, Gyula

    2004-10-01

    Since the introduction of RDCs in high-resolution NMR studies of macromolecules, there is a growing interest in the development of accurate, and sensitive methods for determining coupling constants. Most methods for extracting these couplings are based on the measurement of the splitting between multiplet components in J-coupled spectra. However, these methods are often unreliable since undesired multiple-bond couplings can considerably broaden the multiplet components and consequently make accurate determination of their position difficult. To demonstrate one approach to this problem, G-BIRD (r) decoupled TROSY sequences are proposed for the measurement of 1JNH and 1JNC' coupling constants. Resolved or unresolved splittings due to remote protons are removed by a G-BIRD (r) module employed during t1 and as a result, spectra with narrow, well-resolved peaks are obtained from which heteronuclear one-bond couplings can be accurately measured. Moreover, introduction of a spin-state-selective α/β-filter in the TROSY sequence allows the separation of the 1JNC' doublet components into two subspectra which contain the same number of peaks as the regular TROSY spectrum. The 1JNC' couplings are obtained from the displacement between the corresponding peaks in the subspectra.

  4. Radiative corrections to the nucleon axial vector coupling constant in the chiral soliton quark model

    SciTech Connect

    Duck, I. )

    1993-04-01

    Second-order radiative corrections to the nucleon axial vector coupling constant from gluon, pion, and sigma meson exchange are calculated in the chiral soliton quark model. Many apparent processes are found not to contribute. The soliton is elastically decoupled from meson radiative corrections which are dominated by a gluon exchange contribution equivalent to a gluonic hybrid component of the nucleon. A 30% radiative reduction of the axial coupling strength is indicated.

  5. SOPPA and CCSD vibrational corrections to NMR indirect spin-spin coupling constants of small hydrocarbons

    NASA Astrophysics Data System (ADS)

    Faber, Rasmus; Sauer, Stephan P. A.

    2015-12-01

    We present zero-point vibrational corrections to the indirect nuclear spin-spin coupling constants in ethyne, ethene, cyclopropene and allene. The calculations have been carried out both at the level of the second order polarization propagator approximation (SOPPA) employing a new implementation in the DALTON program, at the density functional theory level with the B3LYP functional employing also the Dalton program and at the level of coupled cluster singles and doubles (CCSD) theory employing the implementation in the CFOUR program. Specialized coupling constant basis sets, aug-cc-pVTZ-J, have been employed in the calculations. We find that on average the SOPPA results for both the equilibrium geometry values and the zero-point vibrational corrections are in better agreement with the CCSD results than the corresponding B3LYP results. Furthermore we observed that the vibrational corrections are in the order of 5 Hz for the one-bond carbon-hydrogen couplings and about 1 Hz or smaller for the other couplings apart from the one-bond carbon-carbon coupling (11 Hz) and the two-bond carbon-hydrogen coupling (4 Hz) in ethyne. However, not for all couplings lead the inclusion of zero-point vibrational corrections to better agreement with experiment.

  6. SOPPA and CCSD vibrational corrections to NMR indirect spin-spin coupling constants of small hydrocarbons

    SciTech Connect

    Faber, Rasmus; Sauer, Stephan P. A.

    2015-12-31

    We present zero-point vibrational corrections to the indirect nuclear spin-spin coupling constants in ethyne, ethene, cyclopropene and allene. The calculations have been carried out both at the level of the second order polarization propagator approximation (SOPPA) employing a new implementation in the DALTON program, at the density functional theory level with the B3LYP functional employing also the Dalton program and at the level of coupled cluster singles and doubles (CCSD) theory employing the implementation in the CFOUR program. Specialized coupling constant basis sets, aug-cc-pVTZ-J, have been employed in the calculations. We find that on average the SOPPA results for both the equilibrium geometry values and the zero-point vibrational corrections are in better agreement with the CCSD results than the corresponding B3LYP results. Furthermore we observed that the vibrational corrections are in the order of 5 Hz for the one-bond carbon-hydrogen couplings and about 1 Hz or smaller for the other couplings apart from the one-bond carbon-carbon coupling (11 Hz) and the two-bond carbon-hydrogen coupling (4 Hz) in ethyne. However, not for all couplings lead the inclusion of zero-point vibrational corrections to better agreement with experiment.

  7. The B{sub s}B*K coupling constant using QCDSR

    SciTech Connect

    Cerqueira, A. Jr.; Rodrigues, B. O.; Bracco, M. E.

    2013-03-25

    In this work we evaluate the coupling constant for the vertex B{sub s}B*K by the QCD Sum Rules. The result was obtained using the heaviest particle off shell of this vertex, the B{sub s} meson, and the lightest particle off shell, the K meson.

  8. A QCDSR calculation for the {phi}D{sub s}D{sub s} coupling constant

    SciTech Connect

    Rodrigues, B. O.; Chiapparini, M.; Bracco, M. E.

    2013-03-25

    In this work, we use the QCD Sum Rules (QCDSR) technique to obtain informations about the strong coupling constant of the three meson vertex {phi}D{sub s}D{sub s}. The calculation is done for the case where the {phi} meson is considered off-shell.

  9. The variation of the fine-structure constant from disformal couplings

    SciTech Connect

    De Bruck, Carsten van; Mifsud, Jurgen; Nunes, Nelson J. E-mail: jmifsud1@sheffield.ac.uk

    2015-12-01

    We study a theory in which the electromagnetic field is disformally coupled to a scalar field, in addition to a usual non-minimal electromagnetic coupling. We show that disformal couplings modify the expression for the fine-structure constant, α. As a result, the theory we consider can explain the non-zero reported variation in the evolution of α by purely considering disformal couplings. We also find that if matter and photons are coupled in the same way to the scalar field, disformal couplings itself do not lead to a variation of the fine-structure constant. A number of scenarios are discussed consistent with the current astrophysical, geochemical, laboratory and the cosmic microwave background radiation constraints on the cosmological evolution of α. The models presented are also consistent with the current type Ia supernovae constraints on the effective dark energy equation of state. We find that the Oklo bound in particular puts strong constraints on the model parameters. From our numerical results, we find that the introduction of a non-minimal electromagnetic coupling enhances the cosmological variation in α. Better constrained data is expected to be reported by ALMA and with the forthcoming generation of high-resolution ultra-stable spectrographs such as PEPSI, ESPRESSO, and ELT-HIRES. Furthermore, an expected increase in the sensitivity of molecular and nuclear clocks will put a more stringent constraint on the theory.

  10. Computational IR spectroscopy of water: OH stretch frequencies, transition dipoles, and intermolecular vibrational coupling constants

    NASA Astrophysics Data System (ADS)

    Choi, Jun-Ho; Cho, Minhaeng

    2013-05-01

    The Hessian matrix reconstruction method initially developed to extract the basis mode frequencies, vibrational coupling constants, and transition dipoles of the delocalized amide I, II, and III vibrations of polypeptides and proteins from quantum chemistry calculation results is used to obtain those properties of delocalized O-H stretch modes in liquid water. Considering the water symmetric and asymmetric O-H stretch modes as basis modes, we here develop theoretical models relating vibrational frequencies, transition dipoles, and coupling constants of basis modes to local water configuration and solvent electric potential. Molecular dynamics simulation was performed to generate an ensemble of water configurations that was in turn used to construct vibrational Hamiltonian matrices. Obtaining the eigenvalues and eigenvectors of the matrices and using the time-averaging approximation method, which was developed by the Skinner group, to calculating the vibrational spectra of coupled oscillator systems, we could numerically simulate the O-H stretch IR spectrum of liquid water. The asymmetric line shape and weak shoulder bands were quantitatively reproduced by the present computational procedure based on vibrational exciton model, where the polarization effects on basis mode transition dipoles and inter-mode coupling constants were found to be crucial in quantitatively simulating the vibrational spectra of hydrogen-bond networking liquid water.

  11. Correlation of 1JCH spin-spin coupling constants and their solvent sensitivities

    NASA Astrophysics Data System (ADS)

    Shahkhatuni, Astghik A.; Sahakyan, Aleksandr B.; Shahkhatuni, Aleksan G.; Mamyan, Suren S.; Panosyan, Henry A.

    2012-07-01

    The solvent induced changes of one-bond spin-spin coupling constants (SSCC) of several substituted methanes are investigated in solvents with different polarities. The correlation between solute SSCC and solvent dielectric constant is used to estimate the solvent effect-free ('pure') values of SSCCs by linear extrapolation to zero in reaction field coordinates. The obtained 'pure' SSCCs are close to the values, measured by gas phase NMR spectroscopy or predicted by quantum chemical calculations for isolated molecules. The slopes of SSCC dependencies, interpreted as solvent sensitivities of each molecule, are linearly correlated with the 'pure' values of SSCC.

  12. Calculation of nuclear spin-spin coupling constants using frozen density embedding

    SciTech Connect

    Götz, Andreas W.; Autschbach, Jochen; Visscher, Lucas

    2014-03-14

    We present a method for a subsystem-based calculation of indirect nuclear spin-spin coupling tensors within the framework of current-spin-density-functional theory. Our approach is based on the frozen-density embedding scheme within density-functional theory and extends a previously reported subsystem-based approach for the calculation of nuclear magnetic resonance shielding tensors to magnetic fields which couple not only to orbital but also spin degrees of freedom. This leads to a formulation in which the electron density, the induced paramagnetic current, and the induced spin-magnetization density are calculated separately for the individual subsystems. This is particularly useful for the inclusion of environmental effects in the calculation of nuclear spin-spin coupling constants. Neglecting the induced paramagnetic current and spin-magnetization density in the environment due to the magnetic moments of the coupled nuclei leads to a very efficient method in which the computationally expensive response calculation has to be performed only for the subsystem of interest. We show that this approach leads to very good results for the calculation of solvent-induced shifts of nuclear spin-spin coupling constants in hydrogen-bonded systems. Also for systems with stronger interactions, frozen-density embedding performs remarkably well, given the approximate nature of currently available functionals for the non-additive kinetic energy. As an example we show results for methylmercury halides which exhibit an exceptionally large shift of the one-bond coupling constants between {sup 199}Hg and {sup 13}C upon coordination of dimethylsulfoxide solvent molecules.

  13. Calculation of nuclear spin-spin coupling constants using frozen density embedding.

    PubMed

    Götz, Andreas W; Autschbach, Jochen; Visscher, Lucas

    2014-03-14

    We present a method for a subsystem-based calculation of indirect nuclear spin-spin coupling tensors within the framework of current-spin-density-functional theory. Our approach is based on the frozen-density embedding scheme within density-functional theory and extends a previously reported subsystem-based approach for the calculation of nuclear magnetic resonance shielding tensors to magnetic fields which couple not only to orbital but also spin degrees of freedom. This leads to a formulation in which the electron density, the induced paramagnetic current, and the induced spin-magnetization density are calculated separately for the individual subsystems. This is particularly useful for the inclusion of environmental effects in the calculation of nuclear spin-spin coupling constants. Neglecting the induced paramagnetic current and spin-magnetization density in the environment due to the magnetic moments of the coupled nuclei leads to a very efficient method in which the computationally expensive response calculation has to be performed only for the subsystem of interest. We show that this approach leads to very good results for the calculation of solvent-induced shifts of nuclear spin-spin coupling constants in hydrogen-bonded systems. Also for systems with stronger interactions, frozen-density embedding performs remarkably well, given the approximate nature of currently available functionals for the non-additive kinetic energy. As an example we show results for methylmercury halides which exhibit an exceptionally large shift of the one-bond coupling constants between (199)Hg and (13)C upon coordination of dimethylsulfoxide solvent molecules.

  14. Non-empirical calculations of NMR indirect carbon-carbon coupling constants. Part 7--spiroalkanes.

    PubMed

    Krivdin, Leonid B

    2004-06-01

    Carbon-carbon spin-spin coupling constants were calculated at the SOPPA level for a series of seven classical spiroalkanes, spiro[2.2]pentane, spiro[2.3]hexane, spiro[2.4]heptane, spiro[2.5]octane, spiro[3.3]heptane, spiro[4.4]nonane and spiro[5.5]undecane, with special focus upon couplings involving and/or across spiro carbons. Many interesting structural trends were investigated originating in specific geometries and unusual bonding environments at the spiro carbon.

  15. Constant-coupling approximation study of spin-1 Blume-Capel model

    NASA Astrophysics Data System (ADS)

    Ekiz, Cesur

    2016-07-01

    In this paper, the equilibrium properties of spin-1 Blume-Capel model are studied by using constant-coupling approximation. The formulation is based on developed by Obokata and Oguchi method, where the dependence upon the thermodynamic variables is determined by a set of two-couple nonlinear algebraic equations. The temperature dependence of the order parameters is examined to characterize the nature (continuous or discontinuous) of the phase transitions and to obtain the metastable and unstable branches. For the system, the effect of the uniaxial anisotropy parameter to phase transitions and stable, metastable and unstable states is discussed on the simple cubic lattice with the coordination number z = 6.

  16. Novel isochronous N-body problems featuring N arbitrary rational coupling constants

    NASA Astrophysics Data System (ADS)

    Calogero, F.

    2016-07-01

    A novel class of N-body problems is identified, with N an arbitrary positive integer (N ≥ 2). These models are characterized by Newtonian ("accelerations equal forces") equations of motion describing N equal point-particles moving in the complex z-plane. These highly nonlinear equations feature N arbitrary coupling constants, yet they can be solved by algebraic operations and if all the N coupling constants are real and rational the corresponding N-body problem is isochronous: its generic solutions are all completely periodic with an overall period T independent of the initial data (but many solutions feature subperiods T/p with p integer). It is moreover shown that these models are Hamiltonian.

  17. Calculations of spin-spin coupling constants in aromatic nitrogen heterocyclics

    NASA Astrophysics Data System (ADS)

    Long, S. A. T.; Memory, J. D.

    HH, CH, NH, CC, and NC spin-spin coupling constants were calculated using the FP-INDO method and the Fermi contact interaction for pyridine, pyridazine, pyrimidine, pyrazine, s-triazine, quinoline, quinoxaline, phthalazine, isoquinoline, cinnoline, quinazoline, acridine, phenazine, benzo[ g]quinoxaline, and benzo[ b]-phenazine. The agreement between theory and experiment was comparable to that for polynuclear aromatic hydrocarbons reported earlier.

  18. J(Si,H) Coupling Constants in Nonclassical Transition-Metal Silane Complexes.

    PubMed

    Scherer, Wolfgang; Meixner, Petra; Batke, Kilian; Barquera-Lozada, José E; Ruhland, Klaus; Fischer, Andreas; Eickerling, Georg; Eichele, Klaus

    2016-09-12

    We will outline that the sign and magnitude of J(Si,H) coupling constants provide a highly sensitive tool to measure the extent of Si-H bond activation in nonclassical silane complexes. Up to now, this structure-property relationship was obscured by erroneous J(Si,H) sign determinations in the literature. These new findings also help to identify the salient control parameters of the Si-H bond activation process in nonclassical silane complexes. PMID:27503583

  19. Limits on the variability of coupling constants from the Oklo natural reactor

    NASA Astrophysics Data System (ADS)

    Irvine, J. M.

    1983-12-01

    The theoretical basis of prehistoric natural nuclear reactors is summarized and the natural reactor at Oklo in Gabon is discussed. An analysis of isotopic abundances at the Oklo site suggests that the extremely narrow neutron capture resonance in Sm-149 has moved by less than 0.01 eV in the past two billion years. This result is used to place limits on the variability of coupling constants over this period.

  20. J(Si,H) Coupling Constants in Nonclassical Transition-Metal Silane Complexes.

    PubMed

    Scherer, Wolfgang; Meixner, Petra; Batke, Kilian; Barquera-Lozada, José E; Ruhland, Klaus; Fischer, Andreas; Eickerling, Georg; Eichele, Klaus

    2016-09-12

    We will outline that the sign and magnitude of J(Si,H) coupling constants provide a highly sensitive tool to measure the extent of Si-H bond activation in nonclassical silane complexes. Up to now, this structure-property relationship was obscured by erroneous J(Si,H) sign determinations in the literature. These new findings also help to identify the salient control parameters of the Si-H bond activation process in nonclassical silane complexes.

  1. Cosmological dynamics with non-minimally coupled scalar field and a constant potential function

    NASA Astrophysics Data System (ADS)

    Hrycyna, Orest; Szydłowski, Marek

    2015-11-01

    Dynamical systems methods are used to investigate global behaviour of the spatially flat Friedmann-Robertson-Walker cosmological model in gravitational theory with a non-minimally coupled scalar field and a constant potential function. We show that the system can be reduced to an autonomous three-dimensional dynamical system and additionally is equipped with an invariant manifold corresponding to an accelerated expansion of the universe. Using this invariant manifold we find an exact solution of the reduced dynamics. We investigate all solutions for all admissible initial conditions using theory of dynamical systems to obtain a classification of all evolutional paths. The right-hand sides of the dynamical system depend crucially on the value of the non-minimal coupling constant therefore we study bifurcation values of this parameter under which the structure of the phase space changes qualitatively. We found a special bifurcation value of the non-minimal coupling constant which is distinguished by dynamics of the model and may suggest some additional symmetry in matter sector of the theory.

  2. Quark masses and strong coupling constant in 2 +1 flavor QCD

    NASA Astrophysics Data System (ADS)

    Maezawa, Y.; Petreczky, P.

    2016-08-01

    We present a determination of the strange, charm, and bottom quark masses as well as the strong coupling constant in 2 +1 flavor lattice QCD simulations using highly improved staggered quark action. The ratios of the charm quark mass to the strange quark mass and the bottom quark mass to the charm quark mass are obtained from the meson masses calculated on the lattice and found to be mc/ms=11.877 (91 ) and mb/mc=4.528 (57 ) in the continuum limit. We also determine the strong coupling constant and the charm quark mass using the moments of pseudoscalar charmonium correlators: αs(μ =mc)=0.3697 (85 ) and mc(μ =mc)=1.267 (12 ) GeV . Our result for αs corresponds to the determination of the strong coupling constant at the lowest energy scale so far and is translated to the value αs(μ =MZ,nf=5 )=0.11622 (84 ).

  3. Constraining axion coupling constants from measuring the Casimir interaction between polarized test bodies

    NASA Astrophysics Data System (ADS)

    Bezerra, V. B.; Klimchitskaya, G. L.; Mostepanenko, V. M.; Romero, C.

    2016-08-01

    We propose an experiment for measuring the effective Casimir pressure between two parallel silicon carbide (SiC) plates with aligned nuclear spins. The prospective constraints on an axion-neutron coupling constant for both hadronic and grand unified theory (GUT) axions are calculated using the process of one-axion exchange. For this purpose, a general expression for the additional pressure arising between two polarized plates due to the exchange of one axion between their constituent fermions is derived. We demonstrate that only the polarization component perpendicular to the plates contributes to the pressure. The obtained pressure can be both repulsive and attractive depending on whether the polarizations of both plates are unidirectional or directed in opposite directions. It is shown that although the constraints on an axion-electron coupling obtained in the case of magnetized plates are not competitive, the constraints on an axion-neutron coupling found for plates with polarized nuclear spins are of the same order of magnitude as those obtained previously for the GUT axions alone using the process of two-axion exchange. The proposed experiment allows us also to strengthen the presently known constraints on the axion-neutron coupling constants of GUT axions by using both processes of one- and two-axion exchange.

  4. NMR J-coupling constants in cisplatin derivatives studied by molecular dynamics and relativistic DFT.

    PubMed

    Sutter, Kiplangat; Truflandier, Lionel A; Autschbach, Jochen

    2011-06-01

    Solvent effects on J((195)Pt-(15)N) one-bond nuclear spin-spin coupling constants (J(PtN)) of cisplatin [cis-diamminedichloroplatinum(II)] and three cisplatin derivatives are investigated using a combination of density functional theory (DFT) based ab initio molecular dynamics (aiMD) and all-electron relativistic DFT NMR calculations employing the two-component relativistic zeroth-order regular approximation (ZORA). Good agreement with experiment is obtained when explicit solvent molecules are considered and when the computations are performed with a hybrid functional. Spin-orbit coupling causes only small effects on J(PtN) . Key factors contributing to the magnitude of coupling constants are elucidated, with the most significant being the presence of solvent as well as the quality of the density functional and basis set combination. The solvent effects are of the same magnitude as J(PtN) calculated for gas-phase geometries. However, the trends of J(PtN) among the complexes are already present in the gas phase. Results obtained with a continuum solvent model agree quite well with the aiMD results, provided that the Pt solvent-accessible radius is carefully chosen. The aiMD results support the existence of a partial hydrogen-bond-like inverse-hydration-type interaction affording a weak (1)J(Pt⋅⋅⋅H(w)) coupling between the complexes and the coordinating water molecule.

  5. Theoretical grounds of relativistic methods for calculation of spin-spin coupling constants in nuclear magnetic resonance spectra

    NASA Astrophysics Data System (ADS)

    Rusakova, I. L.; Rusakov, Yu Yu; Krivdin, L. B.

    2016-04-01

    The theoretical grounds of the modern relativistic methods for quantum chemical calculation of spin-spin coupling constants in nuclear magnetic resonance spectra are considered. Examples and prospects of application of relativistic calculations of these constants in the structural studies of organic and heteroorganic compounds are discussed. Practical recommendations on relativistic calculations of spin-spin coupling constants using the available software are given. The bibliography includes 622 references.

  6. Theoretical grounds of relativistic methods for calculation of spin–spin coupling constants in nuclear magnetic resonance spectra

    NASA Astrophysics Data System (ADS)

    Rusakova, I. L.; Rusakov, Yu Yu; Krivdin, L. B.

    2016-04-01

    The theoretical grounds of the modern relativistic methods for quantum chemical calculation of spin–spin coupling constants in nuclear magnetic resonance spectra are considered. Examples and prospects of application of relativistic calculations of these constants in the structural studies of organic and heteroorganic compounds are discussed. Practical recommendations on relativistic calculations of spin–spin coupling constants using the available software are given. The bibliography includes 622 references.

  7. Analytic and 'frozen' coupling constants in QCD up to NNLO from DIS data

    SciTech Connect

    Kotikov, A. V.; Krivokhizhin, V. G. Shaikhatdenov, B. G.

    2012-04-15

    Deep inelastic scattering data on the F{sub 2} structure function provided by the BCDMS, SLAC, and NMC Collaborations are analyzed in the nonsinglet approximation with the analytic and 'frozen' modifications of the strong-coupling constant featuring no unphysical singularity (the Landau pole). Improvement of agreement between theory and experiment, with respect to the case of the standard perturbative definition of {alpha}{sub s} considered recently, is observed and the higher-twist terms are shown to reduce at the next-to-next-to-leading order accuracy thus confirming earlier studies.

  8. NMR spin-spin coupling constants: bond angle dependence of the sign and magnitude of the vicinal (3)JHF coupling.

    PubMed

    Viesser, Renan V; Ducati, Lucas C; Autschbach, Jochen; Tormena, Cláudio F

    2016-08-24

    The dependence of the magnitude and sign of (3)JHFF on the bond angle in fluoro-cycloalkene compounds is evaluated by electronic structure calculations using different levels of theory, viz. DFT, SOPPA(CCSD) and SOPPA(CC2). Localized molecular orbital contributions to (3)JHFF are analyzed to assess which orbitals are responsible for (3)JHFF and which are the most important coupling transmission mechanisms for each compound. Fluoro-ethylene is used as a model system to evaluate the dependence of the (3)JHFF coupling constant on the angle between the σCα-F and σCα'-HF vectors. Through-space and hyperconjugative transmission pathways and ring strain are identified as responsible for the opposite trend between (3)JHFF and bond angle, and for the negative signs obtained for the two molecules, respectively. One of the fluorine lone pairs, σCα'-HF, σCα-F, σCα'-Cβ' bonding orbitals and the σ*Cα-F antibonding orbital are involved in the J-coupling pathways, according to analyses of pairwise-steric and hyperconjugative energies. PMID:27526856

  9. NMR spin-spin coupling constants: bond angle dependence of the sign and magnitude of the vicinal (3)JHF coupling.

    PubMed

    Viesser, Renan V; Ducati, Lucas C; Autschbach, Jochen; Tormena, Cláudio F

    2016-08-24

    The dependence of the magnitude and sign of (3)JHFF on the bond angle in fluoro-cycloalkene compounds is evaluated by electronic structure calculations using different levels of theory, viz. DFT, SOPPA(CCSD) and SOPPA(CC2). Localized molecular orbital contributions to (3)JHFF are analyzed to assess which orbitals are responsible for (3)JHFF and which are the most important coupling transmission mechanisms for each compound. Fluoro-ethylene is used as a model system to evaluate the dependence of the (3)JHFF coupling constant on the angle between the σCα-F and σCα'-HF vectors. Through-space and hyperconjugative transmission pathways and ring strain are identified as responsible for the opposite trend between (3)JHFF and bond angle, and for the negative signs obtained for the two molecules, respectively. One of the fluorine lone pairs, σCα'-HF, σCα-F, σCα'-Cβ' bonding orbitals and the σ*Cα-F antibonding orbital are involved in the J-coupling pathways, according to analyses of pairwise-steric and hyperconjugative energies.

  10. Molecular properties in the Tamm-Dancoff approximation: indirect nuclear spin-spin coupling constants

    NASA Astrophysics Data System (ADS)

    Cheng, Chi Y.; Ryley, Matthew S.; Peach, Michael J. G.; Tozer, David J.; Helgaker, Trygve; Teale, Andrew M.

    2015-07-01

    The Tamm-Dancoff approximation (TDA) can be applied to the computation of excitation energies using time-dependent Hartree-Fock (TD-HF) and time-dependent density-functional theory (TD-DFT). In addition to simplifying the resulting response equations, the TDA has been shown to significantly improve the calculation of triplet excitation energies in these theories, largely overcoming issues associated with triplet instabilities of the underlying reference wave functions. Here, we examine the application of the TDA to the calculation of another response property involving triplet perturbations, namely the indirect nuclear spin-spin coupling constant. Particular attention is paid to the accuracy of the triplet spin-dipole and Fermi-contact components. The application of the TDA in HF calculations leads to vastly improved results. For DFT calculations, the TDA delivers improved stability with respect to geometrical variations but does not deliver higher accuracy close to equilibrium geometries. These observations are rationalised in terms of the ground- and excited-state potential energy surfaces and, in particular, the severity of the triplet instabilities associated with each method. A notable feature of the DFT results within the TDA is their similarity across a wide range of different functionals. The uniformity of the TDA results suggests that some conventional evaluations may exploit error cancellations between approximations in the functional forms and those arising from triplet instabilities. The importance of an accurate treatment of correlation for evaluating spin-spin coupling constants is highlighted by this comparison.

  11. Effect of Hartree-Fock exact exchange on intramolecular magnetic coupling constants of organic diradicals

    SciTech Connect

    Cho, Daeheum; Ko, Kyoung Chul; Lee, Jin Yong; Ikabata, Yasuhiro; Wakayama, Kazufumi; Yoshikawa, Takeshi; Nakai, Hiromi

    2015-01-14

    The intramolecular magnetic coupling constant (J) of diradical systems linked with five- or six-membered aromatic rings was calculated to obtain the scaling factor (experimental J/calculated J ratio) for various density functional theory (DFT) functionals. Scaling factors of group A (PBE, TPSSh, B3LYP, B97-1, X3LYP, PBE0, and BH and HLYP) and B (M06-L, M06, M06-2X, and M06-HF) were shown to decrease as the amount of Hartree-Fock exact exchange (HFx) increases, in other words, overestimation of calculated J becomes more severe as the HFx increases. We further investigated the effect of HFx fraction of DFT functional on J value, spin contamination, and spin density distributions by comparing the B3LYP analogues containing different amount of HFx. It was revealed that spin contamination and spin densities at each atom increases as the HFx increases. Above all, newly developed BLYP-5 functional, which has 5% of HFx, was found to have the scaling factor of 1.029, indicating that calculated J values are very close to that of experimental values without scaling. BLYP-5 has potential to be utilized for accurate evaluation of intramolecular magnetic coupling constant (J) of diradicals linked by five- or six-membered aromatic ring couplers.

  12. Femtosecond frequency comb measurement of absolute frequencies and hyperfine coupling constants in cesium vapor

    SciTech Connect

    Stalnaker, Jason E.; Mbele, Vela; Gerginov, Vladislav; Fortier, Tara M.; Diddams, Scott A.; Hollberg, Leo; Tanner, Carol E.

    2010-04-15

    We report measurements of absolute transition frequencies and hyperfine coupling constants for the 8S{sub 1/2}, 9S{sub 1/2}, 7D{sub 3/2}, and 7D{sub 5/2} states in {sup 133}Cs vapor. The stepwise excitation through either the 6P{sub 1/2} or 6P{sub 3/2} intermediate state is performed directly with broadband laser light from a stabilized femtosecond laser optical-frequency comb. The laser beam is split, counterpropagated, and focused into a room-temperature Cs vapor cell. The repetition rate of the frequency comb is scanned and we detect the fluorescence on the 7P{sub 1/2,3/2{yields}}6S{sub 1/2} branches of the decay of the excited states. The excitations to the different states are isolated by the introduction of narrow-bandwidth interference filters in the laser beam paths. Using a nonlinear least-squares method we find measurements of transition frequencies and hyperfine coupling constants that are in agreement with other recent measurements for the 8S state and provide improvement by 2 orders of magnitude over previously published results for the 9S and 7D states.

  13. NMR spin-spin coupling constants in polymethine dyes as polarity indicators.

    PubMed

    Murugan, N Arul; Aidas, Kestutis; Kongsted, Jacob; Rinkevicius, Zilvinas; Ågren, Hans

    2012-09-10

    Herein, we explore the use of spin-spin coupling constants (SSCCs) in merocyanine (MCYNE) dyes as indicators of polarity. For this purpose, we use Car-Parrinello hybrid quantum mechanics/molecular mechanics (QM/MM) to determine the structures of MCYNE in solvents of different polarity, followed by computations of the SSCCs by using QM/MM linear-response theory. The molecular geometry of MCYNE switches between neutral, cyanine-like, and zwitterionic depending on the polarity of the solvent. This structural variation is clearly reflected in the proton SSCCs in the polymethine backbone, which are highly sensitive to the dielectric nature of the environment; this mechanism can be used as a "polarity indicator" for different microenvironments. This result is highlighted by computing the SSCCs of the MCYNE probe in the cavity of the beta-lactoglobulin protein. The computed SSCCs clearly indicate a non-polar hydrophobic dielectric nature of this cavity. PMID:22887687

  14. New limits on coupling of fundamental constants to gravity using 87Sr optical lattice clocks.

    PubMed

    Blatt, S; Ludlow, A D; Campbell, G K; Thomsen, J W; Zelevinsky, T; Boyd, M M; Ye, J; Baillard, X; Fouché, M; Le Targat, R; Brusch, A; Lemonde, P; Takamoto, M; Hong, F-L; Katori, H; Flambaum, V V

    2008-04-11

    The 1S0-3P0 clock transition frequency nuSr in neutral 87Sr has been measured relative to the Cs standard by three independent laboratories in Boulder, Paris, and Tokyo over the last three years. The agreement on the 1 x 10(-15) level makes nuSr the best agreed-upon optical atomic frequency. We combine periodic variations in the 87Sr clock frequency with 199Hg+ and H-maser data to test local position invariance by obtaining the strongest limits to date on gravitational-coupling coefficients for the fine-structure constant alpha, electron-proton mass ratio mu, and light quark mass. Furthermore, after 199Hg+, 171Yb+, and H, we add 87Sr as the fourth optical atomic clock species to enhance constraints on yearly drifts of alpha and mu.

  15. New Limits on Coupling of Fundamental Constants to Gravity Using {sup 87}Sr Optical Lattice Clocks

    SciTech Connect

    Blatt, S.; Ludlow, A. D.; Campbell, G. K.; Thomsen, J. W.; Zelevinsky, T.; Boyd, M. M.; Ye, J.; Baillard, X.; Fouche, M.; Le Targat, R.; Brusch, A.; Lemonde, P.; Takamoto, M.; Hong, F.-L.; Katori, H.; Flambaum, V. V.

    2008-04-11

    The {sup 1}S{sub 0}-{sup 3}P{sub 0} clock transition frequency {nu}{sub Sr} in neutral {sup 87}Sr has been measured relative to the Cs standard by three independent laboratories in Boulder, Paris, and Tokyo over the last three years. The agreement on the 1x10{sup -15} level makes {nu}{sub Sr} the best agreed-upon optical atomic frequency. We combine periodic variations in the {sup 87}Sr clock frequency with {sup 199}Hg{sup +} and H-maser data to test local position invariance by obtaining the strongest limits to date on gravitational-coupling coefficients for the fine-structure constant {alpha}, electron-proton mass ratio {mu}, and light quark mass. Furthermore, after {sup 199}Hg{sup +}, {sup 171}Yb{sup +}, and H, we add {sup 87}Sr as the fourth optical atomic clock species to enhance constraints on yearly drifts of {alpha} and {mu}.

  16. Nuclear Quadrupole Coupling Constants in Niobium Pentachloride and Related Compounds (I) Halogen Nuclei

    NASA Astrophysics Data System (ADS)

    Okubo, Noriaki

    1982-02-01

    35Cl NQR spectrum in NbCl5 has been investigated from 4.2 K to 480 K. The lines of about 7 MHz have larger multiplicity and show positive temperature dependence in contrast to the usual negative one for the line of about 13 MHz. The former lines are further separated into two groups having different temperature dependences. The expressions for the chlorine coupling constant are derived according to Townes-Dailey’s method on the basis of the pπ-dπ bond. The NQR data are analysed and the lines are assigned to the axial, equatorial and bridging chlorine atoms in the Nb2Cl10 dimer. The theory is applied to other related compounds.

  17. Nuclear Quadrupole Coupling Constants of Two Chemically Distinct Nitrogen Atoms in 4-Aminobenzonitrile

    PubMed Central

    2014-01-01

    The rotational spectrum of 4-aminobenzonitrile in the gas phase between 2 and 8.5 GHz is reported. Due to the two chemically distinct nitrogen atoms, the observed transitions showed a rich hyperfine structure. From the determination of the nuclear quadrupole coupling constants, information about the electronic environment of these atoms could be inferred. The results are compared to data for related molecules, especially with respect to the absence of dual fluorescence in 4-aminobenzonitrile. In addition, the two-photon ionization spectrum of this molecule was recorded using a time-of-flight mass spectrometer integrated into the setup. This new experimental apparatus is presented here for the first time. PMID:24911139

  18. Measurement of the strong coupling constant from inclusive jet production at the Tevatron pp collider.

    PubMed

    Affolder, T; Akimoto, H; Akopian, A; Albrow, M G; Amaral, P; Amidei, D; Anikeev, K; Antos, J; Apollinari, G; Arisawa, T; Artikov, A; Asakawa, T; Ashmanskas, W; Azfar, F; Azzi-Bacchetta, P; Bacchetta, N; Bachacou, H; Bailey, S; de Barbaro, P; Barbaro-Galtieri, A; Barnes, V E; Barnett, B A; Baroiant, S; Barone, M; Bauer, G; Bedeschi, F; Belforte, S; Bell, W H; Bellettini, G; Bellinger, J; Benjamin, D; Bensinger, J; Beretvas, A; Berge, J P; Berryhill, J; Bhatti, A; Binkley, M; Bisello, D; Bishai, M; Blair, R E; Blocker, C; Bloom, K; Blumenfeld, B; Blusk, S R; Bocci, A; Bodek, A; Bokhari, W; Bolla, G; Bonushkin, Y; Bortoletto, D; Boudreau, J; Brandl, A; van den Brink, S; Bromberg, C; Brozovic, M; Brubaker, E; Bruner, N; Buckley-Geer, E; Budagov, J; Budd, H S; Burkett, K; Busetto, G; Byon-Wagner, A; Byrum, K L; Cabrera, S; Calafiura, P; Campbell, M; Carithers, W; Carlson, J; Carlsmith, D; Caskey, W; Castro, A; Cauz, D; Cerri, A; Chan, A W; Chang, P S; Chang, P T; Chapman, J; Chen, C; Chen, Y C; Cheng, M-T; Chertok, M; Chiarelli, G; Chirikov-Zorin, I; Chlachidze, G; Chlebana, F; Christofek, L; Chu, M L; Chung, Y S; Ciobanu, C I; Clark, A G; Colijn, A P; Connolly, A; Convery, M; Conway, J; Cordelli, M; Cranshaw, J; Cropp, R; Culbertson, R; Dagenhart, D; D'Auria, S; DeJongh, F; Dell'Agnello, S; Dell'Orso, M; Demers, S; Demortier, L; Deninno, M; Derwent, P F; Devlin, T; Dittmann, J R; Dominguez, A; Donati, S; Done, J; D'Onofrio, M; Dorigo, T; Eddy, N; Einsweiler, K; Elias, J E; Engels, E; Erbacher, R; Errede, D; Errede, S; Fan, Q; Fang, H-C; Feild, R G; Fernandez, J P; Ferretti, C; Field, R D; Fiori, I; Flaugher, B; Foster, G W; Franklin, M; Freeman, J; Friedman, J; Fukui, Y; Furic, I; Galeotti, S; Gallas, A; Gallinaro, M; Gao, T; Garcia-Sciveres, M; Garfinkel, A F; Gatti, P; Gay, C; Gerdes, D W; Giannetti, P; Giromini, P; Glagolev, V; Glenzinski, D; Gold, M; Goldstein, J; Gorelov, I; Goshaw, A T; Gotra, Y; Goulianos, K; Green, C; Grim, G; Gris, P; Groer, L; Grosso-Pilcher, C; Guenther, M; Guillian, G; Guimaraes da Costa, J; Haas, R M; Haber, C; Hahn, S R; Hall, C; Handa, T; Handler, R; Hao, W; Happacher, F; Hara, K; Hardman, A D; Harris, R M; Hartmann, F; Hatakeyama, K; Hauser, J; Heinrich, J; Heiss, A; Herndon, M; Hill, C; Hoffman, K D; Holck, C; Hollebeek, R; Holloway, L; Huffman, B T; Hughes, R; Huston, J; Huth, J; Ikeda, H; Incandela, J; Introzzi, G; Ivanov, A; Iwai, J; Iwata, Y; James, E; Jones, M; Joshi, U; Kambara, H; Kamon, T; Kaneko, T; Karr, K; Kartal, S; Kasha, H; Kato, Y; Keaffaber, T A; Kelley, K; Kelly, M; Khazins, D; Kikuchi, T; Kilminster, B; Kim, B J; Kim, D H; Kim, H S; Kim, M J; Kim, S B; Kim, S H; Kim, Y K; Kirby, M; Kirk, M; Kirsch, L; Klimenko, S; Koehn, P; Kondo, K; Konigsberg, J; Korn, A; Korytov, A; Kovacs, E; Kroll, J; Kruse, M; Kuhlmann, S E; Kurino, K; Kuwabara, T; Laasanen, A T; Lai, N; Lami, S; Lammel, S; Lancaster, J; Lancaster, M; Lander, R; Lath, A; Latino, G; LeCompte, T; Lee, A M; Lee, K; Leone, S; Lewis, J D; Lindgren, M; Liss, T M; Liu, J B; Liu, Y C; Litvintsev, D O; Lobban, O; Lockyer, N; Loken, J; Loreti, M; Lucchesi, D; Lukens, P; Lusin, S; Lyons, L; Lys, J; Madrak, R; Maeshima, K; Maksimovic, P; Malferrari, L; Mangano, M; Mariotti, M; Martignon, G; Martin, A; Matthews, J A J; Mayer, J; Mazzanti, P; McFarland, K S; McIntyre, P; McKigney, E; Menguzzato, M; Menzione, A; Merkel, P; Mesropian, C; Meyer, A; Miao, T; Miller, R; Miller, J S; Minato, H; Miscetti, S; Mishina, M; Mitselmakher, G; Miyazaki, Y; Moggi, N; Moore, E; Moore, R; Morita, Y; Moulik, T; Mulhearn, M; Mukherjee, A; Muller, T; Munar, A; Murat, P; Murgia, S; Nachtman, J; Nagaslaev, V; Nahn, S; Nakada, H; Nakano, I; Nelson, C; Nelson, T; Neu, C; Neuberger, D; Newman-Holmes, C; Ngan, C-Y P; Niu, H; Nodulman, L; Nomerotski, A; Oh, S H; Oh, Y D; Ohmoto, T; Ohsugi, T; Oishi, R; Okusawa, T; Olsen, J; Orejudos, W; Pagliarone, C; Palmonari, F; Paoletti, R; Papadimitriou, V; Partos, D; Patrick, J; Pauletta, G; Paulini, M; Paus, C; Pellett, D; Pescara, L; Phillips, T J; Piacentino, G; Pitts, K T; Pompos, A; Pondrom, L; Pope, G; Popovic, M; Prokoshin, F; Proudfoot, J; Ptohos, F; Pukhov, O; Punzi, G; Rakitine, A; Ratnikov, F; Reher, D; Reichold, A; Renton, P; Ribon, A; Riegler, W; Rimondi, F; Ristori, L; Riveline, M; Robertson, W J; Robinson, A; Rodrigo, T; Rolli, S; Rosenson, L; Roser, R; Rossin, R; Rott, C; Roy, A; Ruiz, A; Safonov, A; St Denis, R; Sakumoto, W K; Saltzberg, D; Sanchez, C; Sansoni, A; Santi, L; Sato, H; Savard, P; Schlabach, P; Schmidt, E E; Schmidt, M P; Schmitt, M; Scodellaro, L; Scott, A; Scribano, A; Segler, S; Seidel, S; Seiya, Y; Semenov, A; Semeria, F; Shah, T; Shapiro, M D; Shepard, P F; Shibayama, T; Shimojima, M; Shochet, M; Sidoti, A; Siegrist, J; Sill, A; Sinervo, P; Singh, P; Slaughter, A J; Sliwa, K; Smith, C; Snider, F D; Solodsky, A; Spalding, J; Speer, T; Sphicas, P; Spinella, F; Spiropulu, M

    2002-01-28

    We report a measurement of the strong coupling constant, alpha(s)(MZ), extracted from inclusive jet production in pp collisions at square root[s] = 1800 GeV. The QCD prediction for the evolution of alpha(s) with jet transverse energy ET is tested over the range 40

  19. High magnetic exchange coupling constants: a density functional theory based study of substituted Schlenk diradicals.

    PubMed

    Latif, Iqbal A; Hansda, Shekhar; Datta, Sambhu N

    2012-08-23

    The Schlenk diradical has been known since 1915. After a detailed experimental work by Rajca, its magnetic nature has remained more or less unexplored. We have investigated by quantum chemical calculations the nature of magnetic coupling in 11 substituted Schlenk diradicals. Substitution has been considered at the fifth carbon atom of the meta-phenylene moiety. The UB3LYP method has been used to study 12 diradicals including the original one. The 6-311G(d,p) basis set has been employed for optimization of molecular geometry in both singlet and triplet states for each species. The singlet optimization has led to the optimization of the broken-symmetry structure for 10 species including the unsubstituted one. This development makes it possible to carry out further broken symmetry calculations in two ways. The triplet calculation has been done using 6-311++G(d,p) basis set and the optimized triplet geometry in both procedures. The broken symmetry calculations have used the optimized geometries of either the triplet states or the broken symmetry solutions. The first method leads to the prediction of electron paramagnetic resonance (EPR) compatible magnetic exchange coupling constant (J) in the range 517-617 cm(-1). A direct optimization of the broken symmetry geometry gives rise to a lower estimate of J, in the range of 411-525 cm(-1) and compatible with macroscopic Curie studies. The calculated J for the unsubstituted Schlenk diradical is 512 cm(-1) that can be compared with 455 cm(-1) estimated by Rajca. In both cases, introduction of groups with +M and +I effects (Ingold's notation) decreases the J value from that for the unsubstituted Schlenk diradical while -I and -M groups at the same position increases J. These trends have been explained in terms of Hammett constants, atomic spin densities, and dihedral angles.

  20. Numerical studies of the ABJM theory for arbitrary N at arbitrary coupling constant

    NASA Astrophysics Data System (ADS)

    Hanada, Masanori; Honda, Masazumi; Honma, Yoshinori; Nishimura, Jun; Shiba, Shotaro; Yoshida, Yutaka

    2012-05-01

    We show that the ABJM theory, which is an {N} = {6} superconformal U( N) × U( N) Chern-Simons gauge theory, can be studied for arbitrary N at arbitrary coupling constant by applying a simple Monte Carlo method to the matrix model that can be derived from the theory by using the localization technique. This opens up the possibility of probing the quantum aspects of M-theory and testing the AdS4/CFT3 duality at the quantum level. Here we calculate the free energy, and confirm the N 3/2 scaling in the M-theory limit predicted from the gravity side. We also find that our results nicely interpolate the analytical formulae proposed previously in the M-theory and type IIA regimes. Furthermore, we show that some results obtained by the Fermi gas approach can be clearly understood from the constant map contribution obtained by the genus expansion. The method can be easily generalized to the calculations of BPS operators and to other theories that reduce to matrix models.

  1. Nonadiabatic rate constants for proton transfer and proton-coupled electron transfer reactions in solution: Effects of quadratic term in the vibronic coupling expansion.

    PubMed

    Soudackov, Alexander V; Hammes-Schiffer, Sharon

    2015-11-21

    Rate constant expressions for vibronically nonadiabatic proton transfer and proton-coupled electron transfer reactions are presented and analyzed. The regimes covered include electronically adiabatic and nonadiabatic reactions, as well as high-frequency and low-frequency proton donor-acceptor vibrational modes. These rate constants differ from previous rate constants derived with the cumulant expansion approach in that the logarithmic expansion of the vibronic coupling in terms of the proton donor-acceptor distance includes a quadratic as well as a linear term. The analysis illustrates that inclusion of this quadratic term in the framework of the cumulant expansion framework may significantly impact the rate constants at high temperatures for proton transfer interfaces with soft proton donor-acceptor modes that are associated with small force constants and weak hydrogen bonds. The effects of the quadratic term may also become significant in these regimes when using the vibronic coupling expansion in conjunction with a thermal averaging procedure for calculating the rate constant. In this case, however, the expansion of the coupling can be avoided entirely by calculating the couplings explicitly for the range of proton donor-acceptor distances sampled. The effects of the quadratic term for weak hydrogen-bonding systems are less significant for more physically realistic models that prevent the sampling of unphysical short proton donor-acceptor distances. Additionally, the rigorous relation between the cumulant expansion and thermal averaging approaches is clarified. In particular, the cumulant expansion rate constant includes effects from dynamical interference between the proton donor-acceptor and solvent motions and becomes equivalent to the thermally averaged rate constant when these dynamical effects are neglected. This analysis identifies the regimes in which each rate constant expression is valid and thus will be important for future applications to proton

  2. Nonadiabatic rate constants for proton transfer and proton-coupled electron transfer reactions in solution: Effects of quadratic term in the vibronic coupling expansion

    SciTech Connect

    Soudackov, Alexander V.; Hammes-Schiffer, Sharon

    2015-11-21

    Rate constant expressions for vibronically nonadiabatic proton transfer and proton-coupled electron transfer reactions are presented and analyzed. The regimes covered include electronically adiabatic and nonadiabatic reactions, as well as high-frequency and low-frequency proton donor-acceptor vibrational modes. These rate constants differ from previous rate constants derived with the cumulant expansion approach in that the logarithmic expansion of the vibronic coupling in terms of the proton donor-acceptor distance includes a quadratic as well as a linear term. The analysis illustrates that inclusion of this quadratic term in the framework of the cumulant expansion framework may significantly impact the rate constants at high temperatures for proton transfer interfaces with soft proton donor-acceptor modes that are associated with small force constants and weak hydrogen bonds. The effects of the quadratic term may also become significant in these regimes when using the vibronic coupling expansion in conjunction with a thermal averaging procedure for calculating the rate constant. In this case, however, the expansion of the coupling can be avoided entirely by calculating the couplings explicitly for the range of proton donor-acceptor distances sampled. The effects of the quadratic term for weak hydrogen-bonding systems are less significant for more physically realistic models that prevent the sampling of unphysical short proton donor-acceptor distances. Additionally, the rigorous relation between the cumulant expansion and thermal averaging approaches is clarified. In particular, the cumulant expansion rate constant includes effects from dynamical interference between the proton donor-acceptor and solvent motions and becomes equivalent to the thermally averaged rate constant when these dynamical effects are neglected. This analysis identifies the regimes in which each rate constant expression is valid and thus will be important for future applications to proton

  3. Nonadiabatic rate constants for proton transfer and proton-coupled electron transfer reactions in solution: Effects of quadratic term in the vibronic coupling expansion.

    PubMed

    Soudackov, Alexander V; Hammes-Schiffer, Sharon

    2015-11-21

    Rate constant expressions for vibronically nonadiabatic proton transfer and proton-coupled electron transfer reactions are presented and analyzed. The regimes covered include electronically adiabatic and nonadiabatic reactions, as well as high-frequency and low-frequency proton donor-acceptor vibrational modes. These rate constants differ from previous rate constants derived with the cumulant expansion approach in that the logarithmic expansion of the vibronic coupling in terms of the proton donor-acceptor distance includes a quadratic as well as a linear term. The analysis illustrates that inclusion of this quadratic term in the framework of the cumulant expansion framework may significantly impact the rate constants at high temperatures for proton transfer interfaces with soft proton donor-acceptor modes that are associated with small force constants and weak hydrogen bonds. The effects of the quadratic term may also become significant in these regimes when using the vibronic coupling expansion in conjunction with a thermal averaging procedure for calculating the rate constant. In this case, however, the expansion of the coupling can be avoided entirely by calculating the couplings explicitly for the range of proton donor-acceptor distances sampled. The effects of the quadratic term for weak hydrogen-bonding systems are less significant for more physically realistic models that prevent the sampling of unphysical short proton donor-acceptor distances. Additionally, the rigorous relation between the cumulant expansion and thermal averaging approaches is clarified. In particular, the cumulant expansion rate constant includes effects from dynamical interference between the proton donor-acceptor and solvent motions and becomes equivalent to the thermally averaged rate constant when these dynamical effects are neglected. This analysis identifies the regimes in which each rate constant expression is valid and thus will be important for future applications to proton

  4. Determination of the hyperfine coupling constant of the cesium 7S1/2 state

    NASA Astrophysics Data System (ADS)

    Yang, Guang; Wang, Jie; Yang, Baodong; Wang, Junmin

    2016-08-01

    We report the hyperfine splitting (HFS) measurement of the cesium (Cs) 7S1/2 state by optical–optical double-resonance spectroscopy with the Cs 6S1/2–6P3/2–7S1/2 (852 nm  +  1470 nm) ladder-type system. The HFS frequency calibration is performed by employing a phase-type waveguide electro-optic modulator together with a stable confocal Fabry–Perot cavity. From the measured HFS between the F″  =  3 and F″  =  4 manifolds of the Cs 7S1/2 state (HFS  =  2183.273  ±  0.062 MHz), we have determined the magnetic dipole hyperfine coupling constant (A  =  545.818  ±  0.016 MHz), which is in good agreement with the previous work but much more precise.

  5. Determination of the hyperfine coupling constant of the cesium 7S1/2 state

    NASA Astrophysics Data System (ADS)

    Yang, Guang; Wang, Jie; Yang, Baodong; Wang, Junmin

    2016-08-01

    We report the hyperfine splitting (HFS) measurement of the cesium (Cs) 7S1/2 state by optical-optical double-resonance spectroscopy with the Cs 6S1/2-6P3/2-7S1/2 (852 nm  +  1470 nm) ladder-type system. The HFS frequency calibration is performed by employing a phase-type waveguide electro-optic modulator together with a stable confocal Fabry-Perot cavity. From the measured HFS between the F″  =  3 and F″  =  4 manifolds of the Cs 7S1/2 state (HFS  =  2183.273  ±  0.062 MHz), we have determined the magnetic dipole hyperfine coupling constant (A  =  545.818  ±  0.016 MHz), which is in good agreement with the previous work but much more precise.

  6. Thermodynamics of dipolar hard spheres with low-to-intermediate coupling constants.

    PubMed

    Elfimova, Ekaterina A; Ivanov, Alexey O; Camp, Philip J

    2012-08-01

    The thermodynamic properties of the dipolar hard-sphere fluid are studied using theory and simulation. A new theory is derived using a convenient mathematical approximation for the Helmholtz free energy relative to that for the hard-sphere fluid. The approximation is designed to give the correct low-density virial expansion. New theoretical and numerical results for the fourth virial coefficient are given. Predictions of thermodynamic functions for dipolar coupling constants λ=1 and 2 show excellent agreement with simulation results, even at the highest value of the particle volume fraction φ. For higher values of λ, there are deviations at high volume fractions, but the correct low-density behavior is retained. The theory is compared critically against the established thermodynamic perturbation theory; it gives significant improvements at low densities and is more convenient in terms of the required numerics. Dipolar hard spheres provide a basic model for ferrofluids, and the theory is accurate for typical experimental parameters λ

  7. Determination of the pion-nucleon coupling constant and scattering lengths

    NASA Astrophysics Data System (ADS)

    Ericson, T. E.; Loiseau, B.; Thomas, A. W.

    2002-07-01

    We critically evaluate the isovector Goldberger-Miyazawa-Oehme (GMO) sum rule for forward πN scattering using the recent precision measurements of π-p and π-d scattering lengths from pionic atoms. We deduce the charged-pion-nucleon coupling constant, with careful attention to systematic and statistical uncertainties. This determination gives, directly from data, g2c(GMO)/ 4π=14.11+/-0.05(statistical)+/-0.19(systematic) or f2c/4π=0.0783(11). This value is intermediate between that of indirect methods and the direct determination from backward np differential scattering cross sections. We also use the pionic atom data to deduce the coherent symmetric and antisymmetric sums of the pion-proton and pion-neutron scattering lengths with high precision, namely, (aπ-p+aπ-n)/2=[- 12+/-2(statistical)+/-8(systematic)]×10-4 m-1π and (aπ-p-aπ- n)/2=[895+/-3(statistical)+/-13 (systematic)]×10-4 m-1π. For the need of the present analysis, we improve the theoretical description of the pion-deuteron scattering length.

  8. Towards quantifying the role of exact exchange in the prediction hydrogen bond spin-spin coupling constants involving fluorine.

    PubMed

    San Fabián, J; Omar, S; García de la Vega, J M

    2016-08-28

    The effect of a fraction of Hartree-Fock exchange on the calculated spin-spin coupling constants involving fluorine through a hydrogen bond is analyzed in detail. Coupling constants calculated using wavefunction methods are revisited in order to get high-level calculations using the same basis set. Accurate MCSCF results are obtained using an additive approach. These constants and their contributions are used as a reference for density functional calculations. Within the density functional theory, the Hartree-Fock exchange functional is split in short- and long-range using a modified version of the Coulomb-attenuating method with the SLYP functional as well as with the original B3LYP. Results support the difficulties for calculating hydrogen bond coupling constants using density functional methods when fluorine nuclei are involved. Coupling constants are very sensitive to the Hartree-Fock exchange and it seems that, contrary to other properties, it is important to include this exchange for short-range interactions. Best functionals are tested in two different groups of complexes: those related with anionic clusters of type [F(HF)n](-) and those formed by difluoroacetylene and either one or two hydrogen fluoride molecules. PMID:27586916

  9. What determines the sign of the Fermi-contact contribution to the NMR spin spin coupling constant?

    NASA Astrophysics Data System (ADS)

    Del Bene, Janet E.; Elguero, José

    2003-11-01

    The Dirac vector model for the sign of the spin-spin coupling constant ( J) between a pair of atoms states that one-bond coupling constants are positive, two-bond negative, three-bond positive, etc. However, this rule is often violated. In an attempt to understand the sign of J, we propose a new model, the Nuclear magnetic resonance triplet wavefunction model (NMRTWM) which is based on the phases of excited triplet state wavefunctions, and the response of magnetic nuclei to these phases. The model demonstrates that, (1) the excited states which contribute to the coupling constant do so in a regular manner; (2) the sign of an individual contribution is determined by the nodal character of the excited-state wavefunction and the response of the nuclei to the phases of this function; and (3) the sign of the total coupling constant is the result of competing positive and negative contributions from various states. NMRTWM provides a fundamental explanation for both the successes and failures of the Dirac vector model, and can be used to gain insight into some puzzling results for the orientation dependence of F-F coupling between two HF molecules.

  10. Non-empirical calculations of NMR indirect carbon-carbon coupling constants. Part 9--Bicyclobutane-containing polycycloalkanes.

    PubMed

    Krivdin, Leonid B

    2004-10-01

    13C--(13)C spin-spin coupling constants characterizing the bicyclobutane moiety of seven well-known bicyclobutane-containing polycycloalkanes were calculated at the SOPPA level. Benchmark calculations on tricyclopentane and octabisvalene revealed an appropriate level of theory and sufficient quality of basis sets used to perform geometry searches and to calculate spin-spin coupling constants. Several experimental uncertainties were resolved and a number of interesting couplings were predicted. The most interesting trend observed in this series of polycycloalkanes is the marked increase (decrease in absolute value) of J(C,C) between bridgehead carbons with increase in the puckering angle of the bicyclobutane moiety. This predicts almost zero coupling between bridgehead carbons of tricyclopentane and explains the positive J(C,C) in tetrahedrane in contrast to the negative bridgehead-bridgehead J(C,C) in bicyclobutane.

  11. Nonadiabatic rate constants for proton transfer and proton-coupled electron transfer reactions in solution: Effects of quadratic term in the vibronic coupling expansion

    SciTech Connect

    Soudackov, Alexander; Hammes-Schiffer, Sharon

    2015-11-17

    Rate constant expressions for vibronically nonadiabatic proton transfer and proton-coupled electron transfer reactions are presented and analyzed. The regimes covered include electronically adiabatic and nonadiabatic reactions, as well as high-frequency and low-frequency regimes for the proton donor-acceptor vibrational mode. These rate constants differ from previous rate constants derived with the cumulant expansion approach in that the logarithmic expansion of the vibronic coupling in terms of the proton donor-acceptor distance includes a quadratic as well as a linear term. The analysis illustrates that inclusion of this quadratic term does not significantly impact the rate constants derived using the cumulant expansion approach in any of the regimes studied. The effects of the quadratic term may become significant when using the vibronic coupling expansion in conjunction with a thermal averaging procedure for calculating the rate constant, however, particularly at high temperatures and for proton transfer interfaces with extremely soft proton donor-acceptor modes that are associated with extraordinarily weak hydrogen bonds. Even with the thermal averaging procedure, the effects of the quadratic term for weak hydrogen-bonding systems are less significant for more physically realistic models that prevent the sampling of unphysical short proton donor-acceptor distances, and the expansion of the coupling can be avoided entirely by calculating the couplings explicitly for the range of proton donor-acceptor distances. This analysis identifies the regimes in which each rate constant expression is valid and thus will be important for future applications to proton transfer and proton-coupled electron transfer in chemical and biological processes. We are grateful for support from National Institutes of Health Grant GM056207 (applications to enzymes) and the Center for Molecular Electrocatalysis, an Energy Frontier Research Center funded by the U.S. Department of Energy

  12. Density-Functional and Coupled-Cluster Singles-and-Doubles Calculations of the Nuclear Shielding and Indirect Nuclear Spin-Spin Coupling Constants of o-Benzyne.

