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Sample records for hydrogen-atom abstraction reaction

  1. Deformylation Reaction by a Nonheme Manganese(III)-Peroxo Complex via Initial Hydrogen-Atom Abstraction.

    Science.gov (United States)

    Barman, Prasenjit; Upadhyay, Pranav; Faponle, Abayomi S; Kumar, Jitendra; Nag, Sayanta Sekhar; Kumar, Devesh; Sastri, Chivukula V; de Visser, Sam P

    2016-09-05

    Metal-peroxo intermediates are key species in the catalytic cycles of nonheme metalloenzymes, but their chemical properties and reactivity patterns are still poorly understood. The synthesis and characterization of a manganese(III)-peroxo complex with a pentadentate bispidine ligand system and its reactivity with aldehydes was studied. Manganese(III)-peroxo can react through hydrogen-atom abstraction reactions instead of the commonly proposed nucleophilic addition reaction. Evidence of the mechanism comes from experiments which identify a primary kinetic isotope effect of 5.4 for the deformylation reaction. Computational modeling supports the established mechanism and identifies the origin of the reactivity preference of hydrogen-atom abstraction over nucleophilic addition.

  2. Learning about Regiochemistry from a Hydrogen-Atom Abstraction Reaction in Water

    Science.gov (United States)

    Sears-Dundes, Christopher; Huon, Yoeup; Hotz, Richard P.; Pinhas, Allan R.

    2011-01-01

    An experiment has been developed in which the hydrogen-atom abstraction and the coupling of propionitrile, using Fenton's reagent, are investigated. Students learn about the regiochemistry of radical formation, the stereochemistry of product formation, and the interpretation of GC-MS data, in a safe reaction that can be easily completed in one…

  3. The selectivity of charged phenyl radicals in hydrogen atom abstraction reactions with isopropanol.

    Science.gov (United States)

    Jing, Linhong; Guler, Leonard P; Pates, George; Kenttämaa, Hilkka I

    2008-10-09

    The vertical electron affinity is demonstrated to be a key factor in controlling the selectivity of charged phenyl radicals in hydrogen atom abstraction from isopropanol in the gas phase. The measurement of the total reaction efficiencies (hydrogen and/or deuterium atom abstraction) for unlabeled and partially deuterium-labeled isopropanol, and the branching ratios of hydrogen and deuterium atom abstraction, by using a Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometer, allowed the determination of the selectivity for each site in the unlabeled isopropanol. Examination of hydrogen atom abstraction from isopropanol by eight structurally different radicals revealed that the preferred site is the CH group. The selectivity of the charged phenyl radicals correlates with the radical's vertical electron affinity and the reaction efficiency. The smaller the vertical electron affinity of a radical, the lower its reactivity, and the greater the preference for the thermodynamically favored CH group over the CH3 group or the OH group. As the vertical electron affinity increases from 4.87 to 6.28 eV, the primary kinetic isotope effects decrease from 2.9 to 1.3 for the CD group, and the mixture of primary and alpha-secondary kinetic isotopes decreases from 6.0 to 2.4 for the CD3 group.

  4. Hydrogen atom abstraction reactions from tertiary amines by benzyloxyl and cumyloxyl radicals: influence of structure on the rate-determining formation of a hydrogen-bonded prereaction complex.

    Science.gov (United States)

    Salamone, Michela; DiLabio, Gino A; Bietti, Massimo

    2011-08-05

    A time-resolved kinetic study on the hydrogen atom abstraction reactions from a series of tertiary amines by the cumyloxyl (CumO(•)) and benzyloxyl (BnO(•)) radicals was carried out. With the sterically hindered triisobutylamine, comparable hydrogen atom abstraction rate constants (k(H)) were measured for the two radicals (k(H)(BnO(•))/k(H)(CumO(•)) = 2.8), and the reactions were described as direct hydrogen atom abstractions. With the other amines, increases in k(H)(BnO(•))/k(H)(CumO(•)) ratios of 13 to 2027 times were observed. k(H) approaches the diffusion limit in the reactions between BnO(•) and unhindered cyclic and bicyiclic amines, whereas a decrease in reactivity is observed with acyclic amines and with the hindered cyclic amine 1,2,2,6,6-pentamethylpiperidine. These results provide additional support to our hypothesis that the reaction proceeds through the rate-determining formation of a C-H/N hydrogen-bonded prereaction complex between the benzyloxyl α-C-H and the nitrogen lone pair wherein hydrogen atom abstraction occurs, and demonstrate the important role of amine structure on the overall reaction mechanism. Additional mechanistic information in support of this picture is obtained from the study of the reactions of the amines with a deuterated benzyloxyl radical (PhCD(2)O(•), BnO(•)-d(2)) and the 3,5-di-tert-butylbenzyloxyl radical.

  5. How solvent modulates hydroxyl radical reactivity in hydrogen atom abstractions.

    Science.gov (United States)

    Mitroka, Susan; Zimmeck, Stephanie; Troya, Diego; Tanko, James M

    2010-03-10

    The hydroxyl radical (HO*) is a highly reactive oxygen-centered radical whose bimolecular rate constants for reaction with organic compounds (hydrogen atom abstraction) approach the diffusion-controlled limit in aqueous solution. The results reported herein show that hydroxyl radical is considerably less reactive in dipolar, aprotic solvents such as acetonitrile. This diminished reactivity is explained on the basis of a polarized transition state for hydrogen abstraction, in which the oxygen of the hydroxyl radical becomes highly negative and can serve as a hydrogen bond acceptor. Because acetonitrile cannot participate as a hydrogen bond donor, the transition state cannot be stabilized by hydrogen bonding, and the reaction rate is lower; the opposite is true when water is the solvent. This hypothesis explains hydroxyl radical reactivity both in solution and in the gas phase and may be the basis for a "containment strategy" used by Nature when hydroxyl radical is produced endogenously.

  6. Hydrogen atom abstraction selectivity in the reactions of alkylamines with the benzyloxyl and cumyloxyl radicals. The importance of structure and of substrate radical hydrogen bonding.

    Science.gov (United States)

    Salamone, Michela; DiLabio, Gino A; Bietti, Massimo

    2011-10-19

    A time-resolved kinetic study on the hydrogen abstraction reactions from a series of primary and secondary amines by the cumyloxyl (CumO(•)) and benzyloxyl (BnO(•)) radicals was carried out. The results were compared with those obtained previously for the corresponding reactions with tertiary amines. Very different hydrogen abstraction rate constants (k(H)) and intermolecular selectivities were observed for the reactions of the two radicals. With CumO(•), k(H) was observed to decrease on going from the tertiary to the secondary and primary amines. The lowest k(H) values were measured for the reactions with 2,2,6,6-tetramethylpiperidine (TMP) and tert-octylamine (TOA), substrates that can only undergo N-H abstraction. The opposite behavior was observed for the reactions of BnO(•), where the k(H) values increased in the order tertiary < secondary < primary. The k(H) values for the reactions of BnO(•) were in all cases significantly higher than those measured for the corresponding reactions of CumO(•), and no significant difference in reactivity was observed between structurally related substrates that could undergo exclusive α-C-H and N-H abstraction. This different behavior is evidenced by the k(H)(BnO(•))/k(H)(CumO(•)) ratios that range from 55-85 and 267-673 for secondary and primary alkylamines up to 1182 and 3388 for TMP and TOA. The reactions of CumO(•) were described in all cases as direct hydrogen atom abstractions. With BnO(•) the results were interpreted in terms of the rate-determining formation of a hydrogen-bonded prereaction complex between the radical α-C-H and the amine lone pair wherein hydrogen abstraction occurs. Steric effects and amine HBA ability play a major role, whereas the strength of the substrate α-C-H and N-H bonds involved appears to be relatively unimportant. The implications of these different mechanistic pictures are discussed.

  7. Effect of metal ions on the reactions of the cumyloxyl radical with hydrogen atom donors. Fine control on hydrogen abstraction reactivity determined by Lewis acid-base interactions.

    Science.gov (United States)

    Salamone, Michela; Mangiacapra, Livia; DiLabio, Gino A; Bietti, Massimo

    2013-01-09

    A time-resolved kinetic study on the effect of metal ions (M(n+)) on hydrogen abstraction reactions from C-H donor substrates by the cumyloxyl radical (CumO(•)) was carried out in acetonitrile. Metal salt addition was observed to increase the CumO(•) β-scission rate constant in the order Li(+) > Mg(2+) > Na(+). These effects were explained in terms of the stabilization of the β-scission transition state determined by Lewis acid-base interactions between M(n+) and the radical. When hydrogen abstraction from 1,4-cyclohexadiene was studied in the presence of LiClO(4) and Mg(ClO(4))(2), a slight increase in rate constant (k(H)) was observed indicating that interaction between M(n+) and CumO(•) can also influence, although to a limited extent, the hydrogen abstraction reactivity of alkoxyl radicals. With Lewis basic C-H donors such as THF and tertiary amines, a decrease in k(H) with increasing Lewis acidity of M(n+) was observed (k(H)(MeCN) > k(H)(Li(+)) > k(H)(Mg(2+))). This behavior was explained in terms of the stronger Lewis acid-base interaction of M(n+) with the substrate as compared to the radical. This interaction reduces the degree of overlap between the α-C-H σ* orbital and a heteroatom lone-pair, increasing the C-H BDE and destabilizing the carbon centered radical formed after abstraction. With tertiary amines, a >2-order of magnitude decrease in k(H) was measured after Mg(ClO(4))(2) addition up to a 1.5:1 amine/Mg(ClO(4))(2) ratio. At higher amine concentrations, very similar k(H) values were measured with and without Mg(ClO(4))(2). These results clearly show that with strong Lewis basic substrates variations in the nature and concentration of M(n+) can dramatically influence k(H), allowing for a fine control of the substrate hydrogen atom donor ability, thus providing a convenient method for C-H deactivation. The implications and generality of these findings are discussed.

  8. Fluorescence Quenching of Benzaldehyde in Water by Hydrogen Atom Abstraction.

    Science.gov (United States)

    Fletcher, Katharyn; Bunz, Uwe H F; Dreuw, Andreas

    2016-09-01

    We computed the mechanism of fluorescence quenching of benzaldehyde in water through relaxed potential energy surface scans. Time-dependent density functional theory calculations along the protonation coordinate from water to benzaldehyde reveal that photoexcitation to the bright ππ* (S3 ) state is immediately followed by ultrafast decay to the nπ* (S1 ) state. Evolving along this state, benzaldehyde (BA) abstracts a hydrogen atom, resulting in a BAH(.) and OH(.) radical pair. Benzaldehyde does not act as photobase in water, but abstracts a hydrogen atom from a nearby solvent molecule. The system finally decays back to the ground state by non-radiative decay and an electron transfers back to the OH(.) radical. Proton transfer from BAH(+) to OH(-) restores the initial situation, BA in water.

  9. Free radical hydrogen atom abstraction from saturated hydrocarbons: A crossed-molecular-beams study of the reaction Cl + C{sub 3}H{sub 8} {yields} HCl + C{sub 3}H{sub 7}

    Energy Technology Data Exchange (ETDEWEB)

    Blank, D.A.; Hemmi, N.; Suits, A.G.; Lee, Y.T. [Lawrence Berkeley National Lab., CA (United States)

    1997-04-01

    The abstraction of hydrogen atoms from saturated hydrocarbons are reactions of fundamental importance in combustion as well as often being the rate limiting step in free radical substitution reactions. The authors have begun studying these reactions under single collision conditions using the crossed molecular beam technique on beamline 9.0.2.1, utilizing VUV undulator radiation to selectively ionize the scattered hydrocarbon free radical products (C{sub x}H{sub 2x+1}). The crossed molecular beam technique involves two reactant molecular beams fixed at 90{degrees}. The molecular beam sources are rotatable in the plane defined by the two beams. The scattered neutral products travel 12.0 cm where they are photoionized using the VUV undulator radiation, mass selected, and counted as a function of time. In the authors initial investigations they are using halogen atoms as protypical free radicals to abstract hydrogen atoms from small alkanes. Their first study has been looking at the reaction of Cl + propane {r_arrow} HCl + propyl radical. In their preliminary efforts the authors have measured the laboratory scattering angular distribution and time of flight spectra for the propyl radical products at collision energies of 9.6 kcal/mol and 14.9 kcal/mol.

  10. Hydrogen Atom Abstraction from Hydrocarbons by a Copper(III)-Hydroxide Complex

    OpenAIRE

    Dhar, Debanjan; Tolman, William B.

    2015-01-01

    With the aim of understanding the basis for the high rate of hydrogen atom abstraction (HAT) from dihydroanthracene (DHA) by the complex LCuOH (1; L = N,N′-bis(2,6-diisopropylphenyl)-2,6-pyridinedicarboxamide), the bond dissociation enthalpy of the reaction product LCu(H2O) (2) was determined through measurement of its pK a and E 1/2 in THF solution. In so doing, an equilibrium between 2 and LCu(THF) was characterized by UV–vis and EPR spectroscopy and cyclic voltammetry (CV). A high pK a of ...

  11. Chemical Kinetics of Hydrogen Atom Abstraction from Allylic Sites by (3)O2; Implications for Combustion Modeling and Simulation.

    Science.gov (United States)

    Zhou, Chong-Wen; Simmie, John M; Somers, Kieran P; Goldsmith, C Franklin; Curran, Henry J

    2017-03-09

    Hydrogen atom abstraction from allylic C-H bonds by molecular oxygen plays a very important role in determining the reactivity of fuel molecules having allylic hydrogen atoms. Rate constants for hydrogen atom abstraction by molecular oxygen from molecules with allylic sites have been calculated. A series of molecules with primary, secondary, tertiary, and super secondary allylic hydrogen atoms of alkene, furan, and alkylbenzene families are taken into consideration. Those molecules include propene, 2-butene, isobutene, 2-methylfuran, and toluene containing the primary allylic hydrogen atom; 1-butene, 1-pentene, 2-ethylfuran, ethylbenzene, and n-propylbenzene containing the secondary allylic hydrogen atom; 3-methyl-1-butene, 2-isopropylfuran, and isopropylbenzene containing tertiary allylic hydrogen atom; and 1-4-pentadiene containing super allylic secondary hydrogen atoms. The M06-2X/6-311++G(d,p) level of theory was used to optimize the geometries of all of the reactants, transition states, products and also the hinder rotation treatments for lower frequency modes. The G4 level of theory was used to calculate the electronic single point energies for those species to determine the 0 K barriers to reaction. Conventional transition state theory with Eckart tunnelling corrections was used to calculate the rate constants. The comparison between our calculated rate constants with the available experimental results from the literature shows good agreement for the reactions of propene and isobutene with molecular oxygen. The rate constant for toluene with O2 is about an order magnitude slower than that experimentally derived from a comprehensive model proposed by Oehlschlaeger and coauthors. The results clearly indicate the need for a more detailed investigation of the combustion kinetics of toluene oxidation and its key pyrolysis and oxidation intermediates. Despite this, our computed barriers and rate constants retain an important internal consistency. Rate constants

  12. Hydrogen atom abstraction from hydrocarbons by a copper(III)-hydroxide complex.

    Science.gov (United States)

    Dhar, Debanjan; Tolman, William B

    2015-01-28

    With the aim of understanding the basis for the high rate of hydrogen atom abstraction (HAT) from dihydroanthracene (DHA) by the complex LCuOH (1; L = N,N'-bis(2,6-diisopropylphenyl)-2,6-pyridinedicarboxamide), the bond dissociation enthalpy of the reaction product LCu(H2O) (2) was determined through measurement of its pK(a) and E(1/2) in THF solution. In so doing, an equilibrium between 2 and LCu(THF) was characterized by UV-vis and EPR spectroscopy and cyclic voltammetry (CV). A high pK(a) of 18.8 ± 1.8 and a low E(1/2) of -0.074 V vs Fc/Fc(+) in THF combined to yield an O-H BDE for 2 of 90 ± 3 kcal mol(-1) that is large relative to values for most transition metal oxo/hydroxo complexes. By taking advantage of the increased stability of 1 observed in 1,2-difluorobenzene (DFB) solvent, the kinetics of the reactions of 1 with a range of substrates with varying BDE values for their C-H bonds were measured. The oxidizing power of 1 was revealed through the accelerated decay of 1 in the presence of the substrates, including THF (BDE = 92 kcal mol(-1)) and cyclohexane (BDE = 99 kcal mol(-1)). CV experiments in THF solvent showed that 1 reacted with THF via rate-determining attack at the THF C-H(D) bonds with a kinetic isotope effect of 10.2. Analysis of the kinetic and thermodynamic data provides new insights into the basis for the high reactivity of 1 and the possible involvement of species like 1 in oxidation catalysis.

  13. Reactions of butadiyne. 1: The reaction with hydrogen atoms

    Science.gov (United States)

    Schwanebeck, W.; Warnatz, J.

    1984-01-01

    The reaction of hydrogen (H) atoms with butadiene (C4H2) was studied at room temperature in a pressure range between w mbar and 10 mbar. The primary step was an addition of H to C4H2 which is in its high pressure range at p 1 mbar. Under these conditions the following addition of a second H atom lies in the transition region between low and high pressure range. Vibrationally excited C4H4 can be deactivated to form buten-(1)-yne-(3)(C4H4) or decomposes into two C2H2 molecules. The rate constant at room temperature for primary step is given. The second order rate constant for the consumption of buten-(1)-yne-(3) is an H atom excess at room temperature is given.

  14. Hot hydrogen atoms reactions of interest in molecular evolution and interstellar chemistry

    Science.gov (United States)

    Becker, R. S.; Hong, K.; Hong, J. H.

    1974-01-01

    Hot hydrogen atoms which are photochemically generated initiate reactions among mixtures of methane, ethane, water and ammonia, to produce ethanol, organic amines, organic acids, and amino acids. Both ethanol and ethyl amine can also act as substrates for formation of amino acids. The one carbon substrate methane is sufficient as a carbon source to produce amino acids. Typical quantum yields for formation of amino acids are approximately 0.00002 to 0.00004. In one experiment, 6 protein amino acids were identified and 8 nonprotein amino acids verified utilizing gas chromatography-mass spectroscopy. We propose that hot atoms, especially hydrogen, initiate reactions in the thermodynamic nonequilibrium environment of interstellar space as well as in the atmospheres of planets.

  15. Slow hydrogen atom transfer reactions of oxo- and hydroxo-vanadium compounds: the importance of intrinsic barriers.

    Science.gov (United States)

    Waidmann, Christopher R; Zhou, Xin; Tsai, Erin A; Kaminsky, Werner; Hrovat, David A; Borden, Weston Thatcher; Mayer, James M

    2009-04-08

    Reactions are described that interconvert vanadium(IV) oxo-hydroxo complexes [V(IV)O(OH)(R(2)bpy)(2)]BF(4) (1a-c) and vanadium(V) dioxo complexes [V(V)O(2)(R(2)bpy)(2)]BF(4) (2a-c) [R(2)bpy = 4,4'-di-tert-butyl-2,2'-bipyridine ((t)Bu(2)bpy), a; 4,4'-dimethyl-2,2'-bipyridine (Me(2)bpy), b; 2,2'-bipyridine (bpy), c]. These are rare examples of pairs of isolated, sterically unencumbered, first-row metal-oxo/hydroxo complexes that differ by a hydrogen atom (H(+) + e(-)). The V(IV)-(t)Bu(2)bpy derivative 1a has a useful (1)H NMR spectrum, despite being paramagnetic. Complex 2a abstracts H(*) from organic substrates with weak O-H and C-H bonds, converting 2,6-(t)Bu(2)-4-MeO-C(6)H(2)OH (ArOH) and 2,2,6,6-tetramethyl-N-hydroxypiperidine (TEMPOH) to their corresponding radicals ArO(*) and TEMPO, hydroquinone to benzoquinone, and dihydroanthracene to anthracene. The equilibrium constant for 2a + ArOH 1a + ArO(*) is (4 +/- 2) x 10(-3), implying that the VO-H bond dissociation free energy (BDFE) is 70.6 +/- 1.2 kcal mol(-1). Consistent with this value, 1a is oxidized by 2,4,6-(t)Bu(3)C(6)H(2)O(*). All of these reactions are surprisingly slow, typically occurring over hours at ambient temperatures. The net hydrogen-atom pseudo-self-exchange 1a + 2b 2a + 1b, using the (t)Bu- and Me-bpy substituents as labels, also occurs slowly, with k(se) = 1.3 x 10(-2) M(-1) s(-1) at 298 K, DeltaH(double dagger) = 15 +/- 2 kcal mol(-1), and DeltaS(double dagger) = 16 +/- 5 cal mol(-1) K. Using this k(se) and the BDFE, the vanadium reactions are shown to follow the Marcus cross relation moderately well, with calculated rate constants within 10(2) of the observed values. The vanadium self-exchange reaction is ca. 10(6) slower than that for the related Ru(IV)O(py)(bpy)(2)(2+)/Ru(III)OH(py)(bpy)(2)(2+) self-exchange. The origin of this dramatic difference has been probed with DFT calculations on the self-exchange reactions of 1c + 2c and on monocationic ruthenium complexes with pyrrolate or

  16. Calculation of activation energies for hydrogen-atom abstractions by radicals containing carbon triple bonds

    Science.gov (United States)

    Brown, R. L.; Laufer, A. H.