    PubMed

    Helgaker, Trygve; Jaszuński, Michał

    2007-01-01

    Density-functional theory (DFT) and coupled-cluster singles-and-doubles (CCSD) theory are applied to compute the nuclear magnetic resonance (NMR) shielding and indirect nuclear spin-spin coupling constants of o-benzyne, whose biradical nature makes it difficult to study both experimentally and theoretically. Because of near-equilibrium triplet instabilities that follow from its biradical character, the calculated DFT NMR properties of o-benzyne are unusually sensitive to details of the exchange-correlation functional. However, this sensitivity is greatly reduced if these properties are calculated at the equilibrium of the chosen functional. A strong correlation is demonstrated between the quality of the calculated indirect spin-spin coupling constants and the quality of the calculated lowest triplet excitation energy in o-benzyne. Orbital-unrelaxed coupled-cluster theory should be less affected by such instabilities, and the CCSD NMR properties were only calculated at the experimental equilibrium geometry. For the shielding constants, the results in best agreement with experimental results are obtained with CCSD theory and with the Keal-Tozer KT1 and KT2 functionals. For the triply bonded carbon atoms, these models yield an isotropic shielding of 1.3, -3.3, and -1.2 ppm, respectively, compared with the experimentally observed shielding of 3.7 ppm for incarcerated o-benzyne. For the indirect spin-spin coupling constants, the CCSD model and the Perdew-Burke-Ernzerhof functional both yield reliable results; for the most interesting spin-spin coupling constant, (1)J (C⋮C), we obtain 210 and 209 Hz with these two models, respectively, somewhat above the recently reported experimental value of 177.9 ± 0.7 Hz for o-benzyne inside a molecular container, suggesting large incarceration effects.

  13. A General Method for Extracting Individual Coupling Constants from Crowded 1H NMR Spectra

    PubMed Central

    Foroozandeh, Mohammadali; Nilsson, Mathias; Morris, Gareth A.

    2015-01-01

    Abstract Couplings between protons, whether scalar or dipolar, provide a wealth of structural information. Unfortunately, the high number of 1H‐1H couplings gives rise to complex multiplets and severe overlap in crowded spectra, greatly complicating their measurement. Many different methods exist for disentangling couplings, but none approaches optimum resolution. Here, we present a general new 2D J‐resolved method, PSYCHEDELIC, in which all homonuclear couplings are suppressed in F 2, and only the couplings to chosen spins appear, as simple doublets, in F 1. This approaches the theoretical limit for resolving 1H‐1H couplings, with close to natural linewidths and with only chemical shifts in F 2. With the same high sensitivity and spectral purity as the parent PSYCHE pure shift experiment, PSYCHEDELIC offers a robust method for chemists seeking to exploit couplings for structural, conformational, or stereochemical analyses. PMID:26636773

  14. Electric field effects on one-bond indirect spin-spin coupling constants and possible biomolecular perspectives.

    PubMed

    Sahakyan, Aleksandr B; Shahkhatuni, Aleksan G; Shahkhatuni, Astghik A; Panosyan, Henry A

    2008-04-24

    Electric field (EF) induced changes of one-bond indirect spin-spin coupling constants are investigated on a wide range of molecules including peptide models. EFs were both externally applied and internally calculated without external EF application by the hybrid density functional theory method. Reliable agreement with experimental data has been obtained for calculated one-bond J-couplings. The role of the EF sign and direction, internal and induced components, hydrogen bonding, internuclear distance and hyperconjugative interactions on the one-bond J-coupling vs EF interconnection is analyzed. A linear dependence of 1J on EF projection along the bond is obtained, if the bound atoms possess different enough electron densities and an EF determined by the electronic polarization exists along the bond. Accentuating the 1JNH couplings as possible EF sensitive parameters, a systematic study is done in two sets of molecules with a large variation of the native internal EF value. The most EF affected component of the 1JNH coupling constant is the spin-dipole term of Ramsey's formulation; however, in the total J-coupling formation, the EF influence on the Fermi contact term is the most significant. The induced EF projection along the bond is 6.7 times weaker in magnitude than the simulated external uniform field. The absolute EF dependence of the one-bond J-coupling involves only the internal field, which is the sum of the induced field (if the external field exists) and the internuclear field determined by the native polarization. That linear and universal dependence joins the corresponding couplings in a diverse set of molecules under various electrostatic conditions. Many types of the one-bond J-couplings can be potentially measured in biomolecules, and the study of their relation with the electrostatic properties at the corresponding sites opens a new avenue to the full exploitation of the NMR measurable parameters with novel and exciting applications. PMID:18363392

  15. Stereochemical dependence of 3JCH coupling constants in 2-substituted 4-t-butyl-cyclohexanone and their alcohol derivatives.

    PubMed

    Favaro, Denize C; Ducati, Lucas C; dos Santos, Francisco P; Contreras, Rubén H; Tormena, Cláudio F

    2011-12-22

    Theoretical and experimental studies on (3)J(C2H6eq) NMR spin-spin coupling constants in both the 2-X-4-t-butyl-cyclohexanone (X = H, CH(3), F, Cl, and Br) and in their alcohol derivatives series are reported. Results thus found are rationalized in terms of the transmission of the Fermi contact contribution to such couplings. To this end, dependencies of (3)J(C2H6eq) couplings versus the C(2)-C(1)-C(6) angle are compared in both series for equatorial and axial X orientations. The main trend is described in terms of the rear lobes interaction. Besides, for X = halogen atom in equatorial orientation a rather strong interaction between oxygen and halogen lone pairs is observed, and its influence on (3)J(C2H6eq) couplings is discussed and rationalized in terms of different Fermi contact transmission pathways.

  16. Determination of size and sign of hetero-nuclear coupling constants from 2D 19F-13C correlation spectra

    NASA Astrophysics Data System (ADS)

    Ampt, Kirsten A. M.; Aspers, Ruud L. E. G.; Dvortsak, Peter; van der Werf, Ramon M.; Wijmenga, Sybren S.; Jaeger, Martin

    2012-02-01

    Fluorinated organic compounds have become increasingly important within the polymer and the pharmaceutical industry as well as for clinical applications. For the structural elucidation of such compounds, NMR experiments with fluorine detection are of great value due to the favorable NMR properties of the fluorine nucleus. For the investigation of three fluorinated compounds, triple resonance 2D HSQC and HMBC experiments were adopted to fluorine detection with carbon and/or proton decoupling to yield F-C, F-C{H}, F-C{Cacq} and F-C{H,Cacq} variants. Analysis of E.COSY type cross-peak patterns in the F-C correlation spectra led, apart from the chemical shift assignments, to determination of size and signs of the JCH, JCF, and JHF coupling constants. In addition, the fully coupled F-C HMQC spectrum of steroid 1 was interpreted in terms of E.COSY type patterns. This example shows how coupling constants due to different nuclei can be determined together with their relative signs from a single spectrum. The analysis of cross-peak patterns, as presented here, not only provides relatively straightforward routes to the determination of size and sign of hetero-nuclear J-couplings in fluorinated compounds, it also provides new and easy ways for the determination of residual dipolar couplings and thus for structure elucidation. The examples and results presented in this study may contribute to a better interpretation and understanding of various F-C correlation experiments and thereby stimulate their utilization.

  17. Probing the flexibility of internal rotation in silylated phenols with the NMR scalar spin-spin coupling constants.

    PubMed

    Sychrovský, Vladimír; Benda, Ladislav; Prokop, Alexandr; Blechta, Vratislav; Schraml, Jan; Spirko, Vladimír

    2008-06-12

    The rotation of a trimethylsiloxy (TMSO) group in three silylated phenols (with three different ortho substituents -H, -CH3, and -C(CH3)3) was studied with the NMR (n)J(Si,C), n = 2, 3, 4, 5, scalar spin-spin coupling between the (29)Si nucleus of the TMSO group and the (13)C nuclei of the phenyl ring. The internal rotation potential calculated with the B3LYP and MP2 calculation methods including the effect of a solvent environment (gas phase, chloroform, and water) was used for the calculation of the dynamical averages of the scalar coupling constants in the framework of the rigid-bender formalism. Solvent effects, the quality of the rotational potential, and the applicability of the classical molecular dynamic to the problem is discussed. Quantum effects have a sizable impact on scalar couplings, particularly for the internal rotational states well localized within the wells of the potential surfaces for the TMSO group. The overall difference between the experimental and theoretical scalar couplings calculated for the global energy-minima structures (static model) decreases substantially for both model potentials (B3LYP, MP2) when the molecular motion of the TMSO group is taken into account. The calculated data indicate that the inclusion of molecular motion is necessary for the accurate calculation of the scalar coupling constants and their reliable structural interpretation for any system which possesses a large-amplitude motion. PMID:18491850

  18. Adiabatic Coupling Constant of Nitrobenzene- n-Alkane Critical Mixtures. Evidence from Ultrasonic Spectra and Thermodynamic Data

    NASA Astrophysics Data System (ADS)

    Mirzaev, Sirojiddin Z.; Kaatze, Udo

    2016-09-01

    Ultrasonic spectra of mixtures of nitrobenzene with n-alkanes, from n-hexane to n-nonane, are analyzed. They feature up to two Debye-type relaxation terms with discrete relaxation times and, near the critical point, an additional relaxation term due to the fluctuations in the local concentration. The latter can be well represented by the dynamic scaling theory. Its amplitude parameter reveals the adiabatic coupling constant of the mixtures of critical composition. The dependence of this thermodynamic parameter upon the length of the n-alkanes corresponds to that of the slope in the pressure dependence of the critical temperature and is thus taken another confirmation of the dynamic scaling model. The change in the variation of the coupling constant and of several other mixture parameters with alkane length probably reflects a structural change in the nitrobenzene- n-alkane mixtures when the number of carbon atoms per alkane exceeds eight.

  19. IPAP-HSQMBC: measurement of long-range heteronuclear coupling constants from spin-state selective multiplets.

    PubMed

    Gil, Sergi; Espinosa, Juan Félix; Parella, Teodor

    2010-12-01

    A new NMR approach is proposed for the measurement of long-range heteronuclear coupling constants ((n)J(XH), n>1) in natural abundance molecules. Two complementary in-phase (IP) and anti-phase (AP) data are separately recorded from a modified HSQMBC experiment and then added/subtracted to provide spin-state-selective α/β-HSQMBC spectra. The magnitude of (n)J(XH) can be directly determined by simple analysis of the relative displacement between α- and β-cross-peaks. The robustness of this IPAP-HSQMBC experiment is evaluated experimentally and by simulation using a variety of different conditions. Important aspects such as signal intensity dependence and presence of unwanted cross-talk effects are discussed and examples on the measurement of small proton-carbon ((n)J(CH)) and proton-nitrogen ((n)J(NH)) coupling constants are provided. PMID:20952232

  20. Effect of lattice deformation on exchange coupling constants in Cr{sub 2}O{sub 3}

    SciTech Connect

    Kota, Yohei; Imamura, Hiroshi; Sasaki, Munetaka

    2014-05-07

    We studied lattice deformation effect on exchange interaction in the corundum-type Cr{sub 2}O{sub 3} theoretically. First-principles electronic structure calculations were performed to evaluate the total energy and exchange coupling constants of Cr{sub 2}O{sub 3} under lattice deformation. We found that a few percent elastic deformation is expected via misfit strain and that the first- and second-nearest neighbor exchange coupling constants of Cr{sub 2}O{sub 3} strongly depend on the lattice deformation. These results imply a possibility for improving the thermal stability of Cr{sub 2}O{sub 3} based magnetoelectric devices by lattice deformation.

  1. Spontaneous mode switching in coupled oscillators competing for constant amounts of resources

    NASA Astrophysics Data System (ADS)

    Hirata, Yoshito; Aono, Masashi; Hara, Masahiko; Aihara, Kazuyuki

    2010-03-01

    We propose a widely applicable scheme of coupling that models competitions among dynamical systems for fixed amounts of resources. Two oscillators coupled in this way synchronize in antiphase. Three oscillators coupled circularly show a number of oscillation modes such as rotation and partially in-phase synchronization. Intriguingly, simple oscillators in the model also produce complex behavior such as spontaneous switching among different modes. The dynamics reproduces well the spatiotemporal oscillatory behavior of a true slime mold Physarum, which is capable of computational optimization.

  2. Spontaneous mode switching in coupled oscillators competing for constant amounts of resources.

    PubMed

    Hirata, Yoshito; Aono, Masashi; Hara, Masahiko; Aihara, Kazuyuki

    2010-03-01

    We propose a widely applicable scheme of coupling that models competitions among dynamical systems for fixed amounts of resources. Two oscillators coupled in this way synchronize in antiphase. Three oscillators coupled circularly show a number of oscillation modes such as rotation and partially in-phase synchronization. Intriguingly, simple oscillators in the model also produce complex behavior such as spontaneous switching among different modes. The dynamics reproduces well the spatiotemporal oscillatory behavior of a true slime mold Physarum, which is capable of computational optimization. PMID:20370272

  3. 15N-15N spin-spin coupling constants through intermolecular hydrogen bonds in the solid state.

    PubMed

    Claramunt, Rosa M; Pérez-Torralba, Marta; María, Dolores Santa; Sanz, Dionisia; Elena, Bénédicte; Alkorta, Ibon; Elguero, José

    2010-10-01

    A 2hJNN intermolecular spin-spin coupling constant (SSCC) of 10.2±0.4 Hz has been measured for the powdered tetrachlorogallate salt of pyridinium solvated by pyridine (pyridine-H+⋯pyridine cation 3). Density Functional Theory (DFT) calculations at the B3LYP/6-311++G(d,p) level reproduced this value and two others reported in the literature for 2hJ intermolecular SSCCs, which were measured for complexes in solution.

  4. Coupled cluster study of spectroscopic constants of ground states of heavy rare gas dimers with spin-orbit interaction

    NASA Astrophysics Data System (ADS)

    Tu, Zhe-Yan; Wang, Wen-Liang; Li, Ren-Zhong; Xia, Cai-Juan; Li, Lian-Bi

    2016-07-01

    The CCSD(T) approach based on two-component relativistic effective core potential with spin-orbit interaction just included in coupled cluster iteration is adopted to study the spectroscopic constants of ground states of Kr2, Xe2 and Rn2 dimers. The spectroscopic constants have significant basis set dependence. Extrapolation to the complete basis set limit provides the most accurate values. The spin-orbit interaction hardly affects the spectroscopic constants of Kr2 and Xe2. However, the equilibrium bond length is shortened about 0.013 Å and the dissociation energy is augmented about 18 cm-1 by the spin-orbit interaction for Rn2 in the complete basis set limit.

  5. Asymptotically AdS{sub 3} solutions to topologically massive gravity at special values of the coupling constants

    SciTech Connect

    Garbarz, Alan; Giribet, Gaston; Vasquez, Yerko

    2009-02-15

    We study exact solutions to cosmological topologically massive gravity coupled to topologically massive electrodynamics at special values of the coupling constants. For the particular case of the so-called chiral point l{mu}{sub G}=1, vacuum solutions (with vanishing gauge field) are exhibited. These correspond to a one-parameter deformation of general relativity solutions, and are continuously connected to the extremal Banados-Teitelboim-Zanelli black hole with bare constants J=-lM. At the chiral point this extremal Banados-Teitelboim-Zanelli black hole turns out to be massless, and thus it can be regarded as a kind of ground state. Although the solution is not asymptotically AdS{sub 3} in the sense of Brown-Henneaux boundary conditions, it does obey the weakened asymptotic recently proposed by Grumiller and Johansson. Consequently, we discuss the holographic computation of the conserved charges in terms of the stress tensor in the boundary. For the case where the coupling constants satisfy the relation l{mu}{sub G}=1+2l{mu}{sub E}, electrically charged analogues to these solutions exist. These solutions are asymptotically AdS{sub 3} in the strongest sense, and correspond to a logarithmic branch of self-dual solutions previously discussed in the literature.

  6. Spectral editing of weakly coupled spins using variable flip angles in PRESS constant echo time difference spectroscopy: Application to GABA

    NASA Astrophysics Data System (ADS)

    Snyder, Jeff; Hanstock, Chris C.; Wilman, Alan H.

    2009-10-01

    A general in vivo magnetic resonance spectroscopy editing technique is presented to detect weakly coupled spin systems through subtraction, while preserving singlets through addition, and is applied to the specific brain metabolite γ-aminobutyric acid (GABA) at 4.7 T. The new method uses double spin echo localization (PRESS) and is based on a constant echo time difference spectroscopy approach employing subtraction of two asymmetric echo timings, which is normally only applicable to strongly coupled spin systems. By utilizing flip angle reduction of one of the two refocusing pulses in the PRESS sequence, we demonstrate that this difference method may be extended to weakly coupled systems, thereby providing a very simple yet effective editing process. The difference method is first illustrated analytically using a simple two spin weakly coupled spin system. The technique was then demonstrated for the 3.01 ppm resonance of GABA, which is obscured by the strong singlet peak of creatine in vivo. Full numerical simulations, as well as phantom and in vivo experiments were performed. The difference method used two asymmetric PRESS timings with a constant total echo time of 131 ms and a reduced 120° final pulse, providing 25% GABA yield upon subtraction compared to two short echo standard PRESS experiments. Phantom and in vivo results from human brain demonstrate efficacy of this method in agreement with numerical simulations.

  7. 17O nuclear quadrupole coupling constants of water bound to a metal ion: A gadolinium(III) case study

    NASA Astrophysics Data System (ADS)

    Yazyev, Oleg V.; Helm, Lothar

    2006-08-01

    Rotational correlation times of metal ion aqua complexes can be determined from O17 NMR relaxation rates if the quadrupole coupling constant of the bound water oxygen-17 nucleus is known. The rotational correlation time is an important parameter for the efficiency of Gd3+ complexes as magnetic resonance imaging contrast agents. Using a combination of density functional theory with classical and Car-Parrinello molecular dynamics simulations we performed a computational study of the O17 quadrupole coupling constants in model aqua ions and the [Gd(DOTA)(H2O)]- complex used in clinical diagnostics. For the inner sphere water molecule in the [Gd(DOTA)(H2O)]- complex the determined quadrupole coupling parameter χ√1+η2/3 of 8.7MHz is very similar to that of the liquid water (9.0MHz ). Very close values were also predicted for the the homoleptic aqua ions of Gd3+ and Ca2+. We conclude that the O17 quadrupole coupling parameters of water molecules coordinated to closed shell and lanthanide metal ions are similar to water molecules in the liquid state.

  8. A theoretical investigation of Ferromagnetic Resonance Linewidth and damping constants in coupled trilayer and spin valve systems

    SciTech Connect

    Layadi, A.

    2015-05-15

    The ferromagnetic resonance intrinsic field linewidth ΔH is investigated for a multilayer system such as a coupled trilayer and a spin valve structure. The magnetic coupling between two ferromagnetic layers separated by a nonmagnetic interlayer will be described by the bilinear J{sub 1} and biquadratic J{sub 2} coupling parameters. The interaction at the interface of the first ferromagnetic layer with the antiferromagnetic one is account for by the exchange anisotropy field, H{sub E}. A general formula is derived for the intrinsic linewidth ΔH. The explicit dependence of ΔH with H{sub E}, J{sub 1} and J{sub 2} will be highlighted. Analytical expressions for each mode field linewidth are found in special cases. Equivalent damping constants will be discussed.

  9. H-H, C-H, and C-C NMR spin-spin coupling constants calculated by the FP-INDO method for aromatic hydrocarbons

    NASA Technical Reports Server (NTRS)

    Long, S. A. T.; Memory, J. D.

    1978-01-01

    The FP-INDO (finite perturbation-intermediate neglect of differential overlap) method is used to calculate the H-H, C-H, and C-C coupling constants in hertz for molecules of six different benzenoid hydrocarbons: benzene, naphthalene, biphenyl, anthracene, phenanthrene, and pyrene. The calculations are based on both the actual and the average molecular geometries. It is found that only the actual molecular geometries can always yield the correct relative order of values for the H-H coupling constants. For the calculated C-C coupling constants, as for the calculated C-H coupling constants, the signs are positive (negative) for an odd (even) number of bonds connecting the two nuclei. Agreements between the calculated and experimental values of the coupling constants for all six molecules are comparable to those reported previously for other molecules.

  10. The position of deuterium in HOD—NNO as determined by structural and nuclear quadrupole coupling constants

    SciTech Connect

    Obenchain, Daniel A.; Frank, Derek S.; Novick, Stewart E.; Klemperer, William

    2015-08-28

    Rotational spectra of the weakly bound H{sub 2}O—N{sub 2}O complex and its HOD—N{sub 2}O isotopologue in a supersonic jet are reported. Rotational constants of the singly substituted deuterium in water and each singly substituted nitrogen-15 are presented. Combinations of isotopic data and high level ab initio calculations place the water in a similar position to those of the isoelectronic H{sub 2}O—CO{sub 2} complex, with a slight tilt of the OH towards the NNO axis. The deuterium nuclear quadrupole coupling constant places the deuterium on the O—H axis quasi-parallel to the NNO axis.

  11. GIAO-DFT isotropic magnetic shielding constants and spin-spin coupling of tartaric acid in water solution

    NASA Astrophysics Data System (ADS)

    Fideles, Bruna; Oliveira, Leonardo B. A.; Colherinhas, Guilherme

    2016-01-01

    We investigate the nuclear isotropic shielding constants and spin-spin coupling for oxygen and carbons atoms of isomers of tartaric acid in gas phase and in water solutions by Monte Carlo simulation and quantum mechanics calculations using the GIAO-B3LYP approach. Solute polarization effects are included iteratively and play an important role in the quantitative determination of shielding constants. Our MP2/aug-cc-pVTZ results show substantial increases of the dipole moment in solution as compared with the gas phase results (61-221%). The solvent effects on the σ(13O) values are in general small. More appreciable solvent effects can be seen on the σ(17O) and J(Csbnd O).

  12. Photodetachment of an electron from selenide ion - The electron affinity and spin-orbit coupling constant for SeH.

    NASA Technical Reports Server (NTRS)

    Smyth, K. C.; Brauman, J. I.

    1972-01-01

    The relative cross section for the gas phase photodetachment of an electron from SeH(-) was determined in the wavelength region 428 to 578 nm. An ion cyclotron resonance spectrometer was used to generate, trap, and detect the negative ions, and a 1000-W xenon arc lamp with a grating monochromator was employed as the light source. The cross section exhibited two sharp thresholds, whose positions remained unchanged for the photodetachment of SeD(-). As a result of these thresholds, the electron affinity and the spin-orbit coupling constant were evaluated.

  13. Strong coupling constant from vacuum polarization functions in three-flavor lattice QCD with dynamical overlap fermions

    SciTech Connect

    Shintani, E.; Aoki, S.; Fukaya, H.; Hashimoto, S.; Kaneko, T.; Onogi, T.; Yamada, N.

    2010-10-25

    We determine the strong coupling constant {alpha}{sub s} from a lattice calculation of vacuum polarization functions (VPF) in three-flavor QCD with dynamical overlap fermions. Fitting lattice data of VPF to the continuum perturbative formula including the operator product expansion, we extract the QCD scale parameter {Lambda}{sub MS}{sup -(3)}. At the Z boson mass scale, we obtain {alpha}{sub s}{sup (5)}(M{sub z}) = 0.1181(3)(+14/-12), where the first error is statistical and the second is our estimate of various systematic uncertainties.

  14. The Spectral Properties of the Strongly Coupled Sturm Hamiltonian of Eventually Constant Type

    NASA Astrophysics Data System (ADS)

    Qu, Yan-Hui

    2016-09-01

    We study the spectral properties of the Sturm Hamiltolian of eventually constant type, which includes the Fibonacci Hamiltonian. Let $s$ be the Hausdorff dimension of the spectrum. For $V>20$, we show that the restriction of the $s$-dimensional Hausdorff measure to the spectrum is a Gibbs type measure; the density of states measure is a Markov measure. Based on the fine structures of these measures, we show that both measures are exact dimensional; we obtain exact asymptotic behaviors for the optimal H\\"older exponent and the Hausdorff dimension of the density of states measure and for the Hausdorff dimension of the spectrum. As a consequence, if the frequency is not silver number type, then for $V$ big enough, we establish strict inequalities between these three spectral characteristics. We achieve them by introducing an auxiliary symbolic dynamical system and applying the thermodynamical and multifractal formalisms of almost additive potentials.

  15. Constraining the photon-axion coupling constant with magnetic white dwarfs

    SciTech Connect

    Gill, Ramandeep; Heyl, Jeremy S.

    2011-10-15

    The light pseudoscalar particle, dubbed the axion, borne out of the Peccei-Quinn solution to the strong CP problem in QCD remains elusive. One avenue of inferring its existence is through its coupling to electromagnetic radiation. So far, laboratory experiments have dedicated all efforts to detect the axion in the mass range 10{sup -6}coupling strength g{sub a}{gamma}{gamma}<10{sup -10} GeV{sup -1}, where the limits are derived from astrophysical considerations. In this study, we present a novel way of constraining g{sub a}{gamma}{gamma} by looking at the level of linear polarization in the radiation emerging from magnetic white dwarfs. We find that photon-axion oscillations in white dwarf magnetospheres can enhance the degree of linear polarization. Observing that most magnetic white dwarfs show only 5% linear polarization, we derive upper limits on g{sub a}{gamma}{gamma} for different axion masses.

  16. Determination of the Strong Coupling Constant and Multijet Cross Section Ratio Measurements

    SciTech Connect

    Wobisch, M.

    2011-06-01

    Concepts and results of determinations of the strong coupling in hadron collisions are discussed. A recent {alpha}{sub s} result from the inclusive jet cross section in p{bar p} collisions at {radical}s = 1.96 TeV is presented which is based on perturbative QCD calculations beyond next-to-leading order. Emphasis is put on the consistency of the conceptual approach. Conceptual limitations in the approach of extracting as from cross section data are discussed and how these can be avoided by using observables that are defined as ratios of cross sections. For one such observable, the multijet cross section ratio R{sub 3/2}, preliminary results are presented.

  17. Experimental, SOPPA(CCSD), and DFT analysis of substitutent effects on NMR 1JCF coupling constants in fluorobenzene derivatives.

    PubMed

    Vilcachagua, Janaina Dantas; Ducati, Lucas C; Rittner, Roberto; Contreras, Rubén H; Tormena, Cláudio F

    2011-02-24

    Interesting insight into the electronic molecular structure changes associated with substituent effects on the Fermi contact (FC) and paramagnetic spin-orbit (PSO) terms of (1)J(CF) NMR coupling constants (SSCCs) in o-X-, m-X-, and p-X-fluorobenzenes (X = NH(2); NO(2)) is presented. The formulation of this approach is based on the influence of different conjugative and hyperconjugative interactions on a second-order property, which can be qualitatively predicted if it is known how they affect the main virtual excitations entering into that second-order property. A set of consistent approximations are introduced in order to analyze the behavior of occupied and virtual orbitals, which define some experimental trends for (1)J(CF) spin-spin coupling constants. In addition, DFT hybrid functionals were used, and a similar degree of confidence to compute the (1)J(CF) with those observed for the SOPPA(CCSD) method was obtained. The (1)J(CF) SSCCs for ezetimibe, a commercially fluorinated drug used to reduce cholesterol levels, were measured and DFT-calculated, and the qualitative approach quoted above was applied. As a byproduct, a possible method to determine experimentally a significant PSO contribution to (1)J(CF) SSCCs is discussed.

  18. Circular Dichroism Reveals Evidence of Coupling Between Immunoglobulin Constant and Variable Region Secondary Structure†

    PubMed Central

    Janda, Alena; Casadevall, Arturo

    2010-01-01

    Antibodies (Ab) are bifunctional molecules with two domains, a constant region (C) that confers effector properties and a variable (V) region responsible of antigen (Ag) binding. Historically the C and V regions were considered to be functionally independent, with Ag specificity being solely determined by the V region. However, recent studies suggest that the C region can affect Ab fine specificity. This has led to the proposal that the CH domain influences the structure of the V region, thus affecting Ab affinity and fine specificity. An inference from this proposal is that V region identical monoclonal Abs (mAbs) differing in C region (eg isotype) would manifest different secondary structures arising from isotype-induced variation in the V-C region after Ag binding. We hypothesized that such effects could translate into differences in Circular Dichroism (CD) upon Ag-Ab complex formation. Consequently we studied the interaction of a set of V region identical IgG1, IgG2a, IgG2b, and IgG3 mAbs with glucuronoxylomannan (GXM). The native CD spectra of the pairs IgG1/IgG2a and IgG3/IgG2b were strikingly similar, implying similar secondary structure content. GXM binding by IgG1, IgG2a, IgG2b and IgG3 produced different CD changes, with the pairs IgG1/IgG2a and IgG3/IgG2b again manifesting qualitatively similar trends in secondary structure changes. The magnitude of the changes differed among the isotypes with IgG2a > IgG3> IgG2b> IgG1. These differences in CD changes were interpreted to reflect differences in V-C secondary structure. PMID:20299100

  19. Dynamical mass generation in QED with magnetic fields: Arbitrary field strength and coupling constant

    NASA Astrophysics Data System (ADS)

    Rojas, Eduardo; Ayala, Alejandro; Bashir, Adnan; Raya, Alfredo

    2008-05-01

    We study the dynamical generation of masses for fundamental fermions in quenched quantum electrodynamics, in the presence of magnetics fields of arbitrary strength, by solving the Schwinger-Dyson equation for the fermion self-energy in the rainbow approximation. We employ the Ritus eigenfunction formalism which provides a neat solution to the technical problem of summing over all Landau levels. It is well known that magnetic fields catalyze the generation of fermion mass m for arbitrarily small values of electromagnetic coupling α. For intense fields it is also well known that m∝eB. Our approach allows us to span all regimes of parameters α and eB. We find that m∝eB provided α is small. However, when α increases beyond the critical value αc which marks the onslaught of dynamical fermion masses in vacuum, we find m∝Λ, the cutoff required to regularize the ultraviolet divergences. Our method permits us to verify the results available in literature for the limiting cases of eB and α. We also point out the relevance of our work for possible physical applications.

  20. SmB6 electron-phonon coupling constant from time- and angle-resolved photoelectron spectroscopy

    NASA Astrophysics Data System (ADS)

    Sterzi, A.; Crepaldi, A.; Cilento, F.; Manzoni, G.; Frantzeskakis, E.; Zacchigna, M.; van Heumen, E.; Huang, Y. K.; Golden, M. S.; Parmigiani, F.

    2016-08-01

    SmB6 is a mixed valence Kondo system resulting from the hybridization between localized f electrons and delocalized d electrons. We have investigated its out-of-equilibrium electron dynamics by means of time- and angle-resolved photoelectron spectroscopy. The transient electronic population above the Fermi level can be described by a time-dependent Fermi-Dirac distribution. By solving a two-temperature model that well reproduces the relaxation dynamics of the effective electronic temperature, we estimate the electron-phonon coupling constant λ to range from 0.13 ±0.03 to 0.04 ±0.01 . These extremes are obtained assuming a coupling of the electrons with either a phonon mode at 10 or 19 meV. A realistic value of the average phonon energy will give an actual value of λ within this range. Our results provide an experimental report on the material electron-phonon coupling, contributing to both the electronic transport and the macroscopic thermodynamic properties of SmB6.

  1. Analytical continuation in coupling constant method; application to the calculation of resonance energies and widths for organic molecules: Glycine, alanine and valine and dimer of formic acid

    NASA Astrophysics Data System (ADS)

    Papp, P.; Matejčík, Š.; Mach, P.; Urban, J.; Paidarová, I.; Horáček, J.

    2013-06-01

    The method of analytic continuation in the coupling constant (ACCC) in combination with use of the statistical Padé approximation is applied to the determination of resonance energy and width of some amino acids and formic acid dimer. Standard quantum chemistry codes provide accurate data which can be used for analytic continuation in the coupling constant to obtain the resonance energy and width of organic molecules with a good accuracy. The obtained results are compared with the existing experimental ones.

  2. Finite-Perturbation Intermediate - Neglect - of - Differential - Overlap Molecular Orbital Calculations of Nuclear Magnetic Resonance Spin-Spin Coupling Constants for Polycyclic Aromatic Hydrocarbons and Aromatic Nitrogen Heterocyclics

    NASA Astrophysics Data System (ADS)

    Long, Sheila Ann Thibeault

    The H-H, C-H, and C-C spin-spin coupling constants were calculated by the finite-perturbation, intermediate -neglect-of-differential-overlap method using the Fermi contact interaction for benzene, naphthalene, biphenyl, anthracene, phenanthrene, and pyrene. The calculations were made using both the actual and the average molecular geometries. For all six of these molecules, the agreements between the calculated and the experimental coupling constants were comparable to those previously reported for other, predominantly smaller, molecules. The actual molecular geometries always gave the correct relative order of values for the H-H coupling constants, whereas the average molecular geometries did not always do so. The magnitudes, but not the signs, of the calculated coupling constants were sensitive to small changes in molecular geometry. The results were the best (next best) for the H-H (C-H) coupling constants. In addition the H-H, C-H, N-H, C-C, and N-C spin -spin coupling constants were calculated in a similar manner for pyridine, pyridazine, pyrimidine, pyrazine, s-triazine, quinoline, quinoxaline, phthalazine, benzo g quinoxaline, and benzo b phenazine. The agreements between the theoretical and the experimental values were comparable to those for the polycyclic aromatic hydrocarbons.

  3. Design and simulation of the AC-coupled burst-mode receiver with the small time constant

    NASA Astrophysics Data System (ADS)

    Huang, Qiuyuan; Liu, Luling; Li, Senmao; Sun, Leijun

    2008-12-01

    Due to the Multipoint-to-Point nature of the uplink, the upstream data transmission in a GPON system is burst-mode, and both the guard time and preamble time are much shorter(32 bits and 44 bits respectively).This burst-mode nature of the GPON uplink brings many challenges for the design of the burst-mode receiver. This paper presents an improved design of the main amplifier which is fit for the AC-coupled burst-mode optical receiver with short time constant. Simulation analysis of this scheme at the aspect of the pattern dependent jitter and the data pattern jitter is also presented. Finally, simulation results are provided to show the feasibility of the scheme.

  4. Precision determination of the πN scattering lengths and the charged πNN coupling constant

    NASA Astrophysics Data System (ADS)

    Ericson, T. E. O.; Loiseau, B.; Thomas, A. W.

    2000-01-01

    We critically evaluate the isovector GMO sumrule for the charged πNN coupling constant using recent precision data from π-p and π-d atoms and with careful attention to systematic errors. From the π-d scattering length we deduce the pion-proton scattering lengths 1/2(aπ-p + aπ-n) = (-20 +/- 6(statistic)+/-10 (systematic) .10-4m-1πc and 1/2(aπ-p - aπ-n) = (903 +/- 14) . 10-4m-1πc. From this a direct evaluation gives g2c(GMO)/4π = 14.20 +/- 0.07 (statistic)+/-0.13(systematic) or f2c/4π = 0.0786 +/- 0.0008.

  5. Calculations of hyperfine coupling constant of copper(II) in aqueous environment. Finite temperature molecular dynamics and relativistic effects.

    PubMed

    Malček, Michal; Bučinský, Lukáš; Valko, Marián; Biskupič, Stanislav

    2015-09-01

    The presented paper is focused on the calculation of hyperfine coupling constants (HFCC) of Cu (2+) ion in water environment. To simulate the conditions of the electron paramagnetic resonance (EPR) experiment in aqueous phase, molecular dynamics using the density functional theory (DFT) was employed. In total three different functionals (BLYP, B3LYP, M06) were employed for studying their suitability in describing coordination of Cu (2+) by water molecules. The system of our interest was composed of one Cu (2+) cation surrounded by a selected number (between thirty and fifty) of water molecules. Besides the non-relativistic HFCCs (Fermi contact terms) of Cu (2+) also the four-component relativistic HFCC calculations are presented. The importance of the proper evaluation of HFCCs, the inclusion of spin-orbit term, for Cu (2+) containing systems (Neese, J. Chem. Phys. 118, 3939 2003; Almeida et al., Chem. Phys. 332, 176 2007) is confirmed at the relativistic four-component level of theory.

  6. Revealing the specific solute-solvent interactions via the measurements of the NMR spin-spin coupling constants

    NASA Astrophysics Data System (ADS)

    Shahkhatuni, Astghik A.; Shahkhatuni, Aleksan G.; Minasyan, Nune S.; Panosyan, Henry A.; Sahakyan, Aleksandr B.

    2015-03-01

    The solvent induced changes of one-bond spin-spin coupling constants (SSCCs) are investigated for a set of substituted methanes in solvents with various ε dielectric constants. Solute-solvent systems with varying types of ε-dependences for the solute SSCCs are outlined. Aliphatic hydrocarbon solvents and their halogen-substituted derivatives comprise the subset, where the SSCC is linearly dependent on the solvent reaction field, f(ε) = 2(ε - 1)/(2ε + 1), hence indicating the absence of specific solute-solvent interactions. In such solvents, SSCCs depend only on bulk dielectric properties of the medium, and, the magnitudes of the solvent sensitivities of SSCCs are fully determined by the initial values of "pure" SSCCs that correspond to the isolated solute molecules. The solvents involved in the second subset have a relatively chaotic distribution of the SSCC/f(ε) relationship, with possible groupings by their chemical nature. There, the conventional linear SSCC/f(ε) dependence is perturbed by additional interactions, such as hydrogen bonding, specific association processes, lone electron pairs, and conjugation.

  7. The performance of hybrid density functional theory for the calculation of indirect nuclear spin-spin coupling constants in substituted hydrocarbons.

    PubMed

    Lutnaes, Ola B; Ruden, Torgeir A; Helgaker, Trygve

    2004-10-01

    Density functional theory, in particular, with the Becke-3-parameter-Lee-Yang-Parr (B3LYP) hybrid functional, has been shown to be a promising method for the calculation of indirect nuclear spin-spin coupling constants. However, no systematic investigation has so far been undertaken to evaluate the capability of B3LYP to calculate these coupling constants accurately, taking properly into account the vibrational contributions. In this work, vibrationally corrected indirect spin-spin coupling constants were calculated using the B3LYP functional for 10 rigid unsubstituted and substituted hydrocarbons: ethyne, ethene, allene, cyclopropene, cyclopropane, cyclobutene, pyrrole, furan, thiophene and benzene. The resulting spin-spin constants were compared with the available experimental values. The basis sets in these calculations give indirect nuclear spin-spin coupling constants of ethyne that are almost converged to the basis-set limit, making the intrinsic error of the computational method and the error in equilibrium geometry the main sources of error. On average, the B3LYP functional overestimates the indirect nuclear spin-spin coupling constants in hydrocarbons by 10%.

  8. The Effect of Approximating Some Molecular Integrals in Coupled-Cluster Calculations: Fundamental Frequencies and Rovibrational Spectroscopic Constants of Cyclopropenylidene

    NASA Technical Reports Server (NTRS)

    Lee, Timothy J.; Dateo, Christopher E.

    2005-01-01

    The singles and doubles coupled-cluster method that includes a perturbational estimate of connected triple excitations, denoted CCSD(T), has been used, in conjunction with approximate integral techniques, to compute highly accurate rovibrational spectroscopic constants of cyclopropenylidene, C3H2. The approximate integral technique was proposed in 1994 by Rendell and Lee in order to avoid disk storage and input/output bottlenecks, and today it will also significantly aid in the development of algorithms for distributed memory, massively parallel computer architectures. It is shown in this study that use of approximate integrals does not impact the accuracy of CCSD(T) calculations. In addition, the most accurate spectroscopic data yet for C3H2 is presented based on a CCSD(T)/cc-pVQZ quartic force field that is modified to include the effects of core-valence electron correlation. Cyclopropenylidene is of great astronomical and astrobiological interest because it is the smallest aromatic ringed compound to be positively identified in the interstellar medium, and is thus involved in the prebiotic processing of carbon and hydrogen. The singles and doubles coupled-cluster method that includes a perturbational estimate of

  9. IFSERF, an isotope-filtered SERF experiment for the precise measurement of proton-proton coupling constants between chemically equivalent protons.

    PubMed

    Nolis, Pau; Roglans, Anna; Parella, Teodor

    2005-04-01

    An isotope-filtered selective refocusing (IFSERF) experiment is presented for the sensitive and precise measurement of the proton-proton coupling constant between chemically equivalent protons. The 2D NMR method combines an initial doubly selective isotope filter based on heteronuclear cross-polarization followed by a selective J-resolved block. The coupling topologies obtained from several 2D variants of the IFSERF experiment are described for the simultaneous measurement of both proton-proton and proton-carbon coupling constants in the involved AA'XX' spin system. Application on the determination of the relative configuration of double bonds in symmetrical molecules is illustrated.

  10. Magnetic coupling constants of self-assembled Cu(II) [3×3] grids: alternative spin model from theoretical calculations.

    PubMed

    Calzado, Carmen J; Ben Amor, Nadia; Maynau, Daniel

    2014-07-14

    This paper reports a theoretical analysis of the electronic structure and magnetic properties of a ferromagnetic Cu(II) [3×3] grid. A two-step strategy, combining calculations on the whole grid and on binuclear fragments, has been employed to evaluate all the magnetic interactions in the grid. The calculations confirm an S = 7/2 ground state, which is in accordance with the magnetisation versus field curve and the thermal dependence of the magnetic moment data. Only the first-neighbour coupling terms present non-negligible amplitudes, all of them in agreement with the structure and arrangement of the Cu 3d magnetic orbitals. The results indicate that the dominant interaction in the system is the antiferromagnetic coupling between the ring and the central Cu sites (J3 = J4 ≈ -31 cm(-1)). In the ring two different interactions can be distinguished, J1 = 4.6 cm(-1) and J2 = -0.1 cm(-1), in contrast to the single J model employed in the magnetic data fit. The calculated J values have been used to determine the energy level distribution of the Heisenberg magnetic states. The effective magnetic moment versus temperature plot resulting from this ab initio energy profile is in good agreement with the experimental curve and the fitting obtained with the simplified spin model, despite the differences between these two spin models. This study underlines the role that the theoretical evaluations of the coupling constants can play on the rationalisation of the magnetic properties of these complex polynuclear systems.

  11. Accurate determination of one-bond heteronuclear coupling constants with “pure shift” broadband proton-decoupled CLIP/CLAP-HSQC experiments

    NASA Astrophysics Data System (ADS)

    Timári, István; Kaltschnee, Lukas; Kolmer, Andreas; Adams, Ralph W.; Nilsson, Mathias; Thiele, Christina M.; Morris, Gareth A.; Kövér, Katalin E.

    2014-02-01

    We report broadband proton-decoupled CLIP/CLAP-HSQC experiments for the accurate determination of one-bond heteronuclear couplings and, by extension, for the reliable measurement of small residual dipolar coupling constants. The combination of an isotope-selective BIRD(d) filter module with a non-selective 1H inversion pulse is employed to refocus proton-proton coupling evolution prior to the acquisition of brief chunks of free induction decay that are subsequently assembled to reconstruct the fully-decoupled signal evolution. As a result, the cross-peaks obtained are split only by the heteronuclear one-bond coupling along the F2 dimension, allowing coupling constants to be extracted by measuring simple frequency differences between singlet maxima. The proton decoupling scheme presented has also been utilized in standard HSQC experiments, resulting in a fully-decoupled pure shift correlation map with significantly improved resolution.

  12. Magnitude of finite-nucleus-size effects in relativistic density functional computations of indirect NMR nuclear spin-spin coupling constants.

    PubMed

    Autschbach, Jochen

    2009-09-14

    A spherical Gaussian nuclear charge distribution model has been implemented for spin-free (scalar) and two-component (spin-orbit) relativistic density functional calculations of indirect NMR nuclear spin-spin coupling (J-coupling) constants. The finite nuclear volume effects on the hyperfine integrals are quite pronounced and as a consequence they noticeably alter coupling constants involving heavy NMR nuclei such as W, Pt, Hg, Tl, and Pb. Typically, the isotropic J-couplings are reduced in magnitude by about 10 to 15 % for couplings between one of the heaviest NMR nuclei and a light atomic ligand, and even more so for couplings between two heavy atoms. For a subset of the systems studied, viz. the Hg atom, Hg(2) (2+), and Tl--X where X=Br, I, the basis set convergence of the hyperfine integrals and the coupling constants was monitored. For the Hg atom, numerical and basis set calculations of the electron density and the 1s and 6s orbital hyperfine integrals are directly compared. The coupling anisotropies of TlBr and TlI increase by about 2 % due to finite-nucleus effects.

  13. On the calculation of nuclear spin-spin coupling constants. The bond length dependence of the Fermi contact term in H 2 and HD

    NASA Astrophysics Data System (ADS)

    Bacskay, George B.

    1995-08-01

    A theoretical study of the Fermi contact contribution to the HH and HD spin-spin coupling constant is reported, with special emphasis on its calculation using quantum chemical techniques over a wide range of internuclear distances, that has necessitated an extension of the existing methodology so the effects of near-degeneracy are properly treated. A detailed configuration interaction calculation on H 2 shows that as the molecule is stretched the coupling constant displays a sharp increase before decaying to zero as the molecule dissociates. Such distance dependence is reflected in the calculated vibrational averages of the coupling constant for HD that show a rapid increase with vibrational excitation.

  14. One-bond {sup 13}C-{sup 1}H spin-coupling constants in aldofuranosyl rings. Effect of conformation on coupling magnitude

    SciTech Connect

    Serianni, A.S.; Carmichael, I.; Wu, J.

    1995-08-23

    One-bond {sup 13}C-{sup 1}H spin-coupling constants ({sup 1}J{sub CH}) have been studied in the model furanose 2-deoxy-{beta}-D-glycero-tetrofuranose (1) as a function of ring geometry in order to assess their utility as conformational probes. Ab initio molecular orbital (MO) calculations were conducted on the ten envelope forms and the planar form of 1 using the second-order Moller Plesset (MP2) electron correlation treatment with a polarized split-valence (6.31 G*) basis set. The derived structures were used to compute {sup 1}J{sub CH} values in conformers of 1 at the Hartree-Fock and MP2 levels of theory which were subsequently sealed using a factor derived from accurate quadratic configuration interaction (QCISD) calculations. MO results indicate that C-H bond lengths in 1 vary with ring geometry, with a given C-H bond longest when quasi-axial and shortest when quasi-equatorial. Computed {sup 1}J{sub CH} values were found to be sensitive to C-H bond orientation, with greater coupling observed when a C-H bond is quasi-equatorial. Computations conducted on {beta}- D-ribofuranose (3) and 2-deoxy- {beta}-D-erythro-pentofurnaose (4) (HF/6-31G* level) show a C-H bond length/orientation dependence similar to that observed in 1. Experimental (NMR) data are presented which support the proposed correlation. These results suggest a role for {sup 1}J{sub CH} in the conformational analysis of furanose rings which may complement current methods based on {sup 3}J{sub HH}, {sup 3}J{sub CH}, and {sup 3}J{sub CH} values. 32 refs., 7 figs.

  15. Coupling between protonation and conformation in cytochrome c oxidase: Insights from constant-pH MD simulations.

    PubMed

    Oliveira, A Sofia F; Campos, Sara R R; Baptista, António M; Soares, Cláudio M

    2016-06-01

    Cytochrome c oxidases (CcOs) are the terminal enzymes of the respiratory chain in mitochondria and most bacteria. These enzymes reduce dioxygen (O(2)) to water and, simultaneously, generate a transmembrane electrochemical proton gradient. Despite their importance in the aerobic metabolism and the large amount of structural and biochemical data available for the A1-type CcO family, there is still no consensually accepted description of the molecular mechanisms operating in this protein. A substantial number of questions about the CcO's working mechanism remain to be answered, including how the protonation behavior of some key residues is modulated during a reduction cycle and how is the conformation of the protein affected by protonation. The main objective of this work was to study the protonation-conformation coupling in CcOs and identify the molecular factors that control the protonation state of some key residues. In order to directly capture the interplay between protonation and conformational effects, we have performed constant-pH MD simulations of an A1-type CcO inserted into a lipid bilayer in two redox states (oxidized and reduced) at physiological pH. From the simulations, we were able to identify several groups with unusual titration behavior that are highly dependent on the protein redox state, including the A-propionate from heme a and the D-propionate from heme a3, two key groups possibly involved in proton pumping. The protonation state of these two groups is heavily influenced by subtle conformational changes in the protein (notably of R481(I) and R482(I)) and by small changes in the hydrogen bond network.

  16. A path integral molecular dynamics study of the hyperfine coupling constants of the muoniated and hydrogenated acetone radicals

    NASA Astrophysics Data System (ADS)

    Oba, Yuki; Kawatsu, Tsutomu; Tachikawa, Masanori

    2016-08-01

    The on-the-fly ab initio density functional path integral molecular dynamics (PIMD) simulations, which can account for both the nuclear quantum effect and thermal effect, were carried out to evaluate the structures and "reduced" isotropic hyperfine coupling constants (HFCCs) for muoniated and hydrogenated acetone radicals (2-muoxy-2-propyl and 2-hydoxy-2-propyl) in vacuo. The reduced HFCC value from a simple geometry optimization calculation without both the nuclear quantum effect and thermal effect is -8.18 MHz, and that by standard ab initio molecular dynamics simulation with only the thermal effect and without the nuclear quantum effect is 0.33 MHz at 300 K, where these two methods cannot distinguish the difference between muoniated and hydrogenated acetone radicals. In contrast, the reduced HFCC value of the muoniated acetone radical by our PIMD simulation is 32.1 MHz, which is about 8 times larger than that for the hydrogenated radical of 3.97 MHz with the same level of calculation. We have found that the HFCC values are highly correlated with the local molecular structures; especially, the Mu—O bond length in the muoniated acetone radical is elongated due to the large nuclear quantum effect of the muon, which makes the expectation value of the HFCC larger. Although our PIMD result calculated in vacuo is about 4 times larger than the measured experimental value in aqueous solvent, the ratio of these HFCC values between muoniated and hydrogenated acetone radicals in vacuo is in reasonable agreement with the ratio of the experimental values in aqueous solvent (8.56 MHz and 0.9 MHz); the explicit presence of solvent molecules has a major effect on decreasing the reduced muon HFCC of in vacuo calculations for the quantitative reproduction.

  17. Indirect spin-spin coupling constants in CH 4, SiH 4 and GeH 4 - Gas-phase NMR experiment and ab initio calculations

    NASA Astrophysics Data System (ADS)

    Antušek, Andrej; Keḑziera, Dariusz; Jackowski, Karol; Jaszuński, Michał; Makulski, Włodzimierz

    2008-09-01

    New values of the indirect spin-spin coupling constants in CH 4, SiH 4 and GeH 4, derived from experiment and ab initio calculations, are reported. The new experimental values of 1J(CH), 1J(SiH) and 1J(GeH) are obtained from gas-phase NMR spectra. The dependence of the measured one-bond coupling constants on the density is analysed and the results are extrapolated to zero-density point to eliminate the effects due to intermolecular forces. In the calculation of the coupling constants, at the nonrelativistic level coupled cluster singles and doubles (CCSD) perturbation theory is used and the basis set convergence of the results is discussed. The relativistic corrections are estimated from Dirac-Hartree-Fock (DHF) calculations. The final theoretical values are obtained adding available estimates of the vibrational and temperature corrections. The agreement of the calculated and experimental 1J(XH), X = C, Si, Ge, constants is very satisfying, the differences are approximately 1-3%.

  18. Analysis of phi and chi 1 torsion angles for hen lysozyme in solution from 1H NMR spin-spin coupling constants.

    PubMed

    Smith, L J; Sutcliffe, M J; Redfield, C; Dobson, C M

    1991-01-29

    Three-bond 3JHN alpha coupling constants have been determined for 106 residues and 3J alpha beta coupling constants have been measured for 57 residues of the 129-residue protein hen egg white lysozyme. These NMR data have been compared with torsion angles defined in the tetragonal and the triclinic crystal forms of the protein. For most residues the measured 3JHN alpha values were consistent with the phi torsion angles found in both crystal forms; the RMS difference between the coupling constants calculated by using the tetragonal crystal structure phi angles and the experimental 3JHN alpha values is 0.88 Hz. Thus there appears to be no significant averaging of the phi torsion angle either in the interior or at the surface of the protein. For 41 of the residues where 3J alpha beta coupling constants have been determined, the values are consistent with a single staggered conformation about the chi 1 torsion angle and there is complete agreement between the NMR data in solution and the torsion angles defined in the crystalline state. In contrast, for the other 16 residues where 3J alpha beta coupling constant values have been measured, the data indicate extensive motional averaging about the chi 1 torsion angle. These residues occur largely on the surface of the protein and examination of the crystal structures shows that many of these residues adopt a different conformation in the triclinic and tetragonal crystal forms and have high crystallographic temperature factors. It appears, however, that in solution conformational flexibility of the side chains of surface residues is significantly more pronounced than in individual crystal structures.

  19. Determination of the magnitude and sign of the 185,187Re nuclear electric quadrupole coupling constants using nuclear acoustic resonance

    NASA Astrophysics Data System (ADS)

    Sundfors, R. K.

    1990-08-01

    Acoustic nuclear electric quadrupole resonance spectra and the magnitude and sign of the coupling constants for 185Re and 187Re in rhenium-metal single crystals have been measured using nuclear acoustic resonance (NAR) in a small magnetic field. These measurements were carried out using a NAR reflection bridge spectrometer in the 37-41 MHz frequency range and at 4.2 and 77.8 K. In this hexagonal crystal, the dynamic coupling between acoustic waves and the Re nuclear spin systems is shown to be via the dynamic quadrupole interaction, which is responsible for the observation of both Δm=+/-1 and +/-2 transitions between the +/-3/2 energy levels and the mixed +/-1/2 energy levels. Magnetic-resonance second moments for angular-independent indirect exchange broadening and angular-dependent static electric quadrupole broadening (from a spread in the electric quadrupole coupling constant value) are determined from the measured linewidths.

  20. Isotope effects and the temperature dependences of the hyperfine coupling constants of muoniated sec-butyl radicals in condensed phases.

    PubMed

    Fleming, Donald G; Bridges, Michael D; Arseneau, Donald J; Chen, Ya Kun; Wang, Yan Alexander

    2011-04-01

    Reported here is the first μSR study of the muon (A(μ)) and proton (A(p)) β-hyperfine coupling constants (Hfcc) of muoniated sec-butyl radicals, formed by muonium (Mu) addition to 1-butene and to cis- and trans-2-butene. The data are compared with in vacuo spin-unrestricted MP2 and hybrid DFT/B3YLP calculations reported in the previous paper (I), which played an important part in the interpretation of the data. The T-dependences of both the (reduced) muon, A(μ)′(T), and proton, A(p)(T), Hfcc are surprisingly well explained by a simple model, in which the calculated Hfcc from paper I at energy minima of 0 and near ±120° are thermally averaged, assuming an energy dependence given by a basic 2-fold torsional potential. Fitted torsional barriers to A(μ)′(T) from this model are similar (~3 kJ/mol) for all muoniated butyl radicals, suggesting that these are dominated by ZPE effects arising from the C−Mu bond, but for A(p)(T) exhibit wide variations depending on environment. For the cis- and trans-2-butyl radicals formed from 2-butene, A(μ)′(T) exhibits clear discontinuities at bulk butene melting points, evidence for molecular interactions enhancing these muon Hfcc in the environment of the solid state, similar to that found in earlier reports for muoniated tert-butyl. In contrast, for Mu−sec-butyl formed from 1-butene, there is no such discontinuity. The muon hfcc for the trans-2-butyl radical are seemingly very well predicted by B3LYP calculations in the solid phase, but for sec-butyl from 1-butene, showing the absence of further interactions, much better agreement is found with the MP2 calculations across the whole temperature range. Examples of large proton Hfcc near 0 K are also reported, due to eclipsed C−H bonds, in like manner to C−Mu, which then also exhibit clear discontinuities in A(p)(T) at bulk melting points. The data suggest that the good agreement found between theory and experiment from the B3LYP calculations for eclipsed bonds in

  1. Communication: Localized molecular orbital analysis of the effect of electron correlation on the anomalous isotope effect in the NMR spin-spin coupling constant in methane

    NASA Astrophysics Data System (ADS)

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

    2014-10-01

    We discuss the effect of electron correlation on the unexpected differential sensitivity (UDS) in the 1J(C-H) coupling constant of CH4 using a decomposition into contributions from localized molecular orbitals and compare with the 1J(N-H) coupling constant in NH3. In particular, we discuss the well known fact that uncorrelated coupled Hartree-Fock (CHF) calculations are not able to reproduce the UDS in methane. For this purpose we have implemented for the first time a localized molecular orbital analysis for the second order polarization propagator approximation with coupled cluster singles and doubles amplitudes—SOPPA(CCSD) in the DALTON program. Comparing the changes in the localized orbital contributions at the correlated SOPPA and SOPPA(CCSD) levels and at the uncorrelated CHF level, we find that the latter overestimates the effect of stretching the bond between the coupled atoms on the contribution to the coupling from the localized bonding orbital between these atoms. This disturbs the subtle balance between the molecular orbital contributions, which lead to the UDS in methane.

  2. Communication: Localized molecular orbital analysis of the effect of electron correlation on the anomalous isotope effect in the NMR spin-spin coupling constant in methane

    SciTech Connect

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

    2014-10-21

    We discuss the effect of electron correlation on the unexpected differential sensitivity (UDS) in the {sup 1}J(C–H) coupling constant of CH{sub 4} using a decomposition into contributions from localized molecular orbitals and compare with the {sup 1}J(N–H) coupling constant in NH{sub 3}. In particular, we discuss the well known fact that uncorrelated coupled Hartree-Fock (CHF) calculations are not able to reproduce the UDS in methane. For this purpose we have implemented for the first time a localized molecular orbital analysis for the second order polarization propagator approximation with coupled cluster singles and doubles amplitudes—SOPPA(CCSD) in the DALTON program. Comparing the changes in the localized orbital contributions at the correlated SOPPA and SOPPA(CCSD) levels and at the uncorrelated CHF level, we find that the latter overestimates the effect of stretching the bond between the coupled atoms on the contribution to the coupling from the localized bonding orbital between these atoms. This disturbs the subtle balance between the molecular orbital contributions, which lead to the UDS in methane.