    1981-01-01

    Activation energies are calculated by the bond-energy-bond-order (BEBO) and the bond-strength-bond-length (BSBL) methods for the reactions of C2H radicals with H2, CH4, and C2H6 and for the reactions of CN radicals with H2 and CH4. The BSBL technique accurately predicts the activation energies for these reactions while the BEBO method yields energies averaging 9 kcal higher than those observed. A possible reason for the disagreement is considered.

  17. Hydrogen atom transfer reactions in thiophenol: photogeneration of two new thione isomers.

    Science.gov (United States)

    Reva, Igor; Nowak, Maciej J; Lapinski, Leszek; Fausto, Rui

    2015-02-21

    Photoisomerization reactions of monomeric thiophenol have been investigated for the compound isolated in low-temperature argon matrices. The initial thiophenol population consists exclusively of the thermodynamically most stable thiol form. Phototransformations were induced by irradiation of the matrices with narrowband tunable UV light. Irradiation at λ > 290 nm did not induce any changes in isolated thiophenol molecules. Upon irradiation at 290-285 nm, the initial thiol form of thiophenol converted into its thione isomer, cyclohexa-2,4-diene-1-thione. This conversion occurs by transfer of an H atom from the SH group to a carbon atom at the ortho position of the ring. Subsequent irradiation at longer wavelengths (300-427 nm) demonstrated that this UV-induced hydrogen-atom transfer is photoreversible. Moreover, upon irradiation at 400-425 nm, the cyclohexa-2,4-diene-1-thione product converts, by transfer of a hydrogen atom from the ortho to para position, into another thione isomer, cyclohexa-2,5-diene-1-thione. The latter thione isomer is also photoreactive and is consumed if irradiated at λ atom-transfer isomerization reactions dominate the unimolecular photochemistry of thiophenol confined in a solid argon matrix. A set of low-intensity infrared bands, observed in the spectra of UV irradiated thiophenol, indicates the presence of a phenylthiyl radical with an H- atom detached from the SH group. Alongside the H-atom-transfer and H-atom-detachment processes, the ring-opening photoreaction occurred in cyclohexa-2,4-diene-1-thione by the cleavage of the C-C bond at the alpha position with respect to the thiocarbonyl C[double bond, length as m-dash]S group. The resulting open-ring conjugated thioketene adopts several isomeric forms, differing by orientations around single and double bonds. The species photogenerated upon UV irradiation of thiophenol were identified by comparison of their experimental infrared spectra with the spectra theoretically calculated for

  18. Rate constants for 1,5- and 1,6-hydrogen atom transfer reactions of mono-, di-, and tri-aryl-substituted donors, models for hydrogen atom transfers in polyunsaturated fatty acid radicals.

    Science.gov (United States)

    DeZutter, Christopher B; Horner, John H; Newcomb, Martin

    2008-03-06

    Rate constants for 1,5- and 1,6-hydrogen atom transfer reactions in models of polyunsaturated fatty acid radicals were measured via laser flash photolysis methods. Photolyses of PTOC (pyridine-2-thioneoxycarbonyl) ester derivatives of carboxylic acids gave primary alkyl radicals that reacted by 1,5-hydrogen transfer from mono-, di-, and tri-aryl-substituted positions or 1,6-hydrogen transfer from di- and tri-aryl-substituted positions to give UV-detectable products. Rate constants for reactions in acetonitrile at room temperature ranged from 1 x 10(4) to 4 x 10(6) s(-1). The activation energies for a matched pair of 1,5- and 1,6-hydrogen atom transfers giving tri-aryl-substituted radicals were approximately equal, as were the primary kinetic isotope effects, but the 1,5-hydrogen atom transfer reaction was 1 order of magnitude faster at room temperature than the 1,6-hydrogen atom transfer reaction due to a less favorable entropy of activation for the 1,6-transfer reaction. Solvent effects on the rate constants for the 1,5-hydrogen atom transfer reaction of the 2-[2-(diphenylmethyl)phenyl]ethyl radical at ambient temperature were as large as a factor of 2 with the reaction increasing in rate in lower polarity solvents. Hybrid density functional theory computations for the 1,5- and 1,6-hydrogen atom transfers of the tri-aryl-substituted donors were in qualitative agreement with the experimental results.

  19. Mechanistic insights into the oxidation of substituted phenols via hydrogen atom abstraction by a cupric-superoxo complex.

    Science.gov (United States)

    Lee, Jung Yoon; Peterson, Ryan L; Ohkubo, Kei; Garcia-Bosch, Isaac; Himes, Richard A; Woertink, Julia; Moore, Cathy D; Solomon, Edward I; Fukuzumi, Shunichi; Karlin, Kenneth D

    2014-07-16

    To obtain mechanistic insights into the inherent reactivity patterns for copper(I)-O2 adducts, a new cupric-superoxo complex [(DMM-tmpa)Cu(II)(O2(•-))](+) (2) [DMM-tmpa = tris((4-methoxy-3,5-dimethylpyridin-2-yl)methyl)amine] has been synthesized and studied in phenol oxidation-oxygenation reactions. Compound 2 is characterized by UV-vis, resonance Raman, and EPR spectroscopies. Its reactions with a series of para-substituted 2,6-di-tert-butylphenols (p-X-DTBPs) afford 2,6-di-tert-butyl-1,4-benzoquinone (DTBQ) in up to 50% yields. Significant deuterium kinetic isotope effects and a positive correlation of second-order rate constants (k2) compared to rate constants for p-X-DTBPs plus cumylperoxyl radical reactions indicate a mechanism that involves rate-limiting hydrogen atom transfer (HAT). A weak correlation of (k(B)T/e) ln k2 versus E(ox) of p-X-DTBP indicates that the HAT reactions proceed via a partial transfer of charge rather than a complete transfer of charge in the electron transfer/proton transfer pathway. Product analyses, (18)O-labeling experiments, and separate reactivity employing the 2,4,6-tri-tert-butylphenoxyl radical provide further mechanistic insights. After initial HAT, a second molar equiv of 2 couples to the phenoxyl radical initially formed, giving a Cu(II)-OO-(ArO') intermediate, which proceeds in the case of p-OR-DTBP substrates via a two-electron oxidation reaction involving hydrolysis steps which liberate H2O2 and the corresponding alcohol. By contrast, four-electron oxygenation (O-O cleavage) mainly occurs for p-R-DTBP which gives (18)O-labeled DTBQ and elimination of the R group.

  20. Mechanistic Insights into the Oxidation of Substituted Phenols via Hydrogen Atom Abstraction by a Cupric–Superoxo Complex

    Science.gov (United States)

    2015-01-01

    To obtain mechanistic insights into the inherent reactivity patterns for copper(I)–O2 adducts, a new cupric–superoxo complex [(DMM-tmpa)CuII(O2•–)]+ (2) [DMM-tmpa = tris((4-methoxy-3,5-dimethylpyridin-2-yl)methyl)amine] has been synthesized and studied in phenol oxidation–oxygenation reactions. Compound 2 is characterized by UV–vis, resonance Raman, and EPR spectroscopies. Its reactions with a series of para-substituted 2,6-di-tert-butylphenols (p-X-DTBPs) afford 2,6-di-tert-butyl-1,4-benzoquinone (DTBQ) in up to 50% yields. Significant deuterium kinetic isotope effects and a positive correlation of second-order rate constants (k2) compared to rate constants for p-X-DTBPs plus cumylperoxyl radical reactions indicate a mechanism that involves rate-limiting hydrogen atom transfer (HAT). A weak correlation of (kBT/e) ln k2 versus Eox of p-X-DTBP indicates that the HAT reactions proceed via a partial transfer of charge rather than a complete transfer of charge in the electron transfer/proton transfer pathway. Product analyses, 18O-labeling experiments, and separate reactivity employing the 2,4,6-tri-tert-butylphenoxyl radical provide further mechanistic insights. After initial HAT, a second molar equiv of 2 couples to the phenoxyl radical initially formed, giving a CuII–OO–(ArO′) intermediate, which proceeds in the case of p-OR-DTBP substrates via a two-electron oxidation reaction involving hydrolysis steps which liberate H2O2 and the corresponding alcohol. By contrast, four-electron oxygenation (O–O cleavage) mainly occurs for p-R-DTBP which gives 18O-labeled DTBQ and elimination of the R group. PMID:24953129

  1. Ring opening reaction dynamics in the reaction of hydrogen atoms with ethylene oxide

    Science.gov (United States)

    Shin, S. K.; Jarek, R. L.; Böhmer, E.; Wittig, C.

    1994-10-01

    Ethylene oxide, C2H4O, is a three-membered ring with a single oxygen atom bridging the two carbons. Reactions of H and D atoms with ethylene oxide have been studied in the gas phase to provide insight into the dynamics of three-membered ring opening. H atoms were produced by photolyzing HI in the wavelength range 240-266 nm. The channel leading to OH+C2H4 was monitored via laser-induced fluorescence (LIF) of the OH A 2Σ←X 2Π system. The D atom reaction yields OD with no hydrogen scrambling. With an available energy of 23 000 cm-1, the average OH D rotational energy is ˜350 cm-1 for OH(v=0) and OD(v=0) and ˜250 cm-1 for OD(v=1). OH(v=1) was not observed, while the OD(v=1) population was about one-tenth that of OD(v=0). There was no apparent bias in populations between Λ doublets in each of the spin-orbit states for both OH and OD. Doppler broadening of OH(v=0) rotational lines was measured to evaluate the average center-of-mass (c.m.) translational energy, which was found to be ˜2300 cm-1. On average, the ring opening process deposits ˜10% of the available energy into c.m. translation, ˜2% into OH rotation, and ˜88% into ethylene internal energy. Comparison with CH2CH2OH unimolecular dissociation dynamics and theoretical transition state calculations leads to a likely mechanism in which hydrogen abstracts oxygen via sequential C-O bond fission without involving a long-lived CH2CH2OH intermediate.

  2. Lewis acid-water/alcohol complexes as hydrogen atom donors in radical reactions.

    Science.gov (United States)

    Povie, Guillaume; Renaud, Philippe

    2013-01-01

    Water or low molecular weight alcohols are, due to their availability, low price and low toxicity ideal reagents for organic synthesis. Recently, it was reported that, despite the very strong BDE of the O-H bond, they can be used as hydrogen atom donors in place of expensive and/or toxic group 14 metal hydrides when boron and titanium(III) Lewis acids are present. This finding represents a considerable innovation and uncovers a new perspective on the paradigm of hydrogen atom transfers to radicals. We discuss here the influence of complex formation and other association processes on the efficacy of the hydrogen transfer step. A delicate balance between activation by complex formation and deactivation by further hydrogen bonding is operative.

  3. O2 insertion into group 9 metal-hydride bonds: evidence for oxygen activation through the hydrogen-atom-abstraction mechanism.

    Science.gov (United States)

    Keith, Jason M; Teets, Thomas S; Nocera, Daniel G

    2012-09-03

    A detailed density functional study was performed to examine the reaction of mixed-valence dirhodium and diiridium species [M(2)(0,II)(tfepma)(2)(CN(t)Bu)(2)(Cl)(2) (1, tfepma = MeN[P(OCH(2)CF(3))(2)](2), CN(t)Bu = tert-butyl isocyaninde)] with HCl and oxygen with an interest in examining the pathways for oxygen insertion into the intermediate metal hydride to form hydroperoxo species. The O(2) hydrogen atom abstraction mechanism for both the Rh and Ir was found to be feasible. This is the first time this mechanism has been applied to a Rh system and only the second time it has been examined for a system other than Pd. The competing trans HCl reductive elimination pathway was also examined and found to be greatly dependent on the stereochemistry of the starting hydride primarily due to the intermediate formed upon the loss of Cl(-). As a result, the reductive elimination pathway was more favorable by 11.5 kcal/mol for the experimentally observed Ir stereoisomer, while the two pathways were isoenergetic for the other stereoisomer of the Rh complex. All findings are consistent with the kinetics study previously performed.

  4. The tert-butoxyl radical mediated hydrogen atom transfer reactions of the Parkinsonian proneurotoxin 1-methyl-4-phenyl-1,2,3,6-tetrahydropyridine and selected tertiary amines.

    Science.gov (United States)

    Suleman, N Kamrudin; Flores, Joey; Tanko, James M; Isin, Emre Mehmet; Castagnoli, Neal

    2008-09-15

    Previous studies have shown that the hydrogen atom transfer (HAT) reactions of tert-butoxyl radical from the Parkinsonian proneurotoxin 1-methyl-4-phenyl-1,2,3,6-tetrahydropyridine (MPTP) occur with low selectivity at the allylic and non-allylic alpha-C-H positions. In this paper, we report a more comprehensive regiochemical study on the reactivity of the tert-butoxyl radical as well as on the associated primary kinetic deuterium isotope effects for the various hydrogen atom abstractions of MPTP. In addition, the results of a computational study to estimate the various C-H bond dissociation energies of MPTP are presented. The results of the present study show the allylic/non-allylic selectivity is approximately 73:21. The behavior of the tert-butoxyl radical mediated oxidation of MPTP contrasts with this reaction as catalyzed by monoamine oxidase B (MAO-B) that occurs selectively at the allylic alpha-carbon. These observations lead to the conclusion that the tert-butoxyl radical is not a good chemical model for the MAO-B-catalyzed bioactivation of MPTP.

  5. The effect of moderators on the reactions of hot hydrogen atoms with methane

    CERN Document Server

    Estrup, Peder J.

    1960-01-01

    The reaction of recoil tritium with methane has been examined in further detail. The previous hypothesis that this system involves a hot displacement reaction of high kinetic energy hydrogen to give CH$_{3}$T, CH$_{2}$T and HT is confirmed. The effect of moderator on this process is studied by the addition of noble gases. As predicted these gases inhibit the hot reaction action, their efficiency in this respect being He > Ne > A > Se. The data are quantitatively in accord with a theory of hot atom kinetics. The mechanism of the hot displacement process is briefly discussed.

  6. The reaction of hydrogen atoms with hydrogen peroxide as a function of temperature

    DEFF Research Database (Denmark)

    Lundström, T.; Christensen, H.; Sehested, K.

    2001-01-01

    The temperature dependence for the reaction of H atoms with H2O2 at pH 1 has been determined using pulse radiolysis technique. The reaction was studied in the temperature range 10-120 degreesC. The rate constant at 25 degreesC was found to be 5.1 +/- 0.5 x 10(7) dm(3) mol(-1) s(-1) and the activa...

  7. Temperature-dependent kinetics of charge transfer, hydrogen-atom transfer, and hydrogen-atom expulsion in the reaction of CO+ with CH4 and CD4.

    Science.gov (United States)

    Melko, Joshua J; Ard, Shaun G; Johnson, Ryan S; Shuman, Nicholas S; Guo, Hua; Viggiano, Albert A

    2014-09-18

    We have determined the rate constants and branching ratios for the reactions of CO(+) with CH4 and CD4 in a variable-temperature selected ion flow tube. We find that the rate constants are collisional for all temperatures measured (193-700 K for CH4 and 193-500 K for CD4). For the CH4 reaction, three product channels are identified, which include charge transfer (CH4(+) + CO), H-atom transfer (HCO(+) + CH3), and H-atom expulsion (CH3CO(+) + H). H-atom transfer is slightly preferred to charge transfer at low temperature, with the charge-transfer product increasing in contribution as the temperature is increased (H-atom expulsion is a minor product for all temperatures). Analogous products are identified for the CD4 reaction. Density functional calculations on the CO(+) + CH4 reaction were also conducted, revealing that the relative temperature dependences of the charge-transfer and H-atom transfer pathways are consistent with an initial charge transfer followed by proton transfer.

  8. Highly regioselective hydride transfer, oxidative dehydrogenation, and hydrogen-atom abstraction in the thermal gas-phase chemistry of [Zn(OH)](+)/C3H8.

    Science.gov (United States)

    Wu, Xiao-Nan; Zhao, Hai-Tao; Li, Jilai; Schlangen, Maria; Schwarz, Helmut

    2014-12-28

    The thermal reactions of [Zn(OH)](+) with C3H8 have been studied by means of gas-phase experiments and computational investigation. Two types of C-H bond activation are observed in the experiment, and pertinent mechanistic features include inter alia: (i) the metal center of [Zn(OH)](+) serves as active site in the hydride transfer to generate [i-C3H7](+) as major product, (ii) generally, a high regioselectivity is accompanied by remarkable chemoselectivity: for example, the activation of a methyl C-H bond results mainly in the formation of water and [Zn(C3,H7)](+). According to computational work, this ionic product corresponds to [HZn(CH3CH=CH2)](+). Attack of the zinc center at a secondary C-H bond leads preferentially to hydride transfer, thus giving rise to the generation of [i-C3H7](+); (iii) upon oxidative dehydrogenation (ODH), liberation of CH3CH2=CH2 occurs to produce [HZn(H2O)](+). Both, ODH as well as H2O loss proceed through the same intermediate which is characterized by the fact that a methylene hydrogen atom from the substrate is transferred to the zinc and one hydrogen atom from the methyl group to the OH group of [Zn(OH)](+). The combined experimental/computational gas-phase study of C-H bond activation by zinc hydroxide provides mechanistic insight into related zinc-catalyzed large-scale processes and identifies the crucial role that the Lewis-acid character of zinc plays.

  9. Hydrogen-atom transfer reactions from ortho-alkoxy-substituted phenols: an experimental approach.

    Science.gov (United States)

    Amorati, Riccardo; Menichetti, Stefano; Mileo, Elisabetta; Pedulli, Gian Franco; Viglianisi, Caterina

    2009-01-01

    The role of intramolecular hydrogen bonding (HB) on the bond-dissociation enthalpy (BDE) of the phenolic O-H and on the kinetics of H-atom transfer to peroxyl radicals (k(inh)) of several 2-alkoxyphenols was experimentally quantified by the EPR equilibration technique and by inhibited autoxidation studies. These compounds can be regarded as useful models for studying the H-atom abstraction from 2-OR phenols, such as many lignans, reduced coenzyme Q and curcumin. The effects of the various substituents on the BDE(O-H) of 2-methoxy, 2-methoxy-4-methyl, 2,4-dimethoxyphenols versus phenol were measured in benzene solution as -1.8; -3.7; -5.4 kcal mol(-1), respectively. In the case of polymethoxyphenols, significant deviations from the BDE(O-H) values predicted by the additive effects of the substituents were found. The logarithms of the k(inh) constants in cumene were inversely related to the BDE(O-H) values, obeying a linear Evans-Polanyi plot with the same slope of other substituted phenols and a y-axis intercept slightly smaller than that of 2,6-dimethyl phenols. In the cases of phenols having the 2-OR substituent included in a five-membered condensed ring (i.e, compounds 9-11), both conformational isomers in which the OH group points toward or away from the oxygen in position 2 were detected by FTIR spectroscopy and the intramolecular HB strength was thus estimated. The contribution to the BDE(O-H) of the ortho-OR substituent in 9, corrected for intramolecular HB formation, was calculated as -5.6 kcal mol(-1). The similar behaviour of cyclic and non-cyclic ortho-alkoxy derivatives clearly showed that the preferred conformation of the OMe group in ortho-methoxyphenoxyl radicals is that in which the methyl group points away from the phenoxyl oxygen, in contrast to the geometries predicted by DFT calculations.

  10. Single step synthesis of gold-amino acid composite, with the evidence of the catalytic hydrogen atom transfer (HAT) reaction, for the electrochemical recognition of Serotonin

    Science.gov (United States)

    Choudhary, Meenakshi; Siwal, Samarjeet; Nandi, Debkumar; Mallick, Kaushik

    2016-03-01

    A composite architecture of amino acid and gold nanoparticles has been synthesized using a generic route of 'in-situ polymerization and composite formation (IPCF)' [1,2]. The formation mechanism of the composite has been supported by a model hydrogen atom (H•≡H++e-) transfer (HAT) type of reaction which belongs to the proton coupled electron transfer (PCET) mechanism. The 'gold-amino acid composite' was used as a catalyst for the electrochemical recognition of Serotonin.

  11. Evidence for a Precursor Complex in C-H Hydrogen Atom Transfer Reactions Mediated by a Manganese(IV) Oxo Complex

    OpenAIRE

    Garcia Bosch, Isaac; Company Casadevall, Anna; Cady, Clyde W.; Styring, Stenbjörn; Browne, Wesley R; Ribas Salamaña, Xavi; Costas Salgueiro, Miquel

    2011-01-01

    HAT trick: [MnIV(OH)2(H,MePytacn)]2+ (A) and [MnIV(O)(OH)(H,MePytacn)]+ (B) differ in their reactions with CH bonds: compound A engages in typical single-step hydrogen atom transfer (HAT) reactions, whereas B first forms a substrate–B encounter complex (C; see scheme). This equilibrium alters the relative CH reactivity from that expected from CH bond dissociation energies Aquest mateix article està publicat a l'edició alemanya d''Angewandte Chemie' (ISSN 0044-8249, EISSN 1521-3757), 2011, ...

  12. Reactions of the cumyloxyl radical with secondary amides. The influence of steric and stereoelectronic effects on the hydrogen atom transfer reactivity and selectivity.

    Science.gov (United States)

    Salamone, Michela; Basili, Federica; Mele, Riccardo; Cianfanelli, Marco; Bietti, Massimo

    2014-12-19

    A time-resolved kinetic study of the hydrogen atom transfer (HAT) reactions from secondary alkanamides to the cumyloxyl radical was carried out in acetonitrile. HAT predominantly occurs from the N-alkyl α-C-H bonds, and a >60-fold decrease in kH was observed by increasing the steric hindrance of the acyl and N-alkyl groups. The role of steric and stereoelectronic effects on the reactivity and selectivity is discussed in the framework of HAT reactions from peptides.

  13. Kinetic Study of the Reaction of the Phthalimide-N-oxyl Radical with Amides: Structural and Medium Effects on the Hydrogen Atom Transfer Reactivity and Selectivity.

    Science.gov (United States)

    Bietti, Massimo; Forcina, Veronica; Lanzalunga, Osvaldo; Lapi, Andrea; Martin, Teo; Mazzonna, Marco; Salamone, Michela

    2016-12-02

    A kinetic study of the hydrogen atom transfer (HAT) reactions from a series of secondary N-(4-X-benzyl)acetamides and tertiary amides to the phthalimide-N-oxyl radical (PINO) has been carried out. The results indicate that HAT is strongly influenced by structural and medium effects; in particular, the addition of Brønsted and Lewis acids determines a significant deactivation of C-H bonds α to the amide nitrogen of these substrates. Thus, by changing the reaction medium, it is possible to carefully control the regioselectivity of the aerobic oxidation of amides catalyzed by N-hydroxyphthalimide, widening the synthetic versatility of this process.

  14. Inside the Hydrogen Atom

    CERN Document Server

    Nowakowski, M; Fierro, D Bedoya; Manjarres, A D Bermudez

    2016-01-01

    We apply the non-linear Euler-Heisenberg theory to calculate the electric field inside the hydrogen atom. We will demonstrate that the electric field calculated in the Euler-Heisenberg theory can be much smaller than the corresponding field emerging from the Maxwellian theory. In the hydrogen atom this happens only at very small distances. This effect reduces the large electric field inside the hydrogen atom calculated from the electromagnetic form-factors via the Maxwell equations. The energy content of the field is below the pair production threshold.

  15. Rate constants and isotope effects for the reaction of H-atom abstraction from RH substrates by PINO radicals

    Science.gov (United States)

    Opeida, I. A.; Litvinov, Yu. E.; Kushch, O. V.; Kompanets, M. A.; Shendrik, A. N.; Matvienko, A. G.; Novokhatko, A. A.

    2016-11-01

    The kinetics of the reactions of hydrogen atom abstraction from the C-H bonds of substrates of different structures by phthalimide- N-oxyl radicals is studied. The rate constants of this reaction are measured and the kinetic isotope effects are determined. It is shown that in addition to the thermodynamic factor, Coulomb forces and donor-acceptor interactions affect the reaction between phthalimide- N-oxyl radicals and substrate molecules, altering the shape of the transition state. This favors the tunneling of hydrogen atoms and leads to a substantial reduction in the activation energy of the process.

  16. Electron-stimulated reactions in layered CO/H{sub 2}O films: Hydrogen atom diffusion and the sequential hydrogenation of CO to methanol

    Energy Technology Data Exchange (ETDEWEB)

    Petrik, Nikolay G.; Kimmel, Greg A., E-mail: gregory.kimmel@pnnl.gov [Physical Sciences Division, Pacific Northwest National Laboratory, MSIN K8-88, P.O. Box 999, Richland, Washington 99352 (United States); Monckton, Rhiannon J.; Koehler, Sven P. K. [School of Chemistry, The University of Manchester, Manchester M13 9PL (United Kingdom); Photon Science Institute, The University of Manchester, Manchester M13 9PL (United Kingdom); UK Dalton Cumbrian Facility, The University of Manchester, Moor Row, Whitehaven CA24 3HA (United Kingdom)

    2014-05-28

    Low-energy (100 eV) electron-stimulated reactions in layered H{sub 2}O/CO/H{sub 2}O ices are investigated. For CO layers buried in amorphous solid water (ASW) films at depths of 50 monolayers (ML) or less from the vacuum interface, both oxidation and reduction reactions are observed. However, for CO buried more deeply in ASW films, only the reduction of CO to methanol is observed. Experiments with layered films of H{sub 2}O and D{sub 2}O show that the hydrogen atoms participating in the reduction of the buried CO originate in the region that is 10–50 ML below the surface of the ASW films and subsequently diffuse through the film. For deeply buried CO layers, the CO reduction reactions quickly increase with temperature above ∼60 K. We present a simple chemical kinetic model that treats the diffusion of hydrogen atoms in the ASW and sequential hydrogenation of the CO to methanol to account for the observations.

  17. Importance of π-stacking interactions in the hydrogen atom transfer reactions from activated phenols to short-lived N-oxyl radicals.

    Science.gov (United States)

    Mazzonna, Marco; Bietti, Massimo; DiLabio, Gino A; Lanzalunga, Osvaldo; Salamone, Michela

    2014-06-06

    A kinetic study of the hydrogen atom transfer from activated phenols (2,6-dimethyl- and 2,6-di-tert-butyl-4-substituted phenols, 2,2,5,7,8-pentamethylchroman-6-ol, caffeic acid, and (+)-cathechin) to a series of N-oxyl radical (4-substituted phthalimide-N-oxyl radicals (4-X-PINO), 6-substituted benzotriazole-N-oxyl radicals (6-Y-BTNO), 3-quinazolin-4-one-N-oxyl radical (QONO), and 3-benzotriazin-4-one-N-oxyl radical (BONO)), was carried out by laser flash photolysis in CH3CN. A significant effect of the N-oxyl radical structure on the hydrogen transfer rate constants (kH) was observed with kH values that monotonically increase with increasing NO-H bond dissociation energy (BDENO-H) of the N-hydroxylamines. The analysis of the kinetic data coupled to the results of theoretical calculations indicates that these reactions proceed by a hydrogen atom transfer (HAT) mechanism where the N-oxyl radical and the phenolic aromatic rings adopt a π-stacked arrangement. Theoretical calculations also showed pronounced structural effects of the N-oxyl radicals on the charge transfer occurring in the π-stacked conformation. Comparison of the kH values measured in this study with those previously reported for hydrogen atom transfer to the cumylperoxyl radical indicates that 6-CH3-BTNO is the best N-oxyl radical to be used as a model for evaluating the radical scavenging ability of phenolic antioxidants.

  18. High-performance liquid chromatographic method to evaluate the hydrogen atom transfer during reaction between 1,1-diphenyl-2-picryl-hydrazyl radical and antioxidants

    Energy Technology Data Exchange (ETDEWEB)

    Boudier, Ariane; Tournebize, Juliana [CITHEFOR - EA 3452, Faculte de Pharmacie, Nancy-Universite, 5 Rue Albert Lebrun, BP 80403, 54001 Nancy Cedex (France); Bartosz, Grzegorz [Department of Molecular Biophysics, University of Lodz, Lodz (Poland); El Hani, Safae; Bengueddour, Rachid [Laboratoire de Nutrition et Sante, Biology Department, Faculty of Sciences, Ibn Tofail University, Kenitra (Morocco); Sapin-Minet, Anne [CITHEFOR - EA 3452, Faculte de Pharmacie, Nancy-Universite, 5 Rue Albert Lebrun, BP 80403, 54001 Nancy Cedex (France); Leroy, Pierre, E-mail: pierre.leroy@pharma.uhp-nancy.fr [CITHEFOR - EA 3452, Faculte de Pharmacie, Nancy-Universite, 5 Rue Albert Lebrun, BP 80403, 54001 Nancy Cedex (France)

    2012-01-20

    Highlights: Black-Right-Pointing-Pointer Both 1,1-diphenyl-2-picrylhydrazyl radical and its product measurement by HPLC. Black-Right-Pointing-Pointer Lowest limit of detection by monitoring 1,1-diphenyl-2-picryl-hydrazine. Black-Right-Pointing-Pointer Adsorption problem of the radical on HPLC parts have been pointed out. - Abstract: 1,1-Diphenyl-2-picrylhydrazyl (DPPH{center_dot}) is a stable nitrogen centred radical widely used to evaluate direct radical scavenging properties of various synthetic or natural antioxidants (AOs). The bleaching rate of DPPH{center_dot} absorbance at 515 nm is usually monitored for this purpose. In order to avoid the interference of complex coloured natural products used as antioxidant supplements or cosmetics, HPLC systems have been reported as alternative techniques to spectrophotometry. They also rely upon measurement of DPPH{center_dot} quenching rate and none of them permits to identify and measure 1,1-diphenyl-2-picryl-hydrazine (DPPH-H), the reduced product of DPPH{center_dot} resulting from hydrogen atom transfer (HAT), which is the main mechanism of the reaction between DPPH{center_dot} and AOs. We presently report an HPLC method devoted to the simultaneous measurement of DPPH{center_dot} and DPPH-H. Both were fully separated on a C18 column eluted with acetonitrile-10 mM ammonium citrate buffer pH 6.8 (70:30, v/v) and detected at 330 nm. Adsorption process of DPPH{center_dot} onto materials of the HPLC system was pointed out. Consequently, the linearity range observed for DPPH{center_dot} was restricted, thus a much lower limit of detection was obtained for DPPH-H than for DPPH{center_dot} using standards (0.02 and 14 {mu}M, respectively). The method was applied to three commonly used AOs, i.e. Trolox{sup Registered-Sign }, ascorbic acid and GSH, and compared with spectrophotometry. Further application to complex matrices (cell culture media, vegetal extracts) and nanomaterials demonstrated (i) its usefulness because of

  19. Steric Effect for Proton, Hydrogen-Atom, andHydride Transfer Reactions with Geometric Isomers of NADH-Model Ruthenium Complexes

    Energy Technology Data Exchange (ETDEWEB)

    Fujita E.; Cohen, B.W.; Polyansky, D.E.; Achord, P.; Cabelli, D.; Muckerman, J.T.; Tanaka, K.; Thummel, R.P.; Zong, R.

    2012-01-01

    Two isomers, [Ru(1)]{sup 2+} (Ru = Ru(bpy){sub 2}, bpy = 2,2{prime}-bipyridine, 1 = 2-(pyrid-2{prime}-yl)-1-azaacridine) and [Ru(2)]{sup 2+} (2 = 3-(pyrid-2{prime}-yl)-4-azaacridine), are bio-inspired model compounds containing the nicotinamide functionality and can serve as precursors for the photogeneration of C-H hydrides for studying reactions pertinent to the photochemical reduction of metal-C{sub 1} complexes and/or carbon dioxide. While it has been shown that the structural differences between the azaacridine ligands of [Ru(1)]{sup 2+} and [Ru(2)]{sup 2+} have a significant effect on the mechanism of formation of the hydride donors, [Ru(1HH)]{sup 2+} and [Ru(2HH)]{sup 2+}, in aqueous solution, we describe the steric implications for proton, net-hydrogen-atom and net-hydride transfer reactions in this work. Protonation of [Ru(2{sup {sm_bullet}-})]{sup +} in aprotic and even protic media is slow compared to that of [Ru(1{sup {sm_bullet}-})]{sup +}. The net hydrogen-atom transfer between *[Ru(1)]{sup 2+} and hydroquinone (H{sub 2}Q) proceeds by one-step EPT, rather than stepwise electron-proton transfer. Such a reaction was not observed for *[Ru(2)]{sup 2+} because the non-coordinated N atom is not easily available for an interaction with H{sub 2}Q. Finally, the rate of the net hydride ion transfer from [Ru(1HH)]{sup 2+} to [Ph{sub 3}C]{sup +} is significantly slower than that of [Ru(2HH)]{sup 2+} owing to steric congestion at the donor site.

  20. Reactivity and selectivity patterns in hydrogen atom transfer from amino acid C-H bonds to the cumyloxyl radical: polar effects as a rationale for the preferential reaction at proline residues.

    Science.gov (United States)

    Salamone, Michela; Basili, Federica; Bietti, Massimo

    2015-04-03

    Absolute rate constants for hydrogen atom transfer (HAT) from the C-H bonds of N-Boc-protected amino acids to the cumyloxyl radical (CumO(•)) were measured by laser flash photolysis. With glycine, alanine, valine, norvaline, and tert-leucine, HAT occurs from the α-C-H bonds, and the stability of the α-carbon radical product plays a negligible role. With leucine, HAT from the α- and γ-C-H bonds was observed. The higher kH value measured for proline was explained in terms of polar effects, with HAT that predominantly occurs from the δ-C-H bonds, providing a rationale for the previous observation that proline residues represent favored HAT sites in the reactions of peptides and proteins with (•)OH. Preferential HAT from proline was also observed in the reactions of CumO(•) with the dipeptides N-BocProGlyOH and N-BocGlyGlyOH. The rate constants measured for CumO(•) were compared with the relative rates obtained previously for the corresponding reactions of different hydrogen-abstracting species. The behavior of CumO(•) falls between those observed for the highly reactive radicals Cl(•) and (•)OH and the significantly more stable Br(•). Taken together, these results provide a general framework for the description of the factors that govern reactivity and selectivity patterns in HAT reactions from amino acid C-H bonds.

  1. Reactions of the phthalimide N-oxyl radical (PINO) with activated phenols: the contribution of π-stacking interactions to hydrogen atom transfer rates.

    Science.gov (United States)

    D'Alfonso, Claudio; Bietti, Massimo; DiLabio, Gino A; Lanzalunga, Osvaldo; Salamone, Michela

    2013-02-01

    The kinetics of reactions of the phthalimide N-oxyl radical (PINO) with a series of activated phenols (2,2,5,7,8-pentamethylchroman-6-ol (PMC), 2,6-dimethyl- and 2,6-di-tert-butyl-4-substituted phenols) were investigated by laser flash photolysis in CH(3)CN and PhCl in order to establish if the reactions with PINO can provide a useful tool for evaluating the radical scavenging ability of phenolic antioxidants. On the basis of the small values of deuterium kinetic isotope effects, the relatively high and negative ρ values in the Hammett correlations and the results of theoretical calculations, we suggest that these reactions proceed by a hydrogen atom transfer (HAT) mechanism having a significant degree of charge transfer resulting from a π-stacked conformation between PINO and the aromatic ring of the phenols. Kinetic solvent effects were analyzed in detail for the hydrogen transfer from 2,4,6-trimethylphenol to PINO and the data obtained are in accordance with the Snelgrove-Ingold equation for HAT. Experimental rate constants for the reactions of PINO with activated phenols are in accordance with those predicted by applying the Marcus cross relation.

  2. Formation of hydrogen peroxide and water from the reaction of cold hydrogen atoms with solid oxygen at 10K

    CERN Document Server

    Miyauchi, N; Chigai, T; Nagaoka, A; Watanabe, N; Kouchi, A

    2008-01-01

    The reactions of cold H atoms with solid O2 molecules were investigated at 10 K. The formation of H2O2 and H2O has been confirmed by in-situ infrared spectroscopy. We found that the reaction proceeds very efficiently and obtained the effective reaction rates. This is the first clear experimental evidence of the formation of water molecules under conditions mimicking those found in cold interstellar molecular clouds. Based on the experimental results, we discuss the reaction mechanism and astrophysical implications.

  3. Reaction of hydrogen atoms with singlet delta oxygen (O2(a 1Δg)). Is everything completely clear?

    Science.gov (United States)

    Chukalovsky, A. A.; Klopovsky, K. S.; Palov, A. P.; Mankelevich, Yu A.; Rakhimova, T. V.

    2016-12-01

    In this paper, a comprehensive analysis of the reaction H  +  O2(a 1Δg)  →  products and its channels, including available experimental data, theoretical estimations and kinetic studies, was carried out. A possible intrinsic mechanism of the reaction H  +  O2(a 1Δg)  →  products, taking into account Renner-Teller coupling between the lowest doublet 2A‧ and 2A″ states of a HO2 molecule was suggested. The proposed mechanism allows qualitative justification of the available data on the high probability for the quenching reaction: H  +  O2(a 1Δg)  →  H  +  O2(3Σg). The effect of the reactions, including electronically excited \\text{HO}2\\ast molecules on the evaluation of temperature dependencies for the total and branching rate constants of the reaction H  +  O2(a 1Δg)  →  products at low temperatures, was investigated. The value of the reaction H  +  O2(a 1Δg)(+M)  →  HO2(2A‧,2A″)(+M) rate constant was evaluated from shock tube experiments on O2(a 1Δg) quenching in a lean H2-O2-O2(a 1Δg) mixture. Based on the obtained results, temperature and pressure dependencies for the rate constants of the reaction H  +  O2(a 1Δg)  →  product channels were recommended for the simulations, together with the proposed kinetic sub-mechanism for O2(a 1Δg) chemistry in H2-O2 mixtures.

  4. Sampling the Hydrogen Atom

    Directory of Open Access Journals (Sweden)

    Graves N.

    2013-01-01

    Full Text Available A model is proposed for the hydrogen atom in which the electron is an objectively real particle orbiting at very near to light speed. The model is based on the postulate that certain velocity terms associated with orbiting bodies can be considered as being af- fected by relativity. This leads to a model for the atom in which the stable electron orbits are associated with orbital velocities where Gamma is n /α , leading to the idea that it is Gamma that is quantized and not angular momentum as in the Bohr and other models. The model provides a mechanism which leads to quantization of energy levels within the atom and also provides a simple mechanical explanation for the Fine Struc- ture Constant. The mechanism is closely associated with the Sampling theorem and the related phenomenon of aliasing developed in the mid-20th century by engineers at Bell labs.

  5. Einstein's Hydrogen Atom

    CERN Document Server

    Kim, Y S

    2011-01-01

    In 1905, Einstein formulated his special relativity for point particles. For those particles, his Lorentz covariance and energy-momentum relation are by now firmly established. How about the hydrogen atom? It is possible to perform Lorentz boosts on the proton assuming that it is a point particle. Then what happens to the electron orbit? The orbit could go through an elliptic deformation, but it is not possible to understand this problem without quantum mechanics, where the orbit is a standing wave leading to a localized probability distribution. Is this concept consistent with Einstein's Lorentz covariance? Dirac, Wigner, and Feynman contributed important building blocks for understanding this problem. The remaining problem is to assemble those blocks to construct a Lorentz-covariant picture of quantum bound states based on standing waves. It is shown possible to assemble those building blocks using harmonic oscillators.