  3. Improved Measurement of 3J(H αi, N i+1 ) Coupling Constants in H 2O Dissolved Proteins

    NASA Astrophysics Data System (ADS)

    Löhr, Frank; Schmidt, Jürgen M.; Maurer, Steffen; Rüterjans, Heinz

    2001-11-01

    A modification to the recently proposed α/β-HN(CO)CA-J TROSY pulse sequence (P. Permi et al., J. Magn. Reson.146, 255-259 (2000)) makes it possible to determine 3J(Hαi, Ni+1) coupling constants from a single E.COSY-type cross-peak pattern rather than from two 1Hα spin-state-edited subspectra. Advantages are increased 15N resolution, critical to extracting accurate 1Hα-15N coupling constants, and minimized differential relaxation due to nested 13Cα and 15N evolution periods. Application of the improved pulse sequence to Desulfovibrio vulgaris flavodoxin results in 3J(Hαi, Ni+1) values being systematically larger than those obtained with the original scheme. Parametrization of the coupling dependence on the protein backbone torsion angle ψ yields the Karplus relation 3J(Hαi, Ni+1)=-1.00 cos2(ψ-120°)+0.65 cos(ψ-120°)-0.15 Hz, with a residual root-mean-square difference of 0.13 Hz between measured and back-calculated coupling constants. The curve compares with data derived from ubiquitin (A. C. Wang and A. Bax, J. Am. Chem. Soc.117, 1810-1813 (1995)), although spanning a slightly larger range of J values in flavodoxin. The orientation of the Ala39/Ser40 peptide link, forming a type-II β-turn in flavodoxin, is twisted against X-ray-derived torsions by approximately 10° in the NMR structure as evident from the analysis of φ- and ψ-related 3J coupling constants. The remaining deviation of some experimental values from the prediction is likely to be due to strong hydrogen bonding, substituent effects, or the additional dependence on the adjacent torsions φ.

  4. Communication: Spin densities within a unitary group based spin-adapted open-shell coupled-cluster theory: Analytic evaluation of isotropic hyperfine-coupling constants for the combinatoric open-shell coupled-cluster scheme

    SciTech Connect

    Datta, Dipayan Gauss, Jürgen

    2015-07-07

    We report analytical calculations of isotropic hyperfine-coupling constants in radicals using a spin-adapted open-shell coupled-cluster theory, namely, the unitary group based combinatoric open-shell coupled-cluster (COSCC) approach within the singles and doubles approximation. A scheme for the evaluation of the one-particle spin-density matrix required in these calculations is outlined within the spin-free formulation of the COSCC approach. In this scheme, the one-particle spin-density matrix for an open-shell state with spin S and M{sub S} = + S is expressed in terms of the one- and two-particle spin-free (charge) density matrices obtained from the Lagrangian formulation that is used for calculating the analytic first derivatives of the energy. Benchmark calculations are presented for NO, NCO, CH{sub 2}CN, and two conjugated π-radicals, viz., allyl and 1-pyrrolyl in order to demonstrate the performance of the proposed scheme.

  5. Perturbation Theory with Convergent Series for Large Values of Coupling Constant:. a Calculation of β-FUNCTION in φ4 Model

    NASA Astrophysics Data System (ADS)

    Belokurov, V. V.; Shavgulidze, E. T.; Solov'yov, Yu. P.; Yudin, I. L.

    2001-04-01

    A new perturbation theory with convergent series is used to calculate quantities given by a finite number of terms of the traditional perturbation theory. As examples of such a problem, the zero-dimensional analog of a functional integral and β-function in gφ4 model in four-dimensional space-time are considered. The results obtained demonstrate high accuracy of the calculation in a wide region of coupling constant values.

  6. The influence of a presence of a heavy atom on the spin-spin coupling constants between two light nuclei in organometallic compounds and halogen derivatives

    NASA Astrophysics Data System (ADS)

    Wodyński, Artur; Pecul, Magdalena

    2014-01-01

    The 1JCC and 1JCH spin-spin coupling constants have been calculated by means of density functional theory (DFT) for a set of derivatives of aliphatic hydrocarbons substituted with I, At, Cd, and Hg in order to evaluate the substituent and relativistic effects for these properties. The main goal was to estimate HALA (heavy-atom-on-light-atom) effects on spin-spin coupling constants and to explore the factors which may influence the HALA effect on these properties, including the nature of the heavy atom substituent and carbon hybridization. The methods applied range, in order of reduced complexity, from Dirac-Kohn-Sham method (density functional theory with four-component Dirac-Coulomb Hamiltonian), through DFT with two- and one-component Zeroth Order Regular Approximation (ZORA) Hamiltonians, to scalar non-relativistic effective core potentials with the non-relativistic Hamiltonian. Thus, we are able to compare the performance of ZORA-DFT and Dirac-Kohn-Sham methods for modelling of the HALA effects on the spin-spin coupling constants.

  7. The influence of a presence of a heavy atom on the spin-spin coupling constants between two light nuclei in organometallic compounds and halogen derivatives

    SciTech Connect

    Wodyński, Artur; Pecul, Magdalena

    2014-01-14

    The {sup 1}J{sub CC} and {sup 1}J{sub CH} spin-spin coupling constants have been calculated by means of density functional theory (DFT) for a set of derivatives of aliphatic hydrocarbons substituted with I, At, Cd, and Hg in order to evaluate the substituent and relativistic effects for these properties. The main goal was to estimate HALA (heavy-atom-on-light-atom) effects on spin-spin coupling constants and to explore the factors which may influence the HALA effect on these properties, including the nature of the heavy atom substituent and carbon hybridization. The methods applied range, in order of reduced complexity, from Dirac-Kohn-Sham method (density functional theory with four-component Dirac-Coulomb Hamiltonian), through DFT with two- and one-component Zeroth Order Regular Approximation (ZORA) Hamiltonians, to scalar non-relativistic effective core potentials with the non-relativistic Hamiltonian. Thus, we are able to compare the performance of ZORA-DFT and Dirac-Kohn-Sham methods for modelling of the HALA effects on the spin-spin coupling constants.

  8. The influence of a presence of a heavy atom on the spin-spin coupling constants between two light nuclei in organometallic compounds and halogen derivatives.

    PubMed

    Wodyński, Artur; Pecul, Magdalena

    2014-01-14

    The (1)JCC and (1)JCH spin-spin coupling constants have been calculated by means of density functional theory (DFT) for a set of derivatives of aliphatic hydrocarbons substituted with I, At, Cd, and Hg in order to evaluate the substituent and relativistic effects for these properties. The main goal was to estimate HALA (heavy-atom-on-light-atom) effects on spin-spin coupling constants and to explore the factors which may influence the HALA effect on these properties, including the nature of the heavy atom substituent and carbon hybridization. The methods applied range, in order of reduced complexity, from Dirac-Kohn-Sham method (density functional theory with four-component Dirac-Coulomb Hamiltonian), through DFT with two- and one-component Zeroth Order Regular Approximation (ZORA) Hamiltonians, to scalar non-relativistic effective core potentials with the non-relativistic Hamiltonian. Thus, we are able to compare the performance of ZORA-DFT and Dirac-Kohn-Sham methods for modelling of the HALA effects on the spin-spin coupling constants.

  9. F···HO intramolecular hydrogen bond as the main transmission mechanism for (1h)J(F,H(O)) coupling constant in 2'-fluoroflavonol.

    PubMed

    Fonseca, Tânia A O; Ramalho, Teodorico C; Freitas, Matheus P

    2012-08-01

    Flavonoids are useful compounds in medicinal chemistry and exhibit conformational isomerism, which is ruled by intramolecular interactions. One of the main intramolecular forces governing the stability of conformations is the hydrogen bond. Hydrogen bond involving fluorine covalently bonded to carbon has been found to be rare, but it appears in 2'-fluoroflavonol, although the F···HO hydrogen bond cannot be considered the main effect governing the conformational stability of this compound. Because (19)F is magnetically active and suitable for NMR studies, the (1h)J(F,H(O)) coupling constant can be used as a probe for such an interaction in 2'-fluoroflavonol. In fact, the (1h)J(F,H(O)) coupling was computationally analyzed in this work, and the F···HO hydrogen bond was found to be its main transmission mechanism, which modulates this coupling in 2'-fluoroflavonol, rather than overlap of proximate electronic clouds, such as in 2-fluorophenol.

  10. A Pure-Phase Homonuclear J-Modulated HMQC Experiment with Tilted Cross-Peak Patterns for an Accurate Determination of Homonuclear Coupling Constants

    NASA Astrophysics Data System (ADS)

    Koź Miń Ski, Wiktor

    1999-11-01

    A new HMQC-based experiment is presented which allows for an efficient determination of accurate homonuclear coupling-constant values. Pure absorption lineshapes with tilted cross-peak patterns are obtained by a combination of the active-coupling-pattern tilting (ACT) scheme with J-scaling. Characteristic features include separate heteronuclear echo and antiecho acquisition with a BIRDy pulse positioned before or after the t1 period, respectively, to refocus I-spin homonuclear coupling evolution. Additionally, due to the incorporation of J-scaling the relative spacing of the S-spin chemical-shift differences and I-spin homonuclear coupling splittings in the F1 domain is largely under experimental control. The most important advantage of the proposed method is that the I-spin homonuclear coupling evolution occurs simultaneously with the evolution of the heteronuclear zero and double-quantum coherences, which exhibit a slower transverse relaxation than I-spin single-quantum coherences. The effectiveness of the new sequence is demonstrated by a determination of the 3JHN,Hα couplings in a peptide sample. Additionally, the broadband property of the new sequence is verified with a sucrose sample.

  11. Improved sphaleron decoupling condition and the Higgs coupling constants in the real singlet-extended standard model

    NASA Astrophysics Data System (ADS)

    Fuyuto, Kaori; Senaha, Eibun

    2014-07-01

    We improve the sphaleron decoupling condition in the real singlet-extended standard model (SM). The sphaleron energy is obtained using the finite-temperature one-loop effective potential with daisy resummation. For moderate values of the model parameters, the sphaleron decoupling condition is found to be vC/TC>(1.1-1.2), where TC denotes a critical temperature and vC is the corresponding vacuum expectation value of the doublet Higgs field at TC. We also investigate the deviation of the triple Higgs boson coupling from its standard model value in the region where the improved sphaleron decoupling condition is satisfied. As a result of the improvement, the deviation of the triple Higgs boson coupling gets more enhanced. In a typical case, if the Higgs couplings to the gauge bosons/fermions deviate from the SM values by about 3 (10)%, the deviation of the triple Higgs boson coupling can be as large as about 16 (50)%, which is about 4 (8)% larger than that based on the conventional criterion vC/TC>1.

  12. Minimalist Relativistic Force Field: Prediction of Proton-Proton Coupling Constants in (1)H NMR Spectra Is Perfected with NBO Hybridization Parameters.

    PubMed

    Kutateladze, Andrei G; Mukhina, Olga A

    2015-05-15

    We previously developed a reliable method for multiparametric scaling of Fermi contacts to achieve fast and accurate prediction of proton-proton spin-spin coupling constants (SSCC) in (1)H NMR. We now report that utilization of NBO hybridization coefficients for carbon atoms in the involved C-H bonds allows for a significant simplification of this parametric scheme, requiring only four general types of SSCCs: geminal, vicinal, 1,3-, and long-range constants. The method is optimized for inexpensive B3LYP/6-31G(d) molecular geometries. A new DU8 basis set, based on a training set of 475 experimental spin-spin coupling constants, is developed for hydrogen and common non-hydrogen atoms (Li, B, C, N, O, F, Si, P, S, Cl, Se, Br, I) to calculate Fermi contacts. On a test set of 919 SSCCs from a diverse collection of natural products and complex synthetic molecules the method gave excellent accuracy of 0.29 Hz (rmsd) with the maximum unsigned error not exceeding 1 Hz.

  13. Minimalist Relativistic Force Field: Prediction of Proton-Proton Coupling Constants in (1)H NMR Spectra Is Perfected with NBO Hybridization Parameters.

    PubMed

    Kutateladze, Andrei G; Mukhina, Olga A

    2015-05-15

    We previously developed a reliable method for multiparametric scaling of Fermi contacts to achieve fast and accurate prediction of proton-proton spin-spin coupling constants (SSCC) in (1)H NMR. We now report that utilization of NBO hybridization coefficients for carbon atoms in the involved C-H bonds allows for a significant simplification of this parametric scheme, requiring only four general types of SSCCs: geminal, vicinal, 1,3-, and long-range constants. The method is optimized for inexpensive B3LYP/6-31G(d) molecular geometries. A new DU8 basis set, based on a training set of 475 experimental spin-spin coupling constants, is developed for hydrogen and common non-hydrogen atoms (Li, B, C, N, O, F, Si, P, S, Cl, Se, Br, I) to calculate Fermi contacts. On a test set of 919 SSCCs from a diverse collection of natural products and complex synthetic molecules the method gave excellent accuracy of 0.29 Hz (rmsd) with the maximum unsigned error not exceeding 1 Hz. PMID:25885091

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

    NASA Astrophysics Data System (ADS)

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

    2015-12-01

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

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

    SciTech Connect

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

    2015-12-28

    It is investigated, whether the number of excited (pseudo)states can be truncated in the sum-over-states expression for indirect spin-spin coupling constants (SSCCs), which is used in the Contributions from Localized Orbitals within the Polarization Propagator Approach and Inner Projections of the Polarization Propagator (IPPP-CLOPPA) approach to analyzing SSCCs in terms of localized orbitals. As a test set we have studied the nine simple compounds, CH{sub 4}, NH{sub 3}, H{sub 2}O, SiH{sub 4}, PH{sub 3}, SH{sub 2}, C{sub 2}H{sub 2}, C{sub 2}H{sub 4}, and C{sub 2}H{sub 6}. The excited (pseudo)states were obtained from time-dependent density functional theory (TD-DFT) calculations with the B3LYP exchange-correlation functional and the specialized core-property basis set, aug-cc-pVTZ-J. We investigated both how the calculated coupling constants depend on the number of (pseudo)states included in the summation and whether the summation can be truncated in a systematic way at a smaller number of states and extrapolated to the total number of (pseudo)states for the given one-electron basis set. We find that this is possible and that for some of the couplings it is sufficient to include only about 30% of the excited (pseudo)states.

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

    PubMed

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

    2015-12-28

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

  17. Homonuclear BIRD-decoupled spectra for measuring one-bond couplings with highest resolution: CLIP/CLAP-RESET and constant-time-CLIP/CLAP-RESET

    NASA Astrophysics Data System (ADS)

    Reinsperger, Tony; Luy, Burkhard

    2014-02-01

    Heteronuclear one-bond couplings are of interest for various aspects of structural analysis of small organic molecules, including for example the distinction of axial and equatorial protons or the use of RDCs as angular constraints. Such couplings are most easily measured from pure doublets in HSQC-type spectra. Recently, the fully decoupled RESET HSQC experiment was reported and several other so-called pure-shift methods followed that allow for the removal of splittings due to homonuclear scalar interactions in one and two-dimensional NMR. In this work we present broadband homonuclear decoupled CLIP/CLAP-RESET experiments based on an isotope-selective BIRD filter element using a recently reported improved version of Zangger-Sterk data chunking. The concatenated FIDs result in multiplets in which most homonuclear splittings are removed while the heteronuclear one-bond couplings are retained. Couplings can be extracted in an IPAP fashion without scaling of subspectra by the use of optimized coherence transfer elements like the COB-INEPT. The method leads to complete homonuclear decoupling for CH groups and CH3 groups in isotropic samples, but leaves residual splittings with antiphase contributions for e.g. CH2 groups due to 2JHH coupling evolution that is not affected by the BIRD element. For this case we present a constant-time version of the proposed BIRD decoupling scheme with full homonuclear decoupling. In addition, the effects of strong coupling are discussed. Strong coupling artifacts cannot be circumvented, but the proposed experiments allow their distinct recognition.

  18. Relative importance of first and second derivatives of nuclear magnetic resonance chemical shifts and spin-spin coupling constants for vibrational averaging.

    PubMed

    Dracínský, Martin; Kaminský, Jakub; Bour, Petr

    2009-03-01

    Relative importance of anharmonic corrections to molecular vibrational energies, nuclear magnetic resonance (NMR) chemical shifts, and J-coupling constants was assessed for a model set of methane derivatives, differently charged alanine forms, and sugar models. Molecular quartic force fields and NMR parameter derivatives were obtained quantum mechanically by a numerical differentiation. In most cases the harmonic vibrational function combined with the property second derivatives provided the largest correction of the equilibrium values, while anharmonic corrections (third and fourth energy derivatives) were found less important. The most computationally expensive off-diagonal quartic energy derivatives involving four different coordinates provided a negligible contribution. The vibrational corrections of NMR shifts were small and yielded a convincing improvement only for very accurate wave function calculations. For the indirect spin-spin coupling constants the averaging significantly improved already the equilibrium values obtained at the density functional theory level. Both first and complete second shielding derivatives were found important for the shift corrections, while for the J-coupling constants the vibrational parts were dominated by the diagonal second derivatives. The vibrational corrections were also applied to some isotopic effects, where the corrected values reasonably well reproduced the experiment, but only if a full second-order expansion of the NMR parameters was included. Contributions of individual vibrational modes for the averaging are discussed. Similar behavior was found for the methane derivatives, and for the larger and polar molecules. The vibrational averaging thus facilitates interpretation of previous experimental results and suggests that it can make future molecular structural studies more reliable. Because of the lengthy numerical differentiation required to compute the NMR parameter derivatives their analytical implementation in

  19. Dynamics, NMR parameters and hyperfine coupling constants of the Fe3O4(1 0 0)-water interface: Implications for MRI probes

    NASA Astrophysics Data System (ADS)

    Gonçalves, Mateus A.; Peixoto, Fernando C.; da Cunha, Elaine F. F.; Ramalho, Teodorico C.

    2014-08-01

    Magnetite is an iron oxide widely used as contrast agent in MRI, receiving considerable interest from nanoscience and nanotechnology. In this work, the face 1 0 0 of the magnetite structure was studied with water in order to obtain 1H hyperfine coupling constants (HFCCs). Molecular dynamics (MD) calculations were performed using the ReaxFF program and for statistical inefficiency, structures were selected for HFCC and NMR calculations. From our theoretical findings, the magnetite in solution considerably increases the 1H HFCC of water molecules. From our results, it is essential to incorporate the dynamics and solvent effects into NMR calculations of relaxation parameters.

  20. The calculation of accurate 17O hyperfine coupling constants in the hydroxyl radical: A difficult problem for current quantum chemical methods

    NASA Astrophysics Data System (ADS)

    Wetmore, Stacey D.; Eriksson, Leif A.; Boyd, Russell J.

    1998-12-01

    The hyperfine coupling constants (HFCCs) in the hydroxyl radical are investigated through comparison of results obtained from a variety of quantum chemical methods. The couplings obtained from the multi-reference configuration interaction (MRCI) wave function, built upon the restricted open-shell Hartree-Fock (ROHF) reference determinant, are investigated in terms of the basis set, the configuration selection energy threshold, and the size of the reference space. Overall results which converge to the experimental couplings are obtained for hydrogen, but not for oxygen. In particular, the MRCI method shows no improvement over density functional theory (the B3LYP functional), for the calculation of Aiso(17O). On the other hand, results in excellent agreement with experiment are obtained through the use of the quadratic configuration interaction (QCISD) method based on the unrestricted HF (UHF) reference determinant with the identical basis sets. Examination of UHF and ROHF based coupled-cluster methods, CCSD and CCSD(T), indicates that once a high enough level of electron correlation is included, the oxygen HFCC is independent of the form of the reference determinant. Unlike the ROHF-CCSD method, which yields reliable results once the effects of triple excitations have been taken into account, the MRCI wave function cannot easily be adjusted to account for the inadequacies of the ROHF reference determinant in order to accurately predict 17O HFCCs.

  1. Magnetic Coupling Constants in Three Electrons Three Centers Problems from Effective Hamiltonian Theory and Validation of Broken Symmetry-Based Approaches.

    PubMed

    Reta, Daniel; Moreira, Ibério de P R; Illas, Francesc

    2016-07-12

    In the most general case of three electrons in three symmetry unrelated centers with Ŝ1 = Ŝ2 = Ŝ3 = 1/2 localized magnetic moments, the low energy spectrum consists of one quartet (Q) and two doublet (D1, D2) pure spin states. The energy splitting between these spin states can be described with the well-known Heisenberg-Dirac-Van Vleck (HDVV) model spin Hamiltonian, and their corresponding energy expressions are expressed in terms of the three different two-body magnetic coupling constants J12, J23, and J13. However, the values of all three magnetic coupling constants cannot be extracted using the calculated energy of the three spin-adapted states since only two linearly independent energy differences between pure spin states exist. This problem has been recently investigated by Reta et al. (J. Chem. Theory Comput. 2015, 11, 3650), resulting in an alternative proposal to the original Noodleman's broken symmetry mapping approach. In the present work, this proposal is validated by means of ab initio effective Hamiltonian theory, which allows a direct extraction of all three J values from the one-to-one correspondence between the matrix elements of both effective and HDVV Hamiltonian. The effective Hamiltonian matrix representation has been constructed from configuration interaction wave functions for the three spin states obtained for two model systems showing a different degree of delocalization of the unpaired electrons. These encompass a trinuclear Cu(II) complex and a π-conjugated purely organic triradical. PMID:27231983

  2. The role of the magnetic orbitals in the calculation of the magnetic coupling constants from multireference perturbation theory methods.

    PubMed

    Angeli, Celestino; Calzado, Carmen J

    2012-07-21

    The use of multireference perturbation theory (MRPT) for the calculation of the magnetic coupling in binuclear complexes has shown to give poor results if applied on a minimal active space complete active space self-consistent field (CASSCF) wavefunction. In this work, we identify the origin of this problem in the starting CASSCF orbitals, which are exceedingly localized on the metal atoms. Focusing on the case of antiferromagnetic systems, it is shown that the form of the active orbitals has a dramatic effect on the relative description of the neutral and ionic structures. Finally, a simple and computational inexpensive strategy is proposed for the calculation of a set of magnetic orbitals describing in a more balanced way the neutral and ionic structures. The use of these orbitals, instead the CASSCF ones, in minimal active space MRPT2 calculations leads to a marked improvement of the J values, which become in reasonable agreement with those obtained with the expensive high level difference dedicated configuration interaction approach and with the experimental values.

  3. Effect of pressure on the proton-proton vicinal coupling constants in 1,1,2-tricholoethane and 1,1,2,2-tetrachloroethane-1- sup 13 C. A new approach to hig-pressure study of molecular conformations

    SciTech Connect

    Yamada, H.; Kazuoka, T.; Sera, A. )

    1988-10-26

    The first observation of a pressure-induced change in the proton-proton vicinal coupling constants, J{sub vic}, are reported here. It is also demonstrated that the experiment possibly provides a new, straightforward approach to conformation studies at high pressure. The pressure effects on coupling constants of 1,1,2-trichloroethane + 10 mol % of cyclopentane, 1,1,2-trichloroethane, and 1,1,2-trichloroethane 1-{sup 13}C are reported. 17 refs., 3 figs.

  4. Precise Determination of the Strong Coupling Constant at NNLO in QCD from the Three-Jet Rate in Electron-Positron Annihilation at LEP

    SciTech Connect

    Dissertori, G.; Gehrmann-DeRidder, A.; Gehrmann, T.; Glover, E. W. N.; Heinrich, G.; Stenzel, H.

    2010-02-19

    We present the first determination of the strong coupling constant from the three-jet rate in e{sup +}e{sup -} annihilation at LEP, based on a next-to-next-to-leading-order (NNLO) perturbative QCD prediction. More precisely, we extract {alpha}{sub s}(M{sub Z}) by fitting perturbative QCD predictions at O({alpha}{sub s}{sup 3}) to data from the ALEPH experiment at LEP. Over a large range of the jet-resolution parameter y{sub cut}, this observable is characterized by small nonperturbative corrections and an excellent stability under renormalization scale variation. We find {alpha}{sub s}(M{sub Z})=0.1175+-0.0020(expt)+-0.0015(theor), which is more accurate than the values of {alpha}{sub s}(M{sub Z}) from e{sup +}e{sup -} event-shape data currently used in the world average.

  5. Calculation of P,T-odd interaction constant of PbF using Z-vector method in the relativistic coupled-cluster framework.

    PubMed

    Sasmal, Sudip; Pathak, Himadri; Nayak, Malaya K; Vaval, Nayana; Pal, Sourav

    2015-08-28

    The effective electric field experienced by the unpaired electron in the ground state of PbF, which is a potential candidate in the search of electron electric dipole moment due to some special characteristics, is calculated using Z-vector method in the coupled cluster single- and double- excitation approximation with four component Dirac spinor. This is an important quantity to set the upper bound limit of the electron electric dipole moment. Further, we have calculated molecular dipole moment and parallel magnetic hyperfine structure constant (A‖) of (207)Pb in PbF to test the accuracy of the wavefunction obtained in the Z-vector method. The outcome of our calculations clearly suggests that the core electrons have significant contribution to the "atom in compound" properties. PMID:26328830

  6. New techniques for the measurement of C'N and C'H(N) J coupling constants across hydrogen bonds in proteins.

    PubMed

    Meissner, A; Sorensen, O W

    2000-04-01

    Two new two- or three-dimensional NMR methods for measuring (3h)J(C'N) and (2h)J(C'H) coupling constants across hydrogen bonds in proteins are presented. They are tailored to suit the size of the TROSY effect, i.e., the degree of interference between dipolar and chemical shift anisotropy relaxation mechanisms. The methods edit 2D or 3D spectra into two separate subspectra corresponding to the two possible spin states of the (1)H(N) spin during evolution of (13)CO coherences. This allows (2h)J(C'H) to be measured in an E.COSY-type way while (3h)J(C'N) can be measured in the so-called quantitative way provided a reference spectrum is also recorded. A demonstration of the new methods is shown for the (15)N,(13)C-labeled protein chymotrypsin inhibitor 2.

  7. Revisiting NMR through-space J(FF) spin-spin coupling constants for getting insight into proximate F---F interactions.

    PubMed

    Contreras, Rubén H; Llorente, Tomás; Ducati, Lucas Colucci; Tormena, Cláudio Francisco

    2014-07-10

    At present times it is usual practice to mark biological compounds replacing an H for an F atom to study, by means of (19)F NMR spectroscopy, aspects such as binding sites and molecular folding features. This interesting methodology could nicely be improved if it is known how proximity interactions on the F atom affect its electronic structure as gauged through high-resolution (19)F NMR spectroscopy. This is the main aim of the present work and, to this end, differently substituted peri-difluoronaphthalenes are chosen as model systems. In such compounds are rationalized some interesting aspects of the diamagnetic and paramagnetic parts of the (19)F nuclear magnetic shielding tensor as well as the transmission mechanisms for the PSO and FC contributions to (4)JF1F8 indirect nuclear spin-spin coupling constants.

  8. First Exact Solutions for Flows of Rate Type Fluids in a Circular Duct that Applies a Constant Couple to the Fluid

    NASA Astrophysics Data System (ADS)

    Fetecau, Corina; Rana, Mehwish; Nigar, Niat; Fetecau, Constantin

    2014-06-01

    Rotational flow of an Oldroyd-B fluid induced by an infinite circular cylinder that applies a constant couple to the fluid is studied by means of integral transforms. Such a problem is not solved in the existing literature for rate type fluids and the present solutions are based on a simple but important remark regarding the governing equation for the non-trivial shear stress. The solutions that have been obtained satisfy all imposed initial and boundary conditions and can easy be reduced to the similar solutions corresponding to Maxwell, second-grade, and Newtonian fluids performing the same motion. Finally, the influence of material parameters on the velocity and shear stress distributions is graphically underlined.

  9. Study of kinetic desorption rate constant in fish muscle and agarose gel model using solid phase microextraction coupled with liquid chromatography with tandem mass spectrometry.

    PubMed

    Togunde, Oluranti Paul; Oakes, Ken; Servos, Mark; Pawliszyn, Janusz

    2012-09-12

    This study aims to use solid phase microextraction (SPME), a simple tool to investigate diffusion rate (time) constant of selected pharmaceuticals in gel and fish muscle by comparing desorption rate of diffusion of the drugs in both agarose gel prepared with phosphate-buffered saline (PBS; pH 7.4) and fish muscle. The gel concentration (agarose gel model) that could be used to simulate tissue matrix (fish muscle) for free diffusion of drugs under in vitro and in vivo conditions was determined to model mass transfer phenomena between fibre polymer coating and environmental matrix such that partition coefficients and desorption time constant (diffusion coefficient) can be determined. SPME procedure involves preloading the extraction phase (fibre) with the standards from spiked PBS for 1h via direct extraction. Subsequently, the preloaded fibre is introduced to the sample such fish or agarose gel for specified time ranging from 0.5 to 60 h. Then, fibre is removed at specified time and desorbed in 100 μL of desorption solution (acetonitrile: water 1:1) for 90 min under agitation speed of 1000 rpm. The samples extract were immediately injected to the instrument and analysed using liquid chromatography coupled with tandem mass spectrometry (LC/MS/MS). The limit of detection of the method in gel and fish muscle was 0.01-0.07 ng mL(-1) and 0.07-0.34 ng g(-1), respectively, while the limit quantification was 0.10-0.20 ng mL(-1) in gel samples and 0.40-0.97 ng g(-1) in fish sample. The reproducibility of the method was good (5-15% RSD). The results suggest that kinetics of desorption of the compounds in fish tissue and different viscosity of gel can be determined using desorption time constant. In this study, desorption time constant which is directly related to desorption rate (diffusion kinetics) of selected drugs from the fibre to the gel matrix is faster as the viscosity of the gel matrix reduces from 2% (w/v) to 0.8% (w/v). As the concentration of gel reduces

  10. Measurement of one-bond 13C α- 1H α residual dipolar coupling constants in proteins by selective manipulation of C αH α spins

    NASA Astrophysics Data System (ADS)

    Ball, Graeme; Meenan, Nicola; Bromek, Krystyna; Smith, Brian O.; Bella, Juraj; Uhrín, Dušan

    2006-05-01

    We have developed new 2D and 3D experiments for the measurement of C α-H α residual dipolar coupling constants in 13C and 15N labelled proteins. Two experiments, 2D (HNCO)-( J-CA)NH and 3D (HN)CO-( J-CA)NH, sample the C α-H α splitting by means of C α magnetization, while 2D ( J-HACACO)NH and 3D J-HA(CACO)NH use H α magnetization to achieve a similar result. In the 2D experiments the coupling evolution is superimposed on the evolution of the 15N chemical shifts and the IPAP principle is used to obtain 1H- 15N HSQC-like spectra from which the splitting is determined. The use of a third dimension in 3D experiments reduces spectral overlap to the point where use of an IPAP scheme may not be necessary. The length of the sampling interval in the J-dimension of these experiments is dictated solely by the relaxation properties of C α or H α nuclei. This was made possible by the use of C α selective pulses in combination with either a DPFGSE or modified BIRD pulses. Inclusion of these pulse sequence elements in the J-evolution periods removes unwanted spin-spin interactions. This allows prolonged sampling periods (˜25 ms) yielding higher precision C α-H α splitting determination than is achievable with existing frequency based methods.

  11. Computation with Inverse States in a Finite Field FP: The Muon Neutrino Mass, the Unified Strong-Electroweak Coupling Constant, and the Higgs Mass

    SciTech Connect

    DAI,YANG; BORISOV,ALEXEY B.; BOYER,KEITH; RHODES,CHARLES K.

    2000-08-11

    The construction of inverse states in a finite field F{sub P{sub {alpha}}} enables the organization of the mass scale with fundamental octets in an eight-dimensional index space that identifies particle states with residue class designations. Conformance with both CPT invariance and the concept of supersymmetry follows as a direct consequence of this formulation. Based on two parameters (P{sub {alpha}} and g{sub {alpha}}) that are anchored on a concordance of physical data, this treatment leads to (1) a prospective mass for the muon neutrino of {approximately}27.68 meV, (2) a value of the unified strong-electroweak coupling constant {alpha}* = (34.26){sup {minus}1} that is physically defined by the ratio of the electron neutrino and muon neutrino masses, and (3) a see-saw congruence connecting the Higgs, the electron neutrino, and the muon neutrino masses. Specific evaluation of the masses of the corresponding supersymmetric Higgs pair reveals that both particles are superheavy (> 10{sup 18}GeV). No renormalization of the Higgs masses is introduced, since the calculational procedure yielding their magnitudes is intrinsically divergence-free. Further, the Higgs fulfills its conjectured role through the see-saw relation as the particle defining the origin of all particle masses, since the electron and muon neutrino systems, together with their supersymmetric partners, are the generators of the mass scale and establish the corresponding index space. Finally, since the computation of the Higgs masses is entirely determined by the modulus of the field P{sub {alpha}}, which is fully defined by the large-scale parameters of the universe through the value of the universal gravitational constant G and the requirement for perfect flatness ({Omega} = 1.0), the see-saw congruence fuses the concepts of mass and space and creates a new unified archetype.

  12. Magnetic circular dichroism studies of matrix-isolated atoms: Excited state spin-orbit coupling constant reduction of copper in the noble gases

    NASA Astrophysics Data System (ADS)

    Vala, Martin; Zeringue, Kyle; ShakhsEmampour, Jalal; Rivoal, Jean-Claude; Pyzalski, Robert

    1984-03-01

    The absorption and magnetic circular dichroism spectra of the 2P←2S transition of matrix-isolated copper atoms have been measured in krypton and xenon matrices. A dramatic reversal in the MCD C term pattern is observed. From a spectral band moment analysis it is shown that: (1) noncubic lattice cage vibrational motions are more important than cubic ones in contributing to the observed bandwidths and (2) the Cu excited state spin-orbit coupling constant (λ) in krypton is reduced to 57% of its gas phase value, whereas in xenon it is reduced to -14% of its gas phase value. Calculations using the Moran model show that the excited state geometry of the metal/rare gas cage is distorted via the Jahn-Teller effect in opposite ways in krypton and xenon matrices. The negative sign of λ in xenon reveals a reversal in the order of the 2P state spin-orbit multiplets. Neither this reversal nor the reduction of λ in krypton can be accounted for by the Jahn-Teller effect. We attribute the spin-orbit constant reduction to the overlap of the Cu 4p orbital with the np of the rare gas matrix cage atoms. The calculated spin-orbit reduction factors (in Ar, Kr, and Xe) agree well with the experimental ones if a contracted Cu 4p orbital is used. In the same way the ground state g factor shift with matrix atom type, observed by Kasai and McLeod, is semiquantitatively accounted for by calculation of the overlaps between the Cu 4s orbital and the np orbitals of the rare gas cage atoms.

  13. Rapid determination of benzo[a]pyrene by membrane enrichment coupled with solid-phase constant-wavelength synchronous fluorescence spectrometry.

    PubMed

    Wang, Lei; Li, Wei; Zhang, Feiyu; Li, Hui; Cai, Guimin; Li, Bing; Qian, Guangbei; Du, Yiping

    2016-09-01

    Normal methods for benzo[a]pyrene (BaP) determination, including gas chromatography-mass spectrometry and liquid chromatography with fluorescence detection, involve expensive instruments and complex separation and purification processes. Based on membrane enrichment, coupled with solid-phase constant-wavelength synchronous fluorescence spectrometry, a simple, fast, sensitive method was proposed for the determination of BaP in water samples. A Nylon membrane was used as the solid-phase extraction material for enrichment. After enrichment, a constant-wavelength synchronous fluorescence spectrum was scanned directly on the membrane-concentrated BaP without elution. Spectral measurement and enrichment conditions were optimized. Under optimum conditions, when using 150 mL sample solutions, the relationship between fluorescence intensity and BaP concentrations in the 0.05-10.00 μg L(-1) range could be fitted by binomial function with an R(2) value of 0.9973. Limit of detection (LOD) was calculated to be 0.0137 μg L(-1) . The volume of the sample solution was increased to 1000 mL to test if the method could be applied to determine lower BaP concentrations. A linear relationship still existed in the range 2.0-20.0 ng L(-1) BaP with an R(2) value of 0.9895, and a LOD of 2.4 ng L(-1) . The method was also used to measure the BaP concentration in several natural water samples, and recoveries were in the 90-110% range with relative standard deviations (RSDs) in the 0.58-7.93% range. Copyright © 2016 John Wiley & Sons, Ltd. PMID:26781918

  14. Conformational study of C8 diazocine turn mimics using {sup 3}J{sub CH} coupling constants with {sup 13}C in natural abundance

    SciTech Connect

    Bean, J.W.; Briand, J.; Burgess, J.L.; Callahan, J.F.

    1994-12-01

    The conformations of two diazocine turn mimics, which were later incorporated into GPIIb/IIIa peptide antagonists, were investigated using nuclear magnetic resonance techniques. The two compounds, methyl (2,5-dioxo-3-(S)-(3-{omega}-tosylguanidino-propyl)-4-methyl-octahydro-1,4-dazocin-1-yl)acetate (1) and methyl (2,5-dioxo-3-(S)-(3-{omega}-tosyl-guanidino-propyl)-octahydro-1,5-diazocin-1-yl)acetate (2), differ only in their substituent at the diazocine position 4 nitrogen, yet this substitution results in a marked difference in the affinity of the resulting analogs for the GPIIb/IIIa receptor. It was of interest to determine if the difference observed in the antagonistic potency between these analogs was related to constitutional or, perhaps, conformational differences. The backbone conformations of these two molecules can be determined by measuring vicinal coupling constants along the trimethylene portion of the C8 ring backbone and by measuring interproton NOE intensities between the diazocine methine proton and the protons of the trimethylene group. For compound 1, {sup 3}J{sub HH} values measured from a P.E.COSY spectrum and interproton distances calculated from ROESY buildup curves indicated the presence of a single C8 ring backbone conformation where the trimethylene bridge adopted a staggered conformation and the H{alpha}1 and H{gamma}1 protons of the trimethylene group were 2.2 A from the methine proton. For compound 2, however, partial overlap of the central H{beta}1 and H{beta}2 protons made it impossible to measure {sup 3}J{sub HH} values from the P.E.COSY spectrum. We therefore used a {sup 13}C-filtered TOCSY experiment to measure the {sup 3}J{sub CH} values in both compounds 1 and 2. These heteronuclear vicinal coupling constants measured with {sup 13}C in natural abundance in conjunction with measured interproton NOE intensities indicate that these compounds share a common C8 ring backbone conformation.

  15. Theoretical prediction of nuclear magnetic shieldings and indirect spin-spin coupling constants in 1,1-, cis-, and trans-1,2-difluoroethylenes

    SciTech Connect

    Nozirov, Farhod E-mail: farhod.nozirov@gmail.com; Stachów, Michał; Kupka, Teobald E-mail: farhod.nozirov@gmail.com

    2014-04-14

    A theoretical prediction of nuclear magnetic shieldings and indirect spin-spin coupling constants in 1,1-, cis- and trans-1,2-difluoroethylenes is reported. The results obtained using density functional theory (DFT) combined with large basis sets and gauge-independent atomic orbital calculations were critically compared with experiment and conventional, higher level correlated electronic structure methods. Accurate structural, vibrational, and NMR parameters of difluoroethylenes were obtained using several density functionals combined with dedicated basis sets. B3LYP/6-311++G(3df,2pd) optimized structures of difluoroethylenes closely reproduced experimental geometries and earlier reported benchmark coupled cluster results, while BLYP/6-311++G(3df,2pd) produced accurate harmonic vibrational frequencies. The most accurate vibrations were obtained using B3LYP/6-311++G(3df,2pd) with correction for anharmonicity. Becke half and half (BHandH) density functional predicted more accurate {sup 19}F isotropic shieldings and van Voorhis and Scuseria's τ-dependent gradient-corrected correlation functional yielded better carbon shieldings than B3LYP. A surprisingly good performance of Hartree-Fock (HF) method in predicting nuclear shieldings in these molecules was observed. Inclusion of zero-point vibrational correction markedly improved agreement with experiment for nuclear shieldings calculated by HF, MP2, CCSD, and CCSD(T) methods but worsened the DFT results. The threefold improvement in accuracy when predicting {sup 2}J(FF) in 1,1-difluoroethylene for BHandH density functional compared to B3LYP was observed (the deviations from experiment were −46 vs. −115 Hz)

  16. Prediction and experimental comparison of deuterium quadrupole coupling constants in some bifluoride salts: An extreme example of symmetric hydrogen bonding in different crystalline environments

    NASA Astrophysics Data System (ADS)

    Bacskay, George B.; Gready, Jill E.

    1988-02-01

    The electric field gradient (EFG) at the deuterium nucleus of the bifluoride ion, a linear symmetrically H-bonded system, has been calculated using ab initio Hartree-Fock SCF, singles and doubles CI, and coupled pair functional methods using basis sets ranging from double zeta to the [7,5,2,1;5,4,2] contracted Gaussian set. For the free DF-2 ion, the EFG and the resulting nuclear quadrupole coupling constant (nqcc) are found to be very low and positive in sign, and to display marked dependences on basis set, and the effects of electron correlation and vibrational averaging. In particular, we note a peculiarly extreme basis-set limit problem for deuterium EFGs in symmetric H-bonded molecules. The effects of the crystal lattice on the nqcc have been calculated for the sodium, potassium, and ammonium bifluorides taking into account: the direct contribution of the lattice to the EFG as modeled by a point-charge distribution; its polarizing effect on an individual DF-2 ion using two different methods; and also the effects of librational averaging. The predicted deuterium nqccs and asymmetry parameters (η) in the bifluoride salts are compared with the free-ion values (η necessarily zero). While our predicted nqcc in KDF2 of 55±3 kHz is consistent with the only reported experimental value of 58±10 kHz [R. Blinc et al., Chem. Phys. Lett. 48, 596 (1977)], the calculated η value of 0.07±0.01 is at serious variance with the experimental value of 0.4±0.1. As our treatment of the crystal lattice effects is quite comprehensive this disagreement requires further investigation. We have predicted a significantly higher nqcc for NaDF2 of 83±3 kHz, but, again, with a very small η value of 0.04±0.01.

  17. Relativistic unitary coupled-cluster study of the electric quadrupole moment and magnetic dipole hyperfine constants of {sup 199}Hg{sup +}

    SciTech Connect

    Sur, Chiranjib; Chaudhuri, Rajat K.

    2007-09-15

    Searching for an accurate optical clock which can serve as a better time standard than the present-day atomic clock is highly demanding from several areas of science and technology. Several attempts have been made to build more accurate clocks with different ion species. In this paper, we discuss the electric quadrupole and hyperfine shifts in the 5d{sup 9}6s{sup 2} {sup 2}D{sub 5/2}(F=0,m{sub F}=0){r_reversible}5d{sup 10}6s {sup 2}S{sub 1/2}(F=2,m{sub F}=0) clock transition in {sup 199}Hg{sup +}, one of the most promising candidates for next-generation optical clocks. We have applied Fock-space unitary coupled-cluster theory to study the electric quadrupole moment of the 5d{sup 9}6s{sup 2} {sup 2}D{sub 5/2} state and magnetic dipole hyperfine constants of 5d{sup 9}6s{sup 2} {sup 2}D{sub 3/2,5/2} and 5d{sup 10}6s{sup 1} {sup 2}S{sub 1/2} states, respectively, of {sup 199}Hg{sup +}. We have also compared our results with available data. To the best of our knowledge, this is the first time a variant of coupled-cluster theories has been applied to study these kinds of properties of Hg{sup +} and is the most accurate estimate of these quantities to date.

  18. Successive ratio subtraction coupled with constant multiplication spectrophotometric method for determination of hydroquinone in complex mixture with its degradation products, tretinoin and methyl paraben

    NASA Astrophysics Data System (ADS)

    Elghobashy, Mohamed R.; Bebawy, Lories I.; Shokry, Rafeek F.; Abbas, Samah S.

    2016-03-01

    A sensitive and selective stability-indicating successive ratio subtraction coupled with constant multiplication (SRS-CM) spectrophotometric method was studied and developed for the spectrum resolution of five component mixture without prior separation. The components were hydroquinone in combination with tretinoin, the polymer formed from hydroquinone alkali degradation, 1,4 benzoquinone and the preservative methyl paraben. The proposed method was used for their determination in their pure form and in pharmaceutical formulation. The zero order absorption spectra of hydroquinone, tretinoin, 1,4 benzoquinone and methyl paraben were determined at 293, 357.5, 245 and 255.2 nm, respectively. The calibration curves were linear over the concentration ranges of 4.00-46.00, 1.00-7.00, 0.60-5.20, and 1.00-7.00 μg mL- 1 for hydroquinone, tretinoin, 1,4 benzoquinone and methyl paraben, respectively. The pharmaceutical formulation was subjected to mild alkali condition and measured by this method resulting in the polymerization of hydroquinone and the formation of toxic 1,4 benzoquinone. The proposed method was validated according to ICH guidelines. The results obtained were statistically analyzed and compared with those obtained by applying the reported method.

  19. Theoretical 13C chemical shift, 14N, and 2H quadrupole coupling- constant studies of hydrogen bonding in L-alanylglycine dipeptide.

    PubMed

    Tafazzoli, M; Amini, S K

    2008-04-01

    (13)C chemical shieldings and (14)N and (2)H electric field gradient (EFG) tensors of L-alanylglycine (L-alagly) dipeptide were calculated at RHF/6-31 + + G** and B3LYP/6-31 + + G** levels of theory respectively. For these calculations a crystal structure of this dipeptide obtained from X-ray crystallography was used. Atomic coordinates of different clusters containing several L-alagly molecules were used as input files for calculations. These clusters consist of central and surrounding L-alagly molecules, the latter forming short, strong, hydrogen bonds with the central molecule. Since the calculations did not converge for these clusters, the surrounding L-alagly molecules were replaced by glycine molecules. In order to improve the accuracy of calculated chemical shifts and nuclear quadrupole coupling constants (NQCCs), different geometry-optimization strategies were applied for hydrogen nuclei. Agreement between calculated and experimental data confirms that our optimized coordinates for hydrogen nuclei are more accurate than those obtained by X-ray diffraction.

  20. A calorimetric measurement of the strong coupling constant in electron-positron annihilation at a center-of-mass energy of 91.6 GeV

    SciTech Connect

    Martirena, S.G.

    1994-04-01

    In this work, a measurement of the strong coupling constant {alpha}{sub s} in e{sup +}e{sup {minus}} annihilation at a center-of-mass energy of 91.6 GeV is presented. The measurement was performed with the SLD at the Stanford Linear Collider facility located at the Stanford Linear Accelerator Center in California. The procedure used consisted of measuring the rate of hard gluon radiation from the primary quarks in a sample of 9,878 hadronic events. After defining the asymptotic manifestation of partons as `jets`, various phenomenological models were used to correct for the hadronization process. A value for the QCD scale parameter {Lambda}{sub bar MS}, defined in the {sub bar MS} renormalization convention with 5 active quark flavors, was then obtained by a direct fit to O({alpha}{sub s}{sup 2}) calculations. The value of {alpha}{sub s} obtained was {alpha}{sub s}(M{sub z0}) = 0.122 {plus_minus} 0.004 {sub {minus}0.007} {sup +0.008} where the uncertainties are experimental (combined statistical and systematic) and theoretical (systematic) respectively. Equivalently, {Lambda}{sub bar MS} = 0.28 {sub {minus}0.10}{sup +0.16} GeV where the experimental and theoretical uncertainties have been combined.

  1. From correlation-consistent to polarization-consistent basis sets estimation of NMR spin spin coupling constant in the B3LYP Kohn Sham basis set limit

    NASA Astrophysics Data System (ADS)

    Kupka, Teobald

    2008-08-01

    Based on B3LYP spin-spin coupling constants (SSCC) of several molecules calculated with cc-pV xZ, cc-pCV xZ, cc-pCV xZ-sd and cc-pCV xZ-sd+ t basis sets, a reasonably fit, using the two-parameter formula, to the Kohn-Sham complete basis set limit (CBS) is shown. Improvement in the CBS values going from cc-pV xZ to the most elaborated cc-pCV xZ-sd+ t basis set family is observed: standard deviation for all data drops from 33.7 to 23.1, and from 6.0 to 4.8 Hz after excluding problematic 1J(F,H) and 1J(F,C). Calculation of water's 1J(OH) using B3LYP/cc-pCV xZ and B3LYP/pcJ- n significantly improved the FC term convergence.

  2. Determination of the strong coupling constant ({alpha}{sub s}) and a test of perturbative QCD using W + jets processes in the D0 detector

    SciTech Connect

    Yu, Jaehoon

    1993-08-01

    The D0 experiment has accumulated data for a study of inclusive W production corresponding to a total integrated luminosity of 14.3 {plus_minus} 1.7 pb{sup {minus}1} during the 1992--1993 Fermilab Tevatron collider run. The total number of W {yields} e + {nu} candidates is 9770. The ratio of the number of W + 1 jet events to that of W + 0 jet events has been measured as a function of jet minimum E{sub T}. Using this ratio the strong coupling constant, {alpha}{sub s} at Q{sup 2} = M{sub W}{sup 2} is measured to be {alpha}{sub s}(M{sub W}{sup 2}) = 0.124 {plus_minus} 0.005(stat) {plus_minus} 0.006(MC) {plus_minus} 0.008(theory){sub {minus}0.022}{sup +0.026}(sys) or ({sub {minus}0.025}{sup +0.028} combined) with a jet minimum E{sub T} of 25 GeV. A quantitative test of perturbative QCD has been made by comparing the experimentally measured ratio with the theoretical predictions. The theoretical predictions of the ratio in both the leading order and next-to-leading order are in good agreement with the measured ratio.

  3. 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.

  4. Successive ratio subtraction coupled with constant multiplication spectrophotometric method for determination of hydroquinone in complex mixture with its degradation products, tretinoin and methyl paraben.

    PubMed

    Elghobashy, Mohamed R; Bebawy, Lories I; Shokry, Rafeek F; Abbas, Samah S

    2016-03-15

    A sensitive and selective stability-indicating successive ratio subtraction coupled with constant multiplication (SRS-CM) spectrophotometric method was studied and developed for the spectrum resolution of five component mixture without prior separation. The components were hydroquinone in combination with tretinoin, the polymer formed from hydroquinone alkali degradation, 1,4 benzoquinone and the preservative methyl paraben. The proposed method was used for their determination in their pure form and in pharmaceutical formulation. The zero order absorption spectra of hydroquinone, tretinoin, 1,4 benzoquinone and methyl paraben were determined at 293, 357.5, 245 and 255.2 nm, respectively. The calibration curves were linear over the concentration ranges of 4.00-46.00, 1.00-7.00, 0.60-5.20, and 1.00-7.00 μg mL(-1) for hydroquinone, tretinoin, 1,4 benzoquinone and methyl paraben, respectively. The pharmaceutical formulation was subjected to mild alkali condition and measured by this method resulting in the polymerization of hydroquinone and the formation of toxic 1,4 benzoquinone. The proposed method was validated according to ICH guidelines. The results obtained were statistically analyzed and compared with those obtained by applying the reported method. PMID:26745510

  5. Toward Reliable Prediction of Hyperfine Coupling Constants Using Ab Initio Density Matrix Renormalization Group Method: Diatomic (2)Σ and Vinyl Radicals as Test Cases.

    PubMed

    Lan, Tran Nguyen; Kurashige, Yuki; Yanai, Takeshi

    2014-05-13

    The density matrix renormalization group (DMRG) method is used in conjunction with the complete active space (CAS) procedure, the CAS configuration interaction (CASCI), and the CAS self-consistent field (CASSCF) to evaluate hyperfine coupling constants (HFCCs) for a series of diatomic (2)Σ radicals (BO, CO(+), CN, and AlO) and vinyl (C2H3) radical. The electron correlation effects on the computed HFCC values were systematically investigated using various levels of active space, which were increasingly extended from single valence space to large-size model space entailing double valence and at least single polarization shells. In addition, the core correlation was treated by including the core orbitals in active space. Reasonably accurate results were obtained by the DMRG-CASSCF method involving orbital optimization, while DMRG-CASCI calculations with Hartree-Fock orbitals provided poor agreement of the HFCCs with the experimental values. To achieve further insights into the accuracy of HFCC calculations, the orbital contributions to the total spin density were analyzed at a given nucleus, which is directly related to the FC term and is numerically sensitive to the level of correlation treatment and basis sets. The convergence of calculated HFCCs with an increasing number of renormalized states was also assessed. This work serves as the first study on the performance of the ab initio DMRG method for HFCC prediction.

  6. Numerical values of the fF,fD , and fS coupling constants in the SU(3) invariant interaction Lagrangian of the vector-meson nonet with 1 /2+ octet baryons

    NASA Astrophysics Data System (ADS)

    Adamuscin, Cyril; Bartos, Erik; Dubnicka, Stanislav; Dubnickova, Anna Zuzana

    2016-05-01

    It is demonstrated how the use of all existing experimental information on electric and magnetic nucleon form factors, described by the unitary and analytic (U&A) nucleon electromagnetic structure model in spacelike and timelike regions simultaneously, can provide numerical values of fF,fD,andfS coupling constants in SU(3) invariant interaction Lagrangian of the vector-meson nonet with 1 /2+ octet baryons. The latter, together with universal vector-meson coupling constants fV, play an essential role in a prediction of 1 /2+ octet hyperon electromagnetic form factor behaviors.

  7. Accurate Prediction of Hyperfine Coupling Constants in Muoniated and Hydrogenated Ethyl Radicals: Ab Initio Path Integral Simulation Study with Density Functional Theory Method.

    PubMed

    Yamada, Kenta; Kawashima, Yukio; Tachikawa, Masanori

    2014-05-13

    We performed ab initio path integral molecular dynamics (PIMD) simulations with a density functional theory (DFT) method to accurately predict hyperfine coupling constants (HFCCs) in the ethyl radical (CβH3-CαH2) and its Mu-substituted (muoniated) compound (CβH2Mu-CαH2). The substitution of a Mu atom, an ultralight isotope of the H atom, with larger nuclear quantum effect is expected to strongly affect the nature of the ethyl radical. The static conventional DFT calculations of CβH3-CαH2 find that the elongation of one Cβ-H bond causes a change in the shape of potential energy curve along the rotational angle via the imbalance of attractive and repulsive interactions between the methyl and methylene groups. Investigation of the methyl-group behavior including the nuclear quantum and thermal effects shows that an unbalanced CβH2Mu group with the elongated Cβ-Mu bond rotates around the Cβ-Cα bond in a muoniated ethyl radical, quite differently from the CβH3 group with the three equivalent Cβ-H bonds in the ethyl radical. These rotations couple with other molecular motions such as the methylene-group rocking motion (inversion), leading to difficulties in reproducing the corresponding barrier heights. Our PIMD simulations successfully predict the barrier heights to be close to the experimental values and provide a significant improvement in muon and proton HFCCs given by the static conventional DFT method. Further investigation reveals that the Cβ-Mu/H stretching motion, methyl-group rotation, methylene-group rocking motion, and HFCC values deeply intertwine with each other. Because these motions are different between the radicals, a proper description of the structural fluctuations reflecting the nuclear quantum and thermal effects is vital to evaluate HFCC values in theory to be comparable to the experimental ones. Accordingly, a fundamental difference in HFCC between the radicals arises from their intrinsic molecular motions at a finite temperature, in

  8. DFT 2H quadrupolar coupling constants of ruthenium complexes: a good probe of the coordination of hydrides in conjuction with experiments.

    PubMed

    del Rosal, Iker; Gutmann, Torsten; Maron, Laurent; Jolibois, Franck; Chaudret, Bruno; Walaszek, Bernadeta; Limbach, Hans-Heinrich; Poteau, Romuald; Buntkowsky, Gerd

    2009-07-21

    Transition metal (TM) hydrides are of great interest in chemistry because of their reactivity and their potential as catalysts for hydrogenation reactions. 2H solid-state NMR can be used in order to get information about the local environment of hydrogen atoms, and more particularly the coordination mode of hydrides in such complexes. In this work we will show that it is possible to establish at the level of density functional theory (DFT) a viable methodological strategy that allows the determination of 2H NMR parameters, namely the quadrupolar coupling constant (C(Q)) respectively the quadrupolar splitting (deltanuQ) and the asymmetry parameter (etaQ). The reliability of the method (B3PW91-DFT) and basis set effects have been first evaluated for simple organic compounds (benzene and fluorene). A good correlation between experimental and theoretical values is systematically obtained if the large basis set cc-pVTZ is used for the computations. 2H NMR properties of five mononuclear ruthenium complexes (namely Cp*RuD3(PPh3), Tp*RuD(THT)2, Tp*RuD(D2)(THT) and Tp*RuD(D2)2 and RuD2(D2)2(PCy3)2) which exhibit different ligands and hydrides involved in different coordination modes (terminal-H or eta2-H2), have been calculated and compared to previous experimental data. The results obtained are in excellent agreement with experiments. Although 2H NMR spectra are not always easy to analyze, assistance by quantum chemistry calculations allows unambiguous assignment of the signals of such spectra. As far as experiments can be achieved at very low temperatures in order to avoid dynamic effects, this hybrid theoretical/experimental tool may give useful insights in the context of the characterization of ruthenium surfaces or nanoparticles with solid-state NMR. PMID:19842483

  9. Are Fundamental Constants Really Constant?

    ERIC Educational Resources Information Center

    Swetman, T. P.

    1972-01-01

    Dirac's classical conclusions, that the values of e2, M and m are constants and the quantity of G decreases with time. Evoked considerable interest among researchers and traces historical development by which further experimental evidence points out that both e and G are constant values. (PS)

  10. COUPLING

    DOEpatents

    Frisch, E.; Johnson, C.G.

    1962-05-15

    A detachable coupling arrangement is described which provides for varying the length of the handle of a tool used in relatively narrow channels. The arrangement consists of mating the key and keyhole formations in the cooperating handle sections. (AEC)

  11. Fully Coriolis-coupled quantum studies of the H + O2 (upsilon i = 0-2, j i = 0,1) --> OH + O reaction on an accurate potential energy surface: integral cross sections and rate constants.

    PubMed

    Lin, Shi Ying; Sun, Zhigang; Guo, Hua; Zhang, Dong Hui; Honvault, Pascal; Xie, Daiqian; Lee, Soo-Y

    2008-01-31

    We present accurate quantum calculations of the integral cross section and rate constant for the H + O2 --> OH + O combustion reaction on a recently developed ab initio potential energy surface using parallelized time-dependent and Chebyshev wavepacket methods. Partial wave contributions up to J = 70 were computed with full Coriolis coupling, which enabled us to obtain the initial state-specified integral cross sections up to 2.0 eV of the collision energy and thermal rate constants up to 3000 K. The integral cross sections show a large reaction threshold due to the quantum endothermicity of the reaction, and they monotonically increase with the collision energy. As a result, the temperature dependence of the rate constant is of the Arrhenius type. In addition, it was found that reactivity is enhanced by reactant vibrational excitation. The calculated thermal rate constant shows a significant improvement over that obtained on the DMBE IV potential, but it still underestimates the experimental consensus.

  12. Theoretical study of hyperfine coupling constants and electron spin g factors for X2Σ diatomics from Groups 1 and 2

    NASA Astrophysics Data System (ADS)

    Bruna, Pablo J.; Grein, Friedrich

    The ESR parameters of the cations Be 2 + , Mg 2 + , Ca 2 + , BeMg + , BeCa + , MgCa + and the mixed radicals ZBe, ZMg, ZCa (Z = Li, Na, K), all having a X 2 Σu + (1 σg 2 1 σu )/X 2 Sigma + (1 σ2 2 σ) ground state, have been studied theoretically. The A iso and A dip constants have been calculated with UHF, CISD, MP2, B3LYP, PW91PW91 wavefunctions, and 6-311+G(2df) basis sets. The electron spin g factors (magnetic moment μs) have been evaluated from correlated (MRDCI) wavefunctions, using a Hamiltonian based on Breit-Pauli theory with perturbation expansions up to second order, and 6-311+ G(2d) basis sets. As expected for s-rich radicals, the hyperfine spectra are governed by the A iso terms. Both Δg|| and Δg Υ̂values are negative, but Δg|| lies close to zero. For Δg Υ̂, the coupling with 1 2 Π(u) dominates the sum-over-states expansions. Although the singly occupied MOs (SOMO) are mostly of s character, the | Δg Υ̂| are relatively large, up to 5200 ppm for cationic, and up to 7850 ppm for neutral radicals. These large values are caused by low excitation energies and high magnetic transition moments, the latter due to the fact that the σ*( s - s ) SOMO has the same nodal properties as a p σorbital. Of the radicals considered here, an ESR spectrum is available only for Mg2+. Our theoretical A iso of-287 MHz reproduces well the matrix result (-291 MHz). Calculated values of-10 ppm for Deltag|| and of-1280 ppm for Deltag Υ̂give an average < Δg> =-860 ppm that lies within the experimental range of-600( ±300) ppm in Ne, and of-1300( ±500) ppm in Ar matrices.

  13. Effects of restricted rotations and dynamic averaging on the calculated isotropic hyperfine coupling constants of the bis-dimethyl and bis-Di(trifluoromethyl) nitroxide radicals.

    PubMed

    Mattar, Saba M; Sanford, Jacob

    2009-10-22

    The rotational effects of the CH(3) and CF(3) groups on the electronic structure and nuclear hyperfine coupling constants (HFCCs) in dimethylnitroxide (DMNO*) and ditrifluoro-methynitroxide (TFMNO*) are investigated using the UB1LYP hybrid density functional method. The CH(3) and CF(3) HFCCs of both radicals are found to obey the McConnell relation during rotation. The two CH(3) groups of the DMNO* do not gear with each other, but the rotation of the first CH(3) group induces only a small rocking effect ( approximately 7 degrees ) in the second group. However, in TFMNO*, the fluorine atoms from different CF(3) groups are close enough so that the steric repulsion between them causes them to act as two interlocked gears, where one drives the other. Therefore, both CF(3) groups undergo full rotation. To the best of our knowledge, this is only the second example of "gearing" to be studied. Stabilization due to hyperconjugation is also a major factor that affects the magnitudes of the HFCCs of the CF(3) groups during rotational averaging. Stable configurations at specific CF(3) group orientations have a large overlap with the NO pi-electron cloud because the lobes of the hybridized p(sigma)(F(2)), p(sigma)(F(3)), p(sigma)(F(5)), and p(sigma)(F(6)) orbitals along the F-C bonds have cylindrical symmetry and are of the correct phases for hyperconjugation to occur. The calculated TFMNO* C(1)-N and C(2)-N bond orders range from 0.91 to 0.95 as the CF(3) groups are rotated. Therefore, the C-N bonds are essentially single bonds. This, in conjunction with the low rotational energy barrier of approximately 50 cm(-1), explains why the EPR intensities of the (19)F hyperfine splittings, in the range of 163-297 K, are characteristic of six equivalent rapidly rotating fluorine atoms. The TFMNO* out-of-plane NO vibrations induce additional s character at the (14)N nucleus. This increases the magnitude of the (14)N HFCC and decreases the (19)F HFCCs. As the temperature increases and

  14. Effects of Restricted Rotations and Dynamic Averaging on the Calculated Isotropic Hyperfine Coupling Constants of the bis-Dimethyl and bis-Di(trifluoromethyl) Nitroxide Radicals

    NASA Astrophysics Data System (ADS)

    Mattar, Saba M.; Sanford, Jacob

    2009-09-01

    The rotational effects of the CH3 and CF3 groups on the electronic structure and nuclear hyperfine coupling constants (HFCCs) in dimethylnitroxide (DMNO·) and ditrifluoro-methynitroxide (TFMNO·) are investigated using the UB1LYP hybrid density functional method. The CH3 and CF3 HFCCs of both radicals are found to obey the McConnell relation during rotation. The two CH3 groups of the DMNO· do not gear with each other, but the rotation of the first CH3 group induces only a small rocking effect (˜7°) in the second group. However, in TFMNO·, the fluorine atoms from different CF3 groups are close enough so that the steric repulsion between them causes them to act as two interlocked gears, where one drives the other. Therefore, both CF3 groups undergo full rotation. To the best of our knowledge, this is only the second example of "gearing" to be studied. Stabilization due to hyperconjugation is also a major factor that affects the magnitudes of the HFCCs of the CF3 groups during rotational averaging. Stable configurations at specific CF3 group orientations have a large overlap with the NO π-electron cloud because the lobes of the hybridized pσ(F2), pσ(F3), pσ(F5), and pσ(F6) orbitals along the F-C bonds have cylindrical symmetry and are of the correct phases for hyperconjugation to occur. The calculated TFMNO· C1-N and C2-N bond orders range from 0.91 to 0.95 as the CF3 groups are rotated. Therefore, the C-N bonds are essentially single bonds. This, in conjunction with the low rotational energy barrier of approximately 50 cm-1, explains why the EPR intensities of the 19F hyperfine splittings, in the range of 163-297 K, are characteristic of six equivalent rapidly rotating fluorine atoms. The TFMNO· out-of-plane NO vibrations induce additional s character at the 14N nucleus. This increases the magnitude of the 14N HFCC and decreases the 19F HFCCs. As the temperature increases and because of mixing of the first excited out-of-plane vibrational state, the NO

  15. Measurement of the inclusive 3-jet production differential cross section in proton-proton collisions at 7 TeV and determination of the strong coupling constant in the TeV range

    NASA Astrophysics Data System (ADS)

    Khachatryan, V.; Sirunyan, A. M.; Tumasyan, A.; Adam, W.; Bergauer, T.; Dragicevic, M.; Erö, J.; Fabjan, C.; Friedl, M.; Frühwirth, R.; Ghete, V. M.; Hartl, C.; Hörmann, N.; Hrubec, J.; Jeitler, M.; Kiesenhofer, W.; Knünz, V.; Krammer, M.; Krätschmer, I.; Liko, D.; Mikulec, I.; Rabady, D.; Rahbaran, B.; Rohringer, H.; Schöfbeck, R.; Strauss, J.; Taurok, A.; Treberer-Treberspurg, W.; Waltenberger, W.; Wulz, C.-E.; Mossolov, V.; Shumeiko, N.; Suarez Gonzalez, J.; Alderweireldt, S.; Bansal, M.; Bansal, S.; Cornelis, T.; De Wolf, E. A.; Janssen, X.; Knutsson, A.; Luyckx, S.; Ochesanu, S.; Rougny, R.; Van De Klundert, M.; Van Haevermaet, H.; Van Mechelen, P.; Van Remortel, N.; Van Spilbeeck, A.; Blekman, F.; Blyweert, S.; D'Hondt, J.; Daci, N.; Heracleous, N.; Keaveney, J.; Lowette, S.; Maes, M.; Olbrechts, A.; Python, Q.; Strom, D.; Tavernier, S.; Van Doninck, W.; Van Mulders, P.; Van Onsem, G. P.; Villella, I.; Caillol, C.; Clerbaux, B.; De Lentdecker, G.; Dobur, D.; Favart, L.; Gay, A. P. R.; Grebenyuk, A.; Léonard, A.; Mohammadi, A.; Perniè, L.; Reis, T.; Seva, T.; Thomas, L.; Vander Velde, C.; Vanlaer, P.; Wang, J.; Zenoni, F.; Adler, V.; Beernaert, K.; Benucci, L.; Cimmino, A.; Costantini, S.; Crucy, S.; Dildick, S.; Fagot, A.; Garcia, G.; Mccartin, J.; Ocampo Rios, A. A.; Ryckbosch, D.; Salva Diblen, S.; Sigamani, M.; Strobbe, N.; Thyssen, F.; Tytgat, M.; Yazgan, E.; Zaganidis, N.; Basegmez, S.; Beluffi, C.; Bruno, G.; Castello, R.; Caudron, A.; Ceard, L.; Da Silveira, G. G.; Delaere, C.; du Pree, T.; Favart, D.; Forthomme, L.; Giammanco, A.; Hollar, J.; Jafari, A.; Jez, P.; Komm, M.; Lemaitre, V.; Nuttens, C.; Pagano, D.; Perrini, L.; Pin, A.; Piotrzkowski, K.; Popov, A.; Quertenmont, L.; Selvaggi, M.; Vidal Marono, M.; Vizan Garcia, J. M.; Beliy, N.; Caebergs, T.; Daubie, E.; Hammad, G. H.; Júnior, W. L. Aldá; Alves, G. A.; Brito, L.; Correa Martins Junior, M.; Martins, T. Dos Reis; Mora Herrera, C.; Pol, M. E.; Carvalho, W.; Chinellato, J.; Custódio, A.; Da Costa, E. M.; De Jesus Damiao, D.; De Oliveira Martins, C.; Fonseca De Souza, S.; Malbouisson, H.; Matos Figueiredo, D.; Mundim, L.; Nogima, H.; Prado Da Silva, W. L.; Santaolalla, J.; Santoro, A.; Sznajder, A.; Tonelli Manganote, E. J.; Vilela Pereira, A.; Bernardes, C. A.; Dogra, S.; Fernandez Perez Tomei, T. R.; Gregores, E. M.; Mercadante, P. G.; Novaes, S. F.; Padula, Sandra S.; Aleksandrov, A.; Genchev, V.; Iaydjiev, P.; Marinov, A.; Piperov, S.; Rodozov, M.; Stoykova, S.; Sultanov, G.; Tcholakov, V.; Vutova, M.; Dimitrov, A.; Glushkov, I.; Hadjiiska, R.; Kozhuharov, V.; Litov, L.; Pavlov, B.; Petkov, P.; Bian, J. G.; Chen, G. M.; Chen, H. S.; Chen, M.; Du, R.; Jiang, C. H.; Plestina, R.; Romeo, F.; Tao, J.; Wang, Z.; Asawatangtrakuldee, C.; Ban, Y.; Li, Q.; Liu, S.; Mao, Y.; Qian, S. J.; Wang, D.; Zou, W.; Avila, C.; Chaparro Sierra, L. F.; Florez, C.; Gomez, J. P.; Gomez Moreno, B.; Sanabria, J. C.; Godinovic, N.; Lelas, D.; Polic, D.; Puljak, I.; Antunovic, Z.; Kovac, M.; Brigljevic, V.; Kadija, K.; Luetic, J.; Mekterovic, D.; Sudic, L.; Attikis, A.; Mavromanolakis, G.; Mousa, J.; Nicolaou, C.; Ptochos, F.; Razis, P. A.; Bodlak, M.; Finger, M.; Finger, M.; Assran, Y.; Ellithi Kamel, A.; Mahmoud, M. A.; Radi, A.; Kadastik, M.; Murumaa, M.; Raidal, M.; Tiko, A.; Eerola, P.; Fedi, G.; Voutilainen, M.; Härkönen, J.; Karimäki, V.; Kinnunen, R.; Kortelainen, M. J.; Lampén, T.; Lassila-Perini, K.; Lehti, S.; Lindén, T.; Luukka, P.; Mäenpää, T.; Peltola, T.; Tuominen, E.; Tuominiemi, J.; Tuovinen, E.; Wendland, L.; Talvitie, J.; Tuuva, T.; Besancon, M.; Couderc, F.; Dejardin, M.; Denegri, D.; Fabbro, B.; Faure, J. L.; Favaro, C.; Ferri, F.; Ganjour, S.; Givernaud, A.; Gras, P.; Hamel de Monchenault, G.; Jarry, P.; Locci, E.; Malcles, J.; Rander, J.; Rosowsky, A.; Titov, M.; Baffioni, S.; Beaudette, F.; Busson, P.; Charlot, C.; Dahms, T.; Dalchenko, M.; Dobrzynski, L.; Filipovic, N.; Florent, A.; Granier de Cassagnac, R.; Mastrolorenzo, L.; Miné, P.; Mironov, C.; Naranjo, I. N.; Nguyen, M.; Ochando, C.; Paganini, P.; Regnard, S.; Salerno, R.; Sauvan, J. B.; Sirois, Y.; Veelken, C.; Yilmaz, Y.; Zabi, A.; Agram, J.-L.; Andrea, J.; Aubin, A.; Bloch, D.; Brom, J.-M.; Chabert, E. C.; Collard, C.; Conte, E.; Fontaine, J.-C.; Gelé, D.; Goerlach, U.; Goetzmann, C.; Le Bihan, A.-C.; Van Hove, P.; Gadrat, S.; Beauceron, S.; Beaupere, N.; Boudoul, G.; Bouvier, E.; Brochet, S.; Carrillo Montoya, C. A.; Chasserat, J.; Chierici, R.; Contardo, D.; Depasse, P.; El Mamouni, H.; Fan, J.; Fay, J.; Gascon, S.; Gouzevitch, M.; Ille, B.; Kurca, T.; Lethuillier, M.; Mirabito, L.; Perries, S.; Ruiz Alvarez, J. D.; Sabes, D.; Sgandurra, L.; Sordini, V.; Vander Donckt, M.; Verdier, P.; Viret, S.; Xiao, H.; Bagaturia, I.; Autermann, C.; Beranek, S.; Bontenackels, M.; Edelhoff, M.; Feld, L.; Hindrichs, O.; Klein, K.; Ostapchuk, A.; Perieanu, A.; Raupach, F.; Sammet, J.; Schael, S.; Weber, H.; Wittmer, B.; Zhukov, V.; Ata, M.; Brodski, M.; Dietz-Laursonn, E.; Duchardt, D.; Erdmann, M.; Fischer, R.; Güth, A.; Hebbeker, T.; Heidemann, C.; Hoepfner, K.; Klingebiel, D.; Knutzen, S.; Kreuzer, P.; Merschmeyer, M.; Meyer, A.; Millet, P.; Olschewski, M.; Padeken, K.; Papacz, P.; Reithler, H.; Schmitz, S. A.; Sonnenschein, L.; Teyssier, D.; Thüer, S.; Weber, M.; Cherepanov, V.; Erdogan, Y.; Flügge, G.; Geenen, H.; Geisler, M.; Haj Ahmad, W.; Heister, A.; Hoehle, F.; Kargoll, B.; Kress, T.; Kuessel, Y.; Künsken, A.; Lingemann, J.; Nowack, A.; Nugent, I. M.; Perchalla, L.; Pooth, O.; Stahl, A.; Asin, I.; Bartosik, N.; Behr, J.; Behrenhoff, W.; Behrens, U.; Bell, A. J.; Bergholz, M.; Bethani, A.; Borras, K.; Burgmeier, A.; Cakir, A.; Calligaris, L.; Campbell, A.; Choudhury, S.; Costanza, F.; Diez Pardos, C.; Dooling, S.; Dorland, T.; Eckerlin, G.; Eckstein, D.; Eichhorn, T.; Flucke, G.; Garcia, J. Garay; Geiser, A.; Gunnellini, P.; Hauk, J.; Hempel, M.; Horton, D.; Jung, H.; Kalogeropoulos, A.; Kasemann, M.; Katsas, P.; Kieseler, J.; Kleinwort, C.; Krücker, D.; Lange, W.; Leonard, J.; Lipka, K.; Lobanov, A.; Lohmann, W.; Lutz, B.; Mankel, R.; Marfin, I.; Melzer-Pellmann, I.-A.; Meyer, A. B.; Mittag, G.; Mnich, J.; Mussgiller, A.; Naumann-Emme, S.; Nayak, A.; Novgorodova, O.; Ntomari, E.; Perrey, H.; Pitzl, D.; Placakyte, R.; Raspereza, A.; Ribeiro Cipriano, P. M.; Roland, B.; Ron, E.; Sahin, M. Ö.; Salfeld-Nebgen, J.; Saxena, P.; Schmidt, R.; Schoerner-Sadenius, T.; Schröder, M.; Seitz, C.; Spannagel, S.; Vargas Trevino, A. D. R.; Walsh, R.; Wissing, C.; Aldaya Martin, M.; Blobel, V.; Centis Vignali, M.; Draeger, A. R.; Erfle, J.; Garutti, E.; Goebel, K.; Görner, M.; Haller, J.; Hoffmann, M.; Höing, R. S.; Kirschenmann, H.; Klanner, R.; Kogler, R.; Lange, J.; Lapsien, T.; Lenz, T.; Marchesini, I.; Ott, J.; Peiffer, T.; Pietsch, N.; Poehlsen, J.; Poehlsen, T.; Rathjens, D.; Sander, C.; Schettler, H.; Schleper, P.; Schlieckau, E.; Schmidt, A.; Seidel, M.; Sola, V.; Stadie, H.; Steinbrück, G.; Troendle, D.; Usai, E.; Vanelderen, L.; Vanhoefer, A.; Barth, C.; Baus, C.; Berger, J.; Böser, C.; Butz, E.; Chwalek, T.; De Boer, W.; Descroix, A.; Dierlamm, A.; Feindt, M.; Frensch, F.; Giffels, M.; Hartmann, F.; Hauth, T.; Husemann, U.; Katkov, I.; Kornmayer, A.; Kuznetsova, E.; Lobelle Pardo, P.; Mozer, M. U.; Müller, Th.; Nürnberg, A.; Quast, G.; Rabbertz, K.; Ratnikov, F.; Röcker, S.; Sieber, G.; Simonis, H. J.; Stober, F. M.; Ulrich, R.; Wagner-Kuhr, J.; Wayand, S.; Weiler, T.; Wolf, R.; Anagnostou, G.; Daskalakis, G.; Geralis, T.; Giakoumopoulou, V. A.; Kyriakis, A.; Loukas, D.; Markou, A.; Markou, C.; Psallidas, A.; Topsis-Giotis, I.; Agapitos, A.; Kesisoglou, S.; Panagiotou, A.; Saoulidou, N.; Stiliaris, E.; Aslanoglou, X.; Evangelou, I.; Flouris, G.; Foudas, C.; Kokkas, P.; Manthos, N.; Papadopoulos, I.; Paradas, E.; Bencze, G.; Hajdu, C.; Hidas, P.; Horvath, D.; Sikler, F.; Veszpremi, V.; Vesztergombi, G.; Zsigmond, A. J.; Beni, N.; Czellar, S.; Karancsi, J.; Molnar, J.; Palinkas, J.; Szillasi, Z.; Raics, P.; Trocsanyi, Z. L.; Ujvari, B.; Swain, S. K.; Beri, S. B.; Bhatnagar, V.; Gupta, R.; Bhawandeep, U.; Kalsi, A. K.; Kaur, M.; Kumar, R.; Mittal, M.; Nishu, N.; Singh, J. B.; Kumar, Ashok; Kumar, Arun; Ahuja, S.; Bhardwaj, A.; Choudhary, B. C.; Kumar, A.; Malhotra, S.; Naimuddin, M.; Ranjan, K.; Sharma, V.; Banerjee, S.; Bhattacharya, S.; Chatterjee, K.; Dutta, S.; Gomber, B.; Jain, Sa.; Jain, Sh.; Khurana, R.; Modak, A.; Mukherjee, S.; Roy, D.; Sarkar, S.; Sharan, M.; Abdulsalam, A.; Dutta, D.; Kailas, S.; Kumar, V.; Mohanty, A. K.; Pant, L. M.; Shukla, P.; Topkar, A.; Aziz, T.; Banerjee, S.; Bhowmik, S.; Chatterjee, R. M.; Dewanjee, R. K.; Dugad, S.; Ganguly, S.; Ghosh, S.; Guchait, M.; Gurtu, A.; Kole, G.; Kumar, S.; Maity, M.; Majumder, G.; Mazumdar, K.; Mohanty, G. B.; Parida, B.; Sudhakar, K.; Wickramage, N.; Bakhshiansohi, H.; Behnamian, H.; Etesami, S. M.; Fahim, A.; Goldouzian, R.; Khakzad, M.; Mohammadi Najafabadi, M.; Naseri, M.; Paktinat Mehdiabadi, S.; Rezaei Hosseinabadi, F.; Safarzadeh, B.; Zeinali, M.; Felcini, M.; Grunewald, M.; Abbrescia, M.; Barbone, L.; Calabria, C.; Chhibra, S. S.; Colaleo, A.; Creanza, D.; De Filippis, N.; De Palma, M.; Fiore, L.; Iaselli, G.; Maggi, G.; Maggi, M.; My, S.; Nuzzo, S.; Pompili, A.; Pugliese, G.; Radogna, R.; Selvaggi, G.; Silvestris, L.; Venditti, R.; Zito, G.; Abbiendi, G.; Benvenuti, A. C.; Bonacorsi, D.; Braibant-Giacomelli, S.; Brigliadori, L.; Campanini, R.; Capiluppi, P.; Castro, A.; Cavallo, F. R.; Codispoti, G.; Cuffiani, M.; Dallavalle, G. M.; Fabbri, F.; Fanfani, A.; Fasanella, D.; Giacomelli, P.; Grandi, C.; Guiducci, L.; Marcellini, S.; Masetti, G.; Montanari, A.; Navarria, F. L.; Perrotta, A.; Rossi, A. M.; Primavera, F.; Rovelli, T.; Siroli, G. P.; Tosi, N.; Travaglini, R.; Albergo, S.; Cappello, G.; Chiorboli, M.; Costa, S.; Giordano, F.; Potenza, R.; Tricomi, A.; Tuve, C.; Barbagli, G.; Ciulli, V.; Civinini, C.; D'Alessandro, R.; Focardi, E.; Gallo, E.; Gonzi, S.; Gori, V.; Lenzi, P.; Meschini, M.; Paoletti, S.; Sguazzoni, G.; Tropiano, A.; Benussi, L.; Bianco, S.; Fabbri, F.; Piccolo, D.; Ferretti, R.; Ferro, F.; Lo Vetere, M.; Robutti, E.; Tosi, S.; Dinardo, M. E.; Fiorendi, S.; Gennai, S.; Gerosa, R.; Ghezzi, A.; Govoni, P.; Lucchini, M. T.; Malvezzi, S.; Manzoni, R. A.; Martelli, A.; Marzocchi, B.; Menasce, D.; Moroni, L.; Paganoni, M.; Pedrini, D.; Ragazzi, S.; Redaelli, N.; Tabarelli de Fatis, T.; Buontempo, S.; Cavallo, N.; Di Guida, S.; Fabozzi, F.; Iorio, A. O. M.; Lista, L.; Meola, S.; Merola, M.; Paolucci, P.; Azzi, P.; Bacchetta, N.; Bisello, D.; Branca, A.; Carlin, R.; Checchia, P.; Dall'Osso, M.; Dorigo, T.; Galanti, M.; Gasparini, F.; Gasparini, U.; Giubilato, P.; Gozzelino, A.; Kanishchev, K.; Lacaprara, S.; Margoni, M.; Meneguzzo, A. T.; Pazzini, J.; Pozzobon, N.; Ronchese, P.; Simonetto, F.; Torassa, E.; Tosi, M.; Vanini, S.; Ventura, S.; Zotto, P.; Zucchetta, A.; Gabusi, M.; Ratti, S. P.; Re, V.; Riccardi, C.; Salvini, P.; Vitulo, P.; Biasini, M.; Bilei, G. M.; Ciangottini, D.; Fanò, L.; Lariccia, P.; Mantovani, G.; Menichelli, M.; Saha, A.; Santocchia, A.; Spiezia, A.; Androsov, K.; Azzurri, P.; Bagliesi, G.; Bernardini, J.; Boccali, T.; Broccolo, G.; Castaldi, R.; Ciocci, M. A.; Dell'Orso, R.; Donato, S.; Fedi, G.; Fiori, F.; Foà, L.; Giassi, A.; Grippo, M. T.; Ligabue, F.; Lomtadze, T.; Martini, L.; Messineo, A.; Moon, C. S.; Palla, F.; Rizzi, A.; Savoy-Navarro, A.; Serban, A. T.; Spagnolo, P.; Squillacioti, P.; Tenchini, R.; Tonelli, G.; Venturi, A.; Verdini, P. G.; Vernieri, C.; Barone, L.; Cavallari, F.; D'imperio, G.; Del Re, D.; Diemoz, M.; Grassi, M.; Jorda, C.; Longo, E.; Margaroli, F.; Meridiani, P.; Micheli, F.; Nourbakhsh, S.; Organtini, G.; Paramatti, R.; Rahatlou, S.; Rovelli, C.; Santanastasio, F.; Soffi, L.; Traczyk, P.; Amapane, N.; Arcidiacono, R.; Argiro, S.; Arneodo, M.; Bellan, R.; Biino, C.; Cartiglia, N.; Casasso, S.; Costa, M.; Degano, A.; Demaria, N.; Finco, L.; Mariotti, C.; Maselli, S.; Migliore, E.; Monaco, V.; Musich, M.; Obertino, M. M.; Ortona, G.; Pacher, L.; Pastrone, N.; Pelliccioni, M.; Pinna Angioni, G. L.; Potenza, A.; Romero, A.; Ruspa, M.; Sacchi, R.; Solano, A.; Staiano, A.; Tamponi, U.; Belforte, S.; Candelise, V.; Casarsa, M.; Cossutti, F.; Della Ricca, G.; Gobbo, B.; La Licata, C.; Marone, M.; Schizzi, A.; Umer, T.; Zanetti, A.; Chang, S.; Kropivnitskaya, T. A.; Nam, S. K.; Kim, D. H.; Kim, G. N.; Kim, M. S.; Kim, M. 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W.; Driga, O.; Elmer, P.; Hebda, P.; Hunt, A.; Koay, S. A.; Lujan, P.; Marlow, D.; Medvedeva, T.; Mooney, M.; Olsen, J.; Piroué, P.; Quan, X.; Saka, H.; Stickland, D.; Tully, C.; Werner, J. S.; Zuranski, A.; Brownson, E.; Mendez, H.; Ramirez Vargas, J. E.; Barnes, V. E.; Benedetti, D.; Bortoletto, D.; De Mattia, M.; Gutay, L.; Hu, Z.; Jha, M. K.; Jones, M.; Jung, K.; Kress, M.; Leonardo, N.; Lopes Pegna, D.; Maroussov, V.; Miller, D. H.; Neumeister, N.; Radburn-Smith, B. C.; Shi, X.; Shipsey, I.; Silvers, D.; Svyatkovskiy, A.; Wang, F.; Xie, W.; Xu, L.; Yoo, H. D.; Zablocki, J.; Zheng, Y.; Parashar, N.; Stupak, J.; Adair, A.; Akgun, B.; Ecklund, K. M.; Geurts, F. J. M.; Li, W.; Michlin, B.; Padley, B. P.; Redjimi, R.; Roberts, J.; Zabel, J.; Betchart, B.; Bodek, A.; Covarelli, R.; de Barbaro, P.; Demina, R.; Eshaq, Y.; Ferbel, T.; Garcia-Bellido, A.; Goldenzweig, P.; Han, J.; Harel, A.; Khukhunaishvili, A.; Petrillo, G.; Vishnevskiy, D.; Ciesielski, R.; Demortier, L.; Goulianos, K.; Lungu, G.; Mesropian, C.; Arora, S.; Barker, A.; Chou, J. P.; Contreras-Campana, C.; Contreras-Campana, E.; Duggan, D.; Ferencek, D.; Gershtein, Y.; Gray, R.; Halkiadakis, E.; Hidas, D.; Kaplan, S.; Lath, A.; Panwalkar, S.; Park, M.; Patel, R.; Salur, S.; Schnetzer, S.; Somalwar, S.; Stone, R.; Thomas, S.; Thomassen, P.; Walker, M.; Rose, K.; Spanier, S.; York, A.; Bouhali, O.; Castaneda Hernandez, A.; Eusebi, R.; Flanagan, W.; Gilmore, J.; Kamon, T.; Khotilovich, V.; Krutelyov, V.; Montalvo, R.; Osipenkov, I.; Pakhotin, Y.; Perloff, A.; Roe, J.; Rose, A.; Safonov, A.; Sakuma, T.; Suarez, I.; Tatarinov, A.; Akchurin, N.; Cowden, C.; Damgov, J.; Dragoiu, C.; Dudero, P. R.; Faulkner, J.; Kovitanggoon, K.; Kunori, S.; Lee, S. W.; Libeiro, T.; Volobouev, I.; Appelt, E.; Delannoy, A. G.; Greene, S.; Gurrola, A.; Johns, W.; Maguire, C.; Mao, Y.; Melo, A.; Sharma, M.; Sheldon, P.; Snook, B.; Tuo, S.; Velkovska, J.; Arenton, M. W.; Boutle, S.; Cox, B.; Francis, B.; Goodell, J.; Hirosky, R.; Ledovskoy, A.; Li, H.; Lin, C.; Neu, C.; Wood, J.; Clarke, C.; Harr, R.; Karchin, P. E.; Kottachchi Kankanamge Don, C.; Lamichhane, P.; Sturdy, J.; Belknap, D. A.; Carlsmith, D.; Cepeda, M.; Dasu, S.; Dodd, L.; Duric, S.; Friis, E.; Hall-Wilton, R.; Herndon, M.; Hervé, A.; Klabbers, P.; Lanaro, A.; Lazaridis, C.; Levine, A.; Loveless, R.; Mohapatra, A.; Ojalvo, I.; Perry, T.; Pierro, G. A.; Polese, G.; Ross, I.; Sarangi, T.; Savin, A.; Smith, W. H.; Taylor, D.; Verwilligen, P.; Vuosalo, C.; Woods, N.; Collaboration, [Authorinst]The CMS

    2015-05-01

    This paper presents a measurement of the inclusive 3-jet production differential cross section at a proton-proton centre-of-mass energy of 7 TeV using data corresponding to an integrated luminosity of 5collected with the CMS detector. The analysis is based on the three jets with the highest transverse momenta. The cross section is measured as a function of the invariant mass of the three jets in a range of 445-3270 GeV and in two bins of the maximum rapidity of the jets up to a value of 2. A comparison between the measurement and the prediction from perturbative QCD at next-to-leading order is performed. Within uncertainties, data and theory are in agreement. The sensitivity of the observable to the strong coupling constant is studied. A fit to all data points with 3-jet masses larger than 664 GeV gives a value of the strong coupling constant of.

  16. A benchmark study of molecular structure by experimental and theoretical methods: Equilibrium structure of thymine from microwave rotational constants and coupled-cluster computations

    NASA Astrophysics Data System (ADS)

    Vogt, Natalja; Demaison, Jean; Ksenafontov, Denis N.; Rudolph, Heinz Dieter

    2014-11-01

    Accurate equilibrium, re, structures of thymine have been determined using two different, and to some extent complementary techniques. The composite ab initio Born-Oppenheimer, re(best ab initio), structural parameters are obtained from the all-electron CCSD(T) and MP2 geometry optimizations using Gaussian basis sets up to quadruple-zeta quality. The semi-experimental mixed estimation method, where internal coordinates are fitted concurrently to equilibrium rotational constants and geometry parameters obtained from a high level of electronic structure theory. The equilibrium rotational constants are derived from experimental effective ground-state rotational constants and rovibrational corrections based on a quantum-chemical cubic force field. Equilibrium molecular structures accurate to 0.002 Å and 0.2° have been determined. This work is one of a few accurate equilibrium structure determinations for large molecules. The poor behavior of Kraitchman's equations is discussed.

  17. The potential utility of predicted one bond carbon-proton coupling constants in the structure elucidation of small organic molecules by NMR spectroscopy.

    PubMed

    Venkata, Chandrasekhar; Forster, Mark J; Howe, Peter W A; Steinbeck, Christoph

    2014-01-01

    NMR spectroscopy is the most popular technique used for structure elucidation of small organic molecules in solution, but incorrect structures are regularly reported. One-bond proton-carbon J-couplings provide additional information about chemical structure because they are determined by different features of molecular structure than are proton and carbon chemical shifts. However, these couplings are not routinely used to validate proposed structures because few software tools exist to predict them. This study assesses the accuracy of Density Functional Theory for predicting them using 396 published experimental observations from a diverse range of small organic molecules. With the B3LYP functional and the TZVP basis set, Density Functional Theory calculations using the open-source software package NWChem can predict one-bond CH J-couplings with good accuracy for most classes of small organic molecule. The root-mean-square deviation after correction is 1.5 Hz for most sp3 CH pairs and 1.9 Hz for sp2 pairs; larger errors are observed for sp3 pairs with multiple electronegative substituents and for sp pairs. These results suggest that prediction of one-bond CH J-couplings by Density Functional Theory is sufficiently accurate for structure validation. This will be of particular use in strained ring systems and heterocycles which have characteristic couplings and which pose challenges for structure elucidation.

  18. The Potential Utility of Predicted One Bond Carbon-Proton Coupling Constants in the Structure Elucidation of Small Organic Molecules by NMR Spectroscopy

    PubMed Central

    Venkata, Chandrasekhar; Forster, Mark J.; Howe, Peter W. A.; Steinbeck, Christoph

    2014-01-01

    NMR spectroscopy is the most popular technique used for structure elucidation of small organic molecules in solution, but incorrect structures are regularly reported. One-bond proton-carbon J-couplings provide additional information about chemical structure because they are determined by different features of molecular structure than are proton and carbon chemical shifts. However, these couplings are not routinely used to validate proposed structures because few software tools exist to predict them. This study assesses the accuracy of Density Functional Theory for predicting them using 396 published experimental observations from a diverse range of small organic molecules. With the B3LYP functional and the TZVP basis set, Density Functional Theory calculations using the open-source software package NWChem can predict one-bond CH J-couplings with good accuracy for most classes of small organic molecule. The root-mean-square deviation after correction is 1.5 Hz for most sp3 CH pairs and 1.9 Hz for sp2 pairs; larger errors are observed for sp3 pairs with multiple electronegative substituents and for sp pairs. These results suggest that prediction of one-bond CH J-couplings by Density Functional Theory is sufficiently accurate for structure validation. This will be of particular use in strained ring systems and heterocycles which have characteristic couplings and which pose challenges for structure elucidation. PMID:25365289

  19. Proton, muon and ¹³C hyperfine coupling constants of C₆₀X and C₇₀X (X = H, Mu).

    PubMed

    Brodovitch, Jean-Claude; Addison-Jones, Brenda; Ghandi, Khashayar; McKenzie, Iain; Percival, Paul W

    2015-01-21

    The reaction of H atoms with fullerene C70 has been investigated by identifying the radical products formed by addition of the atom muonium (Mu) to the fullerene in solution. Four of the five possible radical isomers of C70Mu were detected by avoided level-crossing resonance (μLCR) spectroscopy, using a dilute solution of enriched (13)C70 in decalin. DFT calculations were used to predict muon and (13)C isotropic hyperfine constants as an aid to assigning the observed μLCR signals. Computational methods were benchmarked against previously published experimental data for (13)C60Mu in solution. Analysis of the μLCR spectrum resulted in the first experimental determination of (13)C hyperfine constants in either C70Mu or C70H. The large number of values confirms predictions that the four radical isomers have extended distributions of unpaired electron spin.

  20. Metal complexes stability constant determination by hyphenation of capillary electrophoresis with inductively coupled plasma mass spectrometry: the case of 1:1 metal-to-ligand stoichiometry.

    PubMed

    Petit, Jeremy; Geertsen, Valérie; Beaucaire, Catherine; Stambouli, Moncef

    2009-05-01

    Nuclear energy development has raised new issues like radionuclides biogeochemistry. The modelling of their biochemical properties involves the accurate determination of thermodynamical data, like stability constants. This can be achieved by using hyphenated capillary electrophoresis (CE)-ICPMS and the method was applied successfully on 1:1 lanthanum-oxalate and uranyl-oxalate complexes. Several significant steps are discussed: choice of analytical conditions, electrophoretic mobility calculation, mathematical treatment of experimental data by using linear regressions, ligand concentration and ionic strength corrections. The following values were obtained with a good precision for lanthanum-oxalate and uranyl-oxalate complexes: log(K degrees (LaOxa(+)))=6.10+/-0.10 and log(K degrees (UO(2)Oxa))=6.40+/-0.30, respectively, at infinite dilution. These values are consistent with the literature data, showing CE-ICPMS potential for metal complexes stability constants determination. PMID:19303078

  1. Dual electron-phonon coupling model for gigantic photoenhancement of the dielectric constant and electronic conductivity in SrTi O3

    NASA Astrophysics Data System (ADS)

    Qiu, Y.; Wu, C. Q.; Nasu, K.

    2005-12-01

    In connection with the recent experimental discovery on photoenhancements of the electronic conductivity and the quasi-static electric susceptibility in SrTiO3 , we theoretically study a photogeneration mechanism of charged and conductive ferroelectric domains in this perovskite type quantum dielectric. The photo-generated electron, being quite itinerant in the 3d band of Ti4+ , is assumed to couple weakly but quadratically with soft-anharmonic T1u phonons in this quantum dielectric, in view of the parity of this lattice vibration. The photo-generated electron is also assumed to couple strongly but linearly with the breathing type high energy phonons. Using a tight-binding model for electrons, we will show that this dual electron-phonon coupling results in two types of polarons, a “super-para-electric (SPE) large polaron” with a quasi-globle parity violation, and an “off-center type self-trapped polaron” with only a local parity violation. This SPE large polaron is shown to be equal to a singly charged (e-) and conductive ferroelectric domain with a quasi-macroscopic range. Two of such large polarons are shown to aggregate and form an SPE large bipolaron, which is still conductive. Various other bipolaron clusters are also shown to be formed in this electron-phonon coupled system. These large polarons have a high mobility and an enhanced quasi-static dielectric susceptibility. Effect of adulteration is also discussed.

  2. Unitaxial constant velocity microactuator

    DOEpatents

    McIntyre, Timothy J.

    1994-01-01

    A uniaxial drive system or microactuator capable of operating in an ultra-high vacuum environment. The mechanism includes a flexible coupling having a bore therethrough, and two clamp/pusher assemblies mounted in axial ends of the coupling. The clamp/pusher assemblies are energized by voltage-operated piezoelectrics therewithin to operatively engage the shaft and coupling causing the shaft to move along its rotational axis through the bore. The microactuator is capable of repeatably positioning to sub-manometer accuracy while affording a scan range in excess of 5 centimeters. Moreover, the microactuator generates smooth, constant velocity motion profiles while producing a drive thrust of greater than 10 pounds. The system is remotely controlled and piezoelectrically driven, hence minimal thermal loading, vibrational excitation, or outgassing is introduced to the operating environment.

  3. Unitaxial constant velocity microactuator

    DOEpatents

    McIntyre, T.J.

    1994-06-07

    A uniaxial drive system or microactuator capable of operating in an ultra-high vacuum environment is disclosed. The mechanism includes a flexible coupling having a bore therethrough, and two clamp/pusher assemblies mounted in axial ends of the coupling. The clamp/pusher assemblies are energized by voltage-operated piezoelectrics therewithin to operatively engage the shaft and coupling causing the shaft to move along its rotational axis through the bore. The microactuator is capable of repeatably positioning to sub-nanometer accuracy while affording a scan range in excess of 5 centimeters. Moreover, the microactuator generates smooth, constant velocity motion profiles while producing a drive thrust of greater than 10 pounds. The system is remotely controlled and piezoelectrically driven, hence minimal thermal loading, vibrational excitation, or outgassing is introduced to the operating environment. 10 figs.

  4. GIAO, DFT, AIM and NBO analysis of the N-H...O intramolecular hydrogen-bond influence on the 1J(N,H) coupling constant in push-pull diaminoenones.

    PubMed

    Afonin, Andrei V; Ushakov, Igor A; Vashchenko, Alexander V; Kondrashov, Evgeniy V; Rulev, Alexander Yu

    2010-09-01

    In the series of diaminoenones, large high-frequency shifts of the (1)H NMR of the N-H group in the cis-position relative to the carbonyl group suggests strong N-H...O intramolecular hydrogen bonding comprising a six-membered chelate ring. The N-H...O hydrogen bond causes an increase of the (1)J(N,H) coupling constant by 2-4 Hz and high-frequency shift of the (15)N signal by 9-10 ppm despite of the lengthening of the relevant N-H bond. These experimental trends are substantiated by gauge-independent atomic orbital and density functional theory calculations of the shielding and coupling constants in the 3,3-bis(isopropylamino)-1-(aryl)prop-2-en-1-one (12) for conformations with the Z- and E-orientations of the carbonyl group relative to the N-H group. The effects of the N-H...O hydrogen-bond on the NMR parameters are analyzed with the atoms-in-molecules (AIM) and natural bond orbital (NBO) methods. The AIM method indicates a weakening of the N-H...O hydrogen bond as compared with that of 1,1-di(pyrrol-2-yl)-2-formylethene (13) where N-H...O hydrogen bridge establishes a seven-membered chelate ring, and the corresponding (1)J(N,H) coupling constant decreases. The NBO method reveals that the LP(O) --> sigma*(N-H) hyperconjugative interaction is weakened on going from the six-membered chelate ring to the seven-membered one due to a more bent hydrogen bond in the former case. A dominating effect of the N-H bond rehybridization, owing to an electrostatic term in the hydrogen bonding, seems to provide an increase of the (1)J(N,H) value as a consequence of the N-H...O hydrogen bonding in the studied diaminoenones.

  5. Synthesis and characterization of a novel N-F reagent derived from the ethano-Tröger's base: (1)J(FN) coupling constants as a signature for the N-F bond.

    PubMed

    Pereira, Raul; Wolstenhulme, Jamie; Sandford, Graham; Claridge, Timothy D W; Gouverneur, Véronique; Cvengroš, Ján

    2016-01-28

    Methylation of 2,8-dimethyl-6H,12H-5,11-ethanodibenzo[b,f][1,5]-diazocine (ethano-Tröger's base) with methyl iodide followed by ion metathesis and fluorination with N-fluoro-2,3,4,5,6-pentachloropyridinium triflate affords a new electrophilic N-F reagent, that is more reactive than Selectfluor. 2D (19)F-(15)N HMQC experiments provide (1)JNF coupling constants which are diagnostic for the N-F functional group. PMID:26658721

  6. /sup 13/C-/sup 13/C spin-spin coupling in structural investigations. VII. Substitution effects and direct carbon-carbon constants of the triple bond in acetyline derivatives

    SciTech Connect

    Krivdin, L.B.; Proidakov, A.G.; Bazhenov, B.N.; Zinchenko, S.V.; Kalabin, G.A.

    1989-01-10

    The effects of substitution on the direct /sup 13/C-/sup 13/C spin-spin coupling constants of the triple bond were studied in 100 derivatives of acetylene. It was established that these parameters exhibit increased sensitivity to the effect of substituents compared with other types of compounds. The main factor which determines their variation is the electronegativity of the substituting groups, and in individual cases the /pi/-electronic effects are appreciable. The effect of the substituents with an element of the silicon subgroup at the /alpha/ position simultaneously at the triple bond or substituent of the above-mentioned type and a halogen atom.

  7. sup 13 C-enriched ribonucleosides: Synthesis and application of sup 13 C- sup 1 H and sup 13 C- sup 13 C spin-coupling constants to assess furanose and N-glycoside bond conformations

    SciTech Connect

    Kline, P.C.; Serianni, A.S. )

    1990-09-26

    Adenosine (1), cytidine (2), guanosine (3), and uridine (4) have been prepared chemically with {sup 13}C enrichment (99 atom %) at C1{prime} and C2{prime} of the ribose ring. Reliable synthetic protocols have been developed to permit access to millimole quantities of labeled ribonucleosides required for structural studies of stable isotopically labeled oligonucleotides and for in vivo metabolism studies. High-resolution {sup 1}H and {sup 13}C NMR spectra of the enriched ribonucleosides have been obtained, and {sup 13}C-{sup 13}C and {sup 13}C-{sup 1}H spin-coupling constants have been measured for pathways within the {beta}-D-ribofuranose ring and across the N-glycoside bond. Related couplings were determined in methyl {alpha}- and {beta}-D-riboruanosides (5,6), and in two conformationally constrained nucleosides, 2,2{prime}-anhydro-(1-{beta}-D-arabinofuranosyl)uracil (7) and 2{prime},3{prime}-O-isopropylidene-2,5{prime}-O-cyclouridine (8). The latter data were used to construct a crude Karplus curve for the {sup 13}C-C-N-{sup 13}C coupling pathway across the N-glycoside bond in 1-4. {sup 1}H-{sup 1}H, {sup 13}C-{sup 1}H, and {sup 13}C-{sup 13}C coupling data are used to evaluate current models describing the conformational dynamics of 1-4 in aqueous solution.

  8. Wall of fundamental constants

    SciTech Connect

    Olive, Keith A.; Peloso, Marco; Uzan, Jean-Philippe

    2011-02-15

    We consider the signatures of a domain wall produced in the spontaneous symmetry breaking involving a dilatonlike scalar field coupled to electromagnetism. Domains on either side of the wall exhibit slight differences in their respective values of the fine-structure constant, {alpha}. If such a wall is present within our Hubble volume, absorption spectra at large redshifts may or may not provide a variation in {alpha} relative to the terrestrial value, depending on our relative position with respect to the wall. This wall could resolve the contradiction between claims of a variation of {alpha} based on Keck/Hires data and of the constancy of {alpha} based on Very Large Telescope data. We derive the properties of the wall and the parameters of the underlying microscopic model required to reproduce the possible spatial variation of {alpha}. We discuss the constraints on the existence of the low-energy domain wall and describe its observational implications concerning the variation of the fundamental constants.

  9. Theoretical Study of the Electrostatic and Steric Effects on the Spectroscopic Characteristics of the Metal-Ligand Unit of Heme Proteins. 2. C-O Vibrational Frequencies, 17O Isotropic Chemical Shifts, and Nuclear Quadrupole Coupling Constants

    PubMed Central

    Kushkuley, Boris; Stavrov, Solomon S.

    1997-01-01

    The quantum chemical calculations, vibronic theory of activation, and London-Pople approach are used to study the dependence of the C-O vibrational frequency, 17O isotropic chemical shift, and nuclear quadrupole coupling constant on the distortion of the porphyrin ring and geometry of the CO coordination, changes in the iron-carbon and iron-imidazole distances, magnitude of the iron displacement out of the porphyrin plane, and presence of the charged groups in the heme environment. It is shown that only the electrostatic interactions can cause the variation of all these parameters experimentally observed in different heme proteins, and the heme distortions could modulate this variation. The correlations between the theoretically calculated parameters are shown to be close to the experimentally observed ones. The study of the effect of the electric field of the distal histidine shows that the presence of the four C-O vibrational bands in the infrared absorption spectra of the carbon monoxide complexes of different myoglobins and hemoglobins can be caused by the different orientations of the different tautomeric forms of the distal histidine. The dependence of the 17O isotropic chemical shift and nuclear quadrupole coupling constant on pH and the distal histidine substitution can be also explained from the same point of view. PMID:9017215

  10. Constraints on parton distribution functions and extraction of the strong coupling constant from the inclusive jet cross section in pp collisions at $$\\sqrt{s} = 7$$ $$\\,\\text {TeV}$$

    DOE PAGES

    Khachatryan, Vardan

    2015-06-26

    The inclusive jet cross section for proton–proton collisions at a centre-of-mass energy of 7TeVwas measured by the CMS Collaboration at the LHC with data corresponding to an integrated luminosity of 5.0fb-1. The measurement covers a phase space up to 2TeV in jet transverse momentum and 2.5 in absolute jet rapidity. The statistical precision of these data leads to stringent constraints on the parton distribution functions of the proton. The data provide important input for the gluon density at high fractions of the proton momentum and for the strong coupling constant at large energy scales. Using predictions from perturbative quantum chromodynamicsmore » at next-to-leading order, complemented with electroweak corrections, the constraining power of these data is investigated and the strong coupling constant at the Z boson mass MZ is determined to be αS(MZ)=0.1185±0.0019(exp)+0.0060-0.0037(theo), which is in agreement with the world average.« less

  11. Measurement of the inclusive 3-jet production differential cross section in proton–proton collisions at 7 TeV and determination of the strong coupling constant in the TeV range

    DOE PAGES

    Khachatryan, Vardan

    2015-05-01

    This article presents a measurement of the inclusive 3-jet production differential cross section at a proton–proton centre-of-mass energy of 7 TeV using data corresponding to an integrated luminosity of 5fb–1 collected with the CMS detector. The analysis is based on the three jets with the highest transverse momenta. The cross section is measured as a function of the invariant mass of the three jets in a range of 445–3270 GeV and in two bins of the maximum rapidity of the jets up to a value of 2. A comparison between the measurement and the prediction from perturbative QCD at next-to-leadingmore » order is performed. Within uncertainties, data and theory are in agreement. The sensitivity of the observable to the strong coupling constant αS is studied. A fit to all data points with 3-jet masses larger than 664 GeV gives a value of the strong coupling constant of αS(MZ) = 0.1171 ± 0.0013(exp)+0.0073–0.0047(theo).« less

  12. Measurement of the inclusive 3-jet production differential cross section in proton–proton collisions at 7 TeV and determination of the strong coupling constant in the TeV range

    SciTech Connect

    Khachatryan, Vardan

    2015-05-01

    This article presents a measurement of the inclusive 3-jet production differential cross section at a proton–proton centre-of-mass energy of 7 TeV using data corresponding to an integrated luminosity of 5fb–1 collected with the CMS detector. The analysis is based on the three jets with the highest transverse momenta. The cross section is measured as a function of the invariant mass of the three jets in a range of 445–3270 GeV and in two bins of the maximum rapidity of the jets up to a value of 2. A comparison between the measurement and the prediction from perturbative QCD at next-to-leading order is performed. Within uncertainties, data and theory are in agreement. The sensitivity of the observable to the strong coupling constant αS is studied. A fit to all data points with 3-jet masses larger than 664 GeV gives a value of the strong coupling constant of αS(MZ) = 0.1171 ± 0.0013(exp)+0.0073–0.0047(theo).

  13. Constraints on parton distribution functions and extraction of the strong coupling constant from the inclusive jet cross section in pp collisions at $\\sqrt{s} = 7$ $\\,\\text {TeV}$

    SciTech Connect

    Khachatryan, Vardan

    2015-06-26

    The inclusive jet cross section for proton–proton collisions at a centre-of-mass energy of 7TeVwas measured by the CMS Collaboration at the LHC with data corresponding to an integrated luminosity of 5.0fb-1. The measurement covers a phase space up to 2TeV in jet transverse momentum and 2.5 in absolute jet rapidity. The statistical precision of these data leads to stringent constraints on the parton distribution functions of the proton. The data provide important input for the gluon density at high fractions of the proton momentum and for the strong coupling constant at large energy scales. Using predictions from perturbative quantum chromodynamics at next-to-leading order, complemented with electroweak corrections, the constraining power of these data is investigated and the strong coupling constant at the Z boson mass MZ is determined to be αS(MZ)=0.1185±0.0019(exp)+0.0060-0.0037(theo), which is in agreement with the world average.

  14. Highly efficient perturbative + variational strategy based on orthogonal valence bond theory for the evaluation of magnetic coupling constants. Application to the trinuclear Cu(ii) site of multicopper oxidases.

    PubMed

    Tenti, Lorenzo; Maynau, Daniel; Angeli, Celestino; Calzado, Carmen J

    2016-07-21

    A new strategy based on orthogonal valence-bond analysis of the wave function combined with intermediate Hamiltonian theory has been applied to the evaluation of the magnetic coupling constants in two AF systems. This approach provides both a quantitative estimate of the J value and a detailed analysis of the main physical mechanisms controlling the coupling, using a combined perturbative + variational scheme. The procedure requires a selection of the dominant excitations to be treated variationally. Two methods have been employed: a brute-force selection, using a logic similar to that of the CIPSI approach, or entanglement measures, which identify the most interacting orbitals in the system. Once a reduced set of excitations (about 300 determinants) is established, the interaction matrix is dressed at the second-order of perturbation by the remaining excitations of the CI space. The diagonalization of the dressed matrix provides J values in good agreement with experimental ones, at a very low-cost. This approach demonstrates the key role of d → d* excitations in the quantitative description of the magnetic coupling, as well as the importance of using an extended active space, including the bridging ligand orbitals, for the binuclear model of the intermediates of multicopper oxidases. The method is a promising tool for dealing with complex systems containing several active centers, as an alternative to both pure variational and DFT approaches.

  15. Investigation of the resonance-assisted hydrogen bond in model β-diketones through localized molecular orbital analysis of the spin-spin coupling constants related to the O-H···O hydrogen bond.

    PubMed

    Zarycz, M Natalia C; Provasi, Patricio F

    2015-02-01

    The resonance-assisted hydrogen bond (HB) phenomenon has been studied theoretically by a localized molecular orbital (LMO) decomposition of the spin-spin coupling constants between atoms either involved or close to the O-H···O system of some β-diketones and their saturated counterparts. The analysis, carried out at the level of the second-order polarization propagator approximation, shows that the contributions in terms of LMO to the paramagnetic spin orbital and the spin dipolar Ramsey terms proof the importance of the delocalized π-electron structure supporting the idea of the existence of the resonance-assisted HB phenomenon phenomenon. The LMO contributions to the Fermi contact term indicate mainly the presence of the HB that may or not be linked to the π-electrons.

  16. Determination of the strong coupling constant from inclusive jet cross section in ppbar collisions at sqrt(s)=1.96 TeV with the D0 experiment

    SciTech Connect

    Sonnenschein, Lars

    2010-06-01

    The strong coupling constant as and its dependence on the momentum scale is determined from the pT dependence of the inclusive jet cross section in p{bar p} collisions at {radical}s = 1.96 TeV measured with the D0 experiment. The jet transverse momentum range of 50 < p{sub T} < 145 GeV contributes to the determination. Using perturbative QCD caclulations to order {theta}({alpha}{sup 3}{sub s}) combined with resummed threshold corrections to order {theta}({alpha}{sup 3}{sub s}) an {alpha}{sub s}(MZ) = 0.1161{sup +0.0041}{sub -0.0048} is obtained. This is the most precise result from a hadron-hadron collider.

  17. V(IV)O versus V(IV) complex formation by tridentate (O, N(arom), O) ligands: prediction of geometry, EPR 51V hyperfine coupling constants, and UV-Vis spectra.

    PubMed

    Pisano, Luisa; Várnagy, Katalin; Timári, Sarolta; Hegetschweiler, Kaspar; Micera, Giovanni; Garribba, Eugenio

    2013-05-01

    Systems formed using the V(IV)O(2+) ion with tridentate ligands containing a (O, N(arom), O) donor set were described. Examined ligands were 3,5-bis(2-hydroxyphenyl)-1-phenyl-1H-1,2,4-triazole (H2hyph(Ph)), 4-[3,5-bis(2-hydroxyphenyl)-1H-1,2,4-triazol-1-yl]benzoic acid (H3hyph(C)), 4-[3,5-bis(2-hydroxyphenyl)-1H-1,2,4-triazol-1-yl]benzenesulfonic acid (H3hyph(S)), and 2,6-bis(2-hydroxyphenyl)pyridine (H2bhpp), with H3hyph(C) being an orally active iron chelator that is commercially available under the name Exjade (Novartis) for treatment of chronic iron overload arising from blood transfusions. The systems were studied using EPR, UV-Vis, and IR spectroscopies, pH potentiometry, and DFT methods. The ligands bind vanadium with the two terminal deprotonated phenol groups and the central aromatic nitrogen to give six-membered chelate rings. In aqueous solution the main species were the mono- and bis-chelated V(IV)O complexes, whereas in the solid state neutral non-oxido V(IV) compounds were formed. [V(hyph(Ph))2] and [V(bhpp)2] are hexacoordinated, with a geometry close to the octahedral and a meridional arrangement of the ligands. DFT calculations allow distinguishing V(IV)O and V(IV) species and predicting their structure, the (51)V hyperfine coupling constant tensor A, and the electronic absorption spectra. Finally, EPR spectra of several non-oxido V(IV) species were compared using relevant geometrical parameters to demonstrate that in the case of tridentate ligands the (51)V hyperfine coupling constant is related to the geometric isomerism (meridional or facial) rather than the twist angle Φ, which measures the distortion of the hexacoordinated structure toward a trigonal prism. PMID:23581472

  18. Hydrogen Interaction with Metal Halides: the Nuclear Quadrupole Coupling Constant of Gold in the {p}{-H}_2{-AuCl} Complex and Trends in the Other Hydrogen-Coinage Metal Halide Interactions

    NASA Astrophysics Data System (ADS)

    Obenchain, Daniel A.; Grubbs, G. S. Grubbs, Ii; Pickett, Herbert M.; Novick, Stewart E.

    2013-06-01

    The rotational spectrum of p-H_2-AuCl has been measured using a laser ablation equipped FTMW cavity spectrometer. The predicted structure, using a 60 electron core potential and an aug-cc-pVQZ at the MP2 level of theory, shows that H_2 has an r_e = 0.91Å. A predicted value for the eQq(χ_{aa}) of gold required a semi-empirical method using the results of previous AuCl complexes in the gas phase. Transitions have been measured across multiple J levels, and have been used to determine the rotational constants, centrifugal distortion constants, and nuclear quadrupole coupling constants of multiple isotopologues. The o-H_2-AuCl has also been observed. While the monomer value of the eQq of ^{197}Au was determined to be 9.63112(13) MHz in ^{197}Au^{35}Cl, we observed a significant change in the eQq of ^{197}Au in p-H_2-^{197}Au^{35}Cl to a value of -817.9983(36) MHz [0.02728556(12) cm^{-1}], giving rise to a Au hyperfine component splittings of approximately 220 MHz [0.007 cm^{-1}] and suggesting a change in electronic structure with the interaction of H_2. We will present a summary of the hydrogen-coinage metal halide talks given at this conference, including trends in eQq and hydrogen metal halide dissociation energies. D. Figgen, G. Rauhut, M. Dolh, H. Stoll J. Chem. Phys. 311(2005) 227. K. A. Peterson, C. Puzzarini, Theor. Chem. Acc. 114 (2005) 283. C. J. Evans, C. L. Gerry J. Mol. Spectrosc. 203 (2000) 105.

  19. Scalar relativistic calculations of hyperfine coupling constants using ab initio density matrix renormalization group method in combination with third-order Douglas-Kroll-Hess transformation: case studies on 4d transition metals.

    PubMed

    Nguyen Lan, Tran; Kurashige, Yuki; Yanai, Takeshi

    2015-01-13

    We have developed a new computational scheme for high-accuracy prediction of the isotropic hyperfine coupling constant (HFCC) of heavy molecules, accounting for the high-level electron correlation effects, as well as the scalar-relativistic effects. For electron correlation, we employed the ab initio density matrix renormalization group (DMRG) method in conjunction with a complete active space model. The orbital-optimization procedure was employed to obtain the optimized orbitals required for accurately determining the isotropic HFCC. For the scalar-relativistic effects, we initially derived and implemented the Douglas-Kroll-Hess (DKH) hyperfine coupling operators up to the third order (DKH3) by using the direct transformation scheme. A set of 4d transition-metal radicals consisting of Ag atom, PdH, and RhH2 were chosen as test cases. Good agreement between the isotropic HFCC values obtained from DMRG/DKH3 and experiment was archived. Because there are no available gas-phase values for PdH and RhH2 radicals in the literature, the results from the present high-level theory may serve as benchmark data.

  20. Computational and ESR studies of electron attachment to decafluorocyclopentane, octafluorocyclobutane, and hexafluorocyclopropane: electron affinities of the molecules and the structures of their stable negative ions as determined from 13C and 19F hyperfine coupling constants.