  6. Kinetic solvent effects on the reactions of the cumyloxyl radical with tertiary amides. Control over the hydrogen atom transfer reactivity and selectivity through solvent polarity and hydrogen bonding.

    Science.gov (United States)

    Salamone, Michela; Mangiacapra, Livia; Bietti, Massimo

    2015-01-16

    A laser flash photolysis study on the role of solvent effects on hydrogen atom transfer (HAT) from the C-H bonds of N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMA), N-formylpyrrolidine (FPRD), and N-acetylpyrrolidine (APRD) to the cumyloxyl radical (CumO(•)) was carried out. From large to very large increases in the HAT rate constant (kH) were measured on going from MeOH and TFE to isooctane (kH(isooctane)/kH(MeOH) = 5-12; kH(isooctane)/kH(TFE) > 80). This behavior was explained in terms of the increase in the extent of charge separation in the amides determined by polar solvents through solvent-amide dipole-dipole interactions and hydrogen bonding, where the latter interactions appear to play a major role with strong HBD solvents such as TFE. These interactions increase the electron deficiency of the amide C-H bonds, deactivating these bonds toward HAT to an electrophilic radical such as CumO(•), indicating that changes in solvent polarity and hydrogen bonding can provide a convenient method for deactivation of the C-H bond of amides toward HAT. With DMF, a solvent-induced change in HAT selectivity was observed, suggesting that solvent effects can be successfully employed to control the reaction selectivity in HAT-based procedures for the functionalization of C-H bonds.

  7. The Unique Gas-Phase Chemistry of the [AuO](+) /CH4 Couple: Selective Oxygen-Atom Transfer to, Rather than Hydrogen-Atom Abstraction from, Methane.

    Science.gov (United States)

    Zhou, Shaodong; Li, Jilai; Schlangen, Maria; Schwarz, Helmut

    2016-08-26

    The thermal reaction of [AuO](+) with methane has been explored using FT-ICR mass spectrometry complemented by high-level quantum chemical calculations. In contrast to the previously studied congener [CuO](+) , and to [AgO](+) , [AuO](+) reacts with CH4 exclusively via oxygen-atom transfer to form CH3 OH, and a novel mechanistic scenario for this selective oxidation process has been revealed. Also, the origin of the inertness of the [AgO](+) /CH4 couple has been addressed computationally.

  8. Kinetic solvent effects on hydrogen abstraction reactions from carbon by the cumyloxyl radical. The importance of solvent hydrogen-bond interactions with the substrate and the abstracting radical.

    Science.gov (United States)

    Salamone, Michela; Giammarioli, Ilaria; Bietti, Massimo

    2011-06-03

    A kinetic study of the hydrogen atom abstraction reactions from propanal (PA) and 2,2-dimethylpropanal (DMPA) by the cumyloxyl radical (CumO•) has been carried out in different solvents (benzene, PhCl, MeCN, t-BuOH, MeOH, and TFE). The corresponding reactions of the benzyloxyl radical (BnO•) have been studied in MeCN. The reaction of CumO• with 1,4-cyclohexadiene (CHD) also has been investigated in TFE solution. With CHD a 3-fold increase in rate constant (k(H)) has been observed on going from benzene, PhCl, and MeCN to TFE. This represents the first observation of a sizable kinetic solvent effect for hydrogen atom abstraction reactions from hydrocarbons by alkoxyl radicals and indicates that strong HBD solvents influence the hydrogen abstraction reactivity of CumO•. With PA and DMPA a significant decrease in k(H) has been observed on going from benzene and PhCl to MeOH and TFE, indicative of hydrogen-bond interactions between the carbonyl lone pair and the solvent in the transition state. The similar k(H) values observed for the reactions of the aldehydes in MeOH and TFE point toward differential hydrogen bond interactions of the latter solvent with the substrate and the radical in the transition state. The small reactivity ratios observed for the reactions of CumO• and BnO• with PA and DMPA (k(H)(BnO•)/k(H)(CumO•) = 1.2 and 1.6, respectively) indicate that with these substrates alkoxyl radical sterics play a minor role.

  9. A combined experimental, theoretical, and Van't Hoff model study for identity methyl, proton, hydrogen atom, and hydride exchange reactions. Correlation with three-center four-, three-, and two-electron systems

    Science.gov (United States)

    Buck, Henk M.

    We have studied carbon transfer reactions following an SN2 reaction profile. With ab initio calculations and experimental geometries concerning the nature of the various complexes indicated as stable, intermediate, and transition state we were able to show the additional value of van't Hoff's tetrahedral configuration by changing its geometry via a trigonal pyramid into a trigonal bipyramid. The ratio of the apical bond and corresponding tetrahedral bond distances is then nearly 1.333. The relevance of this approach has also been shown for identity proton-(hydrogen atom-, and hydride-) in-line reactions. The use of this geometrical transmission will be demonstrated for the hydrogen bonding distances in e.g., DNA duplexes and other biological (supra) molecular systems.

  10. A DFT-based investigation of hydrogen abstraction reactions from methylated polycyclic aromatic hydrocarbons.

    Science.gov (United States)

    Hemelsoet, Karen; Van Speybroeck, Veronique; Waroquier, Michel

    2008-11-10

    The growth of polycyclic aromatic hydrocarbons (PAHs) is in many areas of combustion and pyrolysis of hydrocarbons an inconvenient side effect that warrants an extensive investigation of the underlying reaction mechanism, which is known to be a cascade of radical reactions. Herein, the focus lies on one of the key reaction classes within the coke formation process: hydrogen abstraction reactions induced by a methyl radical from methylated benzenoid species. It has been shown previously that hydrogen abstractions determine the global PAH formation rate. In particular, the influence of the polyaromatic environment on the thermodynamic and kinetic properties is the subject of a thorough exploration. Reaction enthalpies at 298 K, reaction barriers at 0 K, rate constants, and kinetic parameters (within the temperature interval 700-1100 K) are calculated by using B3LYP/6-31+G(d,p) geometries and BMK/6-311+G(3df,2p) single-point energies. This level of theory has been validated with available experimental data for the abstraction at toluene. The enhanced stability of the product benzylic radicals and its influence on the reaction enthalpies is highlighted. Corrections for tunneling effects and hindered (or free) rotations of the methyl group are taken into account. The largest spreading in thermochemical and kinetic data is observed in the series of linear acenes, and a normal reactivity-enthalpy relationship is obtained. The abstraction of a methyl hydrogen atom at one of the center rings of large methylated acenes is largely preferred. Geometrical and electronic aspects lie at the basis of this striking feature. Comparison with hydrogen abstractions leading to arylic radicals is also made.

  11. Theoretical studies on concerted versus two steps hydrogen atom transfer reaction by non-heme Mn(IV/III)=O complexes: how important is the oxo ligand basicity in the C-H activation step?

    Science.gov (United States)

    Jaccob, Madhavan; Ansari, Azaj; Pandey, Bhawana; Rajaraman, Gopalan

    2013-12-21

    High-valent metal-oxo complexes have been extensively studied over the years due to their intriguing properties and their abundant catalytic potential. The majority of the catalytic reactions performed by these metal-oxo complexes involves a C-H activation step and extensive efforts over the years have been undertaken to understand the mechanistic aspects of this step. The C-H activation by metal-oxo complexes proceeds via a hydrogen atom transfer reaction and this could happen by multiple pathways, (i) via a proton-transfer followed by an electron transfer (PT-ET), (ii) via an electron-transfer followed by a proton transfer (ET-PT), (iii) via a concerted proton-coupled electron transfer (PCET) mechanism. Identifying the right mechanism is a surging topic in this area and here using [Mn(III)H3buea(O)](2-) (1) and [Mn(IV)H3buea(O)](-) (2) species (where H3buea = tris[(N'-tert-butylureaylato)-N-ethylene]aminato) and its C-H activation reaction with dihydroanthracene (DHA), we have explored the mechanism of hydrogen atom transfer reactions. The experimental kinetic data reported earlier (T. H. Parsell, M.-Y. Yang and A. S. Borovik, J. Am. Chem. Soc., 2009, 131, 2762) suggests that the mechanism between 1 and 2 is drastically different. By computing the transition states, reaction energies and by analyzing the wavefunction of the reactant and transitions states, we authenticate the proposal that the Mn(III)=O undergoes a step wise PT-ET mechanism where as the Mn(IV)=O species undergo a concerted PCET mechanism. Both the species pass through a [Mn(III)-OH] intermediate and the stability of this species hold the key to the difference in the reactivity. The electronic origin for the difference in reactivity is routed back to the strength and basicity of the Mn-oxo bond and the computed results are in excellent agreement with the experimental results.

  12. 单取代氧/硫杂紫菜嗪内氢迁移反应的理论研究%Theoretical study on transfer reaction of inner hydrogen atoms in oxa-and thiaporphyrazine

    Institute of Scientific and Technical Information of China (English)

    廖玉婷; 饶火瑜; 王海江; 邹丽霞; 胡宝群

    2011-01-01

    采用B3LYP/6-31G**方法在Gaussian 03程序下,对氧杂紫菜嗪,硫杂紫菜嗪的稳定结构和能量进行优化,并寻找与内氢迁移反应相关的过渡态构型.计算结果表明,芳香性与各体系构象稳定性密切相关,但并不是决定构象稳定性的唯一因素;在中心空穴较小的紫菜嗪体系中,空间位阻,静电作用才是影响构象稳定性的关键因素.由于分子内氢键的存在,氧杂化会明显降低内氢迁移正负反应速率;而S杂化体系的IHAT速率降低则与静电斥力和空间位阻密切相关.%The theoretical study of the mechanism and kinetics of the inner hydrogen atom-transfer process in oxa- porphyrazine, thia-porphyrazine was presented. The structures and energies of reactants, products and transition-states in the transfer reaction of inner hydrogen atoms in OPzH and SPzH were calculated with B3LYP/6-31G** method under certain symmetry restriction. The results show that the relative stability of conformations are directly correlated to aromaticity, but aromaticity is not the only determining factor which affects the relative stability of conformations; while in the porphyrazine systems with smaller central holes, the steric hindrance and the electrostatic interaction are more important factors which should not be neglected. The results also represent that oxa- can reduce speeds of positive and negative reactions, which is due to the existence of intra-molecular hydrogen bonds; but the decrease of NAT reaction speeds of thia-systems is resulted from steric hindrance and electrostatic interaction.

  13. Alkane desaturation by concerted double hydrogen atom transfer to benzyne.

    Science.gov (United States)

    Niu, Dawen; Willoughby, Patrick H; Woods, Brian P; Baire, Beeraiah; Hoye, Thomas R

    2013-09-26

    The removal of two vicinal hydrogen atoms from an alkane to produce an alkene is a challenge for synthetic chemists. In nature, desaturases and acetylenases are adept at achieving this essential oxidative functionalization reaction, for example during the biosynthesis of unsaturated fatty acids, eicosanoids, gibberellins and carotenoids. Alkane-to-alkene conversion almost always involves one or more chemical intermediates in a multistep reaction pathway; these may be either isolable species (such as alcohols or alkyl halides) or reactive intermediates (such as carbocations, alkyl radicals, or σ-alkyl-metal species). Here we report a desaturation reaction of simple, unactivated alkanes that is mechanistically unique. We show that benzynes are capable of the concerted removal of two vicinal hydrogen atoms from a hydrocarbon. The discovery of this exothermic, net redox process was enabled by the simple thermal generation of reactive benzyne intermediates through the hexadehydro-Diels-Alder cycloisomerization reaction of triyne substrates. We are not aware of any single-step, bimolecular reaction in which two hydrogen atoms are simultaneously transferred from a saturated alkane. Computational studies indicate a preferred geometry with eclipsed vicinal C-H bonds in the alkane donor.

  14. Structural and medium effects on the reactions of the cumyloxyl radical with intramolecular hydrogen bonded phenols. The interplay between hydrogen-bonding and acid-base interactions on the hydrogen atom transfer reactivity and selectivity.

    Science.gov (United States)

    Salamone, Michela; Amorati, Riccardo; Menichetti, Stefano; Viglianisi, Caterina; Bietti, Massimo

    2014-07-03

    A time-resolved kinetic study on the reactions of the cumyloxyl radical (CumO(•)) with intramolecularly hydrogen bonded 2-(1-piperidinylmethyl)phenol (1) and 4-methoxy-2-(1-piperidinylmethyl)phenol (2) and with 4-methoxy-3-(1-piperidinylmethyl)phenol (3) has been carried out. In acetonitrile, intramolecular hydrogen bonding protects the phenolic O-H of 1 and 2 from attack by CumO(•) and hydrogen atom transfer (HAT) exclusively occurs from the C-H bonds that are α to the piperidine nitrogen (α-C-H bonds). With 3 HAT from both the phenolic O-H and the α-C-H bonds is observed. In the presence of TFA or Mg(ClO4)2, protonation or Mg(2+) complexation of the piperidine nitrogen removes the intramolecular hydrogen bond in 1 and 2 and strongly deactivates the α-C-H bonds of the three substrates. Under these conditions, HAT to CumO(•) exclusively occurs from the phenolic O-H group of 1-3. These results clearly show that in these systems the interplay between intramolecular hydrogen bonding and Brønsted and Lewis acid-base interactions can drastically influence both the HAT reactivity and selectivity. The possible implications of these findings are discussed in the framework of the important role played by tyrosyl radicals in biological systems.

  15. Formation of noble-gas hydrides and decay of solvated protons revisited: diffusion-controlled reactions and hydrogen atom losses in solid noble gases.

    Science.gov (United States)

    Tanskanen, Hanna; Khriachtchev, Leonid; Lignell, Antti; Räsänen, Markku; Johansson, Susanna; Khyzhniy, Ivan; Savchenko, Elena

    2008-02-07

    UV photolysis and annealing of C2H2/Xe, C2H2/Xe/Kr, and HBr/Xe matrices lead to complicated photochemical processes and reactions. The dominating products in these experiments are noble-gas hydrides with general formula HNgY (Ng = noble-gas atom, Y = electronegative fragment). We concentrate on distinguishing the local and global mobility and losses of H atoms, barriers of the reactions, and the decay of solvated protons. Different deposition temperatures change the amount of lattice imperfections and thus the amount of traps for H atoms. The averaged distance between reacting species influencing the reaction kinetics is controlled by varying the precursor concentration. A number of solid-state processes connected to the formation of noble-gas hydrides and decay of solvated protons are discussed using a simple kinetic model. The most efficient formation of noble-gas hydrides is connected with global (long-range) mobility of H atoms leading to the H + Xe + Y reaction. The highest concentration of noble-gas hydrides was obtained in matrices of highest optical quality, which probably have the lowest concentration of defects and H-atom losses. In matrices with high amount of geometrical imperfections, the product formation is inefficient and dominated by a local (short-range) process. The decay of solvated protons is rather local than a global process, which is different from the formation of noble-gas molecules. However, the present data do not allow distinguishing local proton and electron mobilities. Our previous results indicate that these are electrons which move to positively-charged centers and neutralize them. It is believed that the image obtained here for solid xenon is applicable to solid krypton whereas the case of argon deserves special attention.

  16. Thermally-generated reactive intermediates: Trapping of the parent ferrocene-based o-quinodimethane and reactions of diradicals generated by hydrogen-atom transfers

    Energy Technology Data Exchange (ETDEWEB)

    Ferguson, J.M.

    1993-09-01

    Ferrocenocyclobutene is prepared by flash vacuum pyrolysis (FVP) of the N-amino-2-phenylaziridine hydrazone of 2-methylferrocenealdehyde. In the second section of this dissertation, a series of hydrocarbon rearrangements were observed. FVP of o-allyltoluene at 0.1 Torr (700--900 C) gives 2-methylindan and indene, accompanied by o-propenyltoluene. FVP of 2-methyl-2`-vinylbiphenyl gives 9-methyl-9,10-dihydrophenanthrene, which fits the proposed mechanism. However, FVP of 2-(o-methylbenzyl)styrene gives mainly anthracene and 1-methylanthracene. This cyclization reaction was also successful with o-allylphenol and o-(2-methylallyl)phenol.

  17. A Luminescence Characterization of Adsorbed Hydrogen Atoms on Plasma Facing Materials

    Energy Technology Data Exchange (ETDEWEB)

    Grankin, V.P. [Azov Sea State Technical Univ., Mariupol (Ukraine). Computer Science Dept.; Styrov, V.V. [Azov Sea State Technical Univ., Mariupol (Ukraine). Phisics Dept.

    2004-06-01

    An atomic probe technique for characterization of hydrogen atoms on fusion related materials is described. The technique for determining surface coverage by hydrogen atoms or isotopes under both non-steady-state and stationary conditions is based on detection of heterogeneous chemiluminescence (HCL) excited in the interaction between adsorbed atoms and the pulsed normalized probing atomic flow. The recombination of hydrogen atoms from the gas phase was found to occur in general case via both collision Rideal-Eley (RE) and diffusion Langmuir-Hinshelwood (LH) mechanisms. The instantaneous optical response allows extracting the contributions of these two mechanisms to the overall reaction rate for various experimental conditions. The HCL method is also applicable for quick measurement of the reactivity of adatoms (in terms of the recombination coefficient {gamma}) for all the materials including metals. The spectra and kinetics of HCL are useful for estimation of heats of adsorption for hydrogen atoms or isotopes.

  18. Fast automated placement of polar hydrogen atoms in protein-ligand complexes

    Directory of Open Access Journals (Sweden)

    Lippert Tobias

    2009-08-01

    Full Text Available Abstract Background Hydrogen bonds play a major role in the stabilization of protein-ligand complexes. The ability of a functional group to form them depends on the position of its hydrogen atoms. An accurate knowledge of the positions of hydrogen atoms in proteins is therefore important to correctly identify hydrogen bonds and their properties. The high mobility of hydrogen atoms introduces several degrees of freedom: Tautomeric states, where a hydrogen atom alters its binding partner, torsional changes where the position of the hydrogen atom is rotated around the last heavy-atom bond in a residue, and protonation states, where the number of hydrogen atoms at a functional group may change. Also, side-chain flips in glutamine and asparagine and histidine residues, which are common crystallographic ambiguities must be identified before structure-based calculations can be conducted. Results We have implemented a method to determine the most probable hydrogen atom positions in a given protein-ligand complex. Optimality of hydrogen bond geometries is determined by an empirical scoring function which is used in molecular docking. This allows to evaluate protein-ligand interactions with an established model. Also, our method allows to resolve common crystallographic ambiguities such as as flipped amide groups and histidine residues. To ensure high speed, we make use of a dynamic programming approach. Conclusion Our results were checked against selected high-resolution structures from an external dataset, for which the positions of the hydrogen atoms have been validated manually. The quality of our results is comparable to that of other programs, with the advantage of being fast enough to be applied on-the-fly for interactive usage or during score evaluation.

  19. Hydrogen Atom Spectrum in Noncommutative Phase Space

    Institute of Scientific and Technical Information of China (English)

    LI Kang; CHAMOUN Nidal

    2006-01-01

    @@ We study the energy levels of the hydrogen atom in the noncommutative phase space with simultaneous spacespace and momentum-momentum noncommutative relations. We find new terms compared to the case that only noncommutative space-space relations are assumed. We also present some comments on a previous paper [Alavi S A hep-th/0501215].

  20. From lattice gauge theories to hydrogen atoms

    Directory of Open Access Journals (Sweden)

    Manu Mathur

    2015-10-01

    Full Text Available We construct canonical transformations to obtain a complete and most economical realization of the physical Hilbert space Hp of pure SU(22+1 lattice gauge theory in terms of Wigner coupled Hilbert spaces of hydrogen atoms. One hydrogen atom is assigned to every plaquette of the lattice. A complete orthonormal description of the Wilson loop basis in Hp is obtained by all possible angular momentum Wigner couplings of hydrogen atom energy eigenstates |n l m〉 describing electric fluxes on the loops. The SU(2 gauge invariance implies that the total angular momenta of all hydrogen atoms vanish. The canonical transformations also enable us to rewrite the Kogut–Susskind Hamiltonian in terms of fundamental Wilson loop operators and their conjugate electric fields. The resulting loop Hamiltonian has a global SU(2 invariance and a simple weak coupling (g2→0 continuum limit. The canonical transformations leading to the loop Hamiltonian are valid for any SU(N. The ideas and techniques can also be extended to higher dimension.