    PubMed

    ElSohly, Adel M; Tschumper, Gregory S; Crocombe, Richard A; Wang, Jih Tzong; Williams, Ffrancon

    2005-08-01

    High-resolution ESR spectra of the ground-state negative ions of hexafluorocyclopropane (c-C3F6*-), octafluorocyclobutane (c-C4F8*-), and decafluorocyclopentane (c-C5F10*-) are reported and their isotropic 19F hyperfine coupling constants (hfcc) of 198.6 +/- 0.4 G, 147.6 +/- 0.4 G, and 117.9 +/- 0.4 G, respectively, are in inverse ratio to the total number of fluorine atoms per anion. Together with the small value of 5.2 +/- 0.4 G determined for the isotropic 13C hfcc of c-C4F8*-, these results indicate that in each case the singly occupied molecular orbital (SOMO) is delocalized over the equivalent fluorines and possesses a nodal plane through the carbon atoms of a time-averaged D(nh) structure. A series of quantum chemical computations were carried out to further characterize these anions and their neutral counterparts. Both the B3LYP density functional and second-order Møller-Plesset perturbation theory (MP2) indicate that c-C3F6*- adopts a D(3h) geometry and a (2)A2'' ground electronic state, that c-C4F8*- adopts a D(4h) geometry and a (2)A2u ground electronic state, and that c-C5F10*- adopts a C(s) structure and a (2)A' electronic state. Moreover, the 19F hyperfine coupling constants computed with the MP2 method and a high quality triple-zeta basis set are within 1% of the experimental values. Also, the values computed for the 13C hfcc of c-C4F8*- are consistent with the experimental value of 5.2 G. Therefore, in keeping with the ESR results, these negative ions derived from first-row elements can be characterized as pi* species. In addition, the hypervalency of these perfluorocycloalkane radical anions has been clarified.

  1. Determination of the top-quark pole mass and strong coupling constant from the t t-bar production cross section in pp collisions at $$\\sqrt{s}$$ = 7 TeV

    DOE PAGES

    Chatrchyan, Serguei

    2014-08-21

    The inclusive cross section for top-quark pair production measured by the CMS experiment in proton-proton collisions at a center-of-mass energy of 7 TeV is compared to the QCD prediction at next-to-next-to-leading order with various parton distribution functions to determine the top-quark pole mass,more » $$m_t^{pole}$$, or the strong coupling constant, $$\\alpha_S$$. With the parton distribution function set NNPDF2.3, a pole mass of 176.7$$^{+3.0}_{-2.8}$$ GeV is obtained when constraining $$\\alpha_S$$ at the scale of the Z boson mass, $m_Z$, to the current world average. Alternatively, by constraining $$m_t^{pole}$$ to the latest average from direct mass measurements, a value of $$\\alpha_S(m_Z)$$ = 0.1151$$^{+0.0028}_{-0.0027}$$ is extracted. This is the first determination of $$\\alpha_S$$ using events from top-quark production.« less

  2. Determination of the tautomeric equilibria of pyridoyl benzoyl β-diketones in the liquid and solid state through the use of deuterium isotope effects on (1)H and (13)C NMR chemical shifts and spin coupling constants.

    PubMed

    Hansen, Poul Erik; Borisov, Eugeny V; Lindon, John C

    2015-02-01

    The tautomeric equilibria for 2-pyridoyl-, 3-pyridoyl-, and 4-pyridoyl-benzoyl methane have been investigated using deuterium isotope effects on (1)H and (13)C chemical shifts both in the liquid and the solid state. Equilibria are established both in the liquid and the solid state. In addition, in the solution state the 2-bond and 3-bond J((1)H-(13)C) coupling constants have been used to confirm the equilibrium positions. The isotope effects due to deuteriation at the OH position are shown to be superior to chemical shift in determination of equilibrium positions of these almost symmetrical -pyridoyl-benzoyl methanes. The assignments of the NMR spectra are supported by calculations of the chemical shifts at the DFT level. The equilibrium positions are shown to be different in the liquid and the solid state. In the liquid state the 4-pyridoyl derivative is at the B-form (C-1 is OH), whereas the 2-and 3-pyridoyl derivatives are in the A-form. In the solid state all three compounds are on the B-form. The 4-pyridoyl derivative shows unusual deuterium isotope effects in the solid, which are ascribed to a change of the crystal structure of the deuteriated compound. PMID:24070650

  3. Determination of the top-quark pole mass and strong coupling constant from the t t-bar production cross section in pp collisions at $\\sqrt{s}$ = 7 TeV

    SciTech Connect

    Chatrchyan, Serguei

    2014-08-21

    The inclusive cross section for top-quark pair production measured by the CMS experiment in proton-proton collisions at a center-of-mass energy of 7 TeV is compared to the QCD prediction at next-to-next-to-leading order with various parton distribution functions to determine the top-quark pole mass, $m_t^{pole}$, or the strong coupling constant, $\\alpha_S$. With the parton distribution function set NNPDF2.3, a pole mass of 176.7$^{+3.0}_{-2.8}$ GeV is obtained when constraining $\\alpha_S$ at the scale of the Z boson mass, $m_Z$, to the current world average. Alternatively, by constraining $m_t^{pole}$ to the latest average from direct mass measurements, a value of $\\alpha_S(m_Z)$ = 0.1151$^{+0.0028}_{-0.0027}$ is extracted. This is the first determination of $\\alpha_S$ using events from top-quark production.

  4. String theory, cosmology and varying constants

    NASA Astrophysics Data System (ADS)

    Damour, Thibault

    In string theory the coupling `constants' appearing in the low-energy effective Lagrangian are determined by the vacuum expectation values of some (a priori) massless scalar fields (dilaton, moduli). This naturally leads one to expect a correlated variation of all the coupling constants, and an associated violation of the equivalence principle. We review some string-inspired theoretical models which incorporate such a spacetime variation of coupling constants while remaining naturally compatible both with phenomenological constraints coming from geochemical data (Oklo; Rhenium decay) and with present equivalence principle tests. Barring a very unnatural fine-tuning of parameters, a variation of the fine-structure constant as large as that recently `observed' by Webb et al. in quasar absorption spectra appears to be incompatible with these phenomenological constraints. Independently of any model, it is emphasized that the best experimental probe of varying constants are high-precision tests of the universality of free fall, such as MICROSCOPE and STEP.

  5. Varying Constants, Gravitation and Cosmology

    NASA Astrophysics Data System (ADS)

    Uzan, Jean-Philippe

    2011-12-01

    Fundamental constants are a cornerstone of our physical laws. Any constant varying in space and/or time would reflect the existence of an almost massless field that couples to matter. This will induce a violation of the universality of free fall. Thus, it is of utmost importance for our understanding of gravity and of the domain of validity of general relativity to test for their constancy. We detail the relations between the constants, the tests of the local position invariance and of the universality of free fall. We then review the main experimental and observational constraints that have been obtained from atomic clocks, the Oklo phenomenon, solar system observations, meteorite dating, quasar absorption spectra, stellar physics, pulsar timing, the cosmic microwave background and big bang nucleosynthesis. At each step we describe the basics of each system, its dependence with respect to the constants, the known systematic effects and the most recent constraints that have been obtained. We then describe the main theoretical frameworks in which the low-energy constants may actually be varying and we focus on the unification mechanisms and the relations between the variation of different constants. To finish, we discuss the more speculative possibility of understanding their numerical values and the apparent fine-tuning that they confront us with.

  6. On geometrically unified fields and universal constants

    NASA Astrophysics Data System (ADS)

    Fabbri, Luca

    2013-07-01

    We consider the Cartan extension of Riemann geometry as the basis upon which to build the Sciama-Kibble completion of Einstein gravity, developing the most general theory in which torsion and metric have two independent coupling constants: the main problem of the ESK theory was that torsion, having the Newton constant, was negligible beyond the Planck scale, but in this {ESK}2 theory torsion, with its own coupling constant, may be relevant much further Planck scales; further consequences of these torsionally-induced interactions will eventually be discussed.

  7. On the Khinchin Constant

    NASA Technical Reports Server (NTRS)

    Bailey, David H.; Borwein, Jonathan M.; Crandall, Richard E.; Craw, James M. (Technical Monitor)

    1995-01-01

    We prove known identities for the Khinchin constant and develop new identities for the more general Hoelder mean limits of continued fractions. Any of these constants can be developed as a rapidly converging series involving values of the Riemann zeta function and rational coefficients. Such identities allow for efficient numerical evaluation of the relevant constants. We present free-parameter, optimizable versions of the identities, and report numerical results.

  8. Time-Varying Fundamental Constants

    NASA Astrophysics Data System (ADS)

    Olive, Keith

    2003-04-01

    Recent data from quasar absorption systems can be interpreted as arising from a time variation in the fine-structure constant. However, there are numerous cosmological, astro-physical, and terrestrial bounds on any such variation. These includes bounds from Big Bang Nucleosynthesis (from the ^4He abundance), the Oklo reactor (from the resonant neutron capture cross-section of Sm), and from meteoretic lifetimes of heavy radioactive isotopes. The bounds on the variation of the fine-structure constant are significantly strengthened in models where all gauge and Yukawa couplings vary in a dependent manner, as would be expected in unified theories. Models which are consistent with all data are severly challenged when Equivalence Principle constraints are imposed.

  9. The hubble constant.

    PubMed

    Huchra, J P

    1992-04-17

    The Hubble constant is the constant of proportionality between recession velocity and distance in the expanding universe. It is a fundamental property of cosmology that sets both the scale and the expansion age of the universe. It is determined by measurement of galaxy The Hubble constant is the constant of proportionality between recession velocity and development of new techniques for the measurements of galaxy distances, both calibration uncertainties and debates over systematic errors remain. Current determinations still range over nearly a factor of 2; the higher values favored by most local measurements are not consistent with many theories of the origin of large-scale structure and stellar evolution. PMID:17743107

  10. The cosmological constant

    NASA Technical Reports Server (NTRS)

    Carroll, Sean M.; Press, William H.; Turner, Edwin L.

    1992-01-01

    The cosmological constant problem is examined in the context of both astronomy and physics. Effects of a nonzero cosmological constant are discussed with reference to expansion dynamics, the age of the universe, distance measures, comoving density of objects, growth of linear perturbations, and gravitational lens probabilities. The observational status of the cosmological constant is reviewed, with attention given to the existence of high-redshift objects, age derivation from globular clusters and cosmic nuclear data, dynamical tests of Omega sub Lambda, quasar absorption line statistics, gravitational lensing, and astrophysics of distant objects. Finally, possible solutions to the physicist's cosmological constant problem are examined.

  11. Emergent cosmological constant from colliding electromagnetic waves

    SciTech Connect

    Halilsoy, M.; Mazharimousavi, S. Habib; Gurtug, O. E-mail: habib.mazhari@emu.edu.tr

    2014-11-01

    In this study we advocate the view that the cosmological constant is of electromagnetic (em) origin, which can be generated from the collision of em shock waves coupled with gravitational shock waves. The wave profiles that participate in the collision have different amplitudes. It is shown that, circular polarization with equal amplitude waves does not generate cosmological constant. We also prove that the generation of the cosmological constant is related to the linear polarization. The addition of cross polarization generates no cosmological constant. Depending on the value of the wave amplitudes, the generated cosmological constant can be positive or negative. We show additionally that, the collision of nonlinear em waves in a particular class of Born-Infeld theory also yields a cosmological constant.

  12. Fundamental Physical Constants

    National Institute of Standards and Technology Data Gateway

    SRD 121 CODATA Fundamental Physical Constants (Web, free access)   This site, developed in the Physics Laboratory at NIST, addresses three topics: fundamental physical constants, the International System of Units (SI), which is the modern metric system, and expressing the uncertainty of measurement results.

  13. Calculation of magnetostriction constants

    NASA Astrophysics Data System (ADS)

    Tatebayashi, T.; Ohtsuka, S.; Ukai, T.; Mori, N.

    1986-02-01

    The magnetostriction constants h1 and h2 for Ni and Fe metals and the anisotropy constants K1 and K2 for Fe metal are calculated on the basis of the approximate d bands obtained by Deegan's prescription, by using Gilat-Raubenheimer's method. The obtained results are compared with the experimental ones.

  14. Space Shuttle astrodynamical constants

    NASA Technical Reports Server (NTRS)

    Cockrell, B. F.; Williamson, B.

    1978-01-01

    Basic space shuttle astrodynamic constants are reported for use in mission planning and construction of ground and onboard software input loads. The data included here are provided to facilitate the use of consistent numerical values throughout the project.

  15. The cosmological constant problem

    SciTech Connect

    Dolgov, A.D.

    1989-05-01

    A review of the cosmological term problem is presented. Baby universe model and the compensating field model are discussed. The importance of more accurate data on the Hubble constant and the Universe age is stressed. 18 refs.

  16. Constant potential pulse polarography

    USGS Publications Warehouse

    Christie, J.H.; Jackson, L.L.; Osteryoung, R.A.

    1976-01-01

    The new technique of constant potential pulse polarography, In which all pulses are to be the same potential, is presented theoretically and evaluated experimentally. The response obtained is in the form of a faradaic current wave superimposed on a constant capacitative component. Results obtained with a computer-controlled system exhibit a capillary response current similar to that observed In normal pulse polarography. Calibration curves for Pb obtained using a modified commercial pulse polarographic instrument are in good accord with theoretical predictions.

  17. Variation of Fundamental Constants

    NASA Astrophysics Data System (ADS)

    Flambaum, V. V.

    2006-11-01

    Theories unifying gravity with other interactions suggest temporal and spatial variation of the fundamental ``constants'' in expanding Universe. The spatial variation can explain a fine tuning of the fundamental constants which allows humans (and any life) to appear. We appeared in the area of the Universe where the values of the fundamental constants are consistent with our existence. We present a review of recent works devoted to the variation of the fine structure constant α, strong interaction and fundamental masses. There are some hints for the variation in quasar absorption spectra. Big Bang nucleosynthesis, and Oklo natural nuclear reactor data. A very promising method to search for the variation of the fundamental constants consists in comparison of different atomic clocks. Huge enhancement of the variation effects happens in transition between accidentally degenerate atomic and molecular energy levels. A new idea is to build a ``nuclear'' clock based on the ultraviolet transition between very low excited state and ground state in Thorium nucleus. This may allow to improve sensitivity to the variation up to 10 orders of magnitude! Huge enhancement of the variation effects is also possible in cold atomic and molecular collisions near Feshbach resonance.

  18. Beyond the Hubble Constant

    NASA Astrophysics Data System (ADS)

    1995-08-01

    of SN 1995K of about 22.7, but the uncertainty of this value is still so large that this measurement alone cannot be used to determine the value of q0. This will require many more observations of supernovae at least as distant as the present one, a daunting task that may nevertheless be possible within this broad, international programme. It is estimated that a reliable measurement of q0 may become possible when about 20 Type Ia supernovae with accurate peak magnitudes have been measured. According to the discovery predictions, this could be possible within the next couple of years. In this connection, it is of some importance that for this investigation, it is in principle not necessary to know the correct value of the Hubble constant H0 in advance; q0 may still be determined by comparing the relative distance scale of distant supernovae with that of nearby ones. This research is described in more detail in a forthcoming article in the September 1995 issue of the ESO Messenger. Notes: [1] Brian P. Schmidt (Mount Stromlo and Siding Spring Observatories, Australia), Bruno Leibundgut, Jason Spyromilio, Jeremy Walsh (ESO), Mark M. Phillips, Nicholas B. Suntzeff, Mario Hamuy, Robert A. Schommer (Cerro Tololo Inter-American Observatory), Roberto Aviles (formerly Cerro Tololo Inter-American Observatory; now at ESO), Robert P. Kirshner, Adam Riess, Peter Challis, Peter Garnavich (Center for Astrophysics, Cambridge, Massachussetts, U.S.A.), Christopher Stubbs, Craig Hogan (University of Washington, Seattle, U.S.A.), Alan Dressler (Carnegie Observatories, U.S.A.) and Robin Ciardullo (Pennsylvania State University, U.S.A.) [2] In astronomy, the redshift denotes the fraction by which the lines in the spectrum of an object are shifted towards longer wavelengths. The observed redshift of a distant galaxy gives a direct estimate of the apparent recession velocity as caused by the universal expansion. Since the expansion rate increases with the distance, the velocity is itself a

  19. Elastic constants of calcite

    USGS Publications Warehouse

    Peselnick, L.; Robie, R.A.

    1962-01-01

    The recent measurements of the elastic constants of calcite by Reddy and Subrahmanyam (1960) disagree with the values obtained independently by Voigt (1910) and Bhimasenachar (1945). The present authors, using an ultrasonic pulse technique at 3 Mc and 25??C, determined the elastic constants of calcite using the exact equations governing the wave velocities in the single crystal. The results are C11=13.7, C33=8.11, C44=3.50, C12=4.82, C13=5.68, and C14=-2.00, in units of 1011 dyncm2. Independent checks of several of the elastic constants were made employing other directions and polarizations of the wave velocities. With the exception of C13, these values substantially agree with the data of Voigt and Bhimasenachar. ?? 1962 The American Institute of Physics.

  20. The Hubble constant

    NASA Technical Reports Server (NTRS)

    Huchra, John P.

    1992-01-01

    The Hubble constant is the constant of proportionality between recession velocity and distance in the expanding universe. It is a fundamental property of cosmology that sets both the scale and the expansion age of the universe. It is determined by measurement of galaxy radial velocities and distances. Although there has been considerable progress in the development of new techniques for the measurements of galaxy distances, both calibration uncertainties and debates over systematic errors remain. Current determinations still range over nearly a factor of 2; the higher values favored by most local measurements are not consistent with many theories of the origin of large-scale structure and stellar evolution.

  1. Compassion is a constant.

    PubMed

    Scott, Tricia

    2015-11-01

    Compassion is a powerful word that describes an intense feeling of commiseration and a desire to help those struck by misfortune. Most people know intuitively how and when to offer compassion to relieve another person's suffering. In health care, compassion is a constant; it cannot be rationed because emergency nurses have limited time or resources to manage increasing demands.

  2. XrayOpticsConstants

    2005-06-20

    This application (XrayOpticsConstants) is a tool for displaying X-ray and Optical properties for a given material, x-ray photon energy, and in the case of a gas, pressure. The display includes fields such as the photo-electric absorption attenuation length, density, material composition, index of refraction, and emission properties (for scintillator materials).

  3. Compassion is a constant.

    PubMed

    Scott, Tricia

    2015-11-01

    Compassion is a powerful word that describes an intense feeling of commiseration and a desire to help those struck by misfortune. Most people know intuitively how and when to offer compassion to relieve another person's suffering. In health care, compassion is a constant; it cannot be rationed because emergency nurses have limited time or resources to manage increasing demands. PMID:26542898

  4. Fluorine detected 2D NMR experiments for the practical determination of size and sign of homonuclear F-F and heteronuclear C-F multiple bond J-coupling constants in multiple fluorinated compounds

    NASA Astrophysics Data System (ADS)

    Aspers, Ruud L. E. G.; Ampt, Kirsten A. M.; Dvortsak, Peter; Jaeger, Martin; Wijmenga, Sybren S.

    2013-06-01

    The use of fluorine in molecules obtained from chemical synthesis has become increasingly important within the pharmaceutical and agricultural industry. NMR characterization of these compounds is of great value with respect to their structure elucidation, their screening in metabolomics investigations and binding studies. The favorable NMR properties of the fluorine nucleus make NMR with fluorine detection of great value in this respect. A suite of NMR 2D F-F- and F-C-correlation experiments with fluorine detection was applied to the assignment of resonances, nJCF- and nJFF-couplings as well as the determination of their size and sign. The utilization of this experiment suite was exemplarily demonstrated for a highly fluorinated vinyl alkyl ether. Especially F-C HSQC and J-scaled F-C HMBC experiments allowed determining the size of the J-couplings of this compound. The relative sign of its homo- and heteronuclear couplings was achieved by different combinations of 2D NMR experiments, including non-selective and F2-selective F-C XLOC, F2-selective F-C HMQC, and F-F COSY. The F2-one/two-site selective F-C XLOC versions were found highly useful, as they led to simplifications of the common E.COSY patterns and resulted in a higher confidence level of the assignment by using selective excitation. The combination of F2-one/two-site selective F-C XLOC experiments with a F2-one-site selective F-C HMQC experiment provided the signs of all nJCF- and nJFF-couplings in the vinyl moiety of the test compound. Other combinations of experiments were found useful as well for special purposes when focusing for example on homonuclear couplings a combination of F-F COSY-10 with a F2-one-site selective F-C HMQC could be used. The E.COSY patterns in the spectra demonstrated were analyzed by use of the spin-selective displacement vectors, and in case of the XLOC also by use of the DQ- and ZQ-displacement vectors. The variety of experiments presented shall contribute to facilitate the

  5. Structures, energies, and spin-spin coupling constants of methyl-substituted 1,3-diborata-2,4-diphosphoniocyclobutanes: four-member B-P-B-P rings B2P2(CH3)(n)H(8-n), with n = 0, 1, 2, 4.

    PubMed

    Del Bene, Janet E; Alkorta, Ibon; Elguero, José

    2011-09-29

    An ab initio study has been carried out to determine the structures, relative stabilities, and spin-spin coupling constants of a set of 17 methyl-substituted 1,3-diborata-2,4-diphosphoniocyclobutanes B(2)P(2)(CH(3))(n)H(8-n), for n = 0, 1, 2, 4, with four-member B-P-B-P rings. The B-P-B-P rings are puckered in a butterfly conformation, in agreement with experimental data for related molecules. Isomers with the CH(3) group bonded to P are more stable than those with CH(3) bonded to B. If there is only one methyl group or if two methyl groups are bonded to two different P or B atoms, isomers with equatorial bonds are more stable than those with axial bonds. However, when two methyl groups are present, the gem isomers are the most stable for molecules B(2)P(2)(CH(3))(2)H(6) with P-C and B-C bonds, respectively. Transition structures present barriers to the interconversion of two equilibrium structures or to the interchange of axial and equatorial positions in the same isomer. These barriers are very low for the isomer with two methyl groups bonded to B in axial positions for the isomer with four axial bonds and for the isomer with geminal B-C bonds at both B atoms. Coupling constants (1)J(B-P), (1)J(P-C), (1)J(B-C), (2)J(P-P), and (3)J(P-C) are capable of providing structural information. They are sensitive to the number of methyl groups present and can discriminate between axial, equatorial, and geminal bonds, although not all do this to the same extent. The one-bond coupling constants (1)J(B-P), (1)J(P-C), and (1)J(B-C) are similar in equilibrium and transition structures, but (3)J(P-C) and (2)J(P-P) are not. These coupling constants and those of the corresponding fluoro-derivatives of the 1,3-diborata-2,4-diphosphoniocyclobutanes demonstrate the great sensitivity of phosphorus coupling to structural and electronic effects. PMID:21895014

  6. 79Br-Nuclear quadrupole coupling in the rotational spectrum of HC15N···D79Br: determination of the H(D)Br oscillation amplitudes and force constant

    NASA Astrophysics Data System (ADS)

    Legon, A. C.

    1987-10-01

    The ground-state rotational spectrum of the linear, hydrogen-bonded isotopomer HC 15N⋯D 79Br has been investigated by pulsednozzle Fourier-transform microwave spectroscopy to give the spectroscopic constants Bo = 1374.4429(3) MHz, dj = 1.790(9) kHz, χ( 79Br) = 438.645(9) MHz and M( 79Br) = 2.4(3) kHz. The HBr subunit oscillation amplitudes /gb avH = 15.069(8)° and β AVD = 12.726 (7)°, determined by combined use of X( 79Br) for HC 15N⋯H 79Br and HC 15N⋯D 79Br, lead to the HBr oscillation force constant kββ=6.93(2) × 10 -20J rad -2. The variation of kββ with kββ is considered for the series B⋯HX, where B = CO, PH 3, HCN and X = Cl or Br.

  7. New improved massive gravity and three-dimensional spacetimes of constant curvature and constant torsion

    NASA Astrophysics Data System (ADS)

    Dereli, Tekin; Yetişmişoǧlu, Cem

    2016-09-01

    We derive the field equations for topologically massive gravity coupled with the most general quadratic curvature terms using the language of exterior differential forms and a first order constrained variational principle. We find variational field equations both in the presence and absence of torsion. We then show that spaces of constant negative curvature (i.e. the anti-de Sitter space AdS3) and constant torsion provide exact solutions.

  8. SpinCouple: Development of a Web Tool for Analyzing Metabolite Mixtures via Two-Dimensional J-Resolved NMR Database.

    PubMed

    Kikuchi, Jun; Tsuboi, Yuuri; Komatsu, Keiko; Gomi, Masahiro; Chikayama, Eisuke; Date, Yasuhiro

    2016-01-01

    A new Web-based tool, SpinCouple, which is based on the accumulation of a two-dimensional (2D) (1)H-(1)H J-resolved NMR database from 598 metabolite standards, has been developed. The spectra include both J-coupling and (1)H chemical shift information; those are applicable to a wide array of spectral annotation, especially for metabolic mixture samples that are difficult to label through the attachment of (13)C isotopes. In addition, the user-friendly application includes an absolute-quantitative analysis tool. Good agreement was obtained between known concentrations of 20-metabolite mixtures versus the calibration curve-based quantification results obtained from 2D-Jres spectra. We have examined the web tool availability using nine series of biological extracts, obtained from animal gut and waste treatment microbiota, fish, and plant tissues. This web-based tool is publicly available via http://emar.riken.jp/spincpl.

  9. SpinCouple: Development of a Web Tool for Analyzing Metabolite Mixtures via Two-Dimensional J-Resolved NMR Database.

    PubMed

    Kikuchi, Jun; Tsuboi, Yuuri; Komatsu, Keiko; Gomi, Masahiro; Chikayama, Eisuke; Date, Yasuhiro

    2016-01-01

    A new Web-based tool, SpinCouple, which is based on the accumulation of a two-dimensional (2D) (1)H-(1)H J-resolved NMR database from 598 metabolite standards, has been developed. The spectra include both J-coupling and (1)H chemical shift information; those are applicable to a wide array of spectral annotation, especially for metabolic mixture samples that are difficult to label through the attachment of (13)C isotopes. In addition, the user-friendly application includes an absolute-quantitative analysis tool. Good agreement was obtained between known concentrations of 20-metabolite mixtures versus the calibration curve-based quantification results obtained from 2D-Jres spectra. We have examined the web tool availability using nine series of biological extracts, obtained from animal gut and waste treatment microbiota, fish, and plant tissues. This web-based tool is publicly available via http://emar.riken.jp/spincpl. PMID:26624790

  10. Varying constants quantum cosmology

    SciTech Connect

    Leszczyńska, Katarzyna; Balcerzak, Adam; Dabrowski, Mariusz P. E-mail: abalcerz@wmf.univ.szczecin.pl

    2015-02-01

    We discuss minisuperspace models within the framework of varying physical constants theories including Λ-term. In particular, we consider the varying speed of light (VSL) theory and varying gravitational constant theory (VG) using the specific ansätze for the variability of constants: c(a) = c{sub 0} a{sup n} and G(a)=G{sub 0} a{sup q}. We find that most of the varying c and G minisuperspace potentials are of the tunneling type which allows to use WKB approximation of quantum mechanics. Using this method we show that the probability of tunneling of the universe ''from nothing'' (a=0) to a Friedmann geometry with the scale factor a{sub t} is large for growing c models and is strongly suppressed for diminishing c models. As for G varying, the probability of tunneling is large for G diminishing, while it is small for G increasing. In general, both varying c and G change the probability of tunneling in comparison to the standard matter content (cosmological term, dust, radiation) universe models.

  11. Change is a Constant.

    PubMed

    Lubowitz, James H; Provencher, Matthew T; Brand, Jefferson C; Rossi, Michael J; Poehling, Gary G

    2015-06-01

    In 2015, Henry P. Hackett, Managing Editor, Arthroscopy, retires, and Edward A. Goss, Executive Director, Arthroscopy Association of North America (AANA), retires. Association is a positive constant, in a time of change. With change comes a need for continuing education, research, and sharing of ideas. While the quality of education at AANA and ISAKOS is superior and most relevant, the unique reason to travel and meet is the opportunity to interact with innovative colleagues. Personal interaction best stimulates new ideas to improve patient care, research, and teaching. Through our network, we best create innovation.

  12. Cosmology with varying constants.

    PubMed

    Martins, Carlos J A P

    2002-12-15

    The idea of possible time or space variations of the 'fundamental' constants of nature, although not new, is only now beginning to be actively considered by large numbers of researchers in the particle physics, cosmology and astrophysics communities. This revival is mostly due to the claims of possible detection of such variations, in various different contexts and by several groups. I present the current theoretical motivations and expectations for such variations, review the current observational status and discuss the impact of a possible confirmation of these results in our views of cosmology and physics as a whole.

  13. About variable constants

    NASA Astrophysics Data System (ADS)

    Blichert-Toft, J.; Albarede, F.

    2011-12-01

    When only modern isotope compositions are concerned, the choice of normalization values is inconsequential provided that their values are universally accepted. No harm is done as long as large amounts of standard reference material with known isotopic differences with respect to the reference value ('anchor point') can be maintained under controlled conditions. For over five decades, the scientific community has been referring to an essentially unavailable SMOW for stable O and H isotopes and to a long-gone belemnite sample for carbon. For radiogenic isotopes, the isotope composition of the daughter element, the parent-daughter ratio, and a particular value of the decay constant are all part of the reference. For the Lu-Hf system, for which the physical measurements of the decay constant have been particularly defective, the reference includes the isotope composition of Hf and the Lu/Hf ratio of an unfortunately heterogeneous chondrite mix that has been successively refined by Patchett and Tatsumoto (1981), Blichert-Toft and Albarede (1997, BTA), and Bouvier et al. (2008, BVP). The \\varepsilonHf(T) difference created by using BTA and BVP is nearly within error (+0.45 epsilon units today and -0.36 at 3 Ga) and therefore of little or no consequence. A more serious issue arises when the chondritic reference is taken to represent the Hf isotope evolution of the Bulk Silicate Earth (BSE): the initial isotope composition of the Solar System, as determined by the indistinguishable intercepts of the external eucrite isochron (Blichert-Toft et al., 2002) and the internal angrite SAH99555 isochron (Thrane et al., 2010), differs from the chondrite value of BTA and BVP extrapolated to 4.56 Ga by ~5 epsilon units. This difference and the overestimated value of the 176Lu decay constant derived from the slopes of these isochrons, have been interpreted as reflecting irradiation of the solar nebula by either gamma (Albarede et al., 2006) or cosmic rays (Thrane et al., 2010) during

  14. Measurement of the solar constant

    NASA Technical Reports Server (NTRS)

    Crommelynck, D.

    1981-01-01

    The absolute value of the solar constant and the long term variations that exist in the absolute value of the solar constant were measured. The solar constant is the total irradiance of the Sun at a distance of one astronomical unit. An absolute radiometer removed from the effects of the atmosphere with its calibration tested in situ was used to measure the solar constant. The importance of an accurate knowledge of the solar constant is emphasized.

  15. The Hubble constant.

    PubMed

    Tully, R B

    1993-06-01

    Five methods of estimating distances have demonstrated internal reproducibility at the level of 5-20% rms accuracy. The best of these are the cepheid (and RR Lyrae), planetary nebulae, and surface-brightness fluctuation techniques. Luminosity-line width and Dn-sigma methods are less accurate for an individual case but can be applied to large numbers of galaxies. The agreement is excellent between these five procedures. It is determined that Hubble constant H0 = 90 +/- 10 km.s-1.Mpc-1 [1 parsec (pc) = 3.09 x 10(16) m]. It is difficult to reconcile this value with the preferred world model even in the low-density case. The standard model with Omega = 1 may be excluded unless there is something totally misunderstood about the foundation of the distance scale or the ages of stars. PMID:11607391

  16. When constants are important

    SciTech Connect

    Beiu, V.

    1997-04-01

    In this paper the authors discuss several complexity aspects pertaining to neural networks, commonly known as the curse of dimensionality. The focus will be on: (1) size complexity and depth-size tradeoffs; (2) complexity of learning; and (3) precision and limited interconnectivity. Results have been obtained for each of these problems when dealt with separately, but few things are known as to the links among them. They start by presenting known results and try to establish connections between them. These show that they are facing very difficult problems--exponential growth in either space (i.e. precision and size) and/or time (i.e., learning and depth)--when resorting to neural networks for solving general problems. The paper will present a solution for lowering some constants, by playing on the depth-size tradeoff.

  17. The Hubble constant.

    PubMed Central

    Tully, R B

    1993-01-01

    Five methods of estimating distances have demonstrated internal reproducibility at the level of 5-20% rms accuracy. The best of these are the cepheid (and RR Lyrae), planetary nebulae, and surface-brightness fluctuation techniques. Luminosity-line width and Dn-sigma methods are less accurate for an individual case but can be applied to large numbers of galaxies. The agreement is excellent between these five procedures. It is determined that Hubble constant H0 = 90 +/- 10 km.s-1.Mpc-1 [1 parsec (pc) = 3.09 x 10(16) m]. It is difficult to reconcile this value with the preferred world model even in the low-density case. The standard model with Omega = 1 may be excluded unless there is something totally misunderstood about the foundation of the distance scale or the ages of stars. PMID:11607391

  18. Constant attitude orbit transfer

    NASA Astrophysics Data System (ADS)

    Cress, Peter; Evans, Michael

    A two-impulse orbital transfer technique is described in which the spacecraft attitude remains constant for both burns, eliminating the need for attitude maneuvers between the burns. This can lead to significant savings in vehicle weight, cost and complexity. Analysis is provided for a restricted class of applications of this transfer between circular orbits. For those transfers with a plane change less than 30 deg, the total velocity cost of the maneuver is less than twelve percent greater than that of an optimum plane split Hohmann transfer. While this maneuver does not minimize velocity requirement, it does provide a means of achieving necessary transfer while substantially reducing the cost and complexity of the spacecraft.

  19. A Constant Pressure Bomb

    NASA Technical Reports Server (NTRS)

    Stevens, F W

    1924-01-01

    This report describes a new optical method of unusual simplicity and of good accuracy suitable to study the kinetics of gaseous reactions. The device is the complement of the spherical bomb of constant volume, and extends the applicability of the relationship, pv=rt for gaseous equilibrium conditions, to the use of both factors p and v. The method substitutes for the mechanical complications of a manometer placed at some distance from the seat of reaction the possibility of allowing the radiant effects of reaction to record themselves directly upon a sensitive film. It is possible the device may be of use in the study of the photoelectric effects of radiation. The method makes possible a greater precision in the measurement of normal flame velocities than was previously possible. An approximate analysis shows that the increase of pressure and density ahead of the flame is negligible until the velocity of the flame approaches that of sound.

  20. Time constants of flat superconducting cables

    SciTech Connect

    Takacs, S.; Yamamoto, J.

    1997-06-01

    The frequency dependence of coupling losses is calculated for flat superconducting cables, including the electromagnetic coupling between different current loops on the cable. It is shown that there are two characteristic time constants for both parallel and transverse coupling losses. The values of these time constants {tau}{sub 0} and {tau}{sub 1} are calculated by introducing effective inductances for the current loops. In both cases, {tau}{sub 1} is considerably smaller than {tau}{sub 0}. As the most important methods of determining {tau}{sub 0} from AC losses - namely, the limiting slope of loss/cycle at zero frequency and the position of the maximum loss/cycle vs. frequency - estimate {tau}{sub 0} and {tau}{sub 1}, respectively, the results are important for practical measurements and evaluation of time constants from AC losses. At larger frequencies, the losses are more likely to those in normal conductors (skin effect). The calculation schemes can be applied to cables with closely wound strands (like the cable-in-conduit conductors), too. However, several other effects should be considered being different and/or more important with respect to other cable types (demagnetization factor of strands and cables, larger regions near the cable edges, smaller number of strands and subcables, etc.).

  1. Constant-time 2D and 3D through-bond correlation NMR spectroscopy of solids under 60 kHz MAS

    NASA Astrophysics Data System (ADS)

    Zhang, Rongchun; Ramamoorthy, Ayyalusamy

    2016-01-01

    Establishing connectivity and proximity of nuclei is an important step in elucidating the structure and dynamics of molecules in solids using magic angle spinning (MAS) NMR spectroscopy. Although recent studies have successfully demonstrated the feasibility of proton-detected multidimensional solid-state NMR experiments under ultrafast-MAS frequencies and obtaining high-resolution spectral lines of protons, assignment of proton resonances is a major challenge. In this study, we first re-visit and demonstrate the feasibility of 2D constant-time uniform-sign cross-peak correlation (CTUC-COSY) NMR experiment on rigid solids under ultrafast-MAS conditions, where the sensitivity of the experiment is enhanced by the reduced spin-spin relaxation rate and the use of low radio-frequency power for heteronuclear decoupling during the evolution intervals of the pulse sequence. In addition, we experimentally demonstrate the performance of a proton-detected pulse sequence to obtain a 3D 1H/13C/1H chemical shift correlation spectrum by incorporating an additional cross-polarization period in the CTUC-COSY pulse sequence to enable proton chemical shift evolution and proton detection in the incrementable t1 and t3 periods, respectively. In addition to through-space and through-bond 13C/1H and 13C/13C chemical shift correlations, the 3D 1H/13C/1H experiment also provides a COSY-type 1H/1H chemical shift correlation spectrum, where only the chemical shifts of those protons, which are bonded to two neighboring carbons, are correlated. By extracting 2D F1/F3 slices (1H/1H chemical shift correlation spectrum) at different 13C chemical shift frequencies from the 3D 1H/13C/1H spectrum, resonances of proton atoms located close to a specific carbon atom can be identified. Overall, the through-bond and through-space homonuclear/heteronuclear proximities determined from the 3D 1H/13C/1H experiment would be useful to study the structure and dynamics of a variety of chemical and biological

  2. Constant-time 2D and 3D through-bond correlation NMR spectroscopy of solids under 60 kHz MAS.

    PubMed

    Zhang, Rongchun; Ramamoorthy, Ayyalusamy

    2016-01-21

    Establishing connectivity and proximity of nuclei is an important step in elucidating the structure and dynamics of molecules in solids using magic angle spinning (MAS) NMR spectroscopy. Although recent studies have successfully demonstrated the feasibility of proton-detected multidimensional solid-state NMR experiments under ultrafast-MAS frequencies and obtaining high-resolution spectral lines of protons, assignment of proton resonances is a major challenge. In this study, we first re-visit and demonstrate the feasibility of 2D constant-time uniform-sign cross-peak correlation (CTUC-COSY) NMR experiment on rigid solids under ultrafast-MAS conditions, where the sensitivity of the experiment is enhanced by the reduced spin-spin relaxation rate and the use of low radio-frequency power for heteronuclear decoupling during the evolution intervals of the pulse sequence. In addition, we experimentally demonstrate the performance of a proton-detected pulse sequence to obtain a 3D (1)H/(13)C/(1)H chemical shift correlation spectrum by incorporating an additional cross-polarization period in the CTUC-COSY pulse sequence to enable proton chemical shift evolution and proton detection in the incrementable t1 and t3 periods, respectively. In addition to through-space and through-bond (13)C/(1)H and (13)C/(13)C chemical shift correlations, the 3D (1)H/(13)C/(1)H experiment also provides a COSY-type (1)H/(1)H chemical shift correlation spectrum, where only the chemical shifts of those protons, which are bonded to two neighboring carbons, are correlated. By extracting 2D F1/F3 slices ((1)H/(1)H chemical shift correlation spectrum) at different (13)C chemical shift frequencies from the 3D (1)H/(13)C/(1)H spectrum, resonances of proton atoms located close to a specific carbon atom can be identified. Overall, the through-bond and through-space homonuclear/heteronuclear proximities determined from the 3D (1)H/(13)C/(1)H experiment would be useful to study the structure and dynamics of

  3. Boson mapping techniques applied to constant gauge fields in QCD

    NASA Technical Reports Server (NTRS)

    Hess, Peter Otto; Lopez, J. C.

    1995-01-01

    Pairs of coordinates and derivatives of the constant gluon modes are mapped to new gluon-pair fields and their derivatives. Applying this mapping to the Hamiltonian of constant gluon fields results for large coupling constants into an effective Hamiltonian which separates into one describing a scalar field and another one for a field with spin two. The ground state is dominated by pairs of gluons coupled to color and spin zero with slight admixtures of color zero and spin two pairs. As color group we used SU(2).

  4. New Quasar Studies Keep Fundamental Physical Constant Constant

    NASA Astrophysics Data System (ADS)

    2004-03-01

    Very Large Telescope sets stringent limit on possible variation of the fine-structure constant over cosmological time Summary Detecting or constraining the possible time variations of fundamental physical constants is an important step toward a complete understanding of basic physics and hence the world in which we live. A step in which astrophysics proves most useful. Previous astronomical measurements of the fine structure constant - the dimensionless number that determines the strength of interactions between charged particles and electromagnetic fields - suggested that this particular constant is increasing very slightly with time. If confirmed, this would have very profound implications for our understanding of fundamental physics. New studies, conducted using the UVES spectrograph on Kueyen, one of the 8.2-m telescopes of ESO's Very Large Telescope array at Paranal (Chile), secured new data with unprecedented quality. These data, combined with a very careful analysis, have provided the strongest astronomical constraints to date on the possible variation of the fine structure constant. They show that, contrary to previous claims, no evidence exist for assuming a time variation of this fundamental constant. PR Photo 07/04: Relative Changes with Redshift of the Fine Structure Constant (VLT/UVES) A fine constant To explain the Universe and to represent it mathematically, scientists rely on so-called fundamental constants or fixed numbers. The fundamental laws of physics, as we presently understand them, depend on about 25 such constants. Well-known examples are the gravitational constant, which defines the strength of the force acting between two bodies, such as the Earth and the Moon, and the speed of light. One of these constants is the so-called "fine structure constant", alpha = 1/137.03599958, a combination of electrical charge of the electron, the Planck constant and the speed of light. The fine structure constant describes how electromagnetic forces hold

  5. Molecular dynamics and information on possible sites of interaction of intramyocellular metabolites in vivo from resolved dipolar couplings in localized 1H NMR spectra

    NASA Astrophysics Data System (ADS)

    Schröder, Leif; Schmitz, Christian; Bachert, Peter

    2004-12-01

    Proton NMR resonances of the endogenous metabolites creatine and phosphocreatine ((P)Cr), taurine (Tau), and carnosine (Cs, β-alanyl- L-histidine) were studied with regard to residual dipolar couplings and molecular mobility. We present an analysis of the direct 1H- 1H interaction that provides information on motional reorientation of subgroups in these molecules in vivo. For this purpose, localized 1H NMR experiments were performed on m. gastrocnemius of healthy volunteers using a 1.5-T clinical whole-body MR scanner. We evaluated the observable dipolar coupling strength SD0 ( S = order parameter) of the (P)Cr-methyl triplet and the Tau-methylene doublet by means of the apparent line splitting. These were compared to the dipolar coupling strength of the (P)Cr-methylene doublet. In contrast to the aliphatic protons of (P)Cr and Tau, the aromatic H2 ( δ = 8 ppm) and H4 ( δ = 7 ppm) protons of the imidazole ring of Cs exhibit second-order spectra at 1.5 T. This effect is the consequence of incomplete transition from Zeeman to Paschen-Back regime and allows a determination of SD0 from H2 and H4 of Cs as an alternative to evaluating the multiplet splitting which can be measured directly in high-resolution 1H NMR spectra. Experimental data showed striking differences in the mobility of the metabolites when the dipolar coupling constant D0 (calculated with the internuclear distance known from molecular geometry in the case of complete absence of molecular dynamics and motion) is used for comparison. The aliphatic signals involve very small order parameters S ≈ (1.4 - 3) × 10 -4 indicating rapid reorientation of the corresponding subgroups in these metabolites. In contrast, analysis of the Cs resonances yielded S ≈ (113 - 137) × 10 -4. Thus, the immobilization of the Cs imidazole ring owing to an anisotropic cellular substructure in human m. gastrocnemius is much more effective than for (P)Cr and Tau subgroups. Furthermore, 1H NMR experiments on aqueous model

  6. Axion decay constants away from the lamppost

    NASA Astrophysics Data System (ADS)

    Conlon, Joseph P.; Krippendorf, Sven

    2016-04-01

    It is unknown whether a bound on axion field ranges exists within quantum gravity. We study axion field ranges using extended supersymmetry, in particular allowing an analysis within strongly coupled regions of moduli space. We apply this strategy to Calabi-Yau compactifications with one and two Kähler moduli. We relate the maximally allowable decay constant to geometric properties of the underlying Calabi-Yau geometry. In all examples we find a maximal field range close to the reduced Planck mass (with the largest field range being 3.25 M P ). On this perspective, field ranges relate to the intersection and instanton numbers of the underlying Calabi-Yau geometry.

  7. Quantum coherence, wormholes, and the cosmological constant

    SciTech Connect

    Unruh, W.G. )

    1989-08-15

    Coleman has argued that if wormhole solutions to the Euclidean action coupled to matter dominate the Euclidean path integral for quantum gravity, they do not lead to a loss of quantum coherence for wave functions in our Universe. Furthermore, they also lead to the prediction that the ultimate'' cosmological constant is zero. I analyze the assumptions that go into this result and argue that the presence of wormhole solutions does lead to a loss of quantum coherence and, furthermore, completely destroys the Euclidean quantum theory by producing a highly nonlocal effective Euclidean action which is violently unbounded from below.

  8. Constant-Pressure Hydraulic Pump

    NASA Technical Reports Server (NTRS)

    Galloway, C. W.

    1982-01-01

    Constant output pressure in gas-driven hydraulic pump would be assured in new design for gas-to-hydraulic power converter. With a force-multiplying ring attached to gas piston, expanding gas would apply constant force on hydraulic piston even though gas pressure drops. As a result, pressure of hydraulic fluid remains steady, and power output of the pump does not vary.

  9. Constants and Variables of Nature

    SciTech Connect

    Sean Carroll

    2009-04-03

    It is conventional to imagine that the various parameters which characterize our physical theories, such as the fine structure constant or Newton’s gravitational constant, are truly “constant”, in the sense that they do not change from place to place or time to time. Recent developments in both theory and observation have led us to re-examine this assumption, and to take seriously the possibility that our supposed constants are actually gradually changing. I will discuss why we might expect these parameters to vary, and what observation and experiment have to say about the issue.

  10. Evaluation of atomic constants for optical radiation, volume 1

    NASA Technical Reports Server (NTRS)

    Kylstra, C. D.; Schneider, R. J.

    1974-01-01

    Atomic constants for optical radiation are discussed which include transition probabilities, line strengths, and oscillator strengths for both dipole and quadrupole transitions, as well as the associated matrix elements needed for line broadening calculations. Atomic constants were computed for a wide selection of elements and lines. An existing computer program was used, with modifications to include, in an approximate manner, the effect of equivalent electrons, and to enable reordering and restructuring of the output for publication. This program is suitable for fast, low cost computation of the optical constants, using the Coulomb approximation formalism for LS coupling.

  11. A fine tuning free resolution of the cosmological constant problem

    SciTech Connect

    Alexander, Stephon; Vaid, Deepak

    2009-07-06

    In a recent paper we discovered that a fermionic condensate is formed from gravitational interactions due to the covariant coupling of fermions in the presence of a torsion-fermion contact interaction.The condensate gap gives a negative contribution to the bare cosmological constant. In this letter, we show that the cosmological constant problem can be solved without fine tuning of the bare cosmological constant. We demonstrate how a universe with a large initial cosmological constant undergoes inflation, during which time the energy gap grows as the volume of the universe. Eventually the gap becomes large enough to cancel out the bare cosmological term, inflation ends and we end up in a universe with an almost vanishing cosmological term. We provide a detailed numerical analysis of the system of equations governing the self regulating relaxation of the cosmological constant.

  12. Distal and proximal ligand interactions in heme proteins: Correlations between C-O and Fe-C vibrational frequencies, oxygen-17 and carbon-13 nuclear magnetic resonance chemical shifts, and oxygen-17 nuclear quadrupole coupling constants in C sup 17 O- and sup 13 CO-labeled species

    SciTech Connect

    Ki Deok Park; Guo, K.; Adebodun, F.; Chiu, M.L.; Sligar, S.G.; Oldfield, E. )

    1991-03-05

    The authors have obtained the oxygen-17 nuclear magnetic resonance (NMR) spectra of a variety of C{sup 17}O-labeled heme proteins, including sperm whale (Physeter catodon) myoglobin, two synthetic sperm whale myoglobin mutants (His E7 {yields} Val E7; His E7 {yields} Phe E7), adult human hemoglobin, rabbit (Oryctolagus cuniculus) hemoglobin, horseradish (Cochlearia armoracia) peroxidase isoenzymes A and C, and Caldariomyces fumago chloroperoxidase, in some cases as a function of pH, and have determined their isotropic {sup 17}O NMR chemical shifts, {delta}{sub i}, and spin-lattice relaxation times, T{sub 1}. They have also obtained similar results on a picket fence prophyrin. The results show an excellent correlation between the infrared C-O vibrational frequencies, {nu}(C-O), and {delta}{sub i}, between {nu}(C-O) and the {sup 17}O nuclear quadrupole coupling constant, and as expected between e{sup 2}qQ/h and {delta}{sub i}. The results suggest the IR and NMR measurements reflect the same interaction, which is thought to be primarily the degree of {pi}-back-bonding from Fe d to CO {pi}* orbitals, as outlined previously.

  13. Methodology for extracting local constants from petroleum cracking flows

    DOEpatents

    Chang, Shen-Lin; Lottes, Steven A.; Zhou, Chenn Q.

    2000-01-01

    A methodology provides for the extraction of local chemical kinetic model constants for use in a reacting flow computational fluid dynamics (CFD) computer code with chemical kinetic computations to optimize the operating conditions or design of the system, including retrofit design improvements to existing systems. The coupled CFD and kinetic computer code are used in combination with data obtained from a matrix of experimental tests to extract the kinetic constants. Local fluid dynamic effects are implicitly included in the extracted local kinetic constants for each particular application system to which the methodology is applied. The extracted local kinetic model constants work well over a fairly broad range of operating conditions for specific and complex reaction sets in specific and complex reactor systems. While disclosed in terms of use in a Fluid Catalytic Cracking (FCC) riser, the inventive methodology has application in virtually any reaction set to extract constants for any particular application and reaction set formulation. The methodology includes the step of: (1) selecting the test data sets for various conditions; (2) establishing the general trend of the parametric effect on the measured product yields; (3) calculating product yields for the selected test conditions using coupled computational fluid dynamics and chemical kinetics; (4) adjusting the local kinetic constants to match calculated product yields with experimental data; and (5) validating the determined set of local kinetic constants by comparing the calculated results with experimental data from additional test runs at different operating conditions.

  14. Constant fields and constant gradients in open ionic channels.

    PubMed

    Chen, D P; Barcilon, V; Eisenberg, R S

    1992-05-01

    Ions enter cells through pores in proteins that are holes in dielectrics. The energy of interaction between ion and charge induced on the dielectric is many kT, and so the dielectric properties of channel and pore are important. We describe ionic movement by (three-dimensional) Nemst-Planck equations (including flux and net charge). Potential is described by Poisson's equation in the pore and Laplace's equation in the channel wall, allowing induced but not permanent charge. Asymptotic expansions are constructed exploiting the long narrow shape of the pore and the relatively high dielectric constant of the pore's contents. The resulting one-dimensional equations can be integrated numerically; they can be analyzed when channels are short or long (compared with the Debye length). Traditional constant field equations are derived if the induced charge is small, e.g., if the channel is short or if the total concentration gradient is zero. A constant gradient of concentration is derived if the channel is long. Plots directly comparable to experiments are given of current vs voltage, reversal potential vs. concentration, and slope conductance vs. concentration. This dielectric theory can easily be tested: its parameters can be determined by traditional constant field measurements. The dielectric theory then predicts current-voltage relations quite different from constant field, usually more linear, when gradients of total concentration are imposed. Numerical analysis shows that the interaction of ion and channel can be described by a mean potential if, but only if, the induced charge is negligible, that is to say, the electric field is spatially constant.

  15. Constant fields and constant gradients in open ionic channels.

    PubMed Central

    Chen, D P; Barcilon, V; Eisenberg, R S

    1992-01-01

    Ions enter cells through pores in proteins that are holes in dielectrics. The energy of interaction between ion and charge induced on the dielectric is many kT, and so the dielectric properties of channel and pore are important. We describe ionic movement by (three-dimensional) Nemst-Planck equations (including flux and net charge). Potential is described by Poisson's equation in the pore and Laplace's equation in the channel wall, allowing induced but not permanent charge. Asymptotic expansions are constructed exploiting the long narrow shape of the pore and the relatively high dielectric constant of the pore's contents. The resulting one-dimensional equations can be integrated numerically; they can be analyzed when channels are short or long (compared with the Debye length). Traditional constant field equations are derived if the induced charge is small, e.g., if the channel is short or if the total concentration gradient is zero. A constant gradient of concentration is derived if the channel is long. Plots directly comparable to experiments are given of current vs voltage, reversal potential vs. concentration, and slope conductance vs. concentration. This dielectric theory can easily be tested: its parameters can be determined by traditional constant field measurements. The dielectric theory then predicts current-voltage relations quite different from constant field, usually more linear, when gradients of total concentration are imposed. Numerical analysis shows that the interaction of ion and channel can be described by a mean potential if, but only if, the induced charge is negligible, that is to say, the electric field is spatially constant. Images FIGURE 1 PMID:1376159

  16. Effective cosmological constant induced by stochastic fluctuations of Newton's constant

    NASA Astrophysics Data System (ADS)

    de Cesare, Marco; Lizzi, Fedele; Sakellariadou, Mairi

    2016-09-01

    We consider implications of the microscopic dynamics of spacetime for the evolution of cosmological models. We argue that quantum geometry effects may lead to stochastic fluctuations of the gravitational constant, which is thus considered as a macroscopic effective dynamical quantity. Consistency with Riemannian geometry entails the presence of a time-dependent dark energy term in the modified field equations, which can be expressed in terms of the dynamical gravitational constant. We suggest that the late-time accelerated expansion of the Universe may be ascribed to quantum fluctuations in the geometry of spacetime rather than the vacuum energy from the matter sector.

  17. Optical constants of solid methane

    NASA Technical Reports Server (NTRS)

    Khare, Bishun N.; Thompson, W. R.; Sagan, C.; Arakawa, E. T.; Bruel, C.; Judish, J. P.; Khanna, R. K.; Pollack, J. B.

    1989-01-01

    Methane is the most abundant simple organic molecule in the outer solar system bodies. In addition to being a gaseous constituent of the atmospheres of the Jovian planets and Titan, it is present in the solid form as a constituent of icy surfaces such as those of Triton and Pluto, and as cloud condensate in the atmospheres of Titan, Uranus, and Neptune. It is expected in the liquid form as a constituent of the ocean of Titan. Cometary ices also contain solid methane. The optical constants for both solid and liquid phases of CH4 for a wide temperature range are needed for radiative transfer calculations, for studies of reflection from surfaces, and for modeling of emission in the far infrared and microwave regions. The astronomically important visual to near infrared measurements of solid methane optical constants are conspicuously absent from the literature. Preliminary results are presented of the optical constants of solid methane for the 0.4 to 2.6 micron region. K is reported for both the amorphous and the crystalline (annealed) states. Using the previously measured values of the real part of the refractive index, n, of liquid methane at 110 K n is computed for solid methane using the Lorentz-Lorentz relationship. Work is in progress to extend the measurements of optical constants n and k for liquid and solid to both shorter and longer wavelengths, eventually providing a complete optical constants database for condensed CH4.

  18. Optical constants of solid methane

    NASA Technical Reports Server (NTRS)

    Khare, Bishun N.; Thompson, W. R.; Sagan, C.; Arakawa, E. T.; Bruel, C.; Judish, J. P.; Khanna, R. K.; Pollack, J. B.

    1990-01-01

    Methane is the most abundant simple organic molecule in the outer solar system bodies. In addition to being a gaseous constituent of the atmospheres of the Jovian planets and Titan, it is present in the solid form as a constituent of icy surfaces such as those of Triton and Pluto, and as cloud condensate in the atmospheres of Titan, Uranus, and Neptune. It is expected in the liquid form as a constituent of the ocean of Titan. Cometary ices also contain solid methane. The optical constants for both solid and liquid phases of CH4 for a wide temperature range are needed for radiative transfer calculations, for studies of reflection from surfaces, and for modeling of emission in the far infrared and microwave regions. The astronomically important visual to near infrared measurements of solid methane optical constants are conspicuously absent from the literature. Preliminary results are presented on the optical constants of solid methane for the 0.4 to 2.6 micrometer region. Deposition onto a substrate at 10 K produces glassy (semi-amorphous) material. Annealing this material at approximately 33 K for approximately 1 hour results in a crystalline material as seen by sharper, more structured bands and negligible background extinction due to scattering. The constant k is reported for both the amorphous and the crystalline (annealed) states. Typical values (at absorption maxima) are in the .001 to .0001 range. Below lambda = 1.1 micrometers the bands are too weak to be detected by transmission through the films less than or equal to 215 micrometers in thickness, employed in the studies to date. Using previously measured values of the real part of the refractive index, n, of liquid methane at 110 K, n is computed for solid methane using the Lorentz-Lorenz relationship. Work is in progress to extend the measurements of optical constants n and k for liquid and solid to both shorter and longer wavelengths, eventually providing a complete optical constants database for

  19. Measurement of. cap alpha. /sub s/. [Strong fine structure constant

    SciTech Connect

    Clavelli, L.

    1983-01-01

    We point out that a number of QCD tests, relatively free of obvious nonperturbative corrections and other theoretical problems, are now available in e/sup +/e/sup -/ annihilation. By focusing on these tests, one can see the beginning of a confirmation of the running of the strong-coupling constant predicted by the renormalization group.

  20. Cosmologies with variable gravitational constant

    SciTech Connect

    Narkikar, J.V.

    1983-03-01

    In 1937 Dirac presented an argument, based on the socalled large dimensionless numbers, which led him to the conclusion that the Newtonian gravitational constant G changes with epoch. Towards the end of the last century Ernst Mach had given plausible arguments to link the property of inertia of matter to the large scale structure of the universe. Mach's principle also leads to cosmological models with a variable gravitational constant. Three cosmologies which predict a variable G are discussed in this paper both from theoretical and observational points of view.

  1. Elastic constants for 8-OCB

    NASA Astrophysics Data System (ADS)

    Czechowski, Grzegorz; Zywucki, B.; Jadzyn, Jan

    1993-10-01

    The Frederiks transitions for the n-octyloxycyanobiphenyl (8-OCB) placed in the external magnetic and electric field as a function of the temperature have been studied. On the basis of threshold values Bc and Uc, the elastic constants for splay, bend and twist modes are determined. The magnetic anisotropy of 8-OCB as a function of temperature has been determined. The K11 and K33 elastic constants show the pretransitional nematic- smectic A effect. The values of critical exponents obtained from the temperature dependence of K11 and K33 in the vicinity of N-SA phase transition are discussed.

  2. Boltzmann's constant: A laboratory experiment

    NASA Astrophysics Data System (ADS)

    Kruglak, Haym

    1989-03-01

    The mean-square displacement of a latex microsphere is determined from its projection on a TV monitor. The distribution of displacement is shown to be Gaussian. Boltzmann's constant, calculated from the pooled data of several observers, is in excellent agreement with the accepted value. The experiment is designed for one laboratory period in the advanced undergraduate laboratory.

  3. Ten Thousand Solar Constants Radiometer

    NASA Technical Reports Server (NTRS)

    Kendall, J. M., Sr.

    1985-01-01

    "Radiometer for Accurate (+ or - 1%) Measurement of Solar Irradiances Equal to 10,000 Solar Constants," gives additional information on radiometer described elsewhere. Self-calibrating, water-cooled, thermopile radiometer measures irradiance produced in solar image formed by parabolic reflector or by multiple-mirror solar installation.

  4. Running cosmological constant with observational tests

    NASA Astrophysics Data System (ADS)

    Geng, Chao-Qiang; Lee, Chung-Chi; Zhang, Kaituo

    2016-09-01

    We investigate the running cosmological constant model with dark energy linearly proportional to the Hubble parameter, Λ = σH +Λ0, in which the ΛCDM limit is recovered by taking σ = 0. We derive the linear perturbation equations of gravity under the Friedmann-Lemaïtre-Robertson-Walker cosmology, and show the power spectra of the CMB temperature and matter density distribution. By using the Markov chain Monte Carlo method, we fit the model to the current observational data and find that σH0 /Λ0 ≲ 2.63 ×10-2 and 6.74 ×10-2 for Λ (t) coupled to matter and radiation-matter, respectively, along with constraints on other cosmological parameters.

  5. The 1% concordance Hubble constant

    SciTech Connect

    Bennett, C. L.; Larson, D.; Weiland, J. L.; Hinshaw, G.

    2014-10-20

    The determination of the Hubble constant has been a central goal in observational astrophysics for nearly a hundred years. Extraordinary progress has occurred in recent years on two fronts: the cosmic distance ladder measurements at low redshift and cosmic microwave background (CMB) measurements at high redshift. The CMB is used to predict the current expansion rate through a best-fit cosmological model. Complementary progress has been made with baryon acoustic oscillation (BAO) measurements at relatively low redshifts. While BAO data do not independently determine a Hubble constant, they are important for constraints on possible solutions and checks on cosmic consistency. A precise determination of the Hubble constant is of great value, but it is more important to compare the high and low redshift measurements to test our cosmological model. Significant tension would suggest either uncertainties not accounted for in the experimental estimates or the discovery of new physics beyond the standard model of cosmology. In this paper we examine in detail the tension between the CMB, BAO, and cosmic distance ladder data sets. We find that these measurements are consistent within reasonable statistical expectations and we combine them to determine a best-fit Hubble constant of 69.6 ± 0.7 km s{sup –1} Mpc{sup –1}. This value is based upon WMAP9+SPT+ACT+6dFGS+BOSS/DR11+H {sub 0}/Riess; we explore alternate data combinations in the text. The combined data constrain the Hubble constant to 1%, with no compelling evidence for new physics.

  6. Variation of fundamental constants: theory

    NASA Astrophysics Data System (ADS)

    Flambaum, Victor

    2008-05-01

    Theories unifying gravity with other interactions suggest temporal and spatial variation of the fundamental ``constants'' in expanding Universe. There are some hints for the variation of different fundamental constants in quasar absorption spectra and Big Bang nucleosynthesis data. A large number of publications (including atomic clocks) report limits on the variations. We want to study the variation of the main dimensionless parameters of the Standard Model: 1. Fine structure constant alpha (combination of speed of light, electron charge and Plank constant). 2. Ratio of the strong interaction scale (LambdaQCD) to a fundamental mass like electron mass or quark mass which are proportional to Higgs vacuum expectation value. The proton mass is propotional to LambdaQCD, therefore, the proton-to-electron mass ratio comes into this second category. We performed necessary atomic, nuclear and QCD calculations needed to study variation of the fundamental constants using the Big Bang Nucleosynthsis, quasar spectra, Oklo natural nuclear reactor and atomic clock data. The relative effects of the variation may be enhanced in transitions between narrow close levels in atoms, molecules and nuclei. If one will study an enhanced effect, the relative value of systematic effects (which are not enhanced) may be much smaller. Note also that the absolute magnitude of the variation effects in nuclei (e.g. in very narrow 7 eV transition in 229Th) may be 5 orders of magnitude larger than in atoms. A different possibility of enhancement comes from the inversion transitions in molecules where splitting between the levels is due to the quantum tunneling amplitude which has strong, exponential dependence on the electron to proton mass ratio. Our study of NH3 quasar spectra has already given the best limit on the variation of electron to proton mass ratio.

  7. Varying Fine-Structure Constant and the Cosmological Constant Problem

    NASA Astrophysics Data System (ADS)

    Fujii, Yasunori

    We start with a brief account of the latest analysis of the Oklo phenomenon providing the still most stringent constraint on time variability of the fine-structure constant α. Comparing this with the recent result from the measurement of distant QSO's appears to indicate a non-uniform time-dependence, which we argue to be related to another recent finding of the accelerating universe. This view is implemented in terms of the scalar-tensor theory, applied specifically to the small but nonzero cosmological constant. Our detailed calculation shows that these two phenomena can be understood in terms of a common origin, a particular behavior of the scalar field, dilaton. We also sketch how this theoretical approach makes it appropriate to revisit non-Newtonian gravity featuring small violation of Weak Equivalence Principle at medium distances.

  8. New Quasar Studies Keep Fundamental Physical Constant Constant

    NASA Astrophysics Data System (ADS)

    2004-03-01

    Very Large Telescope sets stringent limit on possible variation of the fine-structure constant over cosmological time Summary Detecting or constraining the possible time variations of fundamental physical constants is an important step toward a complete understanding of basic physics and hence the world in which we live. A step in which astrophysics proves most useful. Previous astronomical measurements of the fine structure constant - the dimensionless number that determines the strength of interactions between charged particles and electromagnetic fields - suggested that this particular constant is increasing very slightly with time. If confirmed, this would have very profound implications for our understanding of fundamental physics. New studies, conducted using the UVES spectrograph on Kueyen, one of the 8.2-m telescopes of ESO's Very Large Telescope array at Paranal (Chile), secured new data with unprecedented quality. These data, combined with a very careful analysis, have provided the strongest astronomical constraints to date on the possible variation of the fine structure constant. They show that, contrary to previous claims, no evidence exist for assuming a time variation of this fundamental constant. PR Photo 07/04: Relative Changes with Redshift of the Fine Structure Constant (VLT/UVES) A fine constant To explain the Universe and to represent it mathematically, scientists rely on so-called fundamental constants or fixed numbers. The fundamental laws of physics, as we presently understand them, depend on about 25 such constants. Well-known examples are the gravitational constant, which defines the strength of the force acting between two bodies, such as the Earth and the Moon, and the speed of light. One of these constants is the so-called "fine structure constant", alpha = 1/137.03599958, a combination of electrical charge of the electron, the Planck constant and the speed of light. The fine structure constant describes how electromagnetic forces hold

  9. Localized (super)gravity and cosmological constant

    NASA Astrophysics Data System (ADS)

    Kakushadze, Zurab

    2000-11-01

    We consider localization of gravity in domain wall solutions of Einstein's gravity coupled to a scalar field with a generic potential. We discuss conditions on the scalar potential such that domain wall solutions are non-singular. Such solutions even exist for appropriate potentials which have no minima at all and are unbounded below. Domain walls of this type have infinite tension, while usual kink type of solutions interpolating between two AdS minima have finite tension. In the latter case the cosmological constant on the domain wall is necessarily vanishing, while in the former case it can be zero or negative. Positive cosmological constant is allowed for singular domain walls. We discuss non-trivial conditions for physically allowed singularities arising from the requirement that truncating the space at the singularities be consistent. Non-singular domain walls with infinite tension might a priori avoid recent "no-go" theorems indicating impossibility of supersymmetric embedding of kink type of domain walls in gauged supergravity. We argue that (non-singular) domain walls are stable even if they have infinite tension. This is essentially due to the fact that localization of gravity in smooth domain walls is a Higgs mechanism corresponding to a spontaneous breakdown of translational invariance. As to discontinuous domain walls arising in the presence of δ-function "brane" sources, they explicitly break translational invariance. Such solutions cannot therefore be thought of as limits of smooth domain walls. We point out that if the scalar potential has no minima and approaches finite negative values at infinity, then higher derivative terms are under control, and do not affect the cosmological constant which is vanishing for such backgrounds. Nonetheless, we also point out that higher curvature terms generically delocalize gravity, so that the desired lower-dimensional Newton's law is no longer reproduced.

  10. Quaternions as astrometric plate constants

    NASA Technical Reports Server (NTRS)

    Jefferys, William H.

    1987-01-01

    A new method for solving problems in relative astrometry is proposed. In it, the relationship between the measured quantities and the components of the position vector of a star is modeled using quaternions, in effect replacing the plate constants of a standard four-plate-constant solution with the four components of a quaternion. The method allows a direct solution for the position vectors of the stars, and hence for the equatorial coordinates. Distortions, magnitude, and color effects are readily incorporated into the formalism, and the method is directly applicable to overlapping-plate problems. The advantages of the method include the simplicity of the resulting equations, their freedom from singularities, and the fact that trigonometric functions and tangential point transformations are not needed to model the plate material. A global solution over the entire sky is possible.

  11. Royal Society, Discussion on the Constants of Physics, London, England, May 25, 26, 1983, Proceedings

    NASA Astrophysics Data System (ADS)

    1983-12-01

    Various topics dealing with the constants of physics are addressed. The subjects considered include: measurement of the fundamental constants; the search for proton decay; the constancy of G; limits on the variability of coupling constants from the Oklo natural reactor; implications of quasar spectroscopy for constancy of constants; theoretical prospects for understanding the values of fundamental constants; the strong, electromagnetic, and weak couplings; and field theories without fundamental gauge symmetries. Also discussed are: Einstein gravitation as a long-wavelength effective field theory; unification and supersymmetry; phase transitions in the early universe; the cosmological constant; large numbers and ratios in astrophysics and cosmology; dependence of macrophysical phenomena on the values of the fundamental constants; dimensionality; and the anthropic principle and its implications for biological evolution.

  12. Cosmological constant implementing Mach principle in general relativity

    NASA Astrophysics Data System (ADS)

    Namavarian, Nadereh; Farhoudi, Mehrdad

    2016-10-01

    We consider the fact that noticing on the operational meaning of the physical concepts played an impetus role in the appearance of general relativity (GR). Thus, we have paid more attention to the operational definition of the gravitational coupling constant in this theory as a dimensional constant which is gained through an experiment. However, as all available experiments just provide the value of this constant locally, this coupling constant can operationally be meaningful only in a local area. Regarding this point, to obtain an extension of GR for the large scale, we replace it by a conformal invariant model and then, reduce this model to a theory for the cosmological scale via breaking down the conformal symmetry through singling out a specific conformal frame which is characterized by the large scale characteristics of the universe. Finally, we come to the same field equations that historically were proposed by Einstein for the cosmological scale (GR plus the cosmological constant) as the result of his endeavor for making GR consistent with the Mach principle. However, we declare that the obtained field equations in this alternative approach do not carry the problem of the field equations proposed by Einstein for being consistent with Mach's principle (i.e., the existence of de Sitter solution), and can also be considered compatible with this principle in the Sciama view.

  13. Ab initio calculation of the NMR shielding constants for histamine

    NASA Astrophysics Data System (ADS)

    Mazurek, A. P.; Dobrowolski, J. Cz.; Sadlej, J.

    1997-12-01

    The gage-independent atomic orbital (GIAO) approach is used within the coupled Hartree-Fock approximation to compute the 1H, 13C and 15N NMR shielding constants in two tautomeric forms of both the histamine molecule and its protonated form. An analysis of the results shows that the protonation on the end of the chain changes its nitrogen shielding constants of the pyridine and pyrrole type. These changes are much higher for the N(3)-H than for the N(1)-H tautomer.

  14. Millikan's measurement of Planck's constant

    NASA Astrophysics Data System (ADS)

    Franklin, Allan

    2013-12-01

    Robert Millikan is famous for measuring the charge of the electron. His result was better than any previous measurement and his method established that there was a fundamental unit of charge, or charge quantization. He is less well-known for his measurement of Planck's constant, although, as discussed below, he is often mistakenly given credit for providing significant evidence in support of Einstein's photon theory of light.1 His Nobel Prize citation was "for his work on the elementary electric charge of electricity and the photoelectric effect," an indication of the significance of his work on the photoelectric effect.

  15. Chandra Independently Determines Hubble Constant

    NASA Astrophysics Data System (ADS)

    2006-08-01

    A critically important number that specifies the expansion rate of the Universe, the so-called Hubble constant, has been independently determined using NASA's Chandra X-ray Observatory. This new value matches recent measurements using other methods and extends their validity to greater distances, thus allowing astronomers to probe earlier epochs in the evolution of the Universe. "The reason this result is so significant is that we need the Hubble constant to tell us the size of the Universe, its age, and how much matter it contains," said Max Bonamente from the University of Alabama in Huntsville and NASA's Marshall Space Flight Center (MSFC) in Huntsville, Ala., lead author on the paper describing the results. "Astronomers absolutely need to trust this number because we use it for countless calculations." Illustration of Sunyaev-Zeldovich Effect Illustration of Sunyaev-Zeldovich Effect The Hubble constant is calculated by measuring the speed at which objects are moving away from us and dividing by their distance. Most of the previous attempts to determine the Hubble constant have involved using a multi-step, or distance ladder, approach in which the distance to nearby galaxies is used as the basis for determining greater distances. The most common approach has been to use a well-studied type of pulsating star known as a Cepheid variable, in conjunction with more distant supernovae to trace distances across the Universe. Scientists using this method and observations from the Hubble Space Telescope were able to measure the Hubble constant to within 10%. However, only independent checks would give them the confidence they desired, considering that much of our understanding of the Universe hangs in the balance. Chandra X-ray Image of MACS J1149.5+223 Chandra X-ray Image of MACS J1149.5+223 By combining X-ray data from Chandra with radio observations of galaxy clusters, the team determined the distances to 38 galaxy clusters ranging from 1.4 billion to 9.3 billion

  16. Henry's law constants of polyols

    NASA Astrophysics Data System (ADS)

    Compernolle, S.; Müller, J.-F.

    2014-05-01

    Henry's law constants (HLC) are derived for several polyols bearing between 2 and 6 hydroxyl groups, based on literature data for water activity, vapour pressure and/or solubility. Depending on the case, infinite dilution activity coefficients (IDACs), solid state pressures or activity coefficient ratios are obtained as intermediary results. For most compounds, these are the first values reported, while others compare favourably with literature data in most cases. Using these values and those from a previous work (Compernolle and Müller, 2014), an assessment is made on the partitioning of polyols, diacids and hydroxy acids to droplet and aqueous aerosol.

  17. Stability constant estimator user`s guide

    SciTech Connect

    Hay, B.P.; Castleton, K.J.; Rustad, J.R.

    1996-12-01

    The purpose of the Stability Constant Estimator (SCE) program is to estimate aqueous stability constants for 1:1 complexes of metal ions with ligands by using trends in existing stability constant data. Such estimates are useful to fill gaps in existing thermodynamic databases and to corroborate the accuracy of reported stability constant values.

  18. ARTSY-J: Convenient and precise measurement of 3JHNHα couplings in medium-size proteins from TROSY-HSQC spectra

    NASA Astrophysics Data System (ADS)

    Roche, Julien; Ying, Jinfa; Shen, Yang; Torchia, Dennis A.; Bax, Ad

    2016-07-01

    A new and convenient method, named ARTSY-J, is introduced that permits extraction of the 3JHNHα couplings in proteins from the relative intensities in a pair of 15N-1H TROSY-HSQC spectra. The pulse scheme includes 3JHNHα dephasing of the narrower TROSY 1HN-{15N} doublet component during a delay, integrated into the regular two-dimensional TROSY-HSQC pulse scheme, and compares the obtained intensity with a reference spectrum where 3JHNHα dephasing is suppressed. The effect of passive 1Hα spin flips downscales the apparent 3JHNHα coupling by a uniform factor that depends approximately linearly on both the duration of the 3JHNHα dephasing delay and the 1H-1H cross relaxation rate. Using such a correction factor, which accounts for the effects of both inhomogeneity of the radiofrequency field and 1Hα spin flips, agreement between prior and newly measured values for the small model protein GB3 is better than 0.3 Hz. Measurement for the HIV-1 protease homodimer (22 kDa) yields 3JHNHα values that agree to better than 0.7 Hz with predictions made on the basis of a previously parameterized Karplus equation. Although for Gly residues the two individual 3JHNHα couplings cannot be extracted from a single set of ARTSY-J spectra, the measurement provides valuable ϕ angle information.

  19. ARTSY-J: Convenient and precise measurement of (3)JHNHα couplings in medium-size proteins from TROSY-HSQC spectra.

    PubMed

    Roche, Julien; Ying, Jinfa; Shen, Yang; Torchia, Dennis A; Bax, Ad

    2016-07-01

    A new and convenient method, named ARTSY-J, is introduced that permits extraction of the (3)JHNHα couplings in proteins from the relative intensities in a pair of (15)N-(1)H TROSY-HSQC spectra. The pulse scheme includes (3)JHNHα dephasing of the narrower TROSY (1)H(N)-{(15)N} doublet component during a delay, integrated into the regular two-dimensional TROSY-HSQC pulse scheme, and compares the obtained intensity with a reference spectrum where (3)JHNHα dephasing is suppressed. The effect of passive (1)H(α) spin flips downscales the apparent (3)JHNHα coupling by a uniform factor that depends approximately linearly on both the duration of the (3)JHNHα dephasing delay and the (1)H-(1)H cross relaxation rate. Using such a correction factor, which accounts for the effects of both inhomogeneity of the radiofrequency field and (1)H(α) spin flips, agreement between prior and newly measured values for the small model protein GB3 is better than 0.3Hz. Measurement for the HIV-1 protease homodimer (22kDa) yields (3)JHNHα values that agree to better than 0.7Hz with predictions made on the basis of a previously parameterized Karplus equation. Although for Gly residues the two individual (3)JHNHα couplings cannot be extracted from a single set of ARTSY-J spectra, the measurement provides valuable ϕ angle information. PMID:27179455

  20. Universal equations and constants of turbulent motion

    NASA Astrophysics Data System (ADS)

    Baumert, H. Z.

    2013-07-01

    This paper presents a parameter-free theory of shear-generated turbulence at asymptotically high Reynolds numbers in incompressible fluids. It is based on a two-fluids concept. Both components are materially identical and inviscid. The first component is an ensemble of quasi-rigid dipole-vortex tubes (vortex filaments, excitations) as quasi-particles in chaotic motion. The second is a superfluid performing evasive motions between the tubes. The local dipole motions follow Helmholtz' law. The vortex radii scale with the energy-containing length scale. Collisions between quasi-particles lead either to annihilation (likewise rotation, turbulent dissipation) or to scattering (counterrotation, turbulent diffusion). There are analogies with birth and death processes of population dynamics and their master equations and with Landau's two-fluid theory of liquid helium. For free homogeneous decay the theory predicts the turbulent kinetic energy to follow t-1. With an adiabatic wall condition it predicts the logarithmic law with von Kármán's constant as 1/\\sqrt {2\\,\\pi }= 0.399 . Likewise rotating couples form localized dissipative patches almost at rest (→ intermittency) wherein under local quasi-steady conditions the spectrum evolves into an ‘Apollonian gear’ as discussed first by Herrmann (1990 Correlation and Connectivity (Dordrecht: Kluwer) pp 108-20). Dissipation happens exclusively at scale zero and at finite scales this system is frictionless and reminds of Prigogine's (1947 Etude Thermodynamique des Phenomenes Irreversibles (Liege: Desoer) p 143) law of minimum (here: zero) entropy production. The theory predicts further the prefactor of the 3D-wavenumber spectrum (a Kolmogorov constant) as \\frac {1}{3}(4\\,\\pi )^{2/3}=1.802 , well within the scatter range of observational, experimental and direct numerical simulation results.

  1. The spectroscopic constants and anharmonic force field of AgSH: An ab initio study

    NASA Astrophysics Data System (ADS)

    Zhao, Yanliang; Wang, Meishan; Yang, Chuanlu; Ma, Xiaoguang; Zhu, Ziliang

    2016-07-01

    The equilibrium structure, spectroscopy constants, and anharmonic force field of silver hydrosulfide (AgSH) have been calculated at B3P86, B3PW91 and MP2 methods employing two basis sets, TZP and QZP, respectively. The calculated geometries, ground state rotational constants, harmonic vibrational wave numbers, and quartic and sextic centrifugal distortion constants are compared with the available experimental and theoretical data. The equilibrium rotational constants, fundamental frequencies, anharmonic constants, and vibration-rotation interaction constants, Coriolis coupling constants, cubic and quartic force constants are predicted. The calculated results show that the MP2/TZP results are in good agreement with experiment observation and are also an advisable choice to study the anharmonic force field of AgSH.

  2. Fundamental Constants as Monitors of Particle Physics and Dark Energy

    NASA Astrophysics Data System (ADS)

    Thompson, Rodger

    2016-03-01

    This contribution considers the constraints on particle physics and dark energy parameter space imposed by the astronomical observational constraints on the variation of the proton to electron mass ratio μ and the fine structure constant α. These constraints impose limits on the temporal variation of these parameters on a time scale greater than half the age of the universe, a time scale inaccessible by laboratory facilities such as the Large Hadron Collider. The limits on the variance of μ and α constrain combinations of the QCD Scale, the Higgs VEV and the Yukawa coupling on the particle physics side and a combination of the temporal variation of rolling scalar field and its coupling to the constants on the dark energy side.

  3. Asympotics with positive cosmological constant

    NASA Astrophysics Data System (ADS)

    Bonga, Beatrice; Ashtekar, Abhay; Kesavan, Aruna

    2014-03-01

    Since observations to date imply that our universe has a positive cosmological constant, one needs an extension of the theory of isolated systems and gravitational radiation in full general relativity from the asymptotically flat to asymptotically de Sitter space-times. In current definitions, one mimics the boundary conditions used in asymptotically AdS context to conclude that the asymptotic symmetry group is the de Sitter group. However, these conditions severely restricts radiation and in fact rules out non-zero flux of energy, momentum and angular momentum carried by gravitational waves. Therefore, these formulations of asymptotically de Sitter space-times are uninteresting beyond non-radiative spacetimes. The situation is compared and contrasted with conserved charges and fluxes at null infinity in asymptotically flat space-times.

  4. Henry's law constants of polyols

    NASA Astrophysics Data System (ADS)

    Compernolle, S.; Müller, J.-F.

    2014-12-01

    Henry's law constants (HLC) are derived for several polyols bearing between 2 and 6 hydroxyl groups, based on literature data for water activity, vapour pressure and/or solubility. While deriving HLC and depending on the case, also infinite dilution activity coefficients (IDACs), solid state vapour pressures or activity coefficient ratios are obtained as intermediate results. An error analysis on the intermediate quantities and the obtained HLC is included. For most compounds, these are the first values reported, while others compare favourably with literature data in most cases. Using these values and those from a previous work (Compernolle and Müller, 2014), an assessment is made on the partitioning of polyols, diacids and hydroxy acids to droplet and aqueous aerosol.

  5. Philicities, Fugalities, and Equilibrium Constants.

    PubMed

    Mayr, Herbert; Ofial, Armin R

    2016-05-17

    The mechanistic model of Organic Chemistry is based on relationships between rate and equilibrium constants. Thus, strong bases are generally considered to be good nucleophiles and poor nucleofuges. Exceptions to this rule have long been known, and the ability of iodide ions to catalyze nucleophilic substitutions, because they are good nucleophiles as well as good nucleofuges, is just a prominent example for exceptions from the general rule. In a reaction series, the Leffler-Hammond parameter α = δΔG(⧧)/δΔG° describes the fraction of the change in the Gibbs energy of reaction, which is reflected in the change of the Gibbs energy of activation. It has long been considered as a measure for the position of the transition state; thus, an α value close to 0 was associated with an early transition state, while an α value close to 1 was considered to be indicative of a late transition state. Bordwell's observation in 1969 that substituent variation in phenylnitromethanes has a larger effect on the rates of deprotonation than on the corresponding equilibrium constants (nitroalkane anomaly) triggered the breakdown of this interpretation. In the past, most systematic investigations of the relationships between rates and equilibria of organic reactions have dealt with proton transfer reactions, because only for few other reaction series complementary kinetic and thermodynamic data have been available. In this Account we report on a more general investigation of the relationships between Lewis basicities, nucleophilicities, and nucleofugalities as well as between Lewis acidities, electrophilicities, and electrofugalities. Definitions of these terms are summarized, and it is suggested to replace the hybrid terms "kinetic basicity" and "kinetic acidity" by "protophilicity" and "protofugality", respectively; in this way, the terms "acidity" and "basicity" are exclusively assigned to thermodynamic properties, while "philicity" and "fugality" refer to kinetics

  6. Turbine blade having a constant thickness airfoil skin

    DOEpatents

    Marra, John J

    2012-10-23

    A turbine blade is provided for a gas turbine comprising: a support structure comprising a base defining a root of the blade and a framework extending radially outwardly from the base, and an outer skin coupled to the support structure framework. The skin has a generally constant thickness along substantially the entire radial extent thereof. The framework and the skin define an airfoil of the blade.

  7. Local surface elastic constants by resonant-ultrasound microscopy

    NASA Astrophysics Data System (ADS)

    Tian, Jiayong; Ogi, Hirotsugu; Tada, Toyokazu; Hirao, Masahiko; Ledbetter, Hassel

    2004-07-01

    We report a method—resonant-ultrasound microscopy—for measuring elastic-constant distribution over a solid's surface. Applying an oscillating electric field to a rectangular-parallelepiped oscillator of langasite (La3Ga5SiO14) crystal by a surrounding solenoid coil, we generated and detected vibrations of the crystal without electrodes and without wires. Acoustic coupling of the specimen to the oscillator is only made at an antinodal vibration point on the crystal's bottom surface. The crystal's resonance-frequency shift reflects elastic constants of the specimen in the contacting area. Point-contact measurement permits sensitive, quantitative evaluation of a material's local elastic constants. As an illustrating example, we measured the elastic-stiffness distribution of a Nb-Ti/Cu resin superconductive wire. We compared our measurements with both static-contact and dynamic-contact models.

  8. Effective cosmological constant from TeV-scale physics

    SciTech Connect

    Klinkhamer, F. R.

    2010-10-15

    It has been suggested previously that the observed cosmological constant {Lambda} corresponds to the remnant vacuum energy density of dynamical processes taking place at a cosmic age set by the mass scale M{approx}E{sub ew} of ultramassive particles with electroweak interactions. Here, a simple modification of the nondissipative dynamic equations of q-theory is presented, which produces a remnant vacuum energy density (effective cosmological constant) of the correct order of magnitude. Combined with the observed value of {Lambda}, a first estimate of the required value of the energy scale E{sub ew} ranges from 3 to 9 TeV, depending on the number of species of ultramassive particles and assuming a dissipative coupling constant of order unity. If correct, this estimate implies the existence of new TeV-scale physics beyond the standard model.

  9. Decay Constants of B and D Mesons from Non-pertubatively Improved Lattice QCD

    SciTech Connect

    K.C. Bowler; L. Del Debbio; J.M. Flynn; G.N, Lacagnina; V.I. Lesk; C.M. Maynard; D.G. Richards

    2000-07-01

    The decay constants of B and D mesons are computed in quenched lattice QCD at two different values of the coupling. The action and operators are ? (a) improved with non-perturbative coefficients where available. The results and systematic errors are discussed in detail. Results for vector decay constants, flavour symmetry breaking ratios of decay constants, the pseudoscalar-vector mass splitting and D meson masses are also presented.

  10. Expanding Taylor bubble under constant heat flux

    NASA Astrophysics Data System (ADS)

    Voirand, Antoine; Benselama, Adel M.; Ayel, Vincent; Bertin, Yves

    2016-09-01

    Modelization of non-isothermal bubbles expanding in a capillary, as a contribution to the understanding of the physical phenomena taking place in Pulsating Heat Pipes (PHPs), is the scope of this paper. The liquid film problem is simplified and solved, while the thermal problem takes into account a constant heat flux density applied at the capillary tube wall, exchanging with the liquid film surrounding the bubble and also with the capillary tube outside medium. The liquid slug dynamics is solved using the Lucas-Washburn equation. Mass and energy balance on the vapor phase allow governing equations of bubble expansion to be written. The liquid and vapor phases are coupled only through the saturation temperature associated with the vapor pressure, assumed to be uniform throughout the bubble. Results show an over-heating of the vapor phase, although the particular thermal boundary condition used here always ensures an evaporative mass flux at the liquid-vapor interface. Global heat exchange is also investigated, showing a strong decreasing of the PHP performance to convey heat by phase change means for large meniscus velocities.

  11. Star polymers rupture induced by constant forces

    NASA Astrophysics Data System (ADS)

    García, N. A.; Febbo, M.; Vega, D. A.; Milchev, A.

    2014-10-01

    In this work, we study the breakage process of an unknotted three-arm star-shaped polymer when it is pulled from its free ends by a constant force. The star polymer configuration is described through an array of monomers coupled by anharmonic bonds, while the rupture process is tracked in three-dimensional space by means of Langevin Molecular Dynamics simulations. The interaction between monomers is described by a Morse potential, while a Weeks-Chandler-Anderson energetic contribution accounts for the excluded volume interaction. We explore the effect of the molecular architecture on the distributions of rupture times over a broad interval of pulling forces and star configurations. It was found that the rupture time distribution of the individual star arms is strongly affected by the star configuration imposed by the pulling forces and the length of the arms. We also observed that for large pulling forces the rupture time distributions resemble the dominant features observed for linear polymer chains. The model introduced here provides the basic ingredients to describe the effects of tensile forces on stress-induced degradation of branched macromolecules and polymer networks.

  12. Star polymers rupture induced by constant forces.

    PubMed

    García, N A; Febbo, M; Vega, D A; Milchev, A

    2014-10-28

    In this work, we study the breakage process of an unknotted three-arm star-shaped polymer when it is pulled from its free ends by a constant force. The star polymer configuration is described through an array of monomers coupled by anharmonic bonds, while the rupture process is tracked in three-dimensional space by means of Langevin Molecular Dynamics simulations. The interaction between monomers is described by a Morse potential, while a Weeks-Chandler-Anderson energetic contribution accounts for the excluded volume interaction. We explore the effect of the molecular architecture on the distributions of rupture times over a broad interval of pulling forces and star configurations. It was found that the rupture time distribution of the individual star arms is strongly affected by the star configuration imposed by the pulling forces and the length of the arms. We also observed that for large pulling forces the rupture time distributions resemble the dominant features observed for linear polymer chains. The model introduced here provides the basic ingredients to describe the effects of tensile forces on stress-induced degradation of branched macromolecules and polymer networks. PMID:25362341

  13. Is There a Cosmological Constant?

    NASA Technical Reports Server (NTRS)

    Kochanek, Christopher; Oliversen, Ronald J. (Technical Monitor)

    2002-01-01

    The grant contributed to the publication of 18 refereed papers and 5 conference proceedings. The primary uses of the funding have been for page charges, travel for invited talks related to the grant research, and the support of a graduate student, Charles Keeton. The refereed papers address four of the primary goals of the proposal: (1) the statistics of radio lenses as a probe of the cosmological model (#1), (2) the role of spiral galaxies as lenses (#3), (3) the effects of dust on statistics of lenses (#7, #8), and (4) the role of groups and clusters as lenses (#2, #6, #10, #13, #15, #16). Four papers (#4, #5, #11, #12) address general issues of lens models, calibrations, and the relationship between lens galaxies and nearby galaxies. One considered cosmological effects in lensing X-ray sources (#9), and two addressed issues related to the overall power spectrum and theories of gravity (#17, #18). Our theoretical studies combined with the explosion in the number of lenses and the quality of the data obtained for them is greatly increasing our ability to characterize and understand the lens population. We can now firmly conclude both from our study of the statistics of radio lenses and our survey of extinctions in individual lenses that the statistics of optically selected quasars were significantly affected by extinction. However, the limits on the cosmological constant remain at lambda < 0.65 at a 2-sigma confidence level, which is in mild conflict with the results of the Type la supernova surveys. We continue to find that neither spiral galaxies nor groups and clusters contribute significantly to the production of gravitational lenses. The lack of group and cluster lenses is strong evidence for the role of baryonic cooling in increasing the efficiency of galaxies as lenses compared to groups and clusters of higher mass but lower central density. Unfortunately for the ultimate objective of the proposal, improved constraints on the cosmological constant, the next

  14. Capacitive Cells for Dielectric Constant Measurement

    ERIC Educational Resources Information Center

    Aguilar, Horacio Munguía; Maldonado, Rigoberto Franco

    2015-01-01

    A simple capacitive cell for dielectric constant measurement in liquids is presented. As an illustrative application, the cell is used for measuring the degradation of overheated edible oil through the evaluation of their dielectric constant.

  15. High voltage compliance constant current ballast

    NASA Technical Reports Server (NTRS)

    Rosenthal, L. A.

    1976-01-01

    A ballast circuit employing a constant current diode and a vacuum tube that can provide a constant current over a voltage range of 1000 volts. The simple circuit can prove useful in studying voltage breakdown characteristics.

  16. Towards a consistent estimate of the chiral low-energy constants

    NASA Astrophysics Data System (ADS)

    Cirigliano, V.; Ecker, G.; Eidemüller, M.; Kaiser, R.; Pich, A.; Portolés, J.

    2006-10-01

    Guided by the large- N limit of QCD, we construct the most general chiral resonance Lagrangian that can generate chiral low-energy constants up to O(p). By integrating out the resonance fields, the low-energy constants are parametrized in terms of resonance masses and couplings. Information on those couplings and on the low-energy constants can be extracted by analysing QCD Green functions of currents both for large and small momenta. The chiral resonance theory generates Green functions that interpolate between QCD and chiral perturbation theory. As specific examples we consider the and Green functions.

  17. Helix coupling

    DOEpatents

    Ginell, W.S.

    1989-04-25

    A coupling for connecting helix members in series, which consists of a pair of U-shaped elements, one of which is attached to each helix end with the "U" sections of the elements interlocked. The coupling is particularly beneficial for interconnecting helical Nitinol elements utilized in thermal actuators or engines. Each coupling half is attached to the associated helix at two points, thereby providing axial load while being easily removed from the helix, and reusable.

  18. Helix coupling

    DOEpatents

    Ginell, W.S.

    1982-03-17

    A coupling for connecting helix members in series, which consists of a pair of U-shaped elements, one of which is attached to each helix end with the U sections of the elements interlocked. The coupling is particularly beneficial for interconnecting helical Nitinol elements utilized in thermal actuators or engines. Each coupling half is attached to the associated helix at two points, thereby providing axial load while being easily removed from the helix, and reusable.

  19. Fundamental Constants and Tests with Simple Atoms

    NASA Astrophysics Data System (ADS)

    Tan, Joseph

    2015-05-01

    Precise measurements with simple atoms provide stringent tests of physical laws, improving the accuracy of fundamental constants--a set of which will be selected to fully define the proposed New International System of Units. This talk focuses on the atomic constants (namely, the Rydberg constant, the fine-structure constant, and the proton charge radius), discussing the impact of the proton radius obtained from the Lamb-shift measurements in muonic hydrogen. Significant discrepancies persist despite years of careful examination: the slightly smaller proton radius obtained from muonic hydrogen requires the Rydberg constant and the fine-structure constant to have values that disagree significantly with the CODATA recommendations. After giving a general overview, I will discuss our effort to produce one-electron ions in Rydberg states, to enable a different test of theory and measurement of the Rydberg constant.

  20. Coupled adaptive complex networks.

    PubMed

    Shai, S; Dobson, S

    2013-04-01

    Adaptive networks, which combine topological evolution of the network with dynamics on the network, are ubiquitous across disciplines. Examples include technical distribution networks such as road networks and the internet, natural and biological networks, and social science networks. These networks often interact with or depend upon other networks, resulting in coupled adaptive networks. In this paper we study susceptible-infected-susceptible (SIS) epidemic dynamics on coupled adaptive networks, where susceptible nodes are able to avoid contact with infected nodes by rewiring their intranetwork connections. However, infected nodes can pass the disease through internetwork connections, which do not change with time: The dependencies between the coupled networks remain constant. We develop an analytical formalism for these systems and validate it using extensive numerical simulation. We find that stability is increased by increasing the number of internetwork links, in the sense that the range of parameters over which both endemic and healthy states coexist (both states are reachable depending on the initial conditions) becomes smaller. Finally, we find a new stable state that does not appear in the case of a single adaptive network but only in the case of weakly coupled networks, in which the infection is endemic in one network but neither becomes endemic nor dies out in the other. Instead, it persists only at the nodes that are coupled to nodes in the other network through internetwork links. We speculate on the implications of these findings. PMID:23679478

  1. Coupled adaptive complex networks

    NASA Astrophysics Data System (ADS)

    Shai, S.; Dobson, S.

    2013-04-01

    Adaptive networks, which combine topological evolution of the network with dynamics on the network, are ubiquitous across disciplines. Examples include technical distribution networks such as road networks and the internet, natural and biological networks, and social science networks. These networks often interact with or depend upon other networks, resulting in coupled adaptive networks. In this paper we study susceptible-infected-susceptible (SIS) epidemic dynamics on coupled adaptive networks, where susceptible nodes are able to avoid contact with infected nodes by rewiring their intranetwork connections. However, infected nodes can pass the disease through internetwork connections, which do not change with time: The dependencies between the coupled networks remain constant. We develop an analytical formalism for these systems and validate it using extensive numerical simulation. We find that stability is increased by increasing the number of internetwork links, in the sense that the range of parameters over which both endemic and healthy states coexist (both states are reachable depending on the initial conditions) becomes smaller. Finally, we find a new stable state that does not appear in the case of a single adaptive network but only in the case of weakly coupled networks, in which the infection is endemic in one network but neither becomes endemic nor dies out in the other. Instead, it persists only at the nodes that are coupled to nodes in the other network through internetwork links. We speculate on the implications of these findings.

  2. Exploring Calcium Oxalate Crystallization: A Constant Composition Approach

    PubMed Central

    Kolbach-Mandel, Ann M.; Kleinman, Jack G.; Wesson, Jeffrey A.

    2015-01-01

    Crystal growth rates have been extensively studied in calcium oxalate monohydrate (COM) crystallization, because COM crystals are the principal component in most kidney stones. Constant composition methods are useful for studying growth rates, but fail to differentiate concurrent nucleation and aggregation events. A constant composition method coupled with particle size determinations that addresses this deficiency was previously published for a calcium phosphate system, and this method was extended to COM crystallization in this report. A seeded constant composition experiment was combined with particle size determination and a separate near-equilibrium aggregation experiment to separate effects of growth rate, nucleation, and aggregation in COM crystal formation and to test the effects of various inhibitors relevant to stone formation. With no inhibitors present, apparent COM growth rates were heavily influenced by secondary nucleation at low seed crystal additions, but growth-related aggregation increased at higher seed crystal densities. Among small molecule inhibitors, citrate demonstrated growth rate inhibition but enhanced growth-related aggregation, while magnesium did not affect COM crystallization. Polyanions (polyaspartate, polyglutamate, or osteopontin) showed strong growth rate inhibition, but large differences in nucleation and aggregation were observed. Polycations (polyarginine) did not affect COM crystal growth or aggregation. Mixtures of polyanions and polycations produced a complicated set of growth rate, nucleation, and aggregation behaviors. These experiments demonstrated the power of combining particle size determinations with constant composition experiments to fully characterize COM crystallization and to obtain detailed knowledge of inhibitor properties that will be critical to understanding kidney stone formation. PMID:26016572

  3. Exploring calcium oxalate crystallization: a constant composition approach.

    PubMed

    Kolbach-Mandel, Ann M; Kleinman, Jack G; Wesson, Jeffrey A

    2015-10-01

    Crystal growth rates have been extensively studied in calcium oxalate monohydrate (COM) crystallization, because COM crystals are the principal component in most kidney stones. Constant composition methods are useful for studying growth rates, but fail to differentiate concurrent nucleation and aggregation events. A constant composition method coupled with particle size determinations that addresses this deficiency was previously published for a calcium phosphate system, and this method was extended to COM crystallization in this report. A seeded constant composition experiment was combined with particle size determination and a separate near-equilibrium aggregation experiment to separate effects of growth rate, nucleation, and aggregation in COM crystal formation and to test the effects of various inhibitors relevant to stone formation. With no inhibitors present, apparent COM growth rates were heavily influenced by secondary nucleation at low seed crystal additions, but growth-related aggregation increased at higher seed crystal densities. Among small molecule inhibitors, citrate demonstrated growth rate inhibition but enhanced growth-related aggregation, while magnesium did not affect COM crystallization. Polyanions (polyaspartate, polyglutamate, or osteopontin) showed strong growth rate inhibition, but large differences in nucleation and aggregation were observed. Polycations (polyarginine) did not affect COM crystal growth or aggregation. Mixtures of polyanions and polycations produced a complicated set of growth rate, nucleation, and aggregation behaviors. These experiments demonstrated the power of combining particle size determinations with constant composition experiments to fully characterize COM crystallization and to obtain detailed knowledge of inhibitor properties that will be critical to understanding kidney stone formation.

  4. Synchronization in chaotic oscillators by cyclic coupling

    NASA Astrophysics Data System (ADS)

    Olusola, O. I.; Njah, A. N.; Dana, S. K.

    2013-07-01

    We introduce a type of cyclic coupling to investigate synchronization of chaotic oscillators. We derive analytical solutions of the critical coupling for stable synchronization under the cyclic coupling for the Rössler system and the Lorenz oscillator as paradigmatic illustration. Based on the master stability function (MSF) approach, the analytical results on critical coupling are verified numerically. An enhancing effect in terms of lowering the critical coupling or enlarging the synchronization window in a critical coupling space is noticed. The cyclic coupling is also applied in other models, Hindmarsh-Rose model, Sprott system, Chen system and forced Duffing system to confirm the enhancing effect. The cyclic coupling allows tuning of two coupling constants in reverse directions when an optimal control of synchronization is feasible.

  5. Effective elastic constants of polycrystalline aggregates

    NASA Astrophysics Data System (ADS)

    Bonilla, Luis L.

    A METHOD is presented for the determination of the effective elastic constants of a transversely isotropic aggregate of weakly anisotropic crystallites with cubic symmetry. The results obtained generalize those given in the literature for the second and third order elastic constants. In addition, the second moments and the binary angular correlations of the second order stiffnesses are obtained. It is also explained how these moments can be used to find the two-point correlations of the elastic constants.

  6. Constant voltage electro-slag remelting control

    DOEpatents

    Schlienger, Max E.

    1996-01-01

    A system for controlling electrode gap in an electro-slag remelt furnace has a constant regulated voltage and an eletrode which is fed into the slag pool at a constant rate. The impedance of the circuit through the slag pool is directly proportional to the gap distance. Because of the constant voltage, the system current changes are inversely proportional to changes in gap. This negative feedback causes the gap to remain stable.

  7. Constant voltage electro-slag remelting control

    DOEpatents

    Schlienger, M.E.

    1996-10-22

    A system for controlling electrode gap in an electro-slag remelt furnace has a constant regulated voltage and an electrode which is fed into the slag pool at a constant rate. The impedance of the circuit through the slag pool is directly proportional to the gap distance. Because of the constant voltage, the system current changes are inversely proportional to changes in gap. This negative feedback causes the gap to remain stable. 1 fig.

  8. Semiclassical Calculation of Reaction Rate Constants for Homolytical Dissociations

    NASA Technical Reports Server (NTRS)

    Cardelino, Beatriz H.

    2002-01-01

    There is growing interest in extending organometallic chemical vapor deposition (OMCVD) to III-V materials that exhibit large thermal decomposition at their optimum growth temperature, such as indium nitride. The group III nitrides are candidate materials for light-emitting diodes and semiconductor lasers operating into the blue and ultraviolet regions. To overcome decomposition of the deposited compound, the reaction must be conducted at high pressures, which causes problems of uniformity. Microgravity may provide the venue for maintaining conditions of laminar flow under high pressure. Since the selection of optimized parameters becomes crucial when performing experiments in microgravity, efforts are presently geared to the development of computational OMCVD models that will couple the reactor fluid dynamics with its chemical kinetics. In the present study, we developed a method to calculate reaction rate constants for the homolytic dissociation of III-V compounds for modeling OMCVD. The method is validated by comparing calculations with experimental reaction rate constants.

  9. Measuring JHH values with a selective constant-time 2D NMR protocol

    NASA Astrophysics Data System (ADS)

    Lin, Liangjie; Wei, Zhiliang; Lin, Yanqin; Chen, Zhong

    2016-11-01

    Proton-proton scalar couplings play important roles in molecule structure elucidation. However, measurements of JHH values in complex coupled spin systems remain challenging. In this study, we develop a selective constant-time (SECT) 2D NMR protocol with which scalar coupling networks involving chosen protons can be revealed, and corresponding JHH values can be measured through doublets along the F1 dimension. All JHH values within a network of n fully coupled protons can be separately determined with (n - 1) SECT experiments. Additionally, the proposed pulse sequence possesses satisfactory sensitivity and handy implementation. Therefore, it will interest scientists who intend to address structural analyzes of molecules with overcrowded spectra, and may greatly facilitate the applications of scalar-coupling constants in molecule structure studies.

  10. Modification of the characteristic gravitational constants

    NASA Astrophysics Data System (ADS)

    Vujičić, V. A.

    2006-08-01

    In the educational and scientific literature the numerical values of gravitational constants are seen as only approximately correct. The numerical values are different in work by various researchers, as also are the formulae and definitions of constants employed. In this paper, on the basis of Newton’s laws and Kepler’s laws we prove that it is necessary to modify the characteristic gravitational constants and their definitions. The formula for the geocentric gravitational constant of the satellites Kosmos N and the Moon are calculated.

  11. Gauge coupling unification in gauge-Higgs grand unification

    NASA Astrophysics Data System (ADS)

    Yamatsu, Naoki

    2016-04-01

    We discuss renormalization group equations for gauge coupling constants in gauge-Higgs grand unification on five-dimensional Randall-Sundrum warped space. We show that all four-dimensional Standard Model gauge coupling constants are asymptotically free and are effectively unified in SO(11) gauge-Higgs grand unified theories on 5D Randall-Sundrum warped space.

  12. Nonadiabatic Coupling

    NASA Astrophysics Data System (ADS)

    Kryachko, Eugene S.

    The general features of the nonadiabatic coupling and its relation to molecular properties are surveyed. Some consequences of the [`]equation of motion', formally expressing a [`]smoothness' of a given molecular property within the diabatic basis, are demonstrated. A particular emphasis is made on the relation between a [`]smoothness' of the electronic dipole moment and the generalized Mulliken-Hush formula for the diabatic electronic coupling.

  13. Very light cosmological scalar fields from a tiny cosmological constant

    SciTech Connect

    Calmet, Xavier

    2007-10-15

    I discuss a mechanism which generates a mass term for a scalar field in an expanding universe. The mass of this field turns out to be generated by the cosmological constant and can be naturally small if protected by a conformal symmetry which is, however, broken in the gravitational sector. The mass is comparable today to the Hubble time. This scalar field could thus impact our Universe today and, for example, be at the origin of a time variation of the couplings and masses of the parameters of the standard model.

  14. Does Quantum Cosmology Predict a Constant Dilatonic Field?

    NASA Astrophysics Data System (ADS)

    Alvarenga, F. G.; Batista, A. B.; Fabris, J. C.

    Quantum cosmology may permit to determine the initial conditions of the Universe. In particular, it may select a specific model between many possible classical models. In this work, we study a quantum cosmological model based on the string effective action coupled to matter. The Schutz's formalism is employed in the description of the fluid. A radiation fluid is considered. In this way, a time coordinate may be identified and the Wheeler-DeWitt equation reduces in the minisuperspace to a Schrödinger-like equation. It is shown that, under some quite natural assumptions, the expectation values indicate a null axionic field and a constant dilatonic field. At the same time the scale factor exhibits a bounce revealing a singularity-free cosmological model. In some cases, the mininum value of the scale factor can be related to the value of gravitational coupling.

  15. Varying constant cosmologies and cosmic singularities

    NASA Astrophysics Data System (ADS)

    Dabrowski, Mariusz P.; Marosek, Konrad

    2013-02-01

    We review standard and non-standard cosmological singularities paying special attention onto those which are of a weak type and do not necessarily exhibit geodesic incompletness. Then, we discuss how these singularities can be weakened, strengthened, or avoided due to the time-variation of the physical constants such as the speed of light c and the gravitational constant G.

  16. Determination of mass density, dielectric, elastic, and piezoelectric constants of bulk GaN crystal.

    PubMed

    Soluch, Waldemar; Brzozowski, Ernest; Lysakowska, Magdalena; Sadura, Jolanta

    2011-11-01

    Mass density, dielectric, elastic, and piezoelectric constants of bulk GaN crystal were determined. Mass density was obtained from the measured ratio of mass to volume of a cuboid. The dielectric constants were determined from the measured capacitances of an interdigital transducer (IDT) deposited on a Z-cut plate and from a parallel plate capacitor fabricated from this plate. The elastic and piezoelectric constants were determined by comparing the measured and calculated SAW velocities and electromechanical coupling coefficients on the Z- and X-cut plates. The following new constants were obtained: mass density p = 5986 kg/m(3); relative dielectric constants (at constant strain S) ε(S)(11)/ε(0) = 8.6 and ε(S)(11)/ε(0) = 10.5, where ε(0) is a dielectric constant of free space; elastic constants (at constant electric field E) C(E)(11) = 349.7, C(E)(12) = 128.1, C(E)(13) = 129.4, C(E)(33) = 430.3, and C(E)(44) = 96.5 GPa; and piezoelectric constants e(33) = 0.84, e(31) = -0.47, and e(15) = -0.41 C/m(2).

  17. FLEXIBLE COUPLING

    DOEpatents

    Babelay, E.F.

    1962-02-13

    A flexible shaft coupling for operation at speeds in excess of 14,000 rpm is designed which requires no lubrication. A driving sleeve member and a driven sleeve member are placed in concentric spaced relationship. A torque force is transmitted to the driven member from the driving member through a plurality of nylon balls symmetrically disposed between the spaced sleeves. The balls extend into races and recesses within the respective sleeve members. The sleeve members have a suitable clearance therebetween and the balls have a suitable radial clearance during operation of the coupling to provide a relatively loose coupling. These clearances accommodate for both parallel and/or angular misalignments and avoid metal-tometal contact between the sleeve members during operation. Thus, no lubrication is needed, and a minimum of vibrations is transmitted between the sleeve members. (AEC)

  18. Prosthesis coupling

    NASA Technical Reports Server (NTRS)

    Reswick, J. B.; Mooney, V.; Bright, C. W.; Owens, L. J. (Inventor)

    1979-01-01

    A coupling for use in an apparatus for connecting a prosthesis to the bone of a stump of an amputated limb is described which permits a bio-compatible carbon sleeve forming a part of the prosthesis connector to float so as to prevent disturbing the skin seal around the carbon sleeve. The coupling includes a flexible member interposed between a socket that is inserted within an intermedullary cavity of the bone and the sleeve. A lock pin is carried by the prosthesis and has a stem portion which is adapted to be coaxially disposed and slideably within the tubular female socket for securing the prosthesis to the stump. The skin around the percutaneous carbon sleeve is able to move as a result of the flexing coupling so as to reduce stresses caused by changes in the stump shape and/or movement between the bone and the flesh portion of the stump.

  19. Major Groove Width Variations in RNA Structures Determined by NMR and Impact of 13C residual chemical shift anisotropy and 1H-13C residual dipolar coupling on refinement

    PubMed Central

    Tolbert, Blanton S; Miyazaki, Yasuyuki; Barton, Shawn; Kinde, Benyam; Starck, Patrice; Singh, Rashmi; Bax, Ad

    2010-01-01

    Ribonucleic acid structure determination by NMR spectroscopy relies primarily on local structural restraints provided by 1H-1H NOEs and J-couplings. When employed loosely, these restraints are broadly compatible with A- and B-like helical geometries and give rise to calculated structures that are highly sensitive to the force fields employed during refinement. A survey of recently reported NMR structures reveals significant variations in helical parameters, particularly the major groove width. Although helical parameters observed in high-resolution X-ray crystal structures of isolated A-form RNA helices are sensitive to crystal packing effects, variations among the published X-ray structures are significantly smaller than those observed in NMR structures. Here we show that restraints derived from aromatic 1H-13C residual dipolar couplings (RDCs) and residual chemical shift anisotropies (RCSAs) can overcome NMR restraint and force field deficiencies and afford structures with helical properties similar to those observed in high-resolution X-ray structures. PMID:20549304

  20. Laser Propulsion and the Constant Momentum Mission

    NASA Astrophysics Data System (ADS)

    Larson, C. William; Mead, Franklin B.; Knecht, Sean D.

    2004-03-01

    We show that perfect propulsion requires a constant momentum mission, as a consequence of Newton's second law. Perfect propulsion occurs when the velocity of the propelled mass in the inertial frame of reference matches the velocity of the propellant jet in the rocket frame of reference. We compare constant momentum to constant specific impulse propulsion, which, for a given specification of the mission delta V, has an optimum specific impulse that maximizes the propelled mass per unit jet kinetic energy investment. We also describe findings of more than 50 % efficiency for conversion of laser energy into jet kinetic energy by ablation of solids.

  1. Laser Propulsion and the Constant Momentum Mission

    SciTech Connect

    Larson, C. William; Mead, Franklin B. Jr.; Knecht, Sean D.

    2004-03-30

    We show that perfect propulsion requires a constant momentum mission, as a consequence of Newton's second law. Perfect propulsion occurs when the velocity of the propelled mass in the inertial frame of reference matches the velocity of the propellant jet in the rocket frame of reference. We compare constant momentum to constant specific impulse propulsion, which, for a given specification of the mission delta V, has an optimum specific impulse that maximizes the propelled mass per unit jet kinetic energy investment. We also describe findings of more than 50 % efficiency for conversion of laser energy into jet kinetic energy by ablation of solids.

  2. Dynamic polarizabilities and hyperfine-structure constants for Sc2 +

    NASA Astrophysics Data System (ADS)

    Dutta, Narendra Nath; Roy, Sourav; Deshmukh, P. C.

    2015-11-01

    In this work, we calculate dynamic polarizabilities and hyperfine-structure A and B constants of a few low-lying states for Sc2 +. The sum-over-states technique is applied to calculate the polarizabilities of the 3 d 2D3 /2 ,3 d 2D5 /2 , and 4 s 2S1 /2 states. The most important and correlation sensitive part of the sum is calculated using a highly correlated relativistic coupled-cluster theory. The remaining part of the sum is calculated using a lower-order many-body perturbation theory and the Dirac-Fock theory. Present dynamic polarizabilities are important to investigate the Stark shifts in the 4 s 2S1 /2 - 3 d 2D5 /2 and 4 s 2S1 /2 - 3 d 2D3 /2 clock transitions of Sc2 +. Magic wavelengths for zero Stark shifts corresponding to these transitions are found in the vacuum-ultraviolet region. The coupled-cluster theory is used to estimate the hyperfine A and B constants with a very high accuracy.

  3. A five dimensional model of varying effective gravitational and fine structure constants

    NASA Astrophysics Data System (ADS)

    Mbelek, J. P.; Lachièze-Rey, M.

    2003-01-01

    We explore the possibility that the reported time variation of the fine structure constant alpha is due to a coupling between electromagnetism and gravitation. We predict such a coupling from a very simple effective theory of physical interactions, under the form of an improved version of the Kaluza-Klein theory. We show that it precisely leads to a variation of the effective fine structure constant with cosmic conditions, and thus with cosmic time. The comparison with the recent data from distant quasars absorption line spectra gives a good agreement; moreover, this may reconcile the claimed results on alpha with the upper limit from the Oklo naturel Uranium fission reactor.

  4. How the cosmological constant affects gravastar formation

    SciTech Connect

    Chan, R.; Silva, M.F.A. da; Rocha, P. E-mail: mfasnic@gmail.com

    2009-12-01

    Here we generalized a previous model of gravastar consisted of an internal de Sitter spacetime, a dynamical infinitely thin shell with an equation of state, but now we consider an external de Sitter-Schwarzschild spacetime. We have shown explicitly that the final output can be a black hole, a ''bounded excursion'' stable gravastar, a stable gravastar, or a de Sitter spacetime, depending on the total mass of the system, the cosmological constants, the equation of state of the thin shell and the initial position of the dynamical shell. We have found that the exterior cosmological constant imposes a limit to the gravastar formation, i.e., the exterior cosmological constant must be smaller than the interior cosmological constant. Besides, we have also shown that, in the particular case where the Schwarzschild mass vanishes, no stable gravastar can be formed, but we still have formation of black hole.

  5. The Solar Constant: A Take Home Lab

    ERIC Educational Resources Information Center

    Eaton, B. G.; And Others

    1977-01-01

    Describes a method that uses energy from the sun, absorbed by aluminum discs, to melt ice, and allows the determination of the solar constant. The take-home equipment includes Styrofoam cups, a plastic syringe, and aluminum discs. (MLH)

  6. Dielectric constant of water in the interface.

    PubMed

    Dinpajooh, Mohammadhasan; Matyushov, Dmitry V

    2016-07-01

    We define the dielectric constant (susceptibility) that should enter the Maxwell boundary value problem when applied to microscopic dielectric interfaces polarized by external fields. The dielectric constant (susceptibility) of the interface is defined by exact linear-response equations involving correlations of statistically fluctuating interface polarization and the Coulomb interaction energy of external charges with the dielectric. The theory is applied to the interface between water and spherical solutes of altering size studied by molecular dynamics (MD) simulations. The effective dielectric constant of interfacial water is found to be significantly lower than its bulk value, and it also depends on the solute size. For TIP3P water used in MD simulations, the interface dielectric constant changes from 9 to 4 when the solute radius is increased from ∼5 to 18 Å.

  7. The Rate Constant for Fluorescence Quenching

    ERIC Educational Resources Information Center

    Legenza, Michael W.; Marzzacco, Charles J.

    1977-01-01

    Describes an experiment that utilizes fluorescence intensity measurements from a Spectronic 20 to determine the rate constant for the fluorescence quenching of various aromatic hydrocarbons by carbon tetrachloride in an ethanol solvent. (MLH)

  8. Disentangling scalar coupling patterns by real-time SERF NMR.

    PubMed

    Gubensäk, Nina; Fabian, Walter M F; Zangger, Klaus

    2014-10-21

    Scalar coupling constants and signal splitting patterns in NMR spectra contain a wealth of short-range structural information. The extraction of these parameters from (1)H NMR spectra is often prohibited by simultaneous scalar coupling interactions with several other protons. Here we present a high-resolution NMR experiment where scalar coupling to only one selected signal is visible. All other couplings are removed from the spectrum. This real-time selectively refocused NMR experiment is achieved by spatially selective homonuclear broadband decoupling combined with selective refocusing during acquisition. It allows the unperturbed extraction of scalar coupling constants from the highly resolved acquisition dimension of NMR spectra.