  1. Spin Trapping of the Phosphorus-centered Radicals Generated from Hydrogen Abstraction Reaction by 2,2-Diphenyl-1-picrylhydrazyl

    Institute of Scientific and Technical Information of China (English)

    2000-01-01

    Two kinds of the phosphorus-centered radicals produced from hydrogen atom abstraction by2,2-diphenyl-1-picrylhydrazyl (DPPH) were trapped by N-tert-butyl-a-phenylnitrone (PBN) and5,5-dimethyl-l-pyrroline N-oxide (DMPO), and investigated by means of EPR spectroscopy.The spin adducts with a characteristic hyperfine coupling constant(hfcc) caused by a phosphorusatom were observed. Based on the hfcc values caused by the phosphorus and hydrogen atoms,the conformational positions of the adducts trapped by PBN and DMPO are discussed.

  2. Hydrogen-atom transfer in reactions of organic radicals with [Co-II(por)](center dot) (por = porphyrinato) and in subsequent addition of [Co(H)(por)] to olefins

    NARCIS (Netherlands)

    de Bruin, B.; Dzik, W.I.; Li, S.; Wayland, B.B.

    2009-01-01

    The mechanisms for hydrogen-atom transfer from the cyanoisopropyl radical C-center dot(CH3)(2)CN to [Co-II(por)](center dot) (yielding [Co-III(H)(por)] and CH2=C(CH3)(CN); por = porphyrinato) and the insertion of vinyl acetate (CH2=CHOAc) into the Co-H bond of [Co(H)(por)] (giving [Co-III{CH-(OAc)CH

  3. Cooperative triple-proton/hydrogen atom relay in 7-azaindole(CH3OH)2 in the gas phase: remarkable change in the reaction mechanism from vibrational-mode specific to statistical fashion with increasing internal energy.

    Science.gov (United States)

    Sakota, Kenji; Inoue, Naomi; Komoto, Yusuke; Sekiya, Hiroshi

    2007-05-31

    The 7-azaindole-methanol 1:2 cluster [7AI(CH(3)OH)2] undergoes excited-state triple-proton/hydrogen atom transfer (ESTPT/HT) along the hydrogen-bonded network in the gas phase. The measurements of the resonance-enhanced multiphoton ionization (REMPI) spectra of 7AI(CH(3)OH)2-d(n) (n = 0-3), where subscript n indicates the number of deuterium, and the fluorescence excitation spectrum of 7AI(CH(3)OH)2-d(0) allowed us to investigate the ESTPT/HT dynamics. By comparing the intensity ratios of the vibronic bands between 7AI(CH(3)OH)2-d(0) and 7AI(CH(3)OH)2-d(3) in REMPI spectra, we obtained the lower limit of an acceleration factor (f(a)(low)) of 7AI(CH(3)OH)2-d(0), which is the ratio of the reaction rate for the excitation of a vibronic state to that of the zero-point state in S(1). The f(a)(low) values are 2.7 +/- 0.83 and 4.0 +/- 1.2 for an in-phase intermolecular stretching vibration (sigma(1)) and its overtone (2sigma(1)) observed at 181 cm(-1) and 359 cm(-1) in the excitation spectrum, respectively, while that of the vibration (nu(2)/sigma(1) or nu(3)/sigma(1)) at 228 cm(-1) is 1.1 +/- 0.83. Thus, vibrational-mode-specific ESTPT/HT occurs in the low-energy region (600 cm(-1)). The excitation of an intramolecular ring mode (nu(intra)) of 7AI at 744 cm(-1) substantially enhances the reaction rate (f(a)(low) = 4.4 +/- 0.98), but the increase of f(a)(low) is not prominent for the excitation of v(intra) + sigma(1) at 926 cm(-1) (f(a)(low) = 5.0 +/- 1.6), although the sigma(1) mode is excited. These results suggest that the ESTPT/HT reaction in 7AI(CH(3)OH)2-d(0) directly proceeds from the photoexcited states with the internal energy less than approximately 600 cm(-1), but it occurs from the isoenergetically vibrational-energy redistributed states when the internal energy is large. This shows a remarkable feature of ESTPT/HT in 7AI(CH(3)OH)2; the nature of the reaction mechanism changes from vibrational-mode specific to statistical fashion with increasing the internal

  4. Quantum Structures of the Hydrogen Atom

    CERN Document Server

    Jeknic-Dugic, J; Francom, A; Arsenijevic, M

    2012-01-01

    Modern quantum theory introduces quantum structures (decompositions into subsystems) as a new discourse that is not fully comparable with the classical-physics counterpart. To this end, so-called Entanglement Relativity appears as a corollary of the universally valid quantum mechanics that can provide for a deeper and more elaborate description of the composite quantum systems. In this paper we employ this new concept to describe the hydrogen atom. We offer a consistent picture of the hydrogen atom as an open quantum system that naturally answers the following important questions: (a) how do the so called "quantum jumps" in atomic excitation and de-excitation occur? and (b) why does the classically and seemingly artificial "center-of-mass + relative degrees of freedom" structure appear as the primarily operable form in most of the experimental reality of atoms?

  5. Hydrogen atom in a Laser-Plasma

    CERN Document Server

    Falaye, Babatunde James; Liman, Muhammed S; Oyewumi, K J; Dong, Shi-Hai

    2016-01-01

    We scrutinize the behaviour of hydrogen atom's eigenvalues in a quantum plasma as it interacts with electric field directed along $\\theta=\\pi$ and exposed to linearly polarized intense laser field radiation. Using the Kramers-Henneberger (KH) unitary transformation, which is semiclassical counterpart of the Block-Nordsieck transformation in the quantized field formalism, the squared vector potential that appears in the equation of motion is eliminated and the resultant equation is expressed in KH frame. Within this frame, the resulting potential and the corresponding wavefunction have been expanded in Fourier series and using Ehlotzky's approximation, we obtain a laser-dressed potential to simulate intense laser field. By fitting the exponential-cosine-screened Coulomb potential into the laser-dressed potential, and then expanding it in Taylor series up to $\\mathcal{O}(r^4,\\alpha_0^9)$, we obtain the eigensolution (eigenvalues and wavefunction) of hydrogen atom in laser-plasma encircled by electric field, wit...

  6. Do Spin State and Spin Density Affect Hydrogen Atom Transfer Reactivity?

    Science.gov (United States)

    Saouma, Caroline T; Mayer, James M

    2014-01-01

    The prevalence of hydrogen atom transfer (HAT) reactions in chemical and biological systems has prompted much interest in establishing and understanding the underlying factors that enable this reactivity. Arguments have been advanced that the electronic spin state of the abstractor and/or the spin-density at the abstracting atom are critical for HAT reactivity. This is consistent with the intuition derived from introductory organic chemistry courses. Herein we present an alternative view on the role of spin state and spin-density in HAT reactions. After a brief introduction, the second section introduces a new and simple fundamental kinetic analysis, which shows that unpaired spin cannot be the dominant effect. The third section examines published computational studies of HAT reactions, which indicates that the spin state affects these reactions indirectly, primarily via changes in driving force. The essay concludes with a broader view of HAT reactivity, including indirect effects of spin and other properties on reactivity. It is suggested that some of the controversy in this area may arise from the diversity of HAT reactions and their overlap with proton-coupled electron transfer (PCET) reactions.

  7. Discrete wave mechanics: The hydrogen atom.

    Science.gov (United States)

    Wall, F T

    1986-08-01

    The quantum mechanical problem of the hydrogen atom is treated by use of a finite difference equation in place of Schrödinger's differential equation. The exact solution leads to a wave vector energy expression that is readily converted to the Bohr-Rydberg formula. (The calculations here reported are limited to spherically symmetric states.) The wave vectors reduce to the familiar solutions of Schrödinger's equation as c --> infinity. The internal consistency and limiting behavior provide support for the view that the equations employed could well constitute an approach to a relativistic formulation of wave mechanics.

  8. Reduction of uranium hexafluoride to tetrafluoride by using the hydrogen atoms

    Science.gov (United States)

    Aleksandrov, B. P.; Gordon, E. B.; Ivanov, A. V.; Kotov, A. A.; Smirnov, V. E.

    2016-09-01

    We consider the reduction of UF6 to UF4 by chemical reaction with hydrogen atoms originated in the powerful chemical generator. The principal design of such a chemical convertor is described. The results of the mathematical modeling of the thermodynamics and kinetics of the UF6 to UF4 reduction process are analyzed. The few options for the hydrogen atom generator design are proposed. A layout of the experimental setup with the chemical reactor is presented. The high efficiency together with the ability of the process scaling without loss of its efficiency makes this approach to the uranium hexafluoride depletion into tetrafluoride promising for its application in the industry.

  9. Time-of-flight spectroscopy of muonic hydrogen atoms and molecules

    Energy Technology Data Exchange (ETDEWEB)

    Fujiwara, M.C. [Dept. of Physics and Astronomy, Univ. of British Columbia, Vancouver, BC (Canada)]|[Dept. of Physics, Faculty of Science, Univ. of Tokyo (Japan); Adamczak, A. [Inst. of Nuclear Physics, Krakow (Poland); Bailey, J.M. [Chester Technology, Chester (United Kingdom); Beer, G.A.; Mason, G.R. [Dept. of Physics and Astronomy, Univ. of Victoria, BC (Canada); Beveridge, J.L.; Marshall, G.M.; Olin, A. [TRIUMF, Vancouver, BC (Canada); Faifman, M.P. [Russian Research Center, Kurchatov Inst., Moscow (Russian Federation); Huber, T.M. [Dept. of Physics, Gustavus Adolphus Coll., St. Peter, MN (United States); Kammel, P. [Dept. of Physics and Lawrence Berkeley National Lab., Univ. of California, Berkeley, CA (United States); Kim, S.K. [Dept. of Physics, Jeonbuk National Univ., Jeonju City (Korea); Knowles, P.E.; Mulhauser, F. [Inst. of Physics, Univ. of Fribourg (Switzerland); Kunselman, A.R. [Dept. of Physics and Astronomy, Univ. of Wyoming, Laramie, WY (United States); Markushin, V.E.; Petitjean, C. [Paul Scherrer Inst., Villigen (Switzerland); Porcelli, T.A. [Dept. of Physics, Univ. of Northern British Columbia, Prince George, BC (Canada); Zmeskal, J. [Inst. for Medium Energy Physics, Austrian Academy of Sciences, Vienna (Austria)

    2001-07-01

    Studies of muonic hydrogen atoms and molecules have been performed traditionally in bulk targets of gas, liquid or solid. At TRIUMF, Canada's meson facility, we have developed a new type of target system using multilayer thin films of solid hydrogen, which provides a beam of muonic hydrogen atoms in vacuum. Using the time-of-flight of the muonic atoms, the energy-dependent information of muonic reactions are obtained in direct manner.We discuss some unique measurements enabled by the new technique, with emphasis on processes relevant to muon catalyzed fusion.

  10. Time-of-Flight Spectroscopy of Muonic Hydrogen Atoms and Molecules

    CERN Document Server

    Fujiwara, M C; Bailey, J M; Beer, G A; Beveridge, J L; Faifman, M P; Huber, T M; Kammel, P; Kim, S K; Knowles, P E; Kunselman, A R; Markushin, V E; Marshall, G M; Mason, G R; Mulhauser, F; Olin, A; Petitjean, C; Porcelli, T A; Zmeskal, J

    2001-01-01

    Studies of muonic hydrogen atoms and molecules have been performed traditionally in bulk targets of gas, liquid or solid. At TRIUMF, Canada's meson facility, we have developed a new type of target system using multilayer thin films of solid hydrogen, which provides a beam of muonic hydrogen atoms in vacuum. Using the time-of-flight of the muonic atoms, the energy-dependent information of muonic reactions are obtained in direct manner. We discuss some unique measurements enabled by the new technique, with emphasis on processes relevant to muon catalyzed fusion.

  11. The Hydrogen Atom in Relativistic Motion

    CERN Document Server

    Jarvinen, M

    2004-01-01

    The Lorentz contraction of bound states in field theory is often appealed to in qualitative descriptions of high energy particle collisions. Surprisingly, the contraction has not been demonstrated explicitly even in simple cases such as the Hydrogen atom. It requires a calculation of wave functions evaluated at equal (ordinary) time for bound states in motion. Such wave functions are not obtained by kinematic boosts from the rest frame. Starting from the exact Bethe-Salpeter equation we derive the equal-time wave function of a fermion-antifermion bound state in QED, i.e., positronium or the Hydrogen atom, in any frame to leading order in alpha. We show explicitly that the bound state energy transforms as the fourth component of a vector and that the wave function of the fermion-antifermion Fock state contracts as expected. Transverse photon exchange contributes at leading order to the binding energy of the bound state in motion. We study the general features of the corresponding fermion-antifermion-photon Foc...

  12. Classical theory of the hydrogen atom

    CERN Document Server

    Rashkovskiy, Sergey

    2016-01-01

    It is shown that all of the basic properties of the hydrogen atom can be consistently described in terms of classical electrodynamics instead of taking the electron to be a particle; we consider an electrically charged classical wave field, an "electron wave", which is held in a limited region of space by the electrostatic field of the proton. It is shown that quantum mechanics must be considered to be not a theory of particles but a classical field theory in the spirit of classical electrodynamics. In this case, we are not faced with difficulties in interpreting the results of the theory. In the framework of classical electrodynamics, all of the well-known regularities of the spontaneous emission of the hydrogen atom are obtained, which is usually derived in the framework of quantum electrodynamics. It is shown that there are no discrete states and discrete energy levels of the atom: the energy of the atom and its states change continuously. An explanation of the conventional corpuscular-statistical interpre...

  13. Static dipole polarizability of shell-confined hydrogen atom

    Science.gov (United States)

    Sen, K. D.; Garza, Jorge; Vargas, Rubicelia; Aquino, Norberto

    2002-04-01

    Using the Sternheimer perturbation-numerical procedure, calculations of static dipole polarizability are reported for the shell-confined hydrogen atom as defined by two impenetrable concentric spherical walls. Unusually high polarizability states are predicted for the hydrogen atom as the inner sphere radius is increased to larger values inside the outer sphere of a constant radius. Implications of this model in mimicking internal compression leading to the metallic behaviour of the shell-confined hydrogen atoms are discussed.

  14. Quantum dynamics of the abstraction reaction of H with cyclopropane.

    Science.gov (United States)

    Shan, Xiao; Clary, David C

    2014-10-30

    The dynamics of the abstraction reaction of H atoms with the cyclopropane molecule is studied using quantum mechanical scattering theory. The quantum scattering calculations are performed in hyperspherical coordinates with a two-dimensional (2D) potential energy surface. The ab initio energy calculations are carried out with CCSD(T)-F12a/cc-pVTZ-F12 level of theory with the geometry and frequency calculations at the MP2/cc-pVTZ level. The contribution to the potential energy surface from the spectator modes is included as the projected zero-point energy correction to the ab initio energy. The 2D surface is fitted with a 29-parameter double Morse potential. An R-matrix propagation scheme is carried out to solve the close-coupled equations. The adiabatic energy barrier and reaction enthalpy are compared with high level computational calculations as well as experimental data. The calculated reaction rate constants shows very good agreement when compared with the experimental data, especially at lower temperature highlighting the importance of quantum tunnelling. The reaction probabilities are also presented and discussed. The special features of performing quantum dynamics calculation on the chemical reaction of a cyclic molecule are discussed.

  15. Pericyclic Reactions: FMO Approach-Abstract of Issue 9904M

    Science.gov (United States)

    Lee, Albert W. M.; So, C. T.; Chan, C. L.; Wu, Y. K.

    1999-05-01

    Reactions: FMO Approach using Macromedia Director (4) to teach the two most important pericyclic reactions: electrocyclic addition and cycloaddition. Pericyclic Reactions: FMO Approach can be used in intermediate or advanced organic chemistry courses. Literature Cited 1. Woodward, R. B.; Hoffmann, R. The Conservation of Orbital Symmetry; Academic: New York, 1971. 2. Fukui, K. Tetrahedron Lett. 1965, 2009, 2427. 3. Lee, A. W. M. Educ. Chem. 1988, 122. 4. Macromedia Director, version 4.0.3; Macromedia, Inc.: San Francisco, 1994. Keywords Lecture Aid; Computer Room; Organic; Pericyclic Reactions; Molecular Orbitals Hardware and Software Requirements for Pericyclic Reactions: FMO Approach Ordering and Information Journal of Chemical Education Software (often called JCE Software) is a publication of the Journal of Chemical Education. There is an Order Form inserted in this issue that provides prices and other ordering information. If this card is not available or if you need additional information, contact: JCE Software, University of Wisconsin-Madison, 1101 University Avenue, Madison, WI 53706-1396; phone: 608/262-5153 or 800/991-5534; fax: 608/265-8094; email: jcesoft@chem.wisc.edu. Information about all our publications (including abstracts, descriptions, updates) is available from our World Wide Web site: http://JChemEd.chem.wisc.edu/JCESoft/

  16. A semi-quantitative equivalence for abstracting from fast reactions

    CERN Document Server

    Galpin, Vashti; Ciocchetta, Federica; 10.4204/EPTCS.67.5

    2011-01-01

    Semantic equivalences are used in process algebra to capture the notion of similar behaviour, and this paper proposes a semi-quantitative equivalence for a stochastic process algebra developed for biological modelling. We consider abstracting away from fast reactions as suggested by the Quasi-Steady-State Assumption. We define a fast-slow bisimilarity based on this idea. We also show congruence under an appropriate condition for the cooperation operator of Bio-PEPA. The condition requires that there is no synchronisation over fast actions, and this distinguishes fast-slow bisimilarity from weak bisimilarity. We also show congruence for an operator which extends the reactions available for a species. We characterise models for which it is only necessary to consider the matching of slow transitions and we illustrate the equivalence on two models of competitive inhibition.

  17. Software for Hydrogenic Atoms and Orbitals Visualization

    Directory of Open Access Journals (Sweden)

    Kowit KITTIWUTTHISAKDI

    2005-06-01

    Full Text Available A program was developed in java for hydrogenic atoms and orbitals visualization. The first 18 atoms in the periodic table were approximated with a hydrogenic wave-function. This simple hydrogenic wave-function allowed quick calculation for real-time interactive visualization. Electron cloud based models were employed and displayed by a ray-tracing technique. One or more orbitals that defined an atom could be selected and displayed. A user could zoom in, zoom out, and rotate the displayed cloud in real time. The approximation method for probability integrals was summation. The intensity of color at each point on the screen directly related to the integrated probability in finding the electron across the viewer%s eye path.

  18. Wave mechanics of the hydrogen atom

    CERN Document Server

    Ogilvie, J F

    2016-01-01

    The hydrogen atom is a system amenable to an exact treatment within Schroedinger's formulation of quantum mechanics according to coordinates in four systems -- spherical polar, paraboloidal, ellipsoidal and spheroconical coordinates; the latter solution is reported for the first time. Applications of these solutions include angular momenta, a quantitative calculation of the absorption spectrum and accurate plots of surfaces of amplitude functions. The shape of an amplitude function, and even the quantum numbers in a particular set to specify such an individual function, depend on the coordinates in a particular chosen system, and are therefore artefacts of that particular coordinate representation within wave mechanics. All discussion of atomic or molecular properties based on such shapes or quantum numbers therefore lacks general significance

  19. Semiclassical treatment of laser excitation of the hydrogen atom

    DEFF Research Database (Denmark)

    Billing, Gert D.; Henriksen, Niels Engholm; Leforestier, C.

    1992-01-01

    We present an alternative method for studying excitation of atoms in intense laser fields. In the present paper we focus upon the optical harmonic generation by hydrogen atoms.......We present an alternative method for studying excitation of atoms in intense laser fields. In the present paper we focus upon the optical harmonic generation by hydrogen atoms....

  20. Kinetics of the reaction of the heaviest hydrogen atom with H2, the 4Heμ + H2 → 4HeμH + H reaction: experiments, accurate quantal calculations, and variational transition state theory, including kinetic isotope effects for a factor of 36.1 in isotopic mass.

    Science.gov (United States)

    Fleming, Donald G; Arseneau, Donald J; Sukhorukov, Oleksandr; Brewer, Jess H; Mielke, Steven L; Truhlar, Donald G; Schatz, George C; Garrett, Bruce C; Peterson, Kirk A

    2011-11-14

    The neutral muonic helium atom (4)Heμ, in which one of the electrons of He is replaced by a negative muon, may be effectively regarded as the heaviest isotope of the hydrogen atom, with a mass of 4.115 amu. We report details of the first muon spin rotation (μSR) measurements of the chemical reaction rate constant of (4)Heμ with molecular hydrogen, (4)Heμ + H(2) → (4)HeμH + H, at temperatures of 295.5, 405, and 500 K, as well as a μSR measurement of the hyperfine coupling constant of muonic He at high pressures. The experimental rate constants, k(Heμ), are compared with the predictions of accurate quantum mechanical (QM) dynamics calculations carried out on a well converged Born-Huang (BH) potential energy surface, based on complete configuration interaction calculations and including a Born-Oppenheimer diagonal correction. At the two highest measured temperatures the agreement between the quantum theory and experiment is good to excellent, well within experimental uncertainties that include an estimate of possible systematic error, but at 295.5 K the quantum calculations for k(Heμ) are below the experimental value by 2.1 times the experimental uncertainty estimates. Possible reasons for this discrepancy are discussed. Variational transition state theory calculations with multidimensional tunneling have also been carried out for k(Heμ) on the BH surface, and they agree with the accurate QM rate constants to within 30% over a wider temperature range of 200-1000 K. Comparisons between theory and experiment are also presented for the rate constants for both the D + H(2) and Mu + H(2) reactions in a novel study of kinetic isotope effects for the H + H(2) reactions over a factor of 36.1 in isotopic mass of the atomic reactant. © 2011 American Institute of Physics

  1. Unparticle physics constraints from the hydrogen atom

    Energy Technology Data Exchange (ETDEWEB)

    Wondrak, Michael Florian; Nicolini, Piero; Bleicher, Marcus [Frankfurt Institute for Advanced Studies (FIAS), Frankfurt am Main (Germany); Institut fuer Theoretische Physik, Johann Wolfgang Goethe-Universitaet Frankfurt am Main, Frankfurt am Main (Germany)

    2016-07-01

    Unparticle stuff has been proposed as an extension of the Standard Model of particle physics by including scale invariant fields. In the framework of effective field theory, it describes the low-energy limit of a so-called Banks-Zaks sector which exhibits scale invariance below an energy scale Λ{sub U}. Unparticle fields are characterized by a non-integer canonical scaling dimension d{sub U}, which leads to unusual properties like resembling a fractional number of (un)particles. The existence of unparticle stuff may be detected experimentally through the interaction with conventional matter. After a review on the unparticle theory and the static potential due to virtual unparticle exchange, we focus on its impact on hydrogen atom energy levels. We obtain the energy shift of the ground state by using Rayleigh-Schroedinger perturbation theory and compare it with experimental data. In this way, bounds on the energy scale Λ{sub U} as a function of d{sub U} are derived. Finally, we offer a comparison with existing constraints in literature like the lepton magnetic anomaly. For some parameter regimes, the hydrogen bound provides competitive results.

  2. Adsorption of hydrogen atoms onto the exterior wall of carbon nanotubes and their thermodynamics properties

    Energy Technology Data Exchange (ETDEWEB)

    Ng, T.Y.; Ren, Y.X. [School of Mechanical and Aerospace Engineering, Nanyang Technological University, 50 Nanyang Avenue, Singapore 639798 (Singapore); Liew, K.M. [Department of Building and Construction, City University of Hong Kong, Tat Chee Avenue, Kowloon (China)

    2010-05-15

    In the present work, we present a systematic analysis of the chemisorption process pathway of hydrogen atoms onto the exterior wall of (5,5) carbon nanotubes using the ONIOM2 (B3LYP(6-31+G(d,p):UFF)) scheme, and we avoid the gross assumption of fixing any of the carbon atoms during the simulation. It is shown that the adsorption of hydrogen atoms onto the sidewall of CNTs are energetically favorable and the most stable state is to form two H-C {sigma}-bonds while the original {sigma}-bond between the carbon atoms is totally severed. In particular, we examined the molecular thermodynamics properties for the reaction at a range of temperatures from 77 K to 1000 K, and the results suggests that the reaction is possible at ambient temperature, but it is less favorable than that at lower temperatures. (author)

  3. Insights into the Hydrogen-Atom Transfer of the Blue Aroxyl.

    Science.gov (United States)

    Bächle, Josua; Marković, Marijana; Kelterer, Anne-Marie; Grampp, Günter

    2017-07-26

    An experimental and theoretical study on hydrogen-atom transfer dynamics in the hydrogen-bonded substituted phenol/phenoxyl complex of the blue aroxyl (2,4,6-tri-tert-butylphenoxyl) is presented. The experimental exchange dynamics is determined in different organic solvents from the temperature-dependent alternating line-width effect in the continuous-wave ESR spectrum. From bent Arrhenius plots, effective tunnelling contributions with parallel heavy-atom motion are concluded. To clarify the transfer mechanism, reaction paths for different conformers of the substituted phenol/phenoxyl complex are modelled theoretically. Various DFT and post-Hartree-Fock methods including multireference methods are applied. From the comparison of experimental and theoretical data it is concluded that the system favours concerted hydrogen-atom transfer along a parabolic reaction path caused by heavy-atom motion. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Radial Matrix Elements of Hydrogen Atom and the Correspondence Principle

    Indian Academy of Sciences (India)

    T. N. Chakrabarty

    2004-03-01

    Radial dipole matrix elements having astrophysical importance have been computed for highly excited states of hydrogen atom. Computation is based on Heisenberg’s form of correspondence principle for Coulomb potential. Particular attention has been paid to the choice of classical analogue (c) of principal quantum number (). The computed radial matrix elements are in good agreement with quantum mechanical results. Further, radial matrix elements for few transitions involving high neighboring states of hydrogen atom are presented.

  5. Effects of hydrogen atoms on surface conductivity of diamond film

    Directory of Open Access Journals (Sweden)

    Fengbin Liu

    2015-04-01

    Full Text Available To investigate the effects of surface chemisorbed hydrogen atoms and hydrogen atoms in the subsurface region of diamond on surface conductivity, models of hydrogen atoms chemisorbed on diamond with (100 orientation and various concentrations of hydrogen atoms in the subsurface layer of the diamond were built. By using the first-principles method based on density functional theory, the equilibrium geometries and densities of states of the models were studied. The results showed that the surface chemisorbed hydrogen alone could not induce high surface conductivity. In addition, isolated hydrogen atoms in the subsurface layer of the diamond prefer to exist at the bond centre site of the C-C bond. However, such a structure would induce deep localized states, which could not improve the surface conductivity. When the hydrogen concentration increases, the C-H-C-H structure and C-3Hbc-C structure in the subsurface region are more stable than other configurations. The former is not beneficial to the increase of the surface conductivity. However, the latter would induce strong surface states near the Fermi level, which would give rise to high surface conductivity. Thus, a high concentration of subsurface hydrogen atoms in diamond would make significant contributions to surface conductivity.

  6. Abstract

    Institute of Scientific and Technical Information of China (English)

    2012-01-01

    Cognitive Structure of Scientific Theory in the Scientist-Philosopher's Eyes、Two Theories of Scientific Abstraction Centered on Practices、Many-worlds Interpretation in Quantum Measurement and Its Meaning、Scientific Instrument: Paradigm Shift from Instrumentalism to Realism and Phenomenology

  7. Abstracts

    Institute of Scientific and Technical Information of China (English)

    2012-01-01

    [ Abstract] Interaction between China and the international system has been a highlighted is- sue and drawing a great deal of attention all over the world. It has been approached from structural point of view and in a way of a conflicting pair of self and the other, which is the prevailing ontological perspective of IR studies. Contrary to it, processual

  8. Abstracts

    Institute of Scientific and Technical Information of China (English)

    2011-01-01

    The Western Theories of War Ethics and Contemporary Controversies Li Xiaodong U Ruijing (4) [ Abstract] In the field of international relations, war ethics is a concept with distinct westem ideological color. Due to factors of history and reality, the in

  9. Abstracts

    Institute of Scientific and Technical Information of China (English)

    2012-01-01

    China' s Dual-identity Dilemma and Its Countermeasm'es Li Shaojun(4) [ Abstract] The international system, as the overall structure for interactions among actors, is the environment and stage for implementation of China' s foreign policy. In this system, identity is a fundamental factor determining China' s international position and interests, and how to achieve them. China has long stressed that it is a "developing country,"

  10. ABSTRACTS

    Institute of Scientific and Technical Information of China (English)

    2012-01-01

    Abstract: The ethylene plant at SINOPEC Shanghai Petrochemical Company Limited ranked in the middle among SINOPEC subsidiaries in terms of ethylene and propylene yields, technical economical indicator and so on, and its performance ranking went no further in chemical sector. By means of feedstock optimization, steam optimization, and energy saving and consumption reduction, the company enhanced its competitiveness in the market and improved its efficiency. In addition, some ideas were put forward on performance improvement of the ethylene plant in the future.

  11. Abstracts

    Institute of Scientific and Technical Information of China (English)

    2011-01-01

    [ Abstract ] The global resurgence of religion and the return of religion from the so-call "Westphalia Exile" to the central stage of international religions have significantly trans- formed the viewpoints of both media and academia toward the role of religion in IR, and the challenges posed by religion to the contemporary international relations are often described as entirely subversive. The author argues that as a second-tier factor in most countries' for- eign policies and international affairs,

  12. Abstracts

    Institute of Scientific and Technical Information of China (English)

    2011-01-01

    The Research of the Subsistent States of the Artists Living in Guilin During the Anti-Japanese Period;A Brief History of Calligraphy Art of Chongqing as Provisional Capital during the Anti-Japanese Period;The Endless Stream and Terraced Mountains:on the Analysisof Spacein Chinese Landscape Painting of Gongxian;Political Vanguard in the Perspective View of the Formalism Aesthetic: 1980s Abstract Painting in China;Comparison of the Early-Stage Spreading of Western Pre-Modem Style Painting and Its Influence in China and Japan.

  13. ABSTRACTS

    Institute of Scientific and Technical Information of China (English)

    2012-01-01

    (1) Lenin's "Unity of Three Dialectics": Notes Science of Logic and The Capital on Philosophy in the Dual Contexts of Sun Zhengyu 4 Lenin's dialectics in Notes on Philosophy is essentially a unity of materialistic logic, dialectics and epistemology that has arisen from interactions between Hegel' s Science of Logic and Marx' s The Capital. Due to a lack of understanding of Lenin' s "unity of three dialectics," people tend to misunderstand his dialectics for the meeting of two extremes of the "sum total of living instances" and "abstract methods,

  14. ABSTRACT

    Institute of Scientific and Technical Information of China (English)

    2011-01-01

    --Based on of Marx's Economic Philosophy Manuscripts of 1844 HE Jian-jin (Philosophy Department, Fujian Provincial Committee Party School, Fuzhou, Fujian 350012, China) Abstract: Socialism with Chinese characteristics has a close relationship with the return and growth of capital in China. To implement the scientific concept of development, we must confront the problem of scientifically controlling the capital. In Economic and Philosophical Manuscripts of 1844, Marx criticized the three old philosophical thinking of treating capital: Object-oriented thinking, intuitive thinking, purely spiritual abstract thinking, and he established his own unique understanding of the capital that is to understand the capital from the human perceptual activities and practical activities. Contemporary Chinese society exist the problem of underdevelopment and abnormal development, and the three heterogeneity problems of pre-modern, modern, postmodern concurrent. In order to implement the scientific concept of development, we must reject any abstract positive or negative to modern basic principles under the guidance of the capital, against the eternal capital theory and capital theory of evil, and we must oppose the thinking that the capital is eternal or evil. Key words: socialism with Chinese characteristics; capital; national economics; scientific concept of development

  15. Non-thermal hydrogen atoms in the terrestrial upper thermosphere.

    Science.gov (United States)

    Qin, Jianqi; Waldrop, Lara

    2016-12-06

    Model predictions of the distribution and dynamical transport of hydrogen atoms in the terrestrial atmosphere have long-standing discrepancies with ultraviolet remote sensing measurements, indicating likely deficiencies in conventional theories regarding this crucial atmospheric constituent. Here we report the existence of non-thermal hydrogen atoms that are much hotter than the ambient oxygen atoms in the upper thermosphere. Analysis of satellite measurements indicates that the upper thermospheric hydrogen temperature, more precisely the mean kinetic energy of the atomic hydrogen population, increases significantly with declining solar activity, contrary to contemporary understanding of thermospheric behaviour. The existence of hot hydrogen atoms in the upper thermosphere, which is the key to reconciling model predictions and observations, is likely a consequence of low atomic oxygen density leading to incomplete collisional thermalization of the hydrogen population following its kinetic energization through interactions with hot atomic or ionized constituents in the ionosphere, plasmasphere or magnetosphere.

  16. ABSTRACTS

    Institute of Scientific and Technical Information of China (English)

    2012-01-01

    Discussion on main hydraulic performance parameters' model acceptance test of mixed flow pump turbine YU Ji-xing, LI Jin-wei, CHEN Liu, REN Shao-cheng, JIANG Ming-li, LI Hai-ling (China Institute of Water Resources and Hydropower Research, Beijing 100038, China) Abstract: Model acceptance test content and main performance parameter' acceptance mode of mixed flow pump turbine were introduced, main hydraulic performance parameters, such as hump of pump high lift region and S unstable region during turbine starting, were discussed, after that, frequency characteristic of pressure fluctuation beside guide blade area were presented in briefly. Key words: pump turbine; model acceptance test; hump region; "S" region; pressure fluctuation

  17. ABSTRACTS

    Institute of Scientific and Technical Information of China (English)

    2012-01-01

    Spiritual Construction and Its Ideological Sources in Contemporary China The spiritual construction in contemporary China is an important ideological task proposed by the historical practice of China. Modernized development often entails the meaning of entering into " modern civilization. " Nevertheless, an abstract understanding of this civilization has covered up its essential stipulation and historical nature. China has pursued its development on a different historical prerequisite from the west, and therefore, only partially belongs to modern capitalist modernization. The practical prospects of Chinese development imply a transformation and remodeling of the general lifestyle, life attitudes and values, which inevitably calls for a new form of philosophy. The ideological sources for this new philosophy are: Chinese philosophy, Western integration of them may point to philosophy and Marxist philosophy. A creative a potentially new type of civilization.

  18. ABSTRACTS

    Institute of Scientific and Technical Information of China (English)

    2012-01-01

    On Rousseau's Equality and Freedom GONG Qun Abstract:Equality and freedom are the two core concepts of political philosophy and Rousseau~s political philosophy is no exception. Freedom and equality in Rousseau in- cludes two levels: natural state and social state under social contract, and among them, there is one state of un-equality. The relationship between the two concepts here is that equality is a necessary precondition of freedom, and that there is no equality, there is no freedom. The achievement of Rousseau~s equality is by one contractual behavior that all the members transfer their rights, especially property rights, and form of the Community. Freedom in Rousseau's mind is through the people's sovereignty in the Community to achieve freedom.

  19. ABSTRACTS

    Institute of Scientific and Technical Information of China (English)

    2012-01-01

    (1) ASEAN Security Community: Power Containment and Norm Construction --From the Perspective of Realist-Constructivism Zheng Ying-qin . 11 . Abstract:Combined of realism and constructivism, realist-constructivism emphasizes the interactions between power and identity through norms and their influence on international relations. From the perspective of realist-con- structivism, this article analyses the construction of ASEAN security community and figures out two main clues in the n of ASEAN : the containment of power system that facilitate the strategic cooperation of ASEAN and norms which promotes the cooperation. ASEAN has made achievements in security cooperation but security community. There are still lots of problems ASEAN needs to tackle, for example, to con- institution as well as to strengthen the regional economic interdependence. The possible way to pro- mote the ASEAN security community may start from the area of non-traditional security cooperation Key Wwords: ASEAN security community ; Realist-Constructivism ; power; norm

  20. ABSTRACTS

    Institute of Scientific and Technical Information of China (English)

    2012-01-01

    On the Construction of Water Conservancy during 1930s in Hubei Yu Tao ( 1 ) Abstract: Two extra-large floods in the 1930s had drawn the National Government's attention to introspect itself. After those disasters, the government had made some progress by a series of measures like repairing the dike, completing water conservancy institutions and enacting regulations in order to strengthen the water conservancy construction in Hubei. The government took water conservancy construction as a complex system project so that they had a relatively comprehensive consideration. It reflects the advancement of modern government to mobilize local people and put such social power into the unified planning. However, thelimitations of the government's policy implementation weakened the effect of water conservancy construction. Keywords: flood; government; water conservancy construction; effect

  1. Abstracts

    Institute of Scientific and Technical Information of China (English)

    2012-01-01

    The Shift of World Center and the Change of the International System Yan Xuetong Abstract: The power transition caused by China' s rise will not only change the international configuration, but could also result in the world cen- ter shifting from Europe to Asia. However, neither a change in the interna- tional configuration nor the shift of the world center implies a change of the type of the international system. The international system is composed of three elements: international actors, international configuration and interna- tional norms. It will be neither possible to distinguish international system from its components nor clarify relations between components and system if changes in one element are treated as change of types of international system.

  2. Abstracts

    Institute of Scientific and Technical Information of China (English)

    2012-01-01

    The Western Characteristics of the Pardims of International Studies in America:With the Huaxla System as a Counterexample Ye Zicheng (4)[ Abstract ] Three flaws are obvious in the three paradigms of International Studies in America. Specifically, their arguments are based on the assumption that the world is anarchic ; they go too far in employing the scientific and rational methodology; they pay little attention to the humans. Hence, the three paradigms of international studies in America aren' t necessarily useful for the explanation of China' s history and culture as well as its relations with the outside world. The Huaxia system, for example, is anarchic but also apparently hierarchical; the approach of pursuing security in understanding the rise of western powers may be meaningless, for the hegemony in the Huaxia System needn't worry about its security; the theory of power-balancing seemingly couldn' t explain why Qin ended up in defeating the alliance of the other six states in the Warring-states period. The Huaxia system is quite open, and has free movement of people, goods, and ideas. Some interstate regimes and institutions were formed through Huimeng (alliance-making) among states. However, this kind of limited and fragile interdependence and cooperation soon came to an end after the hegemonies of Qi, Jin and Wei. There does exit the identity problem among states in the Huaxia System, but this problem doesn't play such a great role as the constructivists expect it would.

  3. Abstracts

    Institute of Scientific and Technical Information of China (English)

    2012-01-01

    Strategic Realism: An Option for China' s Grand Strategy Song Dexing (4) [ Abstract] As a non-Western emerging power, China should positively adapt its grand strategy to the strategic psychological traits in the 21st century, maintain a realist tone consistent with the national conditions of China, and avoid adventurist policies while awaring both strategic strength and weakness. In the 21st century, China' s grand strategy should be based on such core values as security, development, peace and justice, especially focusing on development in particular, which we named "strategic realism". Given the profound changes in China and the world, strategic realism encourages active foreign policy to safe- guard the long-term national interests of China. Following the self-help logic and the fun- damental values of security and prosperity, strategic realism concerns national interests as its top-priority. It advocates smart use of power, and aims to achieve its objectives by optimizing both domestic and international conditions. From the perspective of diplomatic phi- losophy, strategic realism is not a summarization of concrete policies but a description of China' s grand strategy orientations in the new century. [ Key Words] China, grand strategy, strategic realism [ Author]Song Dexing, Professor, Ph.D. Supervisor, and Director of the Center for International Strategic Studies, University of International Studies of PLA.