  9. General relativity with small cosmological constant from spontaneous compactification of Lovelock theory in vacuum

    SciTech Connect

    Canfora, Fabrizio; Willison, Steven; Giacomini, Alex; Troncoso, Ricardo

    2009-08-15

    It is shown that Einstein gravity in four dimensions with small cosmological constant and small extra dimensions can be obtained by spontaneous compactification of Lovelock gravity in vacuum. Assuming that the extra dimensions are compact spaces of constant curvature, general relativity is recovered within a certain class of Lovelock theories possessing necessarily cubic or higher order terms in curvature. This bounds the higher dimension to at least 7. Remarkably, the effective gauge coupling and Newton constant in four dimensions are not proportional to the gravitational constant in higher dimensions, but are shifted with respect to their standard values. This effect opens up new scenarios where a maximally symmetric solution in higher dimensions could decay into the compactified spacetime either by tunneling or through a gravitational analog of ghost condensation. Indeed, this is what occurs requiring both the extra dimensions and the four-dimensional cosmological constant to be small.

  10. Inflation with a constant rate of roll

    NASA Astrophysics Data System (ADS)

    Motohashi, Hayato; Starobinsky, Alexei A.; Yokoyama, Jun'ichi

    2015-09-01

    We consider an inflationary scenario where the rate of inflaton roll defined by ̈phi/H dot phi remains constant. The rate of roll is small for slow-roll inflation, while a generic rate of roll leads to the interesting case of 'constant-roll' inflation. We find a general exact solution for the inflaton potential required for such inflaton behaviour. In this model, due to non-slow evolution of background, the would-be decaying mode of linear scalar (curvature) perturbations may not be neglected. It can even grow for some values of the model parameter, while the other mode always remains constant. However, this always occurs for unstable solutions which are not attractors for the given potential. The most interesting particular cases of constant-roll inflation remaining viable with the most recent observational data are quadratic hilltop inflation (with cutoff) and natural inflation (with an additional negative cosmological constant). In these cases even-order slow-roll parameters approach non-negligible constants while the odd ones are asymptotically vanishing in the quasi-de Sitter regime.

  11. Improved in situ spring constant calibration for colloidal probe atomic force microscopy.

    PubMed

    McBride, Sean P; Law, Bruce M

    2010-11-01

    In colloidal probe atomic force microscopy (AFM) surface forces cannot be measured without an accurate determination of the cantilever spring constant. The effective spring constant k depends upon the cantilever geometry and therefore should be measured in situ; additionally, k may be coupled to other measurement parameters. For example, colloidal probe AFM is frequently used to measure the slip length b at solid/liquid boundaries by comparing the measured hydrodynamic force with Vinogradova slip theory (V-theory). However, in this measurement k and b are coupled, hence, b cannot be accurately determined without knowing k to high precision. In this paper, a new in situ spring constant calibration method based upon the residuals, namely, the difference between experimental force-distance data and V-theory is presented and contrasted with two other popular spring constant determination methods. In this residuals calibration method, V-theory is fitted to the experimental force-distance data for a range of systematically varied spring constants where the only adjustable parameter in V-theory is the slip length b. The optimal spring constant k is that value where the residuals are symmetrically displaced about zero for all colloidal probe separations. This residual spring constant calibration method is demonstrated by studying three different liquids (n-decanol, n-hexadecane, and n-octane) and two different silane coated colloidal probe-silicon wafer systems (n-hexadecyltrichlorosilane and n-dodecyltrichlorosilane).

  12. Improved in situ spring constant calibration for colloidal probe atomic force microscopy

    SciTech Connect

    McBride, Sean P.; Law, Bruce M.

    2010-11-15

    In colloidal probe atomic force microscopy (AFM) surface forces cannot be measured without an accurate determination of the cantilever spring constant. The effective spring constant k depends upon the cantilever geometry and therefore should be measured in situ; additionally, k may be coupled to other measurement parameters. For example, colloidal probe AFM is frequently used to measure the slip length b at solid/liquid boundaries by comparing the measured hydrodynamic force with Vinogradova slip theory (V-theory). However, in this measurement k and b are coupled, hence, b cannot be accurately determined without knowing k to high precision. In this paper, a new in situ spring constant calibration method based upon the residuals, namely, the difference between experimental force-distance data and V-theory is presented and contrasted with two other popular spring constant determination methods. In this residuals calibration method, V-theory is fitted to the experimental force-distance data for a range of systematically varied spring constants where the only adjustable parameter in V-theory is the slip length b. The optimal spring constant k is that value where the residuals are symmetrically displaced about zero for all colloidal probe separations. This residual spring constant calibration method is demonstrated by studying three different liquids (n-decanol, n-hexadecane, and n-octane) and two different silane coated colloidal probe-silicon wafer systems (n-hexadecyltrichlorosilane and n-dodecyltrichlorosilane).

  13. How does pressure gravitate? Cosmological constant problem confronts observational cosmology

    SciTech Connect

    Narimani, Ali; Scott, Douglas; Afshordi, Niayesh E-mail: nafshordi@pitp.ca

    2014-08-01

    An important and long-standing puzzle in the history of modern physics is the gross inconsistency between theoretical expectations and cosmological observations of the vacuum energy density, by at least 60 orders of magnitude, otherwise known as the cosmological constant problem. A characteristic feature of vacuum energy is that it has a pressure with the same amplitude, but opposite sign to its energy density, while all the precision tests of General Relativity are either in vacuum, or for media with negligible pressure. Therefore, one may wonder whether an anomalous coupling to pressure might be responsible for decoupling vacuum from gravity. We test this possibility in the context of the Gravitational Aether proposal, using current cosmological observations, which probe the gravity of relativistic pressure in the radiation era. Interestingly, we find that the best fit for anomalous pressure coupling is about half-way between General Relativity (GR), and Gravitational Aether (GA), if we include Planck together with WMAP and BICEP2 polarization cosmic microwave background (CMB) observations. Taken at face value, this data combination excludes both GR and GA at around the 3 σ level. However, including higher resolution CMB observations (''highL'') or baryonic acoustic oscillations (BAO) pushes the best fit closer to GR, excluding the Gravitational Aether solution to the cosmological constant problem at the 4- 5 σ level. This constraint effectively places a limit on the anomalous coupling to pressure in the parametrized post-Newtonian (PPN) expansion, ζ{sub 4} = 0.105 ± 0.049 (+highL CMB), or ζ{sub 4} = 0.066 ± 0.039 (+BAO). These represent the most precise measurement of this parameter to date, indicating a mild tension with GR (for ΛCDM including tensors, with 0ζ{sub 4}=), and also among different data sets.

  14. Base units of the SI, fundamental constants and modern quantum physics.

    PubMed

    Bordé, Christian J

    2005-09-15

    Over the past 40 years, a number of discoveries in quantum physics have completely transformed our vision of fundamental metrology. This revolution starts with the frequency stabilization of lasers using saturation spectroscopy and the redefinition of the metre by fixing the velocity of light c. Today, the trend is to redefine all SI base units from fundamental constants and we discuss strategies to achieve this goal. We first consider a kinematical frame, in which fundamental constants with a dimension, such as the speed of light c, the Planck constant h, the Boltzmann constant k(B) or the electron mass m(e) can be used to connect and redefine base units. The various interaction forces of nature are then introduced in a dynamical frame, where they are completely characterized by dimensionless coupling constants such as the fine structure constant alpha or its gravitational analogue alpha(G). This point is discussed by rewriting the Maxwell and Dirac equations with new force fields and these coupling constants. We describe and stress the importance of various quantum effects leading to the advent of this new quantum metrology. In the second part of the paper, we present the status of the seven base units and the prospects of their possible redefinitions from fundamental constants in an experimental perspective. The two parts can be read independently and they point to these same conclusions concerning the redefinitions of base units. The concept of rest mass is directly related to the Compton frequency of a body, which is precisely what is measured by the watt balance. The conversion factor between mass and frequency is the Planck constant, which could therefore be fixed in a realistic and consistent new definition of the kilogram based on its Compton frequency. We discuss also how the Boltzmann constant could be better determined and fixed to replace the present definition of the kelvin.

  15. Study on Dendrobium officinale O-acetyl-glucomannan (Dendronan®): part II. Fine structures of O-acetylated residues.

    PubMed

    Xing, Xiaohui; Cui, Steve W; Nie, Shaoping; Phillips, Glyn O; Goff, H Douglas; Wang, Qi

    2015-03-01

    Main objective of this study was to investigate the detailed structural information about O-acetylated sugar residues in Dendronan(®). A water solution (2%, w/w) of Dendronan(®) was treated with endo-β-mannanase to produce oligosaccharides rich in O-acetylated sugar residues. The oligosaccharides were partly recovered by ethanol precipitation (70%, w/w). The recovered sample (designated Hydrolyzed Dendrobium officinale Polysaccharide, HDOP) had a yield of 24.7% based on the dry weight of Dendronan(®) and was highly O-acetylated. A D2O solution of HDOP (6%, w/w) generated strong signals in (1)H, (13)C, 2D (1)H-(1)H COSY, 2D (1)H-(1)H TOCSY, 2D (1)H-(1)H NOESY, 2D (1)H-(13)C HMQC, and 2D (1)H-(13)C HMBC NMR spectra. Results of NMR analyses showed that the majority of O-acetylated mannoses were mono-substituted with acetyl groups at O-2 or O-3 position. There were small amounts of mannose residues with di-O-acetyl substitution at both O-2 and O-3 positions. Minor levels of mannoses with 6-O-acetyl, 2,6-di-O-acetyl, and 3,6-di-O-acetyl substitutions were also identified. Much information about sugar residue sequence was extracted from 2D (1)H-(13)C HMBC and 2D (1)H-(1)H NOESY spectra. (1)J(C-H) coupling constants of major sugar residues were obtained. Evidences for the existence of branches or O-acetylated glucoses in HDOP were not found. The major structure of Dendronan(®) is shown as follows: [Formula: see text] M: β-D-mannopyranose; G: β-D-glucopyranose; a: O-acetyl group.

  16. Absolute radiometry and the solar constant

    NASA Technical Reports Server (NTRS)

    Willson, R. C.

    1974-01-01

    A series of active cavity radiometers (ACRs) are described which have been developed as standard detectors for the accurate measurement of irradiance in absolute units. It is noted that the ACR is an electrical substitution calorimeter, is designed for automatic remote operation in any environment, and can make irradiance measurements in the range from low-level IR fluxes up to 30 solar constants with small absolute uncertainty. The instrument operates in a differential mode by chopping the radiant flux to be measured at a slow rate, and irradiance is determined from two electrical power measurements together with the instrumental constant. Results are reported for measurements of the solar constant with two types of ACRs. The more accurate measurement yielded a value of 136.6 plus or minus 0.7 mW/sq cm (1.958 plus or minus 0.010 cal/sq cm per min).

  17. Estimation of Henry's Law Constant for a Diverse Set of Organic Compounds from Molecular Structure

    EPA Science Inventory

    The SPARC (SPARC Performs Automated Reasoning in Chemistry) vapor pressure and activity coefficient models were coupled to estimate Henry’s Law Constant (HLC) in water and in hexadecane for a wide range of non-polar and polar organic compounds without modification or additional p...

  18. Coupled quantum Otto cycle.

    PubMed

    Thomas, George; Johal, Ramandeep S

    2011-03-01

    We study the one-dimensional isotropic Heisenberg model of two spin-1/2 systems as a quantum heat engine. The engine undergoes a four-step Otto cycle where the two adiabatic branches involve changing the external magnetic field at a fixed value of the coupling constant. We find conditions for the engine efficiency to be higher than in the uncoupled model; in particular, we find an upper bound which is tighter than the Carnot bound. A domain of parameter values is pointed out which was not feasible in the interaction-free model. Locally, each spin seems to cause a flow of heat in a direction opposite to the global temperature gradient. This feature is explained by an analysis of the local effective temperature of the spins.

  19. Optimizing constant wavelength neutron powder diffractometers

    NASA Astrophysics Data System (ADS)

    Cussen, Leo D.

    2016-06-01

    This article describes an analytic method to optimize constant wavelength neutron powder diffractometers. It recasts the accepted mathematical description of resolution and intensity in terms of new variables and includes terms for vertical divergence, wavelength and some sample scattering effects. An undetermined multiplier method is applied to the revised equations to minimize the RMS value of resolution width at constant intensity and fixed wavelength. A new understanding of primary spectrometer transmission (presented elsewhere) can then be applied to choose beam elements to deliver an optimum instrument. Numerical methods can then be applied to choose the best wavelength.

  20. Dielectric constants of soils at microwave frequencies

    NASA Technical Reports Server (NTRS)

    Geiger, F. E.; Williams, D.

    1972-01-01

    A knowledge of the complex dielectric constant of soils is essential in the interpretation of microwave airborne radiometer data of the earth's surface. Measurements were made at 37 GHz on various soils from the Phoenix, Ariz., area. Extensive data have been obtained for dry soil and soil with water content in the range from 0.6 to 35 percent by dry weight. Measurements were made in a two arm microwave bridge and results were corrected for reflections at the sample interfaces by solution of the parallel dielectric plate problem. The maximum dielectric constants are about a factor of 3 lower than those reported for similar soils at X-band frequencies.

  1. Microfabricated microengine with constant rotation rate

    SciTech Connect

    Romero, L.A.; Dickey, F.M.

    1999-09-21

    A microengine uses two synchronized linear actuators as a power source and converts oscillatory motion from the actuators into constant rotational motion via direct linkage connection to an output gear or wheel. The microengine provides output in the form of a continuously rotating output gear that is capable of delivering drive torque at a constant rotation to a micromechanism. The output gear can have gear teeth on its outer perimeter for directly contacting a micromechanism requiring mechanical power. The gear is retained by a retaining means which allows said gear to rotate freely. The microengine is microfabricated of polysilicon on one wafer using surface micromachining batch fabrication.

  2. Atomic Weights No Longer Constants of Nature

    SciTech Connect

    Coplen, T.B.; Holden, N.

    2011-03-01

    Many of us grew up being taught that the standard atomic weights we found in the back of our chemistry textbooks or on the Periodic Table of the Chemical Elements hanging on the wall of our chemistry classroom are constants of nature. This was common knowledge for more than a century and a half, but not anymore. The following text explains how advances in chemical instrumentation and isotopic analysis has changed the way we view atomic weights and why they are no longer constants of nature.

  3. Atomic weights: no longer constants of nature

    USGS Publications Warehouse

    Coplen, Tyler B.; Holden, Norman E.

    2011-01-01

    Many of us were taught that the standard atomic weights we found in the back of our chemistry textbooks or on the Periodic Table of the Chemical Elements hanging on the wall of our chemistry classroom are constants of nature. This was common knowledge for more than a century and a half, but not anymore. The following text explains how advances in chemical instrumentation and isotopic analysis have changed the way we view atomic weights and why they are no longer constants of nature

  4. TOPICAL REVIEW The cosmological constant puzzle

    NASA Astrophysics Data System (ADS)

    Bass, Steven D.

    2011-04-01

    The accelerating expansion of the Universe points to a small positive vacuum energy density and negative vacuum pressure. A strong candidate is the cosmological constant in Einstein's equations of general relativity. Possible contributions are zero-point energies and the condensates associated with spontaneous symmetry breaking. The vacuum energy density extracted from astrophysics is 1056 times smaller than the value expected from quantum fields and standard model particle physics. Is the vacuum energy density time dependent? We give an introduction to the cosmological constant puzzle and ideas how to solve it.

  5. Cosmological constant in scale-invariant theories

    SciTech Connect

    Foot, Robert; Kobakhidze, Archil; Volkas, Raymond R.

    2011-10-01

    The incorporation of a small cosmological constant within radiatively broken scale-invariant models is discussed. We show that phenomenologically consistent scale-invariant models can be constructed which allow a small positive cosmological constant, providing certain relation between the particle masses is satisfied. As a result, the mass of the dilaton is generated at two-loop level. Another interesting consequence is that the electroweak symmetry-breaking vacuum in such models is necessarily a metastable ''false'' vacuum which, fortunately, is not expected to decay on cosmological time scales.

  6. Our Universe from the cosmological constant

    SciTech Connect

    Barrau, Aurélien; Linsefors, Linda E-mail: linda.linsefors@lpsc.in2p3.fr

    2014-12-01

    The issue of the origin of the Universe and of its contents is addressed in the framework of bouncing cosmologies, as described for example by loop quantum gravity. If the current acceleration is due to a true cosmological constant, this constant is naturally conserved through the bounce and the Universe should also be in a (contracting) de Sitter phase in the remote past. We investigate here the possibility that the de Sitter temperature in the contracting branch fills the Universe with radiation that causes the bounce and the subsequent inflation and reheating. We also consider the possibility that this gives rise to a cyclic model of the Universe and suggest some possible tests.

  7. Microfabricated microengine with constant rotation rate

    DOEpatents

    Romero, Louis A.; Dickey, Fred M.

    1999-01-01

    A microengine uses two synchronized linear actuators as a power source and converts oscillatory motion from the actuators into constant rotational motion via direct linkage connection to an output gear or wheel. The microengine provides output in the form of a continuously rotating output gear that is capable of delivering drive torque at a constant rotation to a micromechanism. The output gear can have gear teeth on its outer perimeter for directly contacting a micromechanism requiring mechanical power. The gear is retained by a retaining means which allows said gear to rotate freely. The microengine is microfabricated of polysilicon on one wafer using surface micromachining batch fabrication.

  8. Constant capacitance in nanopores of carbon monoliths.

    PubMed

    García-Gómez, Alejandra; Moreno-Fernández, Gelines; Lobato, Belén; Centeno, Teresa A

    2015-06-28

    The results obtained for binder-free electrodes made of carbon monoliths with narrow micropore size distributions confirm that the specific capacitance in the electrolyte (C2H5)4NBF4/acetonitrile does not depend significantly on the micropore size and support the foregoing constant result of 0.094 ± 0.011 F m(-2).

  9. Damping constant estimation in magnetoresistive readers

    SciTech Connect

    Stankiewicz, Andrzej Hernandez, Stephanie

    2015-05-07

    The damping constant is a key design parameter in magnetic reader design. Its value can be derived from bulk or sheet film ferromagnetic resonance (FMR) line width. However, dynamics of nanodevices is usually defined by presence of non-uniform modes. It triggers new damping mechanisms and produces stronger damping than expected from traditional FMR. This work proposes a device-level technique for damping evaluation, based on time-domain analysis of thermally excited stochastic oscillations. The signal is collected using a high bandwidth oscilloscope, by direct probing of a biased reader. Recorded waveforms may contain different noise signals, but free layer FMR is usually a dominating one. The autocorrelation function is a reflection of the damped oscillation curve, averaging out stochastic contributions. The damped oscillator formula is fitted to autocorrelation data, producing resonance frequency and damping constant values. Restricting lag range allows for mitigation of the impact of other phenomena (e.g., reader instability) on the damping constant. For a micromagnetically modeled reader, the technique proves to be much more accurate than the stochastic FMR line width approach. Application to actual reader waveforms yields a damping constant of ∼0.03.

  10. Variations of the Solar Constant. [conference

    NASA Technical Reports Server (NTRS)

    Sofia, S. (Editor)

    1981-01-01

    The variations in data received from rocket-borne and balloon-borne instruments are discussed. Indirect techniques to measure and monitor the solar constant are presented. Emphasis is placed on the correlation of data from the Solar Maximum Mission and the Nimbus 7 satellites.

  11. Unified Technical Concepts. Module 12: Time Constants.

    ERIC Educational Resources Information Center

    Technical Education Research Center, Waco, TX.

    This concept module on time constants is one of thirteen modules that provide a flexible, laboratory-based physics instructional package designed to meet the specialized needs of students in two-year, postsecondary technical schools. Each of the thirteen concept modules discusses a single physics concept and how it is applied to each energy…

  12. The ideal Kolmogorov inertial range and constant

    NASA Technical Reports Server (NTRS)

    Zhou, YE

    1993-01-01

    The energy transfer statistics measured in numerically simulated flows are found to be nearly self-similar for wavenumbers in the inertial range. Using the measured self-similar form, an 'ideal' energy transfer function and the corresponding energy flux rate were deduced. From this flux rate, the Kolmogorov constant was calculated to be 1.5, in excellent agreement with experiments.

  13. The Elastic Constants for Wrought Aluminum Alloys

    NASA Technical Reports Server (NTRS)

    Templin, R L; Hartmann, E C

    1945-01-01

    There are several constants which have been devised as numerical representations of the behavior of metals under the action of loadings which stress the metal within the range of elastic action. Some of these constants, such as Young's modulus of elasticity in tension and compression, shearing modulus of elasticity, and Poisson's ratio, are regularly used in engineering calculations. Precise tests and experience indicate that these elastic constants are practically unaffected by many of the factors which influence the other mechanical properties of materials and that a few careful determinations under properly controlled conditions are more useful and reliable than many determinations made under less favorable conditions. It is the purpose of this paper to outline the methods employed by the Aluminum Research Laboratories for the determination of some of these elastic constants, to list the values that have been determined for some of the wrought aluminum alloys, and to indicate the variations in the values that may be expected for some of the commercial products of these alloys.

  14. The Cosmological Constant and its Interpretation

    NASA Astrophysics Data System (ADS)

    Liddle, A.; Murdin, P.

    2002-12-01

    The cosmological constant was first introduced into the equations of general relativity by Einstein himself, who later famously criticized this move as his `greatest blunder'. His main motivation had been to allow cosmological models featuring a static universe, but this possibility swiftly became redundant with Edwin Hubble's discovery of the expansion of the universe. Despite this, it has period...

  15. Can compactifications solve the cosmological constant problem?

    NASA Astrophysics Data System (ADS)

    Hertzberg, Mark P.; Masoumi, Ali

    2016-06-01

    Recently, there have been claims in the literature that the cosmological constant problem can be dynamically solved by specific compactifications of gravity from higher-dimensional toy models. These models have the novel feature that in the four-dimensional theory, the cosmological constant Λ is much smaller than the Planck density and in fact accumulates at Λ = 0. Here we show that while these are very interesting models, they do not properly address the real cosmological constant problem. As we explain, the real problem is not simply to obtain Λ that is small in Planck units in a toy model, but to explain why Λ is much smaller than other mass scales (and combinations of scales) in the theory. Instead, in these toy models, all other particle mass scales have been either removed or sent to zero, thus ignoring the real problem. To this end, we provide a general argument that the included moduli masses are generically of order Hubble, so sending them to zero trivially sends the cosmological constant to zero. We also show that the fundamental Planck mass is being sent to zero, and so the central problem is trivially avoided by removing high energy physics altogether. On the other hand, by including various large mass scales from particle physics with a high fundamental Planck mass, one is faced with a real problem, whose only known solution involves accidental cancellations in a landscape.

  16. Spray Gun With Constant Mixing Ratio

    NASA Technical Reports Server (NTRS)

    Simpson, William G.

    1987-01-01

    Conceptual mechanism mounted in handle of spray gun maintains constant ratio between volumetric flow rates in two channels leading to spray head. With mechanism, possible to keep flow ratio near 1:1 (or another desired ratio) over range of temperatures, orifice or channel sizes, or clogging conditions.

  17. Asymptotically Vanishing Cosmological Constant in the Multiverse

    NASA Astrophysics Data System (ADS)

    Kawai, Hikaru; Okada, Takashi

    We study the problem of the cosmological constant in the context of the multiverse in Lorentzian space-time, and show that the cosmological constant will vanish in the future. This sort of argument was started by Sidney Coleman in 1989, and he argued that the Euclidean wormholes make the multiverse partition function a superposition of various values of the cosmological constant Λ, which has a sharp peak at Λ = 0. However, the implication of the Euclidean analysis to our Lorentzian space-time is unclear. With this motivation, we analyze the quantum state of the multiverse in Lorentzian space-time by the WKB method, and calculate the density matrix of our universe by tracing out the other universes. Our result predicts vanishing cosmological constant. While Coleman obtained the enhancement at Λ = 0 through the action itself, in our Lorentzian analysis the similar enhancement arises from the front factor of eiS in the universe wave function, which is in the next leading order in the WKB approximation.

  18. A tunable CMOS constant current source

    NASA Technical Reports Server (NTRS)

    Thelen, D.

    1991-01-01

    A constant current source has been designed which makes use of on chip electrically erasable memory to adjust the magnitude and temperature coefficient of the output current. The current source includes a voltage reference based on the difference between enhancement and depletion transistor threshold voltages. Accuracy is +/- 3% over the full range of power supply, process variations, and temperature using eight bits for tuning.

  19. Man's Size in Terms of Fundamental Constants.

    ERIC Educational Resources Information Center

    Press, William H.

    1980-01-01

    Reviews calculations that derive an order of magnitude expression for the size of man in terms of fundamental constants, assuming that man satifies these three properties: he is made of complicated molecules; he requires an atmosphere which is not hydrogen and helium; he is as large as possible. (CS)

  20. Factorization of the constants of motion

    NASA Astrophysics Data System (ADS)

    Nash, P. L.; Chen, L. Y.

    2006-08-01

    A complete set of first integrals, or constants of motion, for a model system is constructed using "factorization", as described below. The system is described by the effective Feynman Lagrangian L = 1/4 [m(x)double over dot(t) + 2m lambda(x)over dot(t) + partial derivative V-x(x(t))](2), with one of the simplest, nontrivial, potentials V (x) = 1/2m omega(2)x(2) selected for study. Four new, explicitly time-dependent, constants of the motion c(i +/-), i = 1, 2 are defined for this system. While partial derivative/partial derivative tc(i +/-) not equal 0, d/tc(i +/-) = partial derivative/partial derivative tc(i +/-) + (x)over dot partial derivative/partial derivative xc(i +/-) + (x)double over dot partial derivative/partial derivative xci +/- + ... = along an extremal of L. The Hamiltonian H is shown to equal a sum of products of the c(i +/-), and verifies partial derivative H/partial derivative t = 0. A second, functionally independent constant of motion is also constructed as a sum of the quadratic products of c(i +/-). It is shown that these derived constants of motion are in involution.

  1. Teaching Nanochemistry: Madelung Constants of Nanocrystals

    ERIC Educational Resources Information Center

    Baker, Mark D.; Baker, A. David

    2010-01-01

    The Madelung constants for binary ionic nanoparticles are determined. The computational method described here sums the Coulombic interactions of each ion in the particle without the use of partial charges commonly used for bulk materials. The results show size-dependent lattice energies. This is a useful concept in teaching how properties such as…

  2. Vacuum-Assisted, Constant-Force Exercise Device

    NASA Technical Reports Server (NTRS)

    Hansen, Christopher P.; Jensen, Scott

    2006-01-01

    The vacuum-assisted, constant-force exercise device (VAC-FED) has been proposed to fill a need for a safe, reliable exercise machine that would provide constant loads that could range from 20 to 250 lb (0.09 to 1.12 kN) with strokes that could range from 6 to 36 in. (0.15 to 0.91 m). The VAC-FED was originally intended to enable astronauts in microgravity to simulate the lifting of free weights, but it could just as well be used on Earth for simulated weight lifting and other constant-force exercises. Because the VAC-FED would utilize atmospheric/vacuum differential pressure instead of weights to generate force, it could weigh considerably less than either a set of free weights or a typical conventional exercise machine based on weights. Also, the use of atmospheric/ vacuum differential pressure to generate force would render the VAC-FED inherently safer, relative to free weights and to conventional exercise machines that utilize springs to generate forces. The overall function of the VAC-FED would be to generate a constant tensile force in an output cable, which would be attached to a bar, handle, or other exercise interface. The primary force generator in the VAC-FED would be a piston in a cylinder. The piston would separate a volume vented to atmosphere at one end of the cylinder from an evacuated volume at the other end of the cylinder (see figure). Hence, neglecting friction at the piston seals, the force generated would be nearly constant equal to the area of the piston multiplied by the atmospheric/vacuum differential pressure. In the vented volume in the cylinder, a direct-force cable would be looped around a pulley on the piston, doubling the stroke and halving the tension. One end of the direct-force cable would be anchored to a cylinder cap; the other end of the direct-force cable would be wrapped around a variable-ratio pulley that would couple tension to the output cable. As its name suggests, the variable-ratio pulley would contain a mechanism that

  3. Confined Dirac fermions in a constant magnetic field

    SciTech Connect

    Jellal, Ahmed; Alhaidari, Abdulaziz D.; Bahlouli, Hocine

    2009-07-15

    We obtain an exact solution of the Dirac equation in (2+1) dimensions in the presence of a constant magnetic field normal to the plane together with a two-dimensional Dirac-oscillator potential coupling. The solution space consists of positive- and negative-energy solutions, each of which splits into two disconnected subspaces depending on the sign of an azimuthal quantum number k=0,{+-}1,{+-}2,... and whether the cyclotron frequency is larger or smaller than the oscillator frequency. The spinor wave function is written in terms of the associated Laguerre polynomials. For negative k, the relativistic energy spectrum is infinitely degenerate due to the fact that it is independent of k. We compare our results with already published work and point out the relevance of these findings to a systematic formulation of the relativistic quantum Hall effect in a confining potential.

  4. Yang-Baxter equations with two Planck constants

    NASA Astrophysics Data System (ADS)

    Levin, A.; Olshanetsky, M.; Zotov, A.

    2016-01-01

    We consider Yang-Baxter equations arising from its associative analog and study the corresponding exchange relations. They generate finite-dimensional quantum algebras which have the form of coupled {{GL}}(N) Sklyanin elliptic algebras. Then we proceed to a natural generalization of the Baxter-Belavin quantum R-matrix to the case {{Mat}}{(N,{{C}})}\\otimes 2\\otimes {{Mat}}{(M,{{C}})}\\otimes 2. It can be viewed as symmetric form of {{GL}}({NM}) R-matrix in the sense that the Planck constant and the spectral parameter enter (almost) symmetrically. Such type (symmetric) R-matrices are also shown to satisfy the Yang-Baxter like quadratic and cubic equations.

  5. Constant-Fluence Area Scaling for Laser Propulsion

    SciTech Connect

    Sinko, John E.

    2008-04-28

    A series of experiments was conducted on polyoxymethylene (POM, trade name Delrin registered ) propellants in air at atmospheric pressure. A TEA CO{sub 2} laser with maximum output power up to 20 J was used to deliver 300 ns pulses of 10.6 {mu}m radiation to POM targets. Ablation at a constant fluence and a range of spot areas was achieved by varying combinations of the laser energy and spot size. Relevant empirical scaling laws governing laser propulsion parameters such as the momentum coupling coefficient (C{sub m}) and specific impulse (I{sub sp}) for spot areas within a range of about 0.05-0.25 cm{sup 2} are presented. Experimental measurements of imparted impulse, C{sub m}, I{sub sp}, and ablated mass per pulse were made using dynamic piezoelectric force sensors and a scientific balance. Finally, Schlieren ICCD imaging of shock waves and vapor plumes was performed and analyzed.

  6. A constant size extension drives bacterial cell size homeostasis

    PubMed Central

    Campos, Manuel; Surovtsev, Ivan V.; Kato, Setsu; Paintdakhi, Ahmad; Beltran, Bruno; Ebmeier, Sarah E.; Jacobs-Wagner, Christine

    2014-01-01

    Cell size control is an intrinsic feature of the cell cycle. In bacteria, cell growth and division are thought to be coupled through a cell size threshold. Here, we provide direct experimental evidence disproving the critical size paradigm. Instead, we show through single-cell microscopy and modeling that the evolutionarily distant bacteria Escherichia coli and Caulobacter crescentus achieve cell size homeostasis by growing on average the same amount between divisions, irrespective of cell length at birth. This simple mechanism provides a remarkably robust cell size control without the need of being precise, abating size deviations exponentially within a few generations. This size homeostasis mechanism is broadly applicable for symmetric and asymmetric divisions as well as for different growth rates. Furthermore, our data suggest that constant size extension is implemented at or close to division. Altogether, our findings provide fundamentally distinct governing principles for cell size and cell cycle control in bacteria. PMID:25480302

  7. Self-gravitating scalar breathers with a negative cosmological constant

    NASA Astrophysics Data System (ADS)

    Fodor, Gyula; Forgács, Péter; Grandclément, Philippe

    2015-07-01

    Breather-type (time-periodic and spatially localized) solutions with spherical symmetry are investigated in a massless scalar field theory coupled to Einstein's gravity with cosmological constant in d spatial dimensions imposing anti-de Sitter (AdS) asymptotics on space-time. Using a code constructed with the Kadath library that enables the use of spectral methods, the phase space of breather solutions is explored in detail for d =3 and d =4 . It is found that there are discrete families of solutions indexed by an integer and by their frequency. Using a time evolution code these AdS breathers are found to be stable for up to a critical central density, in analogy to boson stars. Using an analytical perturbative expansion small amplitude breathers are worked out for arbitrary dimensions d .

  8. Non-minimal coupling in Higgs–Yukawa model with asymptotically safe gravity

    NASA Astrophysics Data System (ADS)

    Oda, Kin-ya; Yamada, Masatoshi

    2016-06-01

    We study the fixed-point structure of the Higgs–Yukawa model, with its scalar being non-minimally coupled to the asymptotically safe gravity, using the functional renormalization group. We have obtained the renormalization group equations for the cosmological and Newton constants, the scalar mass squared and quartic coupling constant, and the Yukawa and non-minimal coupling constants, taking into account all the scalar, fermion, and graviton loops. We find that switching on the fermionic quantum fluctuations makes the non-minimal coupling constant irrelevant around the Gaussian-matter fixed point with asymptotically safe gravity.

  9. Constant current loop impedance measuring system that is immune to the effects of parasitic impedances

    NASA Technical Reports Server (NTRS)

    Anderson, Karl F. (Inventor)

    1994-01-01

    A constant current loop measuring system is provided for measuring a characteristic of an environment. The system comprises a first impedance positionable in the environment, a second impedance coupled in series with said first impedance and a parasitic impedance electrically coupled to the first and second impedances. A current generating device, electrically coupled in series with the first and second impedances, provides a constant current through the first and second impedances to produce first and second voltages across the first and second impedances, respectively, and a parasitic voltage across the parasitic impedance. A high impedance voltage measuring device measures a voltage difference between the first and second voltages independent of the parasitic voltage to produce a characteristic voltage representative of the characteristic of the environment.

  10. Construction of Lines of Constant Density and Constant Refractive Index for Ternary Liquid Mixtures.

    ERIC Educational Resources Information Center

    Tasic, Aleksandar Z.; Djordjevic, Bojan D.

    1983-01-01

    Demonstrates construction of density constant and refractive index constant lines in triangular coordinate system on basis of systematic experimental determinations of density and refractive index for both homogeneous (single-phase) ternary liquid mixtures (of known composition) and the corresponding binary compositions. Background information,…

  11. Brane induced gravity, its ghost and the cosmological constant problem

    SciTech Connect

    Hassan, S.F.; Strauss, Mikael von; Hofmann, Stefan E-mail: stefan.hofmann@physik.lmu.de

    2011-01-01

    ''Brane Induced Gravity'' is regarded as a promising framework for addressing the cosmological constant problem, but it also suffers from a ghost instability for parameter values that make it phenomenologically viable. We carry out a detailed analysis of codimension > 2 models employing gauge invariant variables in a flat background approximation. It is argued that using instead a curved background sourced by the brane would not resolve the ghost issue, unless a very specific condition is satisfied (if satisfiable at all). As for other properties of the model, from an explicit analysis of the 4-dimensional graviton propagator we extract a mass, a decay width and a momentum dependent modification of the gravitational coupling for the spin 2 mode. In the flat space approximation, the mass of the problematic spin 0 ghost is instrumental in filtering out a brane cosmological constant. The mass replaces a background curvature that would have had the same function. The optical theorem is used to demonstrate the suppression of graviton leakage into the uncompactified bulk. Then, we derive the 4-dimensional effective action for gravity and show that general covariance is spontaneously broken by the bulk-brane setup. This provides a natural realization of the gravitational Higgs mechanism. We also show that the addition of extrinsic curvature dependent terms has no bearing on linearized brane gravity.

  12. Dark coupling

    SciTech Connect

    Gavela, M.B.; Hernández, D.; Honorez, L. Lopez; Mena, O.; Rigolin, S. E-mail: d.hernandez@uam.es E-mail: omena@ific.uv.es

    2009-07-01

    The two dark sectors of the universe—dark matter and dark energy—may interact with each other. Background and linear density perturbation evolution equations are developed for a generic coupling. We then establish the general conditions necessary to obtain models free from non-adiabatic instabilities. As an application, we consider a viable universe in which the interaction strength is proportional to the dark energy density. The scenario does not exhibit ''phantom crossing'' and is free from instabilities, including early ones. A sizeable interaction strength is compatible with combined WMAP, HST, SN, LSS and H(z) data. Neutrino mass and/or cosmic curvature are allowed to be larger than in non-interacting models. Our analysis sheds light as well on unstable scenarios previously proposed.

  13. Thermoacoustic couple

    DOEpatents

    Wheatley, J.C.; Swift, G.W.; Migliori, A.

    1983-10-04

    An apparatus and method for determining acoustic power density level and its direction in a fluid using a single sensor are disclosed. The preferred embodiment of the apparatus, which is termed a thermoacoustic couple, consists of a stack of thin, spaced apart polymeric plates, selected ones of which include multiple bimetallic thermocouple junctions positioned along opposite end edges thereof. The thermocouple junctions are connected in series in the nature of a thermopile, and are arranged so as to be responsive to small temperature differences between the opposite edges of the plates. The magnitude of the temperature difference, as represented by the magnitude of the electrical potential difference generated by the thermopile, is found to be directly related to the level of acoustic power density in the gas.

  14. Henry's Law Constant of Organic Nitriles Measured with GC-FID

    NASA Astrophysics Data System (ADS)

    Brewer, B.; Gangoda, M.; Lee, S.

    2012-12-01

    Nitriles are important atmospheric VOCs that paly key roles in the atmospheric nitrogen cycle and secondary aerosol formation. Nitriles and their oxidation products also have serious health effects and thus are important air pollutants. Henry's law constant is an important physical and chemical parameter to determine how gas phase species participate into gas-to-particle conversion and cloud formation and affect human health. Yet, measurements of Henry's law constants of nitriles are entirely lacking. We have developed a simple measurement technique to detect Henry's law constants of organic compounds using gas chromatography flame ionization detector (GC-FID) coupled with a bubble column. In this presentation, we will show Henry's law constants of a number of atmospherically relevant organic nitrile compounds and their temperature dependence.

  15. An alternate side coupled structure for the Fermilab LINAC upgrade

    SciTech Connect

    Jurgens, T.G.; Kerns, Q.A.; Fritz, J.R.; May, M.A.

    1988-10-01

    An alternate side coupled structure (SCS) is being investigated. Comparisons are made to the traditional SCS. Mechanical comparisons include the relative cost and ease of fabrication. This discussion also addresses the use of CNC machining. Electrical comparisons include field distributions and coupling constants. Measured and numerical data are presented. The coupling constant of the alternate SCS is adjusted by independently changing either the separation of the coupling and accelerating cavity centers or the length of the slot. These two parameters are not independent in the traditional SCS design. 4 refs., 5 figs

  16. Components of Dielectric Constants of Ionic Liquids

    NASA Astrophysics Data System (ADS)

    Izgorodina, Ekaterina I.

    2010-03-01

    In this study ab initio-based methods were used to calculate electronic polarizability and dipole moment of ions comprising ionic liquids [1]. The test set consisted of a number of anions and cations routinely used in the ionic liquid field. As expected, in the first approximation electronic polarizability volume turned out to be proportional to the ion volume, also calculated by means of ab initio theory. For ionic liquid ions this means that their electronic polarizabilities are at least an order of magnitude larger than those of traditional molecular solvents like water and DMSO. On this basis it may seem surprising that most of ionic liquids actually possess modest dielectric constants, falling the narrow range between 10 and 15. The lower than first expected dielectric constants of ionic liquids has been explored in this work via explicit calculations of the electronic and orientation polarization contributions to the dielectric constant using the Clausius-Mossotti equation and the Onsager theory for polar dielectric materials. We determined that the electronic polarization contribution to the dielectric constant was rather small (between 1.9 and 2.2) and comparable to that of traditional molecular solvents. These findings were explained by the interplay between two quantities, increasing electronic polarizability of ions and decreasing number of ions present in the unit volume; although electronic polarizability is usually relatively large for ionic liquid ions, due to their size there are fewer ions present per unit volume (by a factor of 10 compared to traditional molecular solvents). For ionic liquids consisting of ions with zero (e.g. BF4) or negligible (e.g. NTf2) dipole moments the calculated orientation polarization does not contribute enough to account for the whole of the measured values of the dielectric constants. We suggest that in ionic liquids an additional type of polarization, ``ionic polarization'', originating from small movements of the

  17. Constant-complexity stochastic simulation algorithm with optimal binning

    SciTech Connect

    Sanft, Kevin R.; Othmer, Hans G.

    2015-08-21

    At the molecular level, biochemical processes are governed by random interactions between reactant molecules, and the dynamics of such systems are inherently stochastic. When the copy numbers of reactants are large, a deterministic description is adequate, but when they are small, such systems are often modeled as continuous-time Markov jump processes that can be described by the chemical master equation. Gillespie’s Stochastic Simulation Algorithm (SSA) generates exact trajectories of these systems, but the amount of computational work required for each step of the original SSA is proportional to the number of reaction channels, leading to computational complexity that scales linearly with the problem size. The original SSA is therefore inefficient for large problems, which has prompted the development of several alternative formulations with improved scaling properties. We describe an exact SSA that uses a table data structure with event time binning to achieve constant computational complexity with respect to the number of reaction channels for weakly coupled reaction networks. We present a novel adaptive binning strategy and discuss optimal algorithm parameters. We compare the computational efficiency of the algorithm to existing methods and demonstrate excellent scaling for large problems. This method is well suited for generating exact trajectories of large weakly coupled models, including those that can be described by the reaction-diffusion master equation that arises from spatially discretized reaction-diffusion processes.

  18. Constant-complexity stochastic simulation algorithm with optimal binning

    NASA Astrophysics Data System (ADS)

    Sanft, Kevin R.; Othmer, Hans G.

    2015-08-01

    At the molecular level, biochemical processes are governed by random interactions between reactant molecules, and the dynamics of such systems are inherently stochastic. When the copy numbers of reactants are large, a deterministic description is adequate, but when they are small, such systems are often modeled as continuous-time Markov jump processes that can be described by the chemical master equation. Gillespie's Stochastic Simulation Algorithm (SSA) generates exact trajectories of these systems, but the amount of computational work required for each step of the original SSA is proportional to the number of reaction channels, leading to computational complexity that scales linearly with the problem size. The original SSA is therefore inefficient for large problems, which has prompted the development of several alternative formulations with improved scaling properties. We describe an exact SSA that uses a table data structure with event time binning to achieve constant computational complexity with respect to the number of reaction channels for weakly coupled reaction networks. We present a novel adaptive binning strategy and discuss optimal algorithm parameters. We compare the computational efficiency of the algorithm to existing methods and demonstrate excellent scaling for large problems. This method is well suited for generating exact trajectories of large weakly coupled models, including those that can be described by the reaction-diffusion master equation that arises from spatially discretized reaction-diffusion processes.

  19. Optical constants of liquid and solid methane

    NASA Technical Reports Server (NTRS)

    Martonchik, John V.; Orton, Glenn S.

    1994-01-01

    The optical constants n(sub r) + in(sub i) of liquid methane and phase 1 solid methane were determined over the entire spectral range by the use of various data sources published in the literature. Kramers-Kronig analyses were performed on the absorption spectra of liquid methane at the boiling point (111 K) and the melting point (90 K) and on the absorption spectra of phase 1 solid methane at the melting point and at 30 K. Measurements of the static dielectric constant at these temperatures and refractive indices determined over limited spectral ranges were used as constraints in the analyses. Applications of methane optical properties to studies of outer solar system bodies are described.

  20. Some Dynamical Effects of the Cosmological Constant

    NASA Astrophysics Data System (ADS)

    Axenides, M.; Floratos, E. G.; Perivolaropoulos, L.

    Newton's law gets modified in the presence of a cosmological constant by a small repulsive term (antigravity) that is proportional to the distance. Assuming a value of the cosmological constant consistent with the recent SnIa data (Λ~=10-52 m-2), we investigate the significance of this term on various astrophysical scales. We find that on galactic scales or smaller (less than a few tens of kpc), the dynamical effects of the vacuum energy are negligible by several orders of magnitude. On scales of 1 Mpc or larger however we find that the vacuum energy can significantly affect the dynamics. For example we show that the velocity data in the local group of galaxies correspond to galactic masses increased by 35% in the presence of vacuum energy. The effect is even more important on larger low density systems like clusters of galaxies or superclusters.

  1. BOREAS RSS-17 Dielectric Constant Profile Measurements

    NASA Technical Reports Server (NTRS)

    Hall, Forrest G. (Editor); Nickeson, Jaime (Editor); McDonald, Kyle C.; Zimmerman, Reiner; Way, JoBea

    2000-01-01

    The BOREAS RSS-17 team acquired and analyzed imaging radar data from the ESA's ERS-1 over a complete annual cycle at the BOREAS sites in Canada in 1994 to detect shifts in radar backscatter related to varying environmental conditions. This data set consists of dielectric constant profile measurements from selected trees at various BOREAS flux tower sites. The relative dielectric constant was measured at C-band (frequency = 5 GHz) as a function of depth into the trunk of three trees at each site, Measurements were made during April 1994 with an Applied Microwave Corporation field PDP fitted with a 0.358-cm (0.141-inch) diameter coaxial probe tip. The data are available in tabular ASCII files. The data files are available on a CD-ROM (see document number 20010000884), or from the Oak Ridge National Laboratory (ORNL) Distributed Active Archive Center (DAAC).

  2. Dielectric Constant Measurements for Characterizing Lunar Soils

    NASA Technical Reports Server (NTRS)

    Anderson, Robert C.; Buehler, M.; Seshadri, S.; Kuhlman, G.; Schaap, M.

    2005-01-01

    The return to the Moon has ignited the need to characterize the lunar regolith using fast, reliable in-situ methods. Characterizing the physical properties of the rocks and soils can be very difficult because of the many complex parameters that influence the measurements. In particular, soil electrical property measurements are influenced by temperature, mineral type, grain size, porosity, and soil conductivity. Determining the dielectric constant of lunar materials may be very important in providing quick characterization of surface deposits, especially for the Moon. A close examination of the lunar regolith samples collected by the Apollo astronauts indicates that the rocks and soils on the Moon are dominated by silicates and oxides. In this presentation, we will show that determining the dielectric constant measurements can provide a simple, quick detection method for minerals that contain titanium, iron, and water. Their presence is manifest by an unusually large imaginary permittivity.

  3. Cosmological constant in the quantum multiverse

    NASA Astrophysics Data System (ADS)

    Larsen, Grant; Nomura, Yasunori; Roberts, Hannes L. L.

    2011-12-01

    Recently, a new framework for describing the multiverse has been proposed which is based on the principles of quantum mechanics. The framework allows for well-defined predictions, both regarding global properties of the universe and outcomes of particular experiments, according to a single probability formula. This provides complete unification of the eternally inflating multiverse and many worlds in quantum mechanics. In this paper, we elucidate how cosmological parameters can be calculated in this framework, and study the probability distribution for the value of the cosmological constant. We consider both positive and negative values, and find that the observed value is consistent with the calculated distribution at an order of magnitude level. In particular, in contrast to the case of earlier measure proposals, our framework prefers a positive cosmological constant over a negative one. These results depend only moderately on how we model galaxy formation and life evolution therein.

  4. Hyperscaling violation and the shear diffusion constant

    NASA Astrophysics Data System (ADS)

    Kolekar, Kedar S.; Mukherjee, Debangshu; Narayan, K.

    2016-09-01

    We consider holographic theories in bulk (d + 1)-dimensions with Lifshitz and hyperscaling violating exponents z , θ at finite temperature. By studying shear gravitational modes in the near-horizon region given certain self-consistent approximations, we obtain the corresponding shear diffusion constant on an appropriately defined stretched horizon, adapting the analysis of Kovtun, Son and Starinets. For generic exponents with d - z - θ > - 1, we find that the diffusion constant has power law scaling with the temperature, motivating us to guess a universal relation for the viscosity bound. When the exponents satisfy d - z - θ = - 1, we find logarithmic behaviour. This relation is equivalent to z = 2 +deff where deff =di - θ is the effective boundary spatial dimension (and di = d - 1 the actual spatial dimension). It is satisfied by the exponents in hyperscaling violating theories arising from null reductions of highly boosted black branes, and we comment on the corresponding analysis in that context.

  5. On determining dose rate constants spectroscopically

    SciTech Connect

    Rodriguez, M.; Rogers, D. W. O.

    2013-01-15

    Purpose: To investigate several aspects of the Chen and Nath spectroscopic method of determining the dose rate constants of {sup 125}I and {sup 103}Pd seeds [Z. Chen and R. Nath, Phys. Med. Biol. 55, 6089-6104 (2010)] including the accuracy of using a line or dual-point source approximation as done in their method, and the accuracy of ignoring the effects of the scattered photons in the spectra. Additionally, the authors investigate the accuracy of the literature's many different spectra for bare, i.e., unencapsulated {sup 125}I and {sup 103}Pd sources. Methods: Spectra generated by 14 {sup 125}I and 6 {sup 103}Pd seeds were calculated in vacuo at 10 cm from the source in a 2.7 Multiplication-Sign 2.7 Multiplication-Sign 0.05 cm{sup 3} voxel using the EGSnrc BrachyDose Monte Carlo code. Calculated spectra used the initial photon spectra recommended by AAPM's TG-43U1 and NCRP (National Council of Radiation Protection and Measurements) Report 58 for the {sup 125}I seeds, or TG-43U1 and NNDC(2000) (National Nuclear Data Center, 2000) for {sup 103}Pd seeds. The emitted spectra were treated as coming from a line or dual-point source in a Monte Carlo simulation to calculate the dose rate constant. The TG-43U1 definition of the dose rate constant was used. These calculations were performed using the full spectrum including scattered photons or using only the main peaks in the spectrum as done experimentally. Statistical uncertainties on the air kerma/history and the dose rate/history were Less-Than-Or-Slanted-Equal-To 0.2%. The dose rate constants were also calculated using Monte Carlo simulations of the full seed model. Results: The ratio of the intensity of the 31 keV line relative to that of the main peak in {sup 125}I spectra is, on average, 6.8% higher when calculated with the NCRP Report 58 initial spectrum vs that calculated with TG-43U1 initial spectrum. The {sup 103}Pd spectra exhibit an average 6.2% decrease in the 22.9 keV line relative to the main peak when

  6. Simple liquid models with corrected dielectric constants.

    PubMed

    Fennell, Christopher J; Li, Libo; Dill, Ken A

    2012-06-14

    Molecular simulations often use explicit-solvent models. Sometimes explicit-solvent models can give inaccurate values for basic liquid properties, such as the density, heat capacity, and permittivity, as well as inaccurate values for molecular transfer free energies. Such errors have motivated the development of more complex solvents, such as polarizable models. We describe an alternative here. We give new fixed-charge models of solvents for molecular simulations--water, carbon tetrachloride, chloroform, and dichloromethane. Normally, such solvent models are parametrized to agree with experimental values of the neat liquid density and enthalpy of vaporization. Here, in addition to those properties, our parameters are chosen to give the correct dielectric constant. We find that these new parametrizations also happen to give better values for other properties, such as the self-diffusion coefficient. We believe that parametrizing fixed-charge solvent models to fit experimental dielectric constants may provide better and more efficient ways to treat solvents in computer simulations.

  7. Pole placement with constant gain output feedback

    NASA Technical Reports Server (NTRS)

    Sridhar, B.; Lindorff, D. P.

    1972-01-01

    Given a linear time invariant multivariable system with m inputs and p outputs, it was shown that p closed loop poles of the system can be preassigned arbitrarily using constant gain output feedback provided (A circumflex, B circumflex) is controllable. These data show that if (A circumflex, B circumflex, C circumflex) is controllable and observable, and Rank B circumflex = m, Rank C circumflex = p, then max (m,p) poles of the system can be assigned arbitarily using constant gain output feedback. Further, it is shown that in some cases more than max (m,p) poles can be arbitrarily assigned. A least square design technique is outlined to approximate the desired pole locations when it is not possible to place all the poles.

  8. A damped simple pendulum of constant amplitude

    NASA Astrophysics Data System (ADS)

    Abdelkader, Mostafa A.

    1984-03-01

    A simple pendulum acted on by gravity and subjected to a resistance proportional to the velocity of the bob is considered. If the length of the string and the mass of the bob are held constant, the amplitude of the bob decreases gradually because of the damping. We want to keep the maximum swing of the bob constant for all time; this we achieve by varying the length of the string, the mass of the bob or both. The key to the solution of our problem is a second-order nonlinear differential equation having arbitrary nonlinearity and an arbitrary coefficient function, for which we give the exact integral. We also give an application of this differential equation to a boundary-value problem for a nonlinear generalization of a hypergeometric equation.

  9. Gravitational constant in multiple field gravity

    SciTech Connect

    Abedi, Habib; Abbassi, Amir M. E-mail: amabasi@khayam.ut.ac.ir

    2015-05-01

    In the present study, we consider general form of the Lagrangian  f(R, φ{sup I}, X) , that is a function of the Ricci scalar, multiple scalar fields and non-canonical kinetic terms. We obtain the effective Newton's constant deep inside the Hubble radius. We use Jordan and Einstein frames, and study the conservation of energy-momentum tensor.

  10. Mars Pathfinder Project: Planetary Constants and Models

    NASA Technical Reports Server (NTRS)

    Vaughan, Robin

    1995-01-01

    This document provides a common set of astrodynamic constants and planetary models for use by the Mars Pathfinder Project. It attempts to collect in a single reference all the quantities and models in use across the project during development and for mission operations. These models are central to the navigation and mission design functions, but they are also used in other aspects of the project such as science observation planning and data reduction.

  11. Casimir effect in spacetimes with cosmological constant

    NASA Astrophysics Data System (ADS)

    Bessa, C. H. G.; Bezerra, V. B.; Silva, J. C. J.

    2016-06-01

    In this work, we study the influence of the gravitational field induced by the presence of a cosmological constant Λ on the Casimir energy density. We consider two metrics with the presence of the Λ-term, namely de Sitter and Schwarzschild-de Sitter (SdS). In the former case, we consider a conformal de Sitter spacetime and in the last one, a weak gravitational SdS spacetime.

  12. Dynamical Cosmological Constant in R 3 Gravity

    NASA Astrophysics Data System (ADS)

    Zare, Nasser; Fathi, Mohsen

    2015-03-01

    In this paper, we go through the famous f( R) theories of gravity, but keeping a peculiar one, namely R 3 modification. Moreover, instead of a coordinate free cosmological parameter, we take it to be a function of time. Having all these stuff, we investigate the notions of standard cosmology model, in the context of R 3 modification to general relativity, and in various regimes, we study the dynamical cosmological constant.

  13. First-principles theory of electron-spin fluctuation coupling and superconducting instabilities in iron selenide

    NASA Astrophysics Data System (ADS)

    Lischner, Johannes; Bazhirov, Timur; MacDonald, Allan H.; Cohen, Marvin L.; Louie, Steven G.

    2015-01-01

    We present first-principles calculations of the coupling of quasiparticles to spin fluctuations in iron selenide and discuss which types of superconducting instabilities this coupling gives rise to. We find that strong antiferromagnetic stripe-phase spin fluctuations lead to large coupling constants for superconducting gaps with s± symmetry, but these coupling constants are significantly reduced by other spin fluctuations with small wave vectors. An accurate description of this competition and an inclusion of band-structure and Stoner parameter renormalization effects lead to a value of the coupling constant for an s±-symmetric gap which can produce a superconducting transition temperature consistent with experimental measurements.

  14. Universal constant for heat production in protists.

    PubMed

    Johnson, Matthew D; Völker, Jens; Moeller, Holly V; Laws, Edward; Breslauer, Kenneth J; Falkowski, Paul G

    2009-04-21

    Using a high sensitivity differential scanning calorimeter in isothermal mode, we directly measured heat production in eukaryotic protists from 5 phyla spanning over 5 orders of magnitude in carbon biomass and 8 orders of magnitude in cell volume. Our results reveal that metabolic heat production normalized to cell mass is virtually constant in these organisms, with a median of 0.037 pW pg C(-1) (95% confidence interval = 0.022-0.061 pW pg C(-1)) at 5 degrees C. Contrary to allometric models, the relationship between heat production and cell carbon content or surface area is isometric (scaling exponents, 1.056 and 1.057, respectively). That heat production per unit cell surface area is constant suggests that heat flux through the cell surface is effectively instantaneous, and hence that cells are isothermal with their environment. The results further suggest that allometric models of metabolism based on metazoans are not applicable to protists, and that the underlying metabolic processes in the latter polyphyletic group are highly constrained by evolutionary selection. We propose that the evolutionary constraint leading to a universally constant heat production in single-celled eukaryotes is related to cytoplasmic packaging of organelles and surface area to volume relationships controlling diffusion of resources to these organelles.

  15. DFT molecular modeling and NMR conformational analysis of a new longipinenetriolone diester

    NASA Astrophysics Data System (ADS)

    Cerda-García-Rojas, Carlos M.; Guerra-Ramírez, Diana; Román-Marín, Luisa U.; Hernández-Hernández, Juan D.; Joseph-Nathan, Pedro

    2006-05-01

    The structure and conformational behavior of the new natural compound (4 R,5 S,7 S,8 R,9 S,10 R,11 R)-longipin-2-en-7,8,9-triol-1-one 7-angelate-9-isovalerate (1) isolated from Stevia eupatoria, were studied by molecular modeling and NMR spectroscopy. A Monte Carlo search followed by DFT calculations at the B3LYP/6-31G* level provided the theoretical conformations of the sesquiterpene framework, which were in full agreement with results derived from the 1H- 1H coupling constant analysis.

  16. Measurement of State-Specific Association Constants in Allosteric Sensors through Molecular Stapling and NMR.

    PubMed

    Moleschi, Kody J; Akimoto, Madoka; Melacini, Giuseppe

    2015-08-26

    Allostery is a ubiquitous mechanism to control biological function and arises from the coupling of inhibitory and binding equilibria. The extent of coupling reflects the inactive vs active state selectivity of the allosteric effector. Hence, dissecting allosteric determinants requires quantification of state-specific association constants. However, observed association constants are typically population-averages, reporting on overall affinities but not on allosteric coupling. Here we propose a general method to measure state-specific association constants in allosteric sensors based on three key elements, i.e., state-selective molecular stapling through disulfide bridges, competition binding saturation transfer experiments and chemical shift correlation analyses to gauge state populations. The proposed approach was applied to the prototypical cyclic adenosine monophosphate (cAMP)-dependent protein kinase (PKA-RIα), for which the structures of the inactive and active states are available, as needed to design the state-selective disulfide bridges. Surprisingly, the PKA-RIα state-specific association constants are comparable to those of a structurally homologous domain with ∼10(3)-fold lower cAMP-affinity, suggesting that the affinity difference arises primarily from changes in the position of the dynamic apo inhibitory equilibrium.