  4. ABSTRACTS

    Institute of Scientific and Technical Information of China (English)

    2012-01-01

    Discussions of Design Highlights for Tailgas Treatment in Sulphuric Acid Plant Using New Technology for Flue Gas Desulfurization Through Catalytic Reduction LI Xin , CAO Long-wen , YIN Hua-qiang , El Yue-li , LI Jian-iun ( 1 ,College of Architecture and Environment, Sichuan University, Chengdu 610065, China;2 ,Daye Nonferrous Metals Co., Ltd., Huangshi 435000, China; 3 ,Tile Sixth Construction Company Ltd. of China National Chemical Engineering Corp., Xiangfan 441021, China) Abstract : For the present situation of tailgas treatment in current sulphuric acid plants and existing problems with commonly used technologies, the fun- damental working principle, process flow and reference project for a new technology for flue gas desulfurization through catalytic redaction which is used for tailgas treatment in a sulphuric acid plant and recovery of sulphur resource are outlined. The design highlights of this technology are analyzed and the are proposed. Compared to conventional technologies, this new technology offers high desulfurization efficiency and unique technology, which can effectively tackle the difficuhies of tailgas treatment in sulphuric acid plants after enforcement of the new standard. This new technology is thought to be significant economic benefit, environmental benefit, as well as a promising future of application.

  5. Abstracts

    Institute of Scientific and Technical Information of China (English)

    2012-01-01

    [Abstract] The essay analyzed the action logic of hegemon with a power approach. Hegemony can be classified as benign or malignant. A benign hegemon should be pro- ductive, inclusive and maintain procedure justice when it uses its power. The power of hegemon can be categorized into two types: the hard power, which is the use of coer- cion and payment and can be measured by public products, and the soft power, which shows the ability to attract and co-opt and can be measured by the relationship-specific investments. The relationship between the input of public products and the relationship -specific investments is not positively correlative. Confusing with the public products and the soft power might lead to strategic misleading. A country rich in power re- sources should comply with the following principles if it wanted to improve its hard power and soft power: first, analyze the scope of the existing hegemon's soft power and avoid investing public products in the scope; second, maintain honesty in a long term and continue to increase others' benefits following the rule of neutral Pareto im- provement; third, provide both public goods and public bads; fourth, be more patient to obtain soft power. [ Key Words] hegemon, soft power, relationship-specific investment, strategic misleading [Authors]Feng Weijiang, Ph.D., Associate Professor, Institute of World Economics and Politics, Chinese Academy of Social Science; Yu Jieya, Master, PBC Shanghai Headquarters.

  6. Site-specific reaction rate constant measurements for various secondary and tertiary H-abstraction by OH radicals

    KAUST Repository

    Badra, Jihad

    2015-02-01

    Reaction rate constants for nine site-specific hydrogen atom (H) abstraction by hydroxyl radicals (OH) have been determined using experimental measurements of the rate constants of Alkane+OH→Products reactions. Seven secondary (S 20, S 21, S 22, S 30, S 31, S 32, and S 33) and two tertiary (T 100 and T 101) site-specific rate constants, where the subscripts refer to the number of carbon atoms (C) connected to the next-nearest-neighbor (N-N-N) C atom, were obtained for a wide temperature range (250-1450K). This was done by measuring the reaction rate constants for H abstraction by OH from a series of carefully selected large branched alkanes. The rate constant of OH with four different alkanes, namely 2,2-dimethyl-pentane, 2,4-dimethyl-pentane, 2,2,4-trimethyl-pentane (iso-octane), and 2,2,4,4-tetramethyl-pentane were measured at high temperatures (822-1367K) using a shock tube and OH absorption diagnostic. Hydroxyl radicals were detected using the narrow-line-width ring-dye laser absorption of the R1(5) transition of OH spectrum near 306.69nm.Previous low-temperature rate constant measurements are added to the current data to generate three-parameter rate expressions that successfully represent the available direct measurements over a wide temperature range (250-1450. K). Similarly, literature values of the low-temperature rate constants for the reaction of OH with seven normal and branched alkanes are combined with the recently measured high-temperature rate constants from our group [1]. Subsequent to that, site-specific rate constants for abstractions from various types of secondary and tertiary H atoms by OH radicals are derived and have the following modified Arrhenius expressions:. S20=8.49×10-17T1.52exp(73.4K/T)cm3molecule-1s-1(250-1450K) S21=1.07×10-15T1.07exp(208.3K/T)cm3molecule-1s-1(296-1440K) S22=2.88×10-13T0.41exp(-291.5K/T)cm3molecule-1s-1(272-1311K) S30=3.35×10-18T1.97exp(323.1K/T)cm3molecule-1s-1(250-1366K) S31=1.60×10-18T2.0exp(500.0K/T)cm3

  7. Variational Perturbation Treatment of the Confined Hydrogen Atom

    Science.gov (United States)

    Montgomery, H. E., Jr.

    2011-01-01

    The Schrodinger equation for the ground state of a hydrogen atom confined at the centre of an impenetrable cavity is treated using variational perturbation theory. Energies calculated from variational perturbation theory are comparable in accuracy to the results from a direct numerical solution. The goal of this exercise is to introduce the…

  8. The Confined Hydrogen Atom with a Moving Nucleus

    Science.gov (United States)

    Fernandez, Francisco M.

    2010-01-01

    We study the hydrogen atom confined to a spherical box with impenetrable walls but, unlike earlier pedagogical articles on the subject, we assume that the nucleus also moves. We obtain the ground-state energy approximately by means of first-order perturbation theory and show that it is greater than that for the case in which the nucleus is clamped…

  9. Convergent variational calculation of positronium-hydrogen-atom scattering lengths

    CERN Document Server

    Adhikari, S K; Adhikari, Sadhan K.; Mandal, Puspajit

    2001-01-01

    We present a convergent variational basis-set calculational scheme for elastic scattering of positronium atom by hydrogen atom in S wave. Highly correlated trial functions with appropriate symmetry are needed for achieving convergence. We report convergent results for scattering lengths in atomic units for both singlet ($=3.49\\pm 0.20$) and triplet ($=2.46\\pm 0.10$) states.

  10. Quantum-Classical Connection for Hydrogen Atom-Like Systems

    Science.gov (United States)

    Syam, Debapriyo; Roy, Arup

    2011-01-01

    The Bohr-Sommerfeld quantum theory specifies the rules of quantization for circular and elliptical orbits for a one-electron hydrogen atom-like system. This article illustrates how a formula connecting the principal quantum number "n" and the length of the major axis of an elliptical orbit may be arrived at starting from the quantum…

  11. On the hydrogen atom via Wigner-Heisenberg algebra

    Energy Technology Data Exchange (ETDEWEB)

    Rodrigues, R. de Lima [Universidade Federal de Campina Grande (UFCG), Cuite, PB (Brazil). Unidade Academica de Educacao]. E-mail: rafael@df.ufcg.edu.br; rafaelr@cbpf.br

    2008-07-01

    We extend the usual Kustaanheimo-Stiefel 4D {yields} 3D mapping to study and discuss a constrained super-Wigner oscillator in four dimensions. We show that the physical hydrogen atom is the system that emerges in the bosonic sector of the mapped super 3D system. (author)

  12. Hydrogen atom spectrum and the lamb shift in noncommutative QED.

    Science.gov (United States)

    Chaichian, M; Sheikh-Jabbari, M M; Tureanu, A

    2001-03-26

    We have calculated the energy levels of the hydrogen atom as well as the Lamb shift within the noncommutative quantum electrodynamics theory. The results show deviations from the usual QED both on the classical and the quantum levels. On both levels, the deviations depend on the parameter of space/space noncommutativity.

  13. On the energy of electric field in hydrogen atom

    OpenAIRE

    Kornyushin, Yuri

    2009-01-01

    It is shown that hydrogen atom is a unique object in physics having negative energy of electric field, which is present in the atom. This refers also to some hydrogen-type atoms: hydrogen anti-atom, atom composed of proton and antiproton, and positronium.

  14. Variational Perturbation Treatment of the Confined Hydrogen Atom

    Science.gov (United States)

    Montgomery, H. E., Jr.

    2011-01-01

    The Schrodinger equation for the ground state of a hydrogen atom confined at the centre of an impenetrable cavity is treated using variational perturbation theory. Energies calculated from variational perturbation theory are comparable in accuracy to the results from a direct numerical solution. The goal of this exercise is to introduce the…

  15. The Confined Hydrogen Atom with a Moving Nucleus

    Science.gov (United States)

    Fernandez, Francisco M.

    2010-01-01

    We study the hydrogen atom confined to a spherical box with impenetrable walls but, unlike earlier pedagogical articles on the subject, we assume that the nucleus also moves. We obtain the ground-state energy approximately by means of first-order perturbation theory and show that it is greater than that for the case in which the nucleus is clamped…

  16. Higher-order Sternheimer shieldings of the hydrogen atom

    Science.gov (United States)

    Fowler, P. W.; Steiner, E.

    Multiple perturbation theory is used to calculate the response of the electric field gradient at the nucleus of the hydrogen atom to external non-uniform fields. The parallel component of the field gradient at the nucleus in an axial field F with gradient F' and second derivative F'' has the perturbation expansion: [Enlarge Image

  17. Relativistic Transitions in the Hydrogenic Atoms

    CERN Document Server

    Boudet, R

    2009-01-01

    When one approaches the study of the quantal relativistic theory of the electron, one may be surprised by the gap which lies between the frame of the experiments, i.e. the real geometry of the space and time, and the abstraction of the complex matrices and spinors formalism employed in the presentation of the theory. This book uses a theory of the electron, introduced by David Hestenes, in which the mathematical language is the same as the one of the geometry of the space and time. Such a language not only allows one to find again the well known results concerning the one-electron atoms theory but furthermore leads easily to the resolution of problems considered for a long time without solution.

  18. Resonant electron transfer in slow collisions of protons with Rydberg hydrogen atoms

    Energy Technology Data Exchange (ETDEWEB)

    Janev, R.K.; Joachain, C.J.; Nedeljkovic, N.N.

    1984-05-01

    The resonant charge-transfer reaction of protons on highly excited hydrogen atoms is considered by taking into account both the tunneling (under-barrier) and the over-barrier (classically allowed) electron transitions. It is demonstrated that in a wide range of variation of the reduced ve- locity v = vn, the classical transition mechanism is predominant. Cross-section calculations for principal quantum numbers n between 10 and 50 are presented. The results for 45< or =n< or =50 are compared with the available experimental data and with other theoretical calculations.

  19. Hydrogen atom kinetics in capacitively coupled plasmas

    Science.gov (United States)

    Nunomura, Shota; Katayama, Hirotaka; Yoshida, Isao

    2017-05-01

    Hydrogen (H) atom kinetics has been investigated in capacitively coupled very high frequency (VHF) discharges at powers of 16-780 mW cm-2 and H2 gas pressures of 0.1-2 Torr. The H atom density has been measured using vacuum ultra violet absorption spectroscopy (VUVAS) with a micro-discharge hollow cathode lamp as a VUV light source. The measurements have been performed in two different electrode configurations of discharges: conventional parallel-plate diode and triode with an intermediate mesh electrode. We find that in the triode configuration, the H atom density is strongly reduced across the mesh electrode. The H atom density varies from ˜1012 cm-3 to ˜1010 cm-3 by crossing the mesh with 0.2 mm in thickness and 36% in aperture ratio. The fluid model simulations for VHF discharge plasmas have been performed to study the H atom generation, diffusion and recombination kinetics. The simulations suggest that H atoms are generated in the bulk plasma, by the electron impact dissociation (e + H2 \\to e + 2H) and the ion-molecule reaction (H2 + + H2 \\to {{{H}}}3+ + H). The diffusion of H atoms is strongly limited by a mesh electrode, and thus the mesh geometry influences the spatial distribution of the H atoms. The loss of H atoms is dominated by the surface recombination.

  20. A discrete variable representation for electron-hydrogen atom scattering

    Energy Technology Data Exchange (ETDEWEB)

    Gaucher, L.F.

    1994-08-01

    A discrete variable representation (DVR) suitable for treating the quantum scattering of a low energy electron from a hydrogen atom is presented. The benefits of DVR techniques (e.g. the removal of the requirement of calculating multidimensional potential energy matrix elements and the availability of iterative sparse matrix diagonalization/inversion algorithms) have for many years been applied successfully to studies of quantum molecular scattering. Unfortunately, the presence of a Coulomb singularity at the electrically unshielded center of a hydrogen atom requires high radial grid point densities in this region of the scattering coordinate, while the presence of finite kinetic energy in the asymptotic scattering electron also requires a sufficiently large radial grid point density at moderate distances from the nucleus. The constraints imposed by these two length scales have made application of current DVR methods to this scattering event difficult.

  1. Dynamical localization: Hydrogen atoms in magnetic and microwave fields

    Energy Technology Data Exchange (ETDEWEB)

    Benvenuto, F.; Casati, G. [Dipartimento di Fisica dellUniversita, Via Castelnuovo 7, 22100 Como (Italy); Shepelyansky, D.L. [Laboratoire de Physique Quantique, UMR C5626 du CNRS, Universite Paul Sabatier, 31062, Toulouse (France)

    1997-03-01

    We show that dynamical localization for excited hydrogen atoms in magnetic and microwave fields takes place at quite low microwave frequency ({omega}n{sup 3}{lt}1). Estimates of the localization length are given for different parameter regimes, showing that the quantum delocalization border drops significantly as compared to the case of zero magnetic field. This opens up broad possibilities for laboratory investigations. {copyright} {ital 1997} {ital The American Physical Society}

  2. Quantum Dynamics Study on D+OD+ Reaction: Competition between Exchange and Abstraction Channels

    Institute of Scientific and Technical Information of China (English)

    Wen-wu Xu; Pei-yu Zhang; Guo-zhong He

    2013-01-01

    Quantum dynamics for the D+OD+ reaction at the collision energy range of 0.0-1.0 eV was studied on an accurate ab initio potential energy surface.Both of the endothermic abstraction (D+OD+-O++D2) and thermoneutral exchange (D+OD+-D+OD+) channels were investigated from the same set of time-dependent quantum wave packets method under centrifugal sudden approximation.The reaction probability dependence with collision energy,the integral cross sections,and the thermal rate constant of the both channels are calculated.It is found that there is a convex structure in the reaction path of the exchange reaction.The calculated time evolution of the wave packet distribution at J=0 clearly indicates that the convex structure significantly influences the dynamics of the exchange and abstraction channels of title reaction.

  3. STEREO Observations of Energetic Neutral Hydrogen Atoms during the 5 December 2006 Solar Flare

    Science.gov (United States)

    Mewaldt, R. A.; Leske, R. A.; Stone, E. C.; Barghouty, A. F.; Labrador, A. W.; Cohen, C. M. S.; Cummings, A. C.; Davis, A. J.; vonRosenvinge, T. T.; Wiedenbeck, M. E.

    2009-01-01

    We report the discovery of energetic neutral hydrogen atoms emitted during the X9 solar event of December 5, 2006. Beginning 1 hour following the onset of this E79 flare, the Low Energy Telescopes (LETs) on both the STEREO A and B spacecraft observed a sudden burst of 1.6 to 15 MeV protons beginning hours before the onset of the main solar energetic particle (SEP) event at Earth. More than 70% of these particles arrived from a longitude within 10 of the Sun, consistent with the measurement resolution. The derived emission profile at the Sun had onset and peak times remarkably similar to the GOES soft X-ray profile and continued for more than an hour. The observed arrival directions and energy spectrum argue strongly that the particle events less than 5 MeV were due to energetic neutral hydrogen atoms (ENAs). To our knowledge, this is the first reported observation of ENA emission from a solar flare/coronal mass ejection. Possible origins for the production of ENAs in a large solar event are considered. We conclude that the observed ENAs were most likely produced in the high corona and that charge-transfer reactions between accelerated protons and partially-stripped coronal ions are an important source of ENAs in solar events.

  4. Wave mechanics in quantum phase space: hydrogen atom

    Institute of Scientific and Technical Information of China (English)

    LU Jun

    2007-01-01

    The rigorous sohutions of the stationary Schr(o)dinger equation for hydrogen atom are solved with the wave-mechanics method within the framework of the quantum phase-space representation established by Torres-Vega and Frederick. The "Fourier-like"projection transformations of wave function from the phase space to position and momentum spaces are extended to three-dimensional systems. The eigenfunctions in general position and momentum spaces could be obtained through the transformations from eigenfunction in the phase space.

  5. Asymptotics of Rydberg states for the hydrogen atom

    Energy Technology Data Exchange (ETDEWEB)

    Thomas, L.E. [Virginia Univ., Charlottesville, VA (United States). Dept. of Mathematics; Villegas-Blas, C. [Universidad Nacional Autonoma de Mexico, Instituto de Matematicas, Unidad Cuernavaca, A. P. 273-3 Admon. 3, Cuernavaca Morelos 62251 (Mexico)

    1997-08-01

    The asymptotics of Rydberg states, i.e., highly excited bound states of the hydrogen atom Hamiltonian, and various expectations involving these states are investigated. We show that suitable linear combinations of these states, appropriately rescaled and regarded as functions either in momentum space or configuration space, are highly concentrated on classical momentum space or configuration space Kepler orbits respectively, for large quantum numbers. Expectations of momentum space or configuration space functions with respect to these states are related to time-averages of these functions over Kepler orbits. (orig.)

  6. Relativistic Ionization of Hydrogen Atoms by Positron Impact

    Directory of Open Access Journals (Sweden)

    Amal Chahboune

    2016-03-01

    Full Text Available Relativistic triple differential cross-sections (TDCS for ionization of hydrogen atoms by positron impact have been calculated in the symmetric coplanar geometry. We have used Dirac wave functions to describe free electron’s and positron’s sates. The relativistic formalism is examined by taking the non relativistic limit. Present results are compared with those for the corresponding electron-impact case. In the first Born approximation, we found that the TDCS for positron impact ionization exceeds that for electron impact for all energies in accordance with the result obtained by several other theories.

  7. Is H Atom Abstraction Important in the Reaction of Cl with 1-Alkenes?

    Science.gov (United States)

    Walavalkar, M P; Vijayakumar, S; Sharma, A; Rajakumar, B; Dhanya, S

    2016-06-23

    The relative yields of products of the reaction of Cl atoms with 1-alkenes (C4-C9) were determined to see whether H atom abstraction is an important channel and if it is to identify the preferred position of abstraction. The presence of all the possible positional isomers of long chain alkenones and alkenols among the products, along with chloroketones and chloroalcohols, confirms the occurrence of H atom abstraction. A consistent pattern of distribution of abstraction products is observed with oxidation at C4 (next to allyl) being the lowest and that at CH2 groups away from the double bond being the highest. This contradicts with the higher stability of allyl (C3) radical. For a better understanding of the relative reactivity, ab initio calculations at MP2/6-311+G (d,p) level of theory are carried out in the case of 1-heptene. The total rate coefficient, calculated using conventional transition state theory, was found to be in good agreement with the experimental value at room temperature. The preferred position of Cl atom addition is predicted to be the terminal carbon atom, which matches with the experimental observation, whereas the rate coefficients calculated for individual channels of H atom abstraction do not explain the observed pattern of products. The distribution of abstraction products except at C4 is found to be better explained by reported structure activity relationship, developed from experimental rate coefficient data. This implies the reactions to be kinetically dictated and emphasizes the importance of secondary reactions.

  8. Spontaneous absorption of an accelerated hydrogen atom near a conducting plane in vacuum

    CERN Document Server

    Yu, H; Yu, Hongwei; Zhu, Zhiying

    2006-01-01

    We study, in the multipolar coupling scheme, a uniformly accelerated multilevel hydrogen atom in interaction with the quantum electromagnetic field near a conducting boundary and separately calculate the contributions of the vacuum fluctuation and radiation reaction to the rate of change of the mean atomic energy. It is found that the perfect balance between the contributions of vacuum fluctuations and radiation reaction that ensures the stability of ground-state atoms is disturbed, making spontaneous transition of ground-state atoms to excited states possible in vacuum with a conducting boundary. The boundary-induced contribution is effectively a nonthermal correction, which enhances or weakens the nonthermal effect already present in the unbounded case, thus possibly making the effect easier to observe. An interesting feature worth being noted is that the nonthermal corrections may vanish for atoms on some particular trajectories.

  9. Theoretical Studies on the Abstraction Reaction of Atomic O(3p) with Si2H6

    Institute of Scientific and Technical Information of China (English)

    QingZhuZHANG; ChunShengWANG; 等

    2002-01-01

    The hydrogen abstraction reaction of O(3P) with Si2H6 has been studied theoretially. Two transition states of 3A″ and 3A′ symmetries have been located for this abstraction reaction. Geometries have been optimized at the UMP2 leve with 6-311G+(d) basis set. G3MP2 has been used for the final single-point energy calculation. The rate constants have been calculated over a wide temperature range of 200-3000K using canonical variational transition-state sheory (CVT) with small curvature tunneling effect(SCT). The calculated CVT/SCT rate constants match well with the experimental value.