  17. Retrofitting gear couplings with diaphragm couplings

    SciTech Connect

    Mancuso, J.R. )

    1988-10-01

    Retrofitting a coupling should not be an afterthought when upgrading a system. Couplings are an integral part of a drive train and should be a major consideration. This article discusses guidelines that should be used when replacing gear couplings with diaphragm couplings. Reviewed are the coupling selection process: how and to what extent the desired diaphragm couplings should be matched to the gear coupling. Also discussed are the details of coupling modification that can be made to accommodate system performance. Included are how changes in materials, configuration and design can help tune a diaphragm coupling to meet the characteristics of the previous gear couplings. The article also discusses the retrofit process for a specific syngas train at International Minerals and Chemical Corp., Sterlington, La.

  18. Microwave fidelity studies by varying antenna coupling

    NASA Astrophysics Data System (ADS)

    Köber, B.; Kuhl, U.; Stöckmann, H.-J.; Gorin, T.; Savin, D. V.; Seligman, T. H.

    2010-09-01

    The fidelity decay in a microwave billiard is considered, where the coupling to an attached antenna is varied. The resulting quantity, coupling fidelity, is experimentally studied for three different terminators of the varied antenna: a hard-wall reflection, an open wall reflection, and a 50Ω load, corresponding to a totally open channel. The model description in terms of an effective Hamiltonian with a complex coupling constant is given. Quantitative agreement is found with the theory obtained from a modified VWZ approach [J. J. M. Verbaarschot , Phys. Rep. 129, 367 (1985)10.1016/0370-1573(85)90070-5].

  19. Stability regions for synchronized τ-periodic orbits of coupled maps with coupling delay τ

    NASA Astrophysics Data System (ADS)

    Karabacak, Özkan; Alikoç, Baran; Atay, Fatihcan M.

    2016-09-01

    Motivated by the chaos suppression methods based on stabilizing an unstable periodic orbit, we study the stability of synchronized periodic orbits of coupled map systems when the period of the orbit is the same as the delay in the information transmission between coupled units. We show that the stability region of a synchronized periodic orbit is determined by the Floquet multiplier of the periodic orbit for the uncoupled map, the coupling constant, the smallest and the largest Laplacian eigenvalue of the adjacency matrix. We prove that the stabilization of an unstable τ-periodic orbit via coupling with delay τ is possible only when the Floquet multiplier of the orbit is negative and the connection structure is not bipartite. For a given coupling structure, it is possible to find the values of the coupling strength that stabilizes unstable periodic orbits. The most suitable connection topology for stabilization is found to be the all-to-all coupling. On the other hand, a negative coupling constant may lead to destabilization of τ-periodic orbits that are stable for the uncoupled map. We provide examples of coupled logistic maps demonstrating the stabilization and destabilization of synchronized τ-periodic orbits as well as chaos suppression via stabilization of a synchronized τ-periodic orbit.

  20. Deflation of the cosmological constant associated with inflation and dark energy

    NASA Astrophysics Data System (ADS)

    Geng, Chao-Qiang; Lee, Chung-Chi

    2016-06-01

    In order to solve the fine-tuning problem of the cosmological constant, we propose a simple model with the vacuum energy non-minimally coupled to the inflaton field. In this model, the vacuum energy decays to the inflaton during pre-inflation and inflation eras, so that the cosmological constant effectively deflates from the Planck mass scale to a much smaller one after inflation and plays the role of dark energy in the late-time of the universe. We show that our deflationary scenario is applicable to arbitrary slow-roll inflation models. We also take two specific inflation potentials to illustrate our results.

  1. Rate constants, timescales, and free energy barriers

    NASA Astrophysics Data System (ADS)

    Salamon, Peter; Wales, David; Segall, Anca; Lai, Yi-An; Schön, J. Christian; Hoffmann, Karl Heinz; Andresen, Bjarne

    2016-01-01

    The traditional connection between rate constants and free energy landscapes is extended to define effective free energy landscapes relevant on any chosen timescale. Although the Eyring-Polanyi transition state theory specifies a fixed timescale of τ=h/kBT}, we introduce instead the timescale of interest for the system in question, e.g. the observation time. The utility of drawing such landscapes using a variety of timescales is illustrated by the example of Holliday junction resolution. The resulting free energy landscapes are easier to interpret, clearly reveal observation time dependent effects like coalescence of short-lived states, and reveal features of interest for the specific system more clearly.

  2. Optical constants of minerals and rocks.

    PubMed

    Aronson, J R; Strong, P F

    1975-12-01

    Lorentz line parameters (and estimates of their standard deviations) have been empirically derived from measured reflectance data for muscovite mica, an anorthosite, a diopsidic pyroxenite, an almandite-pyrope garnet, and a soda lime glass. These parameters provide a useful starting point for computer calculations requiring optical constants as a function of frequency and are therefore given here. A novel method of fitting the reflectance data by least squares is described in detail, as is the statistical procedure for estimating the standard deviations of the parameters found. PMID:20155132

  3. The fine structure constant and habitable planets

    NASA Astrophysics Data System (ADS)

    Sandora, McCullen

    2016-08-01

    We use the existence of habitable planets to impose anthropic requirements on the fine structure constant, α. To this effect, we present two considerations that restrict its value to be very near the one observed. The first, that the end product of stellar fusion is iron and not one of its neighboring elements, restricts α-1 to be 145± 50. The second, that radiogenic heat in the Earth's interior remains adequately productive for billions of years, restricts it to be 145±9. A connection with the grand unified theory window is discussed, effectively providing a route to probe ultra-high energy physics with upcoming advances in planetary science.

  4. Constant-Elasticity-of-Substitution Simulation

    NASA Technical Reports Server (NTRS)

    Reiter, G.

    1986-01-01

    Program simulates constant elasticity-of-substitution (CES) production function. CES function used by economic analysts to examine production costs as well as uncertainties in production. User provides such input parameters as price of labor, price of capital, and dispersion levels. CES minimizes expected cost to produce capital-uncertainty pair. By varying capital-value input, one obtains series of capital-uncertainty pairs. Capital-uncertainty pairs then used to generate several cost curves. CES program menu driven and features specific print menu for examining selected output curves. Program written in BASIC for interactive execution and implemented on IBM PC-series computer.

  5. Optical constants of minerals and rocks.

    PubMed

    Aronson, J R; Strong, P F

    1975-12-01

    Lorentz line parameters (and estimates of their standard deviations) have been empirically derived from measured reflectance data for muscovite mica, an anorthosite, a diopsidic pyroxenite, an almandite-pyrope garnet, and a soda lime glass. These parameters provide a useful starting point for computer calculations requiring optical constants as a function of frequency and are therefore given here. A novel method of fitting the reflectance data by least squares is described in detail, as is the statistical procedure for estimating the standard deviations of the parameters found.

  6. Characterization of a constant current charge detector.

    PubMed

    Mori, Masanobu; Chen, Yongjing; Ohira, Shin-Ichi; Dasgupta, Purnendu K

    2012-12-15

    Ion exchangers are ionic equivalents of doped semiconductors, where cations and anions are equivalents of holes and electrons as charge carriers in solid state semiconductors. We have previously demonstrated an ion exchange membrane (IEM) based electrolyte generator which behaves similar to a light-emitting diode and a charge detector (ChD) which behaves analogous to a p-i-n photodiode. The previous work on the charge detector, operated at a constant voltage, established its unique ability to respond to the charge represented by the analyte ions regardless of their redox properties, rather than to their conductivities. It also suggested that electric field induced dissociation (EFID) of water occurs at one or both ion exchange membranes. A logical extension is to study the behavior of the same device, operated in a constant current mode (ChD(i)). The evidence indicates that in the present operational mode the device also responds to the charge represented by the analytes and not their conductivity. Injection of a base into a charge detector operated in the constant voltage mode was not previously examined; in the constant current mode, base injection appears to inhibit EFID. The effects of applied current, analyte residence time and outer channel fluid composition were individually examined; analyte ions of different mobilities as well as affinities for the respective IEMs were used. While the exact behavior is somewhat dependent on the applied current, strong electrolytes, both acids and salts, respond the highest and in a near-uniform fashion, weak acids and their salts respond in an intermediate fashion and bases produce the lowest responses. A fundamentally asymmetric behavior is observed. Injected bases but not injected acids produce a poor response; the effects of incorporating a strong base as the electrolyte in the anion exchange membrane (AEM) compartment is far greater than incorporating an acid in the cation exchange membrane (CEM) compartment. These

  7. TASI Lectures on the cosmological constant

    SciTech Connect

    Bousso, Raphael; Bousso, Raphael

    2007-08-30

    The energy density of the vacuum, Lambda, is at least 60 orders of magnitude smaller than several known contributions to it. Approaches to this problem are tightly constrained by data ranging from elementary observations to precision experiments. Absent overwhelming evidence to the contrary, dark energy can only be interpreted as vacuum energy, so the venerable assumption that Lambda=0 conflicts with observation. The possibility remains that Lambda is fundamentally variable, though constant over large spacetime regions. This can explain the observed value, but only in a theory satisfying a number of restrictive kinematic and dynamical conditions. String theory offers a concrete realization through its landscape of metastable vacua.

  8. The fine structure constant and habitable planets

    NASA Astrophysics Data System (ADS)

    Sandora, McCullen

    2016-08-01

    We use the existence of habitable planets to impose anthropic requirements on the fine structure constant, α. To this effect, we present two considerations that restrict its value to be very near the one observed. The first, that the end product of stellar fusion is iron and not one of its neighboring elements, restricts α‑1 to be 145± 50. The second, that radiogenic heat in the Earth's interior remains adequately productive for billions of years, restricts it to be 145±9. A connection with the grand unified theory window is discussed, effectively providing a route to probe ultra-high energy physics with upcoming advances in planetary science.

  9. The Boltzmann constant from a snifter

    NASA Astrophysics Data System (ADS)

    Tyukodi, B.; Sárközi, Zs; Néda, Z.; Tunyagi, A.; Györke, E.

    2012-03-01

    Evaporation of a small glass of ethylic alcohol is studied both experimentally and through an elementary thermal physics approach. For a cylindrical beaker and no air flow in the room, a simple quadratic relation is found between the evaporation time and the mass of evaporated liquid. This problem and the obtained results offer excellent possibilities for simple student experiments and for testing basic principles of thermal physics. As an example, we use the obtained results for estimating the value of the Boltzmann constant from evaporation experiments.

  10. Radiation balances and the solar constant

    NASA Astrophysics Data System (ADS)

    Crommelynck, D.

    1981-07-01

    The radiometric concepts are defined in order to consider various types of radiation balances and relate them to the diabetic form of the energy balance. Variability in space and time of the components of the radiation field are presented. A specific concept for sweeping which is tailored to the requirements is proposed. Finally, after establishing the truncated character of the present knowledge of the radiation balance. The results of the last observations of the solar constant are given. Ground and satellite measurement techniques are discussed.

  11. Optical constants of minerals and rocks

    NASA Technical Reports Server (NTRS)

    Aronson, J. R.; Strong, P. F.

    1975-01-01

    Lorentz line parameters (and estimates of their standard deviations) have been empirically derived from measured reflectance data for muscovite mica, an anorthosite, a diopsidic pyroxenite, an almandite-pyrope garnet, and a soda lime glass. These parameters provide a useful starting point for computer calculations requiring optical constants as a function and are therefore given here. A novel method of fitting the reflectance data by least squares is described in detail, as is the statistical procedure for estimating the standard deviations of the parameters found.

  12. Variable energy constant current accelerator structure

    DOEpatents

    Anderson, Oscar A.

    1990-01-01

    A variable energy, constant current ion beam accelerator structure is disclosed comprising an ion source capable of providing the desired ions, a pre-accelerator for establishing an initial energy level, a matching/pumping module having means for focusing means for maintaining the beam current, and at least one main accelerator module for continuing beam focus, with means capable of variably imparting acceleration to the beam so that a constant beam output current is maintained independent of the variable output energy. In a preferred embodiment, quadrupole electrodes are provided in both the matching/pumping module and the one or more accelerator modules, and are formed using four opposing cylinder electrodes which extend parallel to the beam axis and are spaced around the beam at 90.degree. intervals with opposing electrodes maintained at the same potential. Adjacent cylinder electrodes of the quadrupole structure are maintained at different potentials to thereby reshape the cross section of the charged particle beam to an ellipse in cross section at the mid point along each quadrupole electrode unit in the accelerator modules. The beam is maintained in focus by alternating the major axis of the ellipse along the x and y axis respectively at adjacent quadrupoles. In another embodiment, electrostatic ring electrodes may be utilized instead of the quadrupole electrodes.

  13. Holographic dark energy with cosmological constant

    NASA Astrophysics Data System (ADS)

    Hu, Yazhou; Li, Miao; Li, Nan; Zhang, Zhenhui

    2015-08-01

    Inspired by the multiverse scenario, we study a heterotic dark energy model in which there are two parts, the first being the cosmological constant and the second being the holographic dark energy, thus this model is named the ΛHDE model. By studying the ΛHDE model theoretically, we find that the parameters d and Ωhde are divided into a few domains in which the fate of the universe is quite different. We investigate dynamical behaviors of this model, and especially the future evolution of the universe. We perform fitting analysis on the cosmological parameters in the ΛHDE model by using the recent observational data. We find the model yields χ2min=426.27 when constrained by Planck+SNLS3+BAO+HST, comparable to the results of the HDE model (428.20) and the concordant ΛCDM model (431.35). At 68.3% CL, we obtain -0.07<ΩΛ0<0.68 and correspondingly 0.04<Ωhde0<0.79, implying at present there is considerable degeneracy between the holographic dark energy and cosmological constant components in the ΛHDE model.

  14. Ventricular fibrillation time constant for swine.

    PubMed

    Wu, Jiun-Yan; Nimunkar, Amit J; Sun, Hongyu; O'Rourke, Ann; Huebner, Shane; Will, James A; Webster, John G

    2008-10-01

    The strength-duration curve for cardiac excitation can be modeled by a parallel resistor-capacitor circuit that has a time constant. Experiments on six pigs were performed by delivering current from the X26 Taser dart at a distance from the heart to cause ventricular fibrillation (VF). The X26 Taser is an electromuscular incapacitation device (EMD), which generates about 50 kV and delivers a pulse train of about 15-19 pulses s(-1) with a pulse duration of about 150 micros and peak current about 2 A. Similarly a continuous 60 Hz alternating current of the amplitude required to cause VF was delivered from the same distance. The average current and duration of the current pulse were estimated in both sets of experiments. The strength-duration equation was solved to yield an average time constant of 2.87 ms +/- 1.90 (SD). Results obtained may help in the development of safety standards for future electromuscular incapacitation devices (EMDs) without requiring additional animal tests.

  15. Superintegrable systems on spaces of constant curvature

    SciTech Connect

    Gonera, Cezary Kaszubska, Magdalena

    2014-07-15

    Construction and classification of two-dimensional (2D) superintegrable systems (i.e. systems admitting, in addition to two global integrals of motion guaranteeing the Liouville integrability, the third global and independent one) defined on 2D spaces of constant curvature and separable in the so-called geodesic polar coordinates are presented. The method proposed is applicable to any value of curvature including the case of Euclidean plane, sphere and hyperbolic plane. The main result is a generalization of Bertrand’s theorem on 2D spaces of constant curvature and covers most of the known separable and superintegrable models on such spaces (in particular, the so-called Tremblay–Turbiner–Winternitz (TTW) and Post–Winternitz (PW) models which have recently attracted some interest). -- Highlights: •Classifying 2D superintegrable, separable (polar coordinates) systems on S{sup 2}, R{sup 2}, H{sup 2}. •Construction of radial, angular potentials leading to superintegrability. •Generalization of Bertrand’s theorem covering known models, e.g. Higgs, TTW, PW, and Coulomb.

  16. Constant-mesh, multiple-shaft transmission

    SciTech Connect

    Rea, J.E.; Mills, D.D.; Sewell, J.S.

    1992-04-21

    This patent describes a multiple-shaft, constant-mesh transmission adapted to establish selectively a reverse torque delivery path and a forward drive torque delivery path and having a torque input means including a torque input shaft, a mainshaft aligned with the input shaft, a countershaft geared to the input shaft in spaced, parallel relationship with respect to the mainshaft, a torque output shaft joined to the mainshaft; multiple mainshaft gear elements journalled on the main airshaft, multiple cluster gear elements carried by the countershaft in meshing engagement with the mainshaft gear elements, one of the cluster gear elements being rotatably journalled on the countershaft; a reverse idle gear, a reverse gear journalled on the countershaft, the reverse idler gear being in constant mesh with the reverse gear and one of the mainshaft gear elements; first clutch means for connecting selectively the reverse gear and the countershaft; second synchronizer clutch means for connecting selectively the one of the mainshaft gear elements to the mainshaft; and third synchronizer clutch means for selectively connecting another of the mainshaft gear elements to the mainshaft; the first clutch means being a double-acting clutch with a first common axially movable clutch element adapted upon movement in one axial direction to drivably connected the reverse gear to the countershaft and adapted upon movement in the opposite axial direction to connect the one cluster gear element to the countershaft.

  17. The Hubble Constant and the Expanding Universe

    NASA Astrophysics Data System (ADS)

    Freedman, Wendy

    2003-01-01

    In 1929 Edwin Hubble proved that our universe is expanding by showing that the farther a galaxy is from us, the faster it is speeding away into space. This velocity-distance relation came to be called Hubble's law, and the value that describes the rate of expansion is known as the Hubble constant, or H0 . Like the speed of light, H0 is a fundamental constant, and it is a key parameter needed to estimate both the age and size of the universe. Since the late 1950s astronomers have been arguing for an H0 value between 50 to 100 kilometers per second per megaparsec, a lack of precision that produced an unacceptably wide range of ages for the universe—anywhere from 10 to 20 billion years. Using the Hubble Space Telescope, Freedman and her colleagues measured H0 to an unprecedented level of accuracy, deriving a value of 72, with an uncertainty of 10 percent—a milestone achievement in cosmology. The new result suggests that our universe is about 13 billion years old, give or take a billion years, and it's a value that sits comfortably alongside the 12 billion years estimated for the age of the oldest stars.

  18. A Constant-Force Resistive Exercise Unit

    NASA Technical Reports Server (NTRS)

    Colosky, Paul; Ruttley, Tara

    2010-01-01

    A constant-force resistive exercise unit (CFREU) has been invented for use in both normal gravitational and microgravitational environments. In comparison with a typical conventional exercise machine, this CFREU weighs less and is less bulky: Whereas weight plates and associated bulky supporting structures are used to generate resistive forces in typical conventional exercise machines, they are not used in this CFREU. Instead, resistive forces are generated in this CFREU by relatively compact, lightweight mechanisms based on constant-torque springs wound on drums. Each such mechanism is contained in a module, denoted a resistive pack, that includes a shaft for making a torque connection to a cable drum. During a stroke of resistive exercise, the cable is withdrawn from the cable drum against the torque exerted by the resistance pack. The CFREU includes a housing, within which can be mounted one or more resistive pack(s). The CFREU also includes mechanisms for engaging any combination of (1) one or more resistive pack(s) and (2) one or more spring(s) within each resistive pack to obtain a desired level of resistance.

  19. Holographic dark energy with cosmological constant

    SciTech Connect

    Hu, Yazhou; Li, Nan; Zhang, Zhenhui; Li, Miao E-mail: mli@itp.ac.cn E-mail: zhangzhh@mail.ustc.edu.cn

    2015-08-01

    Inspired by the multiverse scenario, we study a heterotic dark energy model in which there are two parts, the first being the cosmological constant and the second being the holographic dark energy, thus this model is named the ΛHDE model. By studying the ΛHDE model theoretically, we find that the parameters d and Ω{sub hde} are divided into a few domains in which the fate of the universe is quite different. We investigate dynamical behaviors of this model, and especially the future evolution of the universe. We perform fitting analysis on the cosmological parameters in the ΛHDE model by using the recent observational data. We find the model yields χ{sup 2}{sub min}=426.27 when constrained by Planck+SNLS3+BAO+HST, comparable to the results of the HDE model (428.20) and the concordant ΛCDM model (431.35). At 68.3% CL, we obtain −0.07<Ω{sub Λ0}<0.68 and correspondingly 0.04<Ω{sub hde0}<0.79, implying at present there is considerable degeneracy between the holographic dark energy and cosmological constant components in the ΛHDE model.

  20. Direct Measures of the Hubble Constant

    NASA Astrophysics Data System (ADS)

    Schechter, P. L.

    1999-05-01

    When astronomers talk about Lutz-Kelker corrections, metallicity dependent zeropoints, statistical parallaxes, Tully-Fisher relations, "fundamental" planes, light curve decline rates and, worst of all, Malmquist bias, physicists begin heading for the exits, showing signs of severe allergic reaction. They respond less violently to so-called "direct" methods of measuring distances which bypass the traditional distance ladder. Two of these, gravitational lens time delay measurements (Refsdal's method) and the Sunyaev-Zeldovich (S-Z) effect, give distance measurements to objects at high redshift which appear to rival more traditional approaches. Present, model mediated interpretations of such measurements give low values for the Hubble constant. But as is often the case with new techniques, initial enthusiasm is followed by increasing concern about systematic errors connected with messy astrophysical details. The single largest source of error in modelling lenses is the difficulty in constraining the degree of central concentration of the lensing galaxy. Sources of systematic error in S-Z distances include the clumpiness of intracluster gas, temperature variations within that gas and a bias toward selecting clusters that are elongated along the line of sight. Present best estimates of the Hubble constant, along with best estimates of the systematic uncertainties, and the prospects for improving upon these, will be presented. Support from NSF grant AST96-16866 is gratefully acknowledged.

  1. Exercise Device Would Exert Selectable Constant Resistance

    NASA Technical Reports Server (NTRS)

    Smith, Damon C.

    2003-01-01

    An apparatus called the resistive exercise device (RED) has been proposed to satisfy a requirement for exercise equipment aboard the International Space Station (ISS) that could passively exert a selectable constant load on both the outward and return strokes. The RED could be used alone; alternatively, the RED could be used in combination with another apparatus called the treadmill with vibration isolation and stabilization (TVIS), in which case the combination would be called the subject load device (SLD). The basic RED would be a passive device, but it could incorporate an electric motor to provide eccentric augmentation (augmentation to make the load during inward movement greater than the load during outward movement). The RED concept represents a unique approach to providing a constant but selectable resistive load for exercise for the maintenance and development of muscles. Going beyond the original ISS application, the RED could be used on Earth as resistive weight training equipment. The advantage of the RED over conventional weight-lifting equipment is that it could be made portable and lightweight.

  2. Non-empirical calculations of NMR indirect carbon-carbon coupling constants. Part 10--carbocages.

    PubMed

    Krivdin, Leonid B

    2004-11-01

    A comprehensive theoretical study of nine classical caged polycycloalkanes (tetrahedrane, prismane, homoprismane, quadricyclane, cubane, pentaprismane, hexaprismane, adamantane and diamantane) was carried out with special focus on the structural behavior of their J(C,C) values calculated at the SOPPA level. The structural behavior of J(C,C) in small carbocages is dominated by steric strain whereas in medium-sized polycycloalkanes the J(C,C) values show no marked peculiarities and follow several well-defined structural trends typical of other alicyclic compounds.

  3. Large-order behavior of a two-coupling-constant φ4 theory with cubic anisotropy

    NASA Astrophysics Data System (ADS)

    Kleinert, H.; Thoms, S.

    1995-11-01

    For an anisotropic Euclidean [u(tsumNi=1 φ2i)2+vtsumNi=1 φ4i] theory with N=2,3 we calculate the imaginary parts of the renormalization group functions in the form of a series expansion in v, i.e., around the isotropic case. Dimensional regularization is used to evaluate fluctuation determinants near the space dimension 4. The vertex functions in the presence of instantons are renormalized with the help of a nonperturbative procedure introduced for the simple gφ4 theory by McKane, Wallace, and de Alcantara Bonfim.

  4. Periodic trends in parity-violating hyperfine coupling constants of open-shell diatomic molecules

    NASA Astrophysics Data System (ADS)

    Isaev, T. A.; Berger, R.

    2014-06-01

    Nuclear spin-dependent parity violation effects are predicted with the help of a quasi-relativistic two-component zeroth order regular approximation (ZORA) approach for a series of open-shell diatomic molecules that feature a 2Σ electronic ground state. The particular focus is on scaling behaviour of the parity violating parameter Wa in the effective spin-rotational Hamiltonion with increasing nuclear charge Z of the heavier atom in the diatomic molecule. Previously (Isaev and Berger, 2012) an approximate R(A,Z)Z2 scaling law, with R(A,Z) denoting a relativistic enhancement factor, was confirmed for Wa in the series of valence isoelectronic group II monofluorides and valence isoelectronic group XII monohydrides, that is along columns of the periodic table of the elements. In this work, a pronounced R(A,Z)Zk scaling is predicted for isolobal 2Σ diatomic molecules along rows of the periodic table, with k being approximately 4 and 6 for the fourth and fifth row, respectively, and even larger for the sixth and seventh row. This observation opens up a another dimension in the systematic search of candidate systems for measuring nuclear spin-dependent parity violating interactions in molecules.

  5. The polysiloxane cyclization equilibrium constant: a theoretical focus on small and intermediate size rings.

    PubMed

    Madeleine-Perdrillat, Claire; Delor-Jestin, Florence; de Sainte Claire, Pascal

    2014-01-01

    The nonlinear dependence of polysiloxane cyclization constants (log(K(x))) with ring size (log(x)) is explained by a thermodynamic model that treats specific torsional modes of the macromolecular chains with a classical coupled hindered rotor model. Several parameters such as the dependence of the internal rotation kinetic energy matrix with geometry, the effect of potential energy hindrance, anharmonicity, and the couplings between internal rotors were investigated. This behavior arises from the competing effects of local molecular entropy that is mainly driven by the intrinsic transformation of vibrations in small cycles into hindered rotations in larger cycles and configurational entropy.

  6. Characterization of all the elastic, dielectric, and piezoelectric constants of uniaxially oriented poled PVDF films.

    PubMed

    Roh, Yongrae; Varadan, Vasundara V; Varadan, Vijay K

    2002-06-01

    Polyvinylidene fluoride (PVDF), a piezoelectric material, has many useful applications, for example, as sensors, transducers, and surface acoustic wave (SAW) devices. Models of performance of these devices would be useful engineering tools. However, the benefit of the model is only as accurate as the material properties used in the model. The purpose of this investigation is to measure the elastic, dielectric and piezoelectric properties over a frequency range, including the imaginary part (loss) of these properties. Measurements are difficult because poled material is available as thin films, and not all quantities can be measured in that form. All components of the elastic stiffness, dielectric tensor, and electromechanical coupling tensor are needed in the models. The material studied here is uniaxially oriented poled PVDF that has orthorhombic mm2 symmetry. Presented are the frequency dependence of all nine complex elastic constants, three complex dielectric constants, and five complex piezoelectric constants. The PVDF was produced at Raytheon Research Division, Lexington, MA. Measurements were made on thin films and on stacked, cubical samples. The elastic constants c44D and C55D, the dielectric constants epsilon11T and epsilon22T, as well as the piezoelectric constants g15 and g24 reported here have not been published before. The values were determined by ultrasonic measurements using an impedance analyzer and a least square data-fitting technique. PMID:12075977

  7. Computing the dielectric constant of liquid water at constant dielectric displacement

    NASA Astrophysics Data System (ADS)

    Zhang, Chao; Sprik, Michiel

    2016-04-01

    The static dielectric constant of liquid water is computed using classical force field based molecular dynamics simulation at fixed electric displacement D . The method to constrain the electric displacement is the finite-temperature classical variant of the constant D method developed by Stengel, Spaldin, and Vanderbilt [Nat. Phys. 5, 304 (2009), 10.1038/nphys1185]. There is also a modification of this scheme imposing fixed values of the macroscopic field E . The method is applied to the popular SPC/E model of liquid water. We compare four different estimates of the dielectric constant, two obtained from fluctuations of the polarization at D =0 and E =0 and two from the variation of polarization with finite D and E . It is found that all four estimates agree when properly converged. The computational effort to achieve convergence varies, however, with constant D calculations being substantially more efficient. We attribute this difference to the much shorter relaxation time of longitudinal polarization compared to transverse polarization accelerating constant D calculations.

  8. Recent Progress in Weakly-Coupled Heterotic String Phenomenology

    SciTech Connect

    Wu, Yi-Yen

    1997-07-28

    Some recent developments in the weakly-coupled heterotic string phenomenology are reviewed. We discuss several important issues such as dilaton/moduli stabilization, supersymmetry breaking (by hidden-sector gaugino condensation), gauge coupling unification (or the Newton's constant), the QCD axion, as well as cosmological problems involving the dilaton/moduli and the axion.

  9. Ideal, constant-loss nanophotonic mode converter using a Lagrangian approach.

    PubMed

    Horth, Alexandre; Cheben, Pavel; Schmid, Jens H; Kashyap, Raman; Quitoriano, Nathaniel J

    2016-03-21

    Coupling light between an optical fiber and a silicon nanophotonic waveguide is a challenge facing the field of silicon photonics to which various mode converters have been proposed. Inverted tapers stand out as a practical solution enabling efficient and broadband mode conversion. Current design approaches often use linearly-shaped tapers and two dimensional approximations; however, these approaches have not been rigorously verified and there is not an overarching design framework to guide the design process. Here, using a Lagrangian formulation, we propose an original, constant-loss framework for designing shape-controlled photonic devices and apply this formalism to derive an ideal constant-loss taper (CLT). We specifically report on the experimental demonstration of a fabrication-tolerant, 15-µm-long CLT coupler, that produces 0.56 dB fiber-chip coupling efficiency, the highest efficiency-per-length ratio ever reported.

  10. Ideal, constant-loss nanophotonic mode converter using a Lagrangian approach.

    PubMed

    Horth, Alexandre; Cheben, Pavel; Schmid, Jens H; Kashyap, Raman; Quitoriano, Nathaniel J

    2016-03-21

    Coupling light between an optical fiber and a silicon nanophotonic waveguide is a challenge facing the field of silicon photonics to which various mode converters have been proposed. Inverted tapers stand out as a practical solution enabling efficient and broadband mode conversion. Current design approaches often use linearly-shaped tapers and two dimensional approximations; however, these approaches have not been rigorously verified and there is not an overarching design framework to guide the design process. Here, using a Lagrangian formulation, we propose an original, constant-loss framework for designing shape-controlled photonic devices and apply this formalism to derive an ideal constant-loss taper (CLT). We specifically report on the experimental demonstration of a fabrication-tolerant, 15-µm-long CLT coupler, that produces 0.56 dB fiber-chip coupling efficiency, the highest efficiency-per-length ratio ever reported. PMID:27136856

  11. Theoretical Evaluation of the Transient Response of Constant Head and Constant Flow-Rate Permeability Tests

    USGS Publications Warehouse

    Zhang, M.; Takahashi, M.; Morin, R.H.; Esaki, T.

    1998-01-01

    A theoretical analysis is presented that compares the response characteristics of the constant head and the constant flowrate (flow pump) laboratory techniques for quantifying the hydraulic properties of geologic materials having permeabilities less than 10-10 m/s. Rigorous analytical solutions that describe the transient distributions of hydraulic gradient within a specimen are developed, and equations are derived for each method. Expressions simulating the inflow and outflow rates across the specimen boundaries during a constant-head permeability test are also presented. These solutions illustrate the advantages and disadvantages of each method, including insights into measurement accuracy and the validity of using Darcy's law under certain conditions. The resulting observations offer practical considerations in the selection of an appropriate laboratory test method for the reliable measurement of permeability in low-permeability geologic materials.

  12. Frank's constant in the hexatic phase.

    PubMed

    Keim, P; Maret, G; von Grünberg, H H

    2007-03-01

    Using videomicroscopy data of a two-dimensional colloidal system the bond-order correlation function G{6} is calculated and used to determine both the orientational correlation length xi{6} in the liquid phase and the modulus of orientational stiffness, Frank's constant F{A}, in the hexatic phase. The latter is an anisotropic fluid phase between the crystalline and the isotropic liquid phase. F{A} is found to be finite within the hexatic phase, takes the value 72/pi at the hexatic<-->isotropic liquid phase transition, and diverges at the hexatic<-->crystal transition as predicted by the Kosterlitz-Thouless-Halperin-Nelson-Young theory. This is a quantitative test of the mechanism of breaking the orientational symmetry by disclination unbinding.

  13. Defect Motifs for Constant Mean Curvature Surfaces

    NASA Astrophysics Data System (ADS)

    Kusumaatmaja, Halim; Wales, David J.

    2013-04-01

    The energy landscapes of electrostatically charged particles embedded on constant mean curvature surfaces are analyzed for a wide range of system size, curvature, and interaction potentials. The surfaces are taken to be rigid, and the basin-hopping method is used to locate the putative global minimum structures. The defect motifs favored by potential energy agree with experimental observations for colloidal systems: extended defects (scars and pleats) for weakly positive and negative Gaussian curvatures, and isolated defects for strongly negative Gaussian curvatures. Near the phase boundary between these regimes, the two motifs are in strong competition, as evidenced from the appearance of distinct funnels in the potential energy landscape. We also report a novel defect motif consisting of pentagon pairs.

  14. Statistical Modelling of the Soil Dielectric Constant

    NASA Astrophysics Data System (ADS)

    Usowicz, Boguslaw; Marczewski, Wojciech; Bogdan Usowicz, Jerzy; Lipiec, Jerzy

    2010-05-01

    The dielectric constant of soil is the physical property being very sensitive on water content. It funds several electrical measurement techniques for determining the water content by means of direct (TDR, FDR, and others related to effects of electrical conductance and/or capacitance) and indirect RS (Remote Sensing) methods. The work is devoted to a particular statistical manner of modelling the dielectric constant as the property accounting a wide range of specific soil composition, porosity, and mass density, within the unsaturated water content. Usually, similar models are determined for few particular soil types, and changing the soil type one needs switching the model on another type or to adjust it by parametrization of soil compounds. Therefore, it is difficult comparing and referring results between models. The presented model was developed for a generic representation of soil being a hypothetical mixture of spheres, each representing a soil fraction, in its proper phase state. The model generates a serial-parallel mesh of conductive and capacitive paths, which is analysed for a total conductive or capacitive property. The model was firstly developed to determine the thermal conductivity property, and now it is extended on the dielectric constant by analysing the capacitive mesh. The analysis is provided by statistical means obeying physical laws related to the serial-parallel branching of the representative electrical mesh. Physical relevance of the analysis is established electrically, but the definition of the electrical mesh is controlled statistically by parametrization of compound fractions, by determining the number of representative spheres per unitary volume per fraction, and by determining the number of fractions. That way the model is capable covering properties of nearly all possible soil types, all phase states within recognition of the Lorenz and Knudsen conditions. In effect the model allows on generating a hypothetical representative of

  15. Maximum terminal velocity turns at constant altitude

    NASA Astrophysics Data System (ADS)

    Eisler, G. Richard; Hull, David G.

    An optimal control problem is formulated for a maneuvering reentry vehicle to execute a maximum terminal velocity turn at constant altitude to a fixed final position. A control solution technique is devised which uses a Newton scheme to repetitively solve a nonlinear algebraic system for two parameters to provide the on-line guidance. The turn control takes advantage of the high dynamic pressure at the beginning of the flight path; the lift solution acts to null deviations from the prescribed altitude. Control solutions are compared for a continuously updated, approximate physical model, for a simulation of the approximate optimal guidance in a true physical model, and for a parameter optimization solution for the true model. End constraint satisfaction is excellent. Overall trajectory agreement is good, if the assumed atmospheric model is reasonably accurate.

  16. Maximum terminal velocity turns at constant altitude

    SciTech Connect

    Eisler, G.R.; Hull, D.G.

    1987-01-01

    An optimal control problem is formulated for a maneuvering reentry vehicle to execute a maximum terminal velocity turn at constant altitude to a fixed final position. A control solution technique is devised which uses a Newton scheme to repetitively solve a nonlinear algebraic system for two parameters to provide the on-line guidance. The turn control takes advantage of the high dynamic pressure at the beginning of the flight path; the lift solution acts to null deviations from the prescribed altitude. Control solutions are compared for a continuously updated, approximate physical model, for a simulation of the approximate optimal guidance in a true physical model, and for a parameter optimization solution for the true model. End constraint satisfaction is excellent. Overall trajectory agreement is good, if the assumed atmospheric model is reasonably accurate.

  17. Measuring the RC time constant with Arduino

    NASA Astrophysics Data System (ADS)

    Pereira, N. S. A.

    2016-11-01

    In this work we use the Arduino UNO R3 open source hardware platform to assemble an experimental apparatus for the measurement of the time constant of an RC circuit. With adequate programming, the Arduino is used as a signal generator, a data acquisition system and a basic signal visualisation tool. Theoretical calculations are compared with direct observations from an analogue oscilloscope. Data processing and curve fitting is performed on a spreadsheet. The results obtained for the six RC test circuits are within the expected interval of values defined by the tolerance of the components. The hardware and software prove to be adequate to the proposed measurements and therefore adaptable to a laboratorial teaching and learning context.

  18. The decay constant of 87Rb

    NASA Astrophysics Data System (ADS)

    Rotenberg, E.; Davis, D. W.; Amelin, Y.

    2009-05-01

    Despite dozens of measurements of the decay constant of 87Rb (λ87), uncertainty surrounding the value remains. Mounting evidence [e.g. 1,2,3] suggests that the actual value is 1-2% lower than the conventional value of 1.42 × 10-11a-1 [4]. Increased precision and accuracy are crucial if meaningful comparisons are to be made between Rb-Sr and U-Pb ages. We have been working on measuring the decay constant by the accumulation of radiogenic 87Sr (87Sr*) in a RbClO4 salt. Our original measurements by this method had large errors [5,6] and tended to agree with the conventional value. Because the samples contained very little common Sr, it was impossible to properly correct for instrumental fractionation, with the result that both precision and accuracy were compromised. Furthermore, the concentration of the 84Sr spike was not determined reliably, which likely affected the accuracy. In order to overcome this, a new 84-86Sr double-spike was prepared, and the experiment was repeated. The spike was calibrated against three different Sr reference solutions. Two were prepared from Sr metal and the third from SrCl2. The isotopic abundance ratios of the 84-86Sr double-spike are: 84/86 = 0.93252, 87/86 = 0.01033, and 88/86 = 0.02240. The concentration was determined to be 832.95 ± 0.26 ng Sr/g solution (MSWD = 2.5). Seventeen measurements of the decay-constant were made by measuring 87Sr* ingrowth in a RbClO4 salt over approximately 32 years. 87Sr* ranges from 125 - 616 pg. The two highest points are eliminated: one due to high procedure blank and the second due to abnormal fractionation behaviour. A weighted average of the remaining fifteen measurements yields a decay constant of 1.3981 × 10-11a-11 ± 0.0009 (0.062%; and a high MSWD = 106. The 2σ standard deviation is 0.004). The data scatter outside of their analytical errors. Recent geological calibrations [1,2] and a carefully controlled decay counting measurement [3] yield λ87 values from 1.395 ± 0.006 to 1.398 ± 0

  19. Constant-parameter capture-recapture models

    USGS Publications Warehouse

    Brownie, C.; Hines, J.E.; Nichols, J.D.

    1986-01-01

    Jolly (1982, Biometrics 38, 301-321) presented modifications of the Jolly-Seber model for capture-recapture data, which assume constant survival and/or capture rates. Where appropriate, because of the reduced number of parameters, these models lead to more efficient estimators than the Jolly-Seber model. The tests to compare models given by Jolly do not make complete use of the data, and we present here the appropriate modifications, and also indicate how to carry out goodness-of-fit tests which utilize individual capture history information. We also describe analogous models for the case where young and adult animals are tagged. The availability of computer programs to perform the analysis is noted, and examples are given using output from these programs.

  20. Hawking temperature of constant curvature black holes

    SciTech Connect

    Cai Ronggen; Myung, Yun Soo

    2011-05-15

    The constant curvature (CC) black holes are higher dimensional generalizations of Banados-Teitelboim-Zanelli black holes. It is known that these black holes have the unusual topology of M{sub D-1}xS{sup 1}, where D is the spacetime dimension and M{sub D-1} stands for a conformal Minkowski spacetime in D-1 dimensions. The unusual topology and time-dependence for the exterior of these black holes cause some difficulties to derive their thermodynamic quantities. In this work, by using a globally embedding approach, we obtain the Hawking temperature of the CC black holes. We find that the Hawking temperature takes the same form when using both the static and global coordinates. Also, it is identical to the Gibbons-Hawking temperature of the boundary de Sitter spaces of these CC black holes.

  1. Constant field gradient planar cavity structure

    SciTech Connect

    Kang, Yoon W.; Kustom, R.L.

    1997-12-01

    A cavity structure is described having at least two opposing planar housing members spaced apart to accommodate the passage of a particle beam through the structure between the members. Each of the housing members have a plurality of serially aligned hollows defined therein, and also passages, formed in the members, which interconnect serially adjacent hollows to provide communication between the hollows. The opposing planar housing members are spaced and aligned such that the hollows in one member cooperate with corresponding hollows in the other member to form a plurality of resonant cavities aligned along the particle beam within the cavity structure. To facilitate the obtaining of a constant field gradient within the cavity structure, the passages are configured so as to be incrementally narrower in the direction of travel of the particle beam. In addition, the spacing distance between the opposing housing members is configured to be incrementally smaller in the direction of travel of the beam.

  2. Consistency tests for the cosmological constant.

    PubMed

    Zunckel, Caroline; Clarkson, Chris

    2008-10-31

    We propose consistency tests for the cosmological constant which provide a direct observational signal if Lambda is wrong, regardless of the densities of matter and curvature. As an example of its utility, our flat case test can warn of a small transition of the equation of state w(z) from w(z)=-1 of 20% from SNAP (Supernova Acceleration Probe) quality data at 4-sigma, even when direct reconstruction techniques see virtually no evidence for deviation from Lambda. It is shown to successfully rule out a wide range of non-Lambda dark energy models with no reliance on knowledge of Omega_{m} using SNAP quality data and a large range for using 10;{5} supernovae as forecasted for the Large Synoptic Survey Telescope. PMID:18999813

  3. Automatic gesture analysis using constant affine velocity.

    PubMed

    Cifuentes, Jenny; Boulanger, Pierre; Pham, Minh Tu; Moreau, Richard; Prieto, Flavio

    2014-01-01

    Hand human gesture recognition has been an important research topic widely studied around the world, as this field offers the ability to identify, recognize, and analyze human gestures in order to control devices or to interact with computer interfaces. In particular, in medical training, this approach is an important tool that can be used to obtain an objective evaluation of a procedure performance. In this paper, some obstetrical gestures, acquired by a forceps, were studied with the hypothesis that, as the scribbling and drawing movements, they obey the one-sixth power law, an empirical relationship which connects path curvature, torsion, and euclidean velocity. Our results show that obstetrical gestures have a constant affine velocity, which is different for each type of gesture and based on this idea this quantity is proposed as an appropriate classification feature in the hand human gesture recognition field. PMID:25570332

  4. Simple Pendulum Determination of the Gravitational Constant

    SciTech Connect

    Parks, Harold V.; Faller, James E.

    2010-09-10

    We determined the Newtonian constant of gravitation G by interferometrically measuring the change in spacing between two free-hanging pendulum masses caused by the gravitational field from large tungsten source masses. We find a value for G of (6.672 34{+-}0.000 14)x10{sup -11} m{sup 3} kg{sup -1} s{sup -2}. This value is in good agreement with the 1986 Committee on Data for Science and Technology (CODATA) value of (6.672 59{+-}0.000 85)x10{sup -11} m{sup 3} kg{sup -1} s{sup -2}[Rev. Mod. Phys. 59, 1121 (1987)] but differs from some more recent determinations as well as the latest CODATA recommendation of (6.674 28{+-}0.000 67)x10{sup -11} m{sup 3} kg{sup -1} s{sup -2}[Rev. Mod. Phys. 80, 633 (2008)].

  5. Molecular dynamics at constant Cauchy stress

    NASA Astrophysics Data System (ADS)

    Miller, Ronald E.; Tadmor, Ellad B.; Gibson, Joshua S.; Bernstein, Noam; Pavia, Fabio

    2016-05-01

    The Parrinello-Rahman algorithm for imposing a general state of stress in periodic molecular dynamics simulations is widely used in the literature and has been implemented in many readily available molecular dynamics codes. However, what is often overlooked is that this algorithm controls the second Piola-Kirchhoff stress as opposed to the true (Cauchy) stress. This can lead to misinterpretation of simulation results because (1) the true stress that is imposed during the simulation depends on the deformation of the periodic cell, (2) the true stress is potentially very different from the imposed second Piola-Kirchhoff stress, and (3) the true stress can vary significantly during the simulation even if the imposed second Piola-Kirchhoff is constant. We propose a simple modification to the algorithm that allows the true Cauchy stress to be controlled directly. We then demonstrate the efficacy of the new algorithm with the example of martensitic phase transformations under applied stress.

  6. Constant-force approach to discontinuous potentials.

    PubMed

    Orea, Pedro; Odriozola, Gerardo

    2013-06-01

    Aiming to approach the thermodynamical properties of hard-core systems by standard molecular dynamics simulation, we propose setting a repulsive constant-force for overlapping particles. That is, the discontinuity of the pair potential is replaced by a linear function with a large negative slope. Hence, the core-core repulsion, usually modeled with a power function of distance, yields a large force as soon as the cores slightly overlap. This leads to a quasi-hardcore behavior. The idea is tested for a triangle potential of short range. The results obtained by replica exchange molecular dynamics for several repulsive forces are contrasted with the ones obtained for the discontinuous potential and by means of replica exchange Monte Carlo. We found remarkable agreements for the vapor-liquid coexistence densities as well as for the surface tension.

  7. The Solar constant: Status of our knowledge

    NASA Astrophysics Data System (ADS)

    Crommelynck, D.

    A historical survey of the observations of the Solar constant up to now is given and commented with respect to the particular conditions in which they were obtained. The continuous series of measurements obtained by J.R. Hickey since 1978, C. Willson since 1980 and R.B. Lee III since 1984 and the differences are analysed to deduce the state of the art of absolute radiometry. Taking into account the large scale monitoring requirements for climatological purposes, the areas in absolute radiometry where improvements are still possible are identified together with the estimated ultimate possible accuracy. A strategy is proposed to guarantee the continuity of the monitoring over large enough climatological periods.

  8. Broadband negative optical constants in composite materials

    NASA Astrophysics Data System (ADS)

    Khosravi, S.; Rostami, A.; Rostami, G.; Dolatyari, M.

    2015-04-01

    Capability of flexible composite substrates, consisting of randomly distributed nanoparticles in polymeric host medium, to illustrate negative effective permittivity and permeability in the mid infrared wavelengths (3-5 μm) is investigated. To produce negative permittivity in the desired wavelength range, we proposed a structure in which plasmonic nanoparticles (doped semiconductors or metallic nanoparticles) are inserted inside polytetrafluoroethylene as the low refractive index polymeric medium. Also, the optical properties of the structures including core/shell nanoparticles in polytetrafluoroethylene host (with polytetrafluoroethylene as core material and dielectric shells possessing higher refractive index compared to refractive index of the host medium) are investigated. It is shown that, high refractive index dielectric shells result in negative μeff in these structures. As a basic idea, to obtain negative optical constants in broad wavelength range, superposition of the mentioned nanoparticles in the polymeric host is examined. The advantages and limitations of the proposed structure are carefully investigated. Moreover, based on the simulation results, we will introduce flexible media that simultaneously display negative permittivity and permeability in the wavelength range of interest. Capability of two types of composites (the first one contains mixture of plasmonic nanoparticles with polymer-dielectric core-shell nanoparticles and the second one includes metal-dielectric core-shell nanoparticles in the polymeric host) to produce both negative effective parameters in the desired wavelength range are investigated and compared together. Finally a polymeric medium with random distribution of core-shell (metal-dielectric) nanoparticles and plasmonic nanoparticles is introduced as an optimal medium to illustrate negative optical constants in mid infrared wavelengths. Clausius-Mossotti formula is used to calculate the effective parameters.

  9. On parasupersymmetric oscillators and relativistic vector mesons in constant magnetic fields

    NASA Technical Reports Server (NTRS)

    Debergh, Nathalie; Beckers, Jules

    1995-01-01

    Johnson-Lippmann considerations on oscillators and their connection with the minimal coupling schemes are visited in order to introduce a new Sakata-Taketani equation describing vector mesons in interaction with a constant magnetic field. This new proposal, based on a specific parasupersymmetric oscillator-like system, is characterized by real energies as opposed to previously pointed out relativistic equations corresponding to this interacting context.

  10. Dependence of macrophysical phenomena on the values of the fundamental constants

    NASA Astrophysics Data System (ADS)

    Press, W. H.; Lightman, A. P.

    1983-12-01

    Using simple arguments, it is considered how the fundamental constants determine the scales of various macroscopic phenomena, including the properties of solid matter; the distinction between rocks, asteroids, planets, and stars; the conditions on habitable planets; the length of the day and year; and the size and athletic ability of human beings. Most of the results, where testable, are accurate to within a couple of orders of magnitude.

  11. Two-loop quantum gravity corrections to the cosmological constant in Landau gauge

    NASA Astrophysics Data System (ADS)

    Hamada, Ken-ji; Matsuda, Mikoto

    2016-03-01

    The anomalous dimensions of the Planck mass and the cosmological constant are calculated in a renormalizable quantum conformal gravity with a single dimensionless coupling, which is formulated using dimensional regularization on the basis of Hathrell's works for conformal anomalies. The dynamics of the traceless tensor field is handled by the Weyl action, while that of the conformal-factor field is described by the induced Wess-Zumino actions, including the Riegert action as the kinetic term. Loop calculations are carried out in Landau gauge in order to reduce the number of Feynman diagrams as well as to avoid some uncertainty. Especially, we calculate two-loop quantum gravity corrections to the cosmological constant. It suggests that there is a dynamical solution to the cosmological constant problem.

  12. Competing bounds on the present-day time variation of fundamental constants

    SciTech Connect

    Dent, Thomas; Stern, Steffen; Wetterich, Christof

    2009-04-15

    We compare the sensitivity of a recent bound on time variation of the fine structure constant from optical clocks with bounds on time-varying fundamental constants from atomic clocks sensitive to the electron-to-proton mass ratio, from radioactive decay rates in meteorites, and from the Oklo natural reactor. Tests of the weak equivalence principle also lead to comparable bounds on present variations of constants. The 'winner in sensitivity' depends on what relations exist between the variations of different couplings in the standard model of particle physics, which may arise from the unification of gauge interactions. Weak equivalence principle tests are currently the most sensitive within unified scenarios. A detection of time variation in atomic clocks would favor dynamical dark energy and put strong constraints on the dynamics of a cosmological scalar field.

  13. Competing bounds on the present-day time variation of fundamental constants

    NASA Astrophysics Data System (ADS)

    Dent, Thomas; Stern, Steffen; Wetterich, Christof

    2009-04-01

    We compare the sensitivity of a recent bound on time variation of the fine structure constant from optical clocks with bounds on time-varying fundamental constants from atomic clocks sensitive to the electron-to-proton mass ratio, from radioactive decay rates in meteorites, and from the Oklo natural reactor. Tests of the weak equivalence principle also lead to comparable bounds on present variations of constants. The “winner in sensitivity” depends on what relations exist between the variations of different couplings in the standard model of particle physics, which may arise from the unification of gauge interactions. Weak equivalence principle tests are currently the most sensitive within unified scenarios. A detection of time variation in atomic clocks would favor dynamical dark energy and put strong constraints on the dynamics of a cosmological scalar field.

  14. Post-Newtonian parameters and cosmological constant of screened modified gravity

    NASA Astrophysics Data System (ADS)

    Zhang, Xing; Zhao, Wen; Huang, He; Cai, Yifu

    2016-06-01

    Screened modified gravity (SMG) is a kind of scalar-tensor theory with screening mechanisms, which can generate a screening effect to suppress the fifth force in high density environments and pass the solar system tests. Meanwhile, the potential of the scalar field in the theories can drive the acceleration of the late Universe. In this paper, we calculate the parametrized post-Newtonian (PPN) parameters γ and β , the effective gravitational constant Geff, and the effective cosmological constant Λ for SMG with a general potential V and coupling function A . The dependence of these parameters on the model parameters of SMG and/or the physical properties of the source object are clearly presented. As an application of these results, we focus on three specific theories of SMG (chameleon, symmetron, and dilaton models). Using the formulas to calculate their PPN parameters and cosmological constant, we derive the constraints on the model parameters by combining the observations on solar system and cosmological scales.

  15. Thermal rectification and negative differential thermal conductance in harmonic chains with nonlinear system-bath coupling.

    PubMed

    Ming, Yi; Li, Hui-Min; Ding, Ze-Jun

    2016-03-01

    Thermal rectification and negative differential thermal conductance were realized in harmonic chains in this work. We used the generalized Caldeira-Leggett model to study the heat flow. In contrast to most previous studies considering only the linear system-bath coupling, we considered the nonlinear system-bath coupling based on recent experiment [Eichler et al., Nat. Nanotech. 6, 339 (2011)]. When the linear coupling constant is weak, the multiphonon processes induced by the nonlinear coupling allow more phonons transport across the system-bath interface and hence the heat current is enhanced. Consequently, thermal rectification and negative differential thermal conductance are achieved when the nonlinear couplings are asymmetric. However, when the linear coupling constant is strong, the umklapp processes dominate the multiphonon processes. Nonlinear coupling suppresses the heat current. Thermal rectification is also achieved. But the direction of rectification is reversed compared to the results of weak linear coupling constant.

  16. Thermal rectification and negative differential thermal conductance in harmonic chains with nonlinear system-bath coupling

    NASA Astrophysics Data System (ADS)

    Ming, Yi; Li, Hui-Min; Ding, Ze-Jun

    2016-03-01

    Thermal rectification and negative differential thermal conductance were realized in harmonic chains in this work. We used the generalized Caldeira-Leggett model to study the heat flow. In contrast to most previous studies considering only the linear system-bath coupling, we considered the nonlinear system-bath coupling based on recent experiment [Eichler et al., Nat. Nanotech. 6, 339 (2011), 10.1038/nnano.2011.71]. When the linear coupling constant is weak, the multiphonon processes induced by the nonlinear coupling allow more phonons transport across the system-bath interface and hence the heat current is enhanced. Consequently, thermal rectification and negative differential thermal conductance are achieved when the nonlinear couplings are asymmetric. However, when the linear coupling constant is strong, the umklapp processes dominate the multiphonon processes. Nonlinear coupling suppresses the heat current. Thermal rectification is also achieved. But the direction of rectification is reversed compared to the results of weak linear coupling constant.

  17. Wave formation by time delays in randomly coupled oscillators.

    PubMed

    Ko, Tae-Wook; Jeong, Seong-Ok; Moon, Hie-Tae

    2004-05-01

    We study the dynamics of randomly coupled oscillators when interactions between oscillators are time delayed due to the finite and constant speed of coupling signals. Numerical simulations show that the time delays, proportional to the Euclidean distances between interacting oscillators, can induce near regular waves in addition to near in-phase synchronous oscillations even though oscillators are randomly coupled. We discuss the stability conditions for the wave states and the in-phase synchronous states.

  18. The effect of interacting dark energy on local measurements of the Hubble constant

    NASA Astrophysics Data System (ADS)

    Odderskov, Io; Baldi, Marco; Amendola, Luca

    2016-05-01

    In the current state of cosmology, where cosmological parameters are being measured to percent accuracy, it is essential to understand all sources of error to high precision. In this paper we present the results of a study of the local variations in the Hubble constant measured at the distance scale of the Coma Cluster, and test the validity of correcting for the peculiar velocities predicted by gravitational instability theory. The study is based on N-body simulations, and includes models featuring a coupling between dark energy and dark matter, as well as two ΛCDM simulations with different values of σ8. It is found that the variance in the local flows is significantly larger in the coupled models, which increases the uncertainty in the local measurements of the Hubble constant in these scenarios. By comparing the results from the different simulations, it is found that most of the effect is caused by the higher value of σ8 in the coupled cosmologies, though this cannot account for all of the additional variance. Given the discrepancy between different estimates of the Hubble constant in the universe today, cosmological models causing a greater cosmic variance is something that we should be aware of.

  19. Accurate quantum thermal rate constants for the three-dimensional H+H2 reaction

    NASA Astrophysics Data System (ADS)

    Park, Tae Jun; Light, J. C.

    1989-07-01

    The rate constants for the three-dimensional H+H2 reaction on the Liu-Siegbahn-Truhlar-Horowitz (LSTH) surface are calculated using Pack-Parker hyperspherical (APH) coordinates and a C2v symmetry adapted direct product discrete variable representation (DVR). The C2v symmetry decomposition and the parity decoupling on the basis are performed for the internal coordinate χ. The symmetry decomposition results in a block diagonal representation of the flux and Hamiltonian operators. The multisurface flux is introduced to represent the multichannel reactive flux. The eigenvalues and eigenvectors of the J=0 internal Hamiltonian are obtained by sequential diagonalization and truncation. The individual symmetry blocks of the flux operator are propagated by the corresponding blocks of the Hamiltonian, and the J=0 rate constant k0(T) is obtained as a sum of the rate constants calculated for each block. k0(T) is compared with the exact k0(T) obtained from thermal averaging of the J=0 reaction probabilities; the errors are within 5%-20% up to T=1500 K. The sequential diagonalization-truncation method reduces the size of the Hamiltonian greatly, but the resulting Hamiltonian matrix still describes the time evolution very accurately. For the J≠0 rate constant calculations, the truncated internal Hamiltonian eigenvector basis is used to construct reduced (JKJ) blocks of the Hamiltonian. The individual (JKJ) blocks are diagonalized neglecting Coriolis coupling and treating the off-diagonal KJ±2 couplings by second order perturbation theory. The full wave function is parity decoupled. The rate constant is obtained as a sum over J of (2J+1)kJ(T). The time evolution of the flux for J≠0 is again very accurately described to give a well converged rate constant.

  20. Are thermal constants constant? A test using two species of ladybird.

    PubMed

    Jarošík, V; Kumar, G; Omkar; Dixon, A F G

    2014-02-01

    There is a controversy about whether the thermal constants, lower developmental threshold, rate of development and corresponding degree days required for development, change when a species is reared under different developmental conditions. We present a more precise way of measuring these constants using the linear relationship between the rate of development and temperature. First we use the equation proposed by Ikemoto and Takai (2000) to determine the linear phase of development and then a generalised linear model having a different variance at low and high temperatures, specific for each condition, to estimate the parameters of the linear relationship. Using this method, we show that providing the difference in food quality is sufficiently great, an aphidophagous ladybird develops significantly faster and starts developing at a significantly lower temperature on a good than on a poor quality diet. Adaptive significance of the thermal constants not remaining constant is discussed in terms of a trade-off between growth and rate of development, when temperature and food quality varies. PMID:24556254