  10. Chemical Reactivity Dynamics and Quantum Chaos in Highly Excited Hydrogen Atoms in an External Field: A Quantum Potential Approach

    Directory of Open Access Journals (Sweden)

    B. Maiti

    2002-04-01

    Full Text Available Abstract: Dynamical behavior of chemical reactivity indices like electronegativity, hardness, polarizability, electrophilicity and nucleophilicity indices is studied within a quantum fluid density functional framework for the interactions of a hydrogen atom in its ground electronic state (n = 1 and an excited electronic state (n = 20 with monochromatic and bichromatic laser pulses. Time dependent analogues of various electronic structure principles like the principles of electronegativity equalization, maximum hardness, minimum polarizability and maximum entropy have been found to be operative. Insights into the variation of intensities of the generated higher order harmonics on the color of the external laser field are obtained. The quantum signature of chaos in hydrogen atom has been studied using a quantum theory of motion and quantum fluid dynamics. A hydrogen atom in the electronic ground state (n = 1 and in an excited electronic state ( n = 20 behaves differently when placed in external oscillating monochromatic and bichromatic electric fields. Temporal evolutions of Shannon entropy, quantum Lyapunov exponent and Kolmogorov – Sinai entropy defined in terms of the distance between two initially close Bohmian trajectories for these two cases show marked differences. It appears that a larger uncertainty product and a smaller hardness value signal a chaotic behavior.

  11. On the combination of a low energy hydrogen atom beam with a cold multipole ion trap

    Energy Technology Data Exchange (ETDEWEB)

    Borodi, Gheorghe

    2008-12-09

    The first part of the activities of this thesis was to develop a sophisticated ion storage apparatus dedicated to study chemical processes with atomic hydrogen. The integration of a differentially pumped radical beam source into an existing temperature variable 22- pole trapping machine has required major modifications. Since astrophysical questions have been in the center of our interest, the introduction first gives a short overview of astrophysics and -chemistry. The basics of ion trapping in temperature variable rf traps is well-documented in the literature; therefore, the description of the basic instrument (Chapter 2) is kept rather short. Much effort has been put into the development of an intense and stable source for hydrogen atoms the kinetic energy of which can be changed. Chapter 3 describes this module in detail with emphasis on the integration of magnetic hexapoles for guiding the atoms and special treatments of the surfaces for reducing H-H recombination. Due to the unique sensitivity of the rf ion trapping technique, this instrument allows one to study a variety of reactions of astrochemical and fundamental interest. The results of this work are summarized in Chapter 4. Reactions of CO{sub 2}{sup +} with hydrogen atoms and molecules have been established as calibration standard for in situ determination of H and H{sub 2} densities over the full temperature range of the apparatus (10 K-300 K). For the first time, reactions of H- and D-atoms with the ionic hydrocarbons CH{sup +}, CH{sub 2}{sup +}, and CH{sub 4}{sup +} have been studied at temperatures of interstellar space. A very interesting, not yet fully understood collision system is the interaction of protonated methane with H. The outlook presents some ideas, how to improve the new instrument and a few reaction systems are mentioned which may be studied next. (orig.)

  12. Chapter 11 Computational Study of the Reaction of n-Bromopropane with OH Radicals and Cl Atoms

    Science.gov (United States)

    Rosado-Reyes, Claudette M.; Martínez-Avilés, Mónica; Francisco, Joseph S.

    Ab initio molecular orbital theory is utilized to study the hydrogen abstraction reaction of n-bromopropane with hydroxyl radical and chlorine atom. The stability of the trans and gauche isomers of n-bromopropane is explored. The potential energy surface of both reactions is characterized by pre- and post-reactive complexes, as well as transition state structures in both trans and gauche isomeric forms. The importance of these two reactions relies on the ultimate product distribution from both reactions. Differences in the reactivity of 1-bromopropane toward OH and Cl are observed. The reaction of n-bromopropane with OH radical favors the abstraction of [beta] hydrogen atoms while the reaction with Cl atoms favors the abstraction of hydrogen atoms at the [alpha] and [beta] carbon sites.

  13. Classical-field model of the hydrogen atom

    Science.gov (United States)

    Rashkovskiy, Sergey A.

    2017-02-01

    It is shown that all of the basic properties of the hydrogen atom can be consistently described in terms of classical electrodynamics if instead of considering the electron to be a particle, we consider an electrically charged classical wave field—an "electron wave"—which is held by the electrostatic field of the proton. It is shown that quantum mechanics must be considered not as a theory of particles but as a classical field theory in the spirit of classical electrodynamics. In this case, we are not faced with difficulties in interpreting the results of the theory. In the framework of classical electrodynamics, all of the well-known regularities of the spontaneous emission of the hydrogen atom are obtained, which is usually derived in the framework of quantum electrodynamics. It is shown that there are no discrete states and discrete energy levels of the atom: the energy of the atom and its states change continuously. An explanation of the conventional corpuscular-statistical interpretation of atomic phenomena is given. It is shown that this explanation is only a misinterpretation of continuous deterministic processes. In the framework of classical electrodynamics, the nonlinear Schrödinger equation is obtained, which accounts for the inverse action of self-electromagnetic radiation of the electron wave and completely describes the spontaneous emissions of an atom.

  14. Plasma screening effects on the energies of hydrogen atom

    Energy Technology Data Exchange (ETDEWEB)

    Soylu, A. [Department of Physics, Nigde University, 51240 Nigde (Turkey)

    2012-07-15

    A more general exponential cosine screened Coulomb potential is used for the first time to investigate the screening effects on the hydrogen atom in plasmas. This potential is examined for four different cases that correspond to four different type potentials when the different parameters are used in the potential within the framework of the well-known asymptotic iteration method. By solving the corresponding the radial Schroedinger equation with the screened and exponential cosine screened Coulomb potentials and comparing the obtained energy eigenvalues with the results of other studies, the applicability of the method to this kind of plasma physics problem is shown. The energy values of more general exponential cosine screened Coulomb potential are presented for various parameters in the potential. One of the advantages of the present potential is that it exhibits stronger screening effect than that of the exponential cosine screened Coulomb potential and it is also reduced to screened Coulomb and exponential cosine screened Coulomb as well as Coulomb potentials for special values of parameters. The parameters in the potential would be useful to model screening effects which cause an increase or decrease in the energy values of hydrogen atom in both Debye and quantum plasmas and in this manner this potential would be useful for the investigations of the atomic structure and collisions in plasmas.

  15. The Unimolecular Decomposition and H Abstraction Reactions by HO and HO2 from n-Butanol

    Science.gov (United States)

    Moc, Jerzy; Black, Gráinne; Simmie, John M.; Curran, Henry J.

    2009-08-01

    By using correlated ab initio (MP2, CCSD(T)) and multi-level (G3, CBS-QB3) methods we have studied unimolecular and bimolecular reactions of n-butanol in the gas phase. The specific processes investigated include H2O elimination and hydrogen abstraction by the hydroxy (HO) and hydroperoxy (HO2) radicals from this alcohol.

  16. Comment on "Wigner phase-space distribution function for the hydrogen atom"

    DEFF Research Database (Denmark)

    Dahl, Jens Peder; Springborg, Michael

    1999-01-01

    We object to the proposal that the mapping of the three-dimensional hydrogen atom into a four-dimensional harmonic oscillator can be readily used to determine the Wigner phase-space distribution function for the hydrogen atom. [S1050-2947(99)07005-5].......We object to the proposal that the mapping of the three-dimensional hydrogen atom into a four-dimensional harmonic oscillator can be readily used to determine the Wigner phase-space distribution function for the hydrogen atom. [S1050-2947(99)07005-5]....

  17. The Quantum Black Hole as a Hydrogen Atom: Microstates Without Strings Attached

    CERN Document Server

    Hooft, Gerard t

    2016-01-01

    Applying an expansion in spherical harmonics, turns the black hole with its microstates into something about as transparent as the hydrogen atom was in the early days of quantum mechanics. It enables us to present a concise description of the evolution laws of these microstates, linking them to perturbative quantum field theory, in the background of the Schwarzschild metric. Three pieces of insight are obtained: One, we learn how the gravitational back reaction, whose dominant component can be calculated exactly, turns particles entering the hole, into particles leaving it, by exchanging the momentum- and position operators; two, we find out how this effect removes firewalls, both on the future and the past event horizon, and three, we discover that the presence of region II in the Penrose diagram forces a topological twist in the background metric, culminating in antipodal identification. Although a cut-off is required that effectively replaces the transverse coordinates by a lattice, the effect of such a cu...

  18. Photoionization microscopy of hydrogen atom near a metal surface

    Institute of Scientific and Technical Information of China (English)

    Yang Hai-Feng; Wang Lei; Liu Xiao-Jun; Liu Hong-Ping

    2011-01-01

    We have studied the ionization of Rydberg hydrogen atom near a metal surface with a semiclassical analysis of photoionization microscopy. Interference patterus of the electron radial distribution are calculated at different scaled energies above the classical saddle point and at various atom-surface distances. We find that different types of trajectories contribute predominantly to different manifolds in a certain interference pattern. As the scaled energy increases, the structure of the interference pattern evolves smoothly and more types of trajectories emerge. As the atom approaches the metal surface closer, there are more types of trajectories contributing to the interference pattern as well. When the Rydberg atom comes very close to the metal surface or the scaled energy approaches the zero field ionization energy,the potential induced by the metal surface will make atomic system chaotic. The results also show that atoms near a metal surface exhibit similar properties like the atoms in the parallel electric and magnetic fields.

  19. Dirac equation in very special relativity for hydrogen atom

    CERN Document Server

    Maluf, R V; Cruz, W T; Almeida, C A S

    2014-01-01

    In this work, we study the modified Dirac equation in the framework of very special relativity (VSR). The low-energy regime is accessed and the nonrelativistic Hamiltonian is obtained. It turns out that this Hamiltonian is similar to that achieved from the Standard Model Extension (SME) via coupling of the spinor field to a Lorentz-violating term, but new features arise inherited from the non-local character of the VSR. In addition, the implications of the VSR-modified Lorentz symmetry on the spectrum of a hydrogen atom is determined by calculating the first-order energy corrections in the context of standard quantum mechanics. Among the results, we highlight that the modified Hamiltonian provides non-vanishing corrections which lift the degeneracy of the energy levels and allow us to find an upper bound upon the VSR-parameter.

  20. Dirac equation in very special relativity for hydrogen atom

    Directory of Open Access Journals (Sweden)

    R.V. Maluf

    2014-11-01

    Full Text Available In this work, we study the modified Dirac equation in the framework of very special relativity (VSR. The low-energy regime is accessed and the nonrelativistic Hamiltonian is obtained. It turns out that this Hamiltonian is similar to that achieved from the Standard Model Extension (SME via coupling of the spinor field to a Lorentz-violating term, but new features arise inherited from the non-local character of the VSR. In addition, the implications of the VSR-modified Lorentz symmetry on the spectrum of a hydrogen atom are determined by calculating the first-order energy corrections in the context of standard quantum mechanics. Among the results, we highlight that the modified Hamiltonian provides non-vanishing corrections which lift the degeneracy of the energy levels and allow us to find an upper bound upon the VSR-parameter.

  1. Schrodinger Equation Solutions that Lead to the Solution for the Hydrogen Atom

    Science.gov (United States)

    Newhouse, Paul F.; McGill, K.C.

    2004-01-01

    Two exercises that would provide beginning quantum theory students with an introduction to more advanced quantum mechanical treatments, especially the hydrogen atom are given. The exercises are stepwise in difficulty, leading naturally to the full hydrogen atom development and greatly extend the pedagogy of most multidimensional Cartesian systems…

  2. Photo-Ionization of Hydrogen Atom in a Circularly Polarized Standing Electromagnetic Wave

    Institute of Scientific and Technical Information of China (English)

    LIU Xiang-Tao; ZHANG Qi-Ren; WANG Wan-Zhang

    2004-01-01

    Applying time-independent non-perturbative formalism to the photo-ionization of hydrogen atom immersed in a strong circularly polarized standing electromagnetic wave, we calculate the shift of energy levels and the distortion of wave functions for the hydrogen atom, the ionization cross section induced by the standing wave, and the angular distribution of photoelectrons and obtain some interesting results.

  3. Explicit expressions and recurrence formulas of radial average value for N-dimensional hydrogen atom

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    In this paper, two recurrence formulas for radial average values of N-dimensional hydrogen atom are derived. Explicit results can be applied to discuss average value of centrifugal potential energy and other physical quantities. The relevant results of the usual hydrogen atom are contained in more general conclusion of this paper as special cases.

  4. Thermodynamics of various F420 coenzyme models as sources of electrons, hydride ions, hydrogen atoms and protons in acetonitrile.

    Science.gov (United States)

    Xia, Ke; Shen, Guang-Bin; Zhu, Xiao-Qing

    2015-06-14

    32 F420 coenzyme models with alkylation of the three different N atoms (N1, N3 and N10) in the core structure (XFH(-)) were designed and synthesized and the thermodynamic driving forces (defined in terms of the molar enthalpy changes or the standard redox potentials in this work) of the 32 XFH(-) releasing hydride ions, hydrogen atoms and electrons, the thermodynamic driving forces of the 32 XFH˙ releasing protons and hydrogen atoms and the thermodynamic driving forces of XF(-)˙ releasing electrons in acetonitrile were determined using titration calorimetry and electrochemical methods. The effects of the methyl group at N1, N3 and N10 and a negative charge on N1 and N10 atoms on the six thermodynamic driving forces of the F420 coenzyme models and their related reaction intermediates were examined; the results show that seating arrangements of the methyl group and the negative charge have remarkably different effects on the thermodynamic properties of the F420 coenzyme models and their related reaction intermediates. The effects of the substituents at C7 and C8 on the six thermodynamic driving forces of the F420 coenzyme models and their related reaction intermediates were also examined; the results show that the substituents at C7 and C8 have good Hammett linear free energy relationships with the six thermodynamic parameters. Meanwhile, a reasonable determination of possible reactions between members of the F420 family and NADH family in vivo was given according to a thermodynamic analysis platform constructed using the elementary step thermodynamic parameter of F420 coenzyme model 2FH(-) and NADH model MNAH releasing hydride ions in acetonitrile. The information disclosed in this work can not only fill a gap in the chemical thermodynamics of F420 coenzyme models as a class of very important organic sources of electrons, hydride ions, hydrogen atoms and protons, but also strongly promote the fast development of the chemistry and applications of F420 coenzyme.

  5. Theoretical and Shock Tube Study of the Rate Constants for Hydrogen Abstraction Reactions of Ethyl Formate

    KAUST Repository

    Wu, Junjun

    2017-08-03

    We report a systematic chemical kinetics study of the H-atom abstractions from ethyl formate (EF) by H, O(3P), CH3, OH, and HO2 radicals. The geometry optimization and frequency calculation of all the species were conducted using the M06 method and the cc-pVTZ basis set. The one-dimensional hindered rotor treatment of the reactants and transition states and the intrinsic reaction coordinate analysis were also performed at the M06/cc-pVTZ level of theory. The relative electronic energies were calculated at the CCSD(T)/cc-pVXZ (where X = D, T) level of theory and further extrapolated to the complete basis set limit. Rate constants for the tittle reactions were calculated over the temperature range of 500‒2500 K by the transition state theory (TST) in conjunction with asymmetric Eckart tunneling effect. In addition, the rate constants of H-abstraction by hydroxyl radical were measured in shock tube experiments at 900‒1321 K and 1.4‒2.0 atm. Our theoretical rate constants of OH + EF → Products agree well with the experimental results within 15% over the experimental temperature range of 900‒1321 K. Branching ratios for the five types of H-abstraction reactions were also determined from their individual site-specific rate constants.

  6. Reaction kinetics of hydrogen abstraction reactions by hydroperoxyl radical from 2-methyltetrahydrofuran and 2,5-dimethyltetrahydrofuran.

    Science.gov (United States)

    Chakravarty, Harish Kumar; Fernandes, Ravi X

    2013-06-20

    Highly accurate rate parameters for H-abstraction reactions by HO2 radicals are needed for development of predictive chemical kinetic models for ignition. In this article, we report the rate coefficients for reaction of hydroperoxyl radical (HO2) with 2-methyltetrahydrofuran (MTHF) and 2,5-dimethyltetrahydrofuran (DMTHF) computed employing CBS-QB3 and CCSD(T)/cc-pVTZ//B3LYP/cc-pVTZ level of theory in the temperature range of 500-2000 K. Conventional transition state theory (CTST) with hindered rotor approximation for low frequency torsional modes and RRHO (rigid-rotor harmonic oscillator) approximation for all other vibrational modes is employed to evaluate the high pressure rate constants as a function of temperature. Rate constant of each individual hydrogen abstraction channel is taken into account to calculate the overall rate constant. Three-parameter Arrhenius expressions have been obtained by fitting to the computed rate constants of all abstraction channels between 500 and 2000 K. Eight transition states have been identified for MTHF and four for slightly more stable trans-DMTHF. Intrinsic reaction coordinates (IRC) calculations were performed to verify the connectivity of all the transition states (TSs) with reactants and products. One dimensional Eckart's asymmetrical method has been used to calculate quantum mechanical tunneling effect. Results of the theoretically calculated rate coefficients indicate that the hydrogen abstraction by HO2 from the C2 carbon of both MTHF and DMTHF is the most dominant path among all reaction pathways attributed to its lowest barrier height. The total rate coefficients of the MTHF and DMTHF with HO2 at CCSD(T)/cc-pVTZ//B3LYP/cc-pVTZ level of theory are k(T) = 8.60T(3.54) exp(-8.92/RT) and k(T)= 3.17T(3.63) exp(-6.59/RT) cm(3) mol(-1) s(-1), respectively. At both the level of theories, the predicted total abstraction rate constant for DMTHF is found to be higher as compared to that of MTHF over an entire temperature range

  7. Photochemical Hydrogen Abstraction and Electron Transfer Reactions of Tetrachlorobenzoquinone with Pyrimidine Nucleobases

    Institute of Scientific and Technical Information of China (English)

    Kun-hui Liu; Li-dan Wu; Xiao-ran Zou; Wen Yang; Qian Du; Hong-mei Su

    2011-01-01

    Pentachlorophenol,a widespread environmental pollutant that is possibly carcinogenic to humans,is metabolically oxidized to tetrachloroquinone (TCBQ) which can result in DNA damage.We have investigated the photochemical reaction dynamics of TCBQ with two pyrimidine type nucleobases (thymine and uracil) upon UVA (355 nm) excitation using the technique of nanosecond time-resolved laser flash photolysis.It has been found that 355 nm excitation populates TCBQ molecules to their triplet state 3TCBQ*,which are highly reactive towards thymine or uracil and undergo two parallel reactions,the hydrogen abstraction and electron transfer,leading to the observed photoproducts of TCBQH.and TCBQ.- in transient absorption spectra.The concomitantly produced nucleobase radicals and radical cations are expected to induce a series of oxidative or strand cleavage damage to DNA afterwards.By characterizing the photochemical hydrogen abstraction and electron transfer reactions,our results provide potentially important molecular reaction mechanisms for understanding the carcinogenic effects of pentachlorophenol and its metabolites TCBQ.

  8. Atmospheric reaction of Cl + methacrolein: a theoretical study on the mechanism, and pressure- and temperature-dependent rate constants.

    Science.gov (United States)

    Sun, Cuihong; Xu, Baoen; Zhang, Shaowen

    2014-05-22

    Methacrolein is a major degradation product of isoprene, the reaction of methacrolein with Cl atoms may play some roles in the degradation of isoprene where these species are relatively abundant. However, the energetics and kinetics of this reaction, which govern the reaction branching, are still not well understood so far. In the present study, two-dimensional potential energy surfaces were constructed to analyze the minimum energy path of the barrierless addition process between Cl and the C═C double bond of methacrolein, which reveals that the terminal addition intermediate is directly formed from the addition reaction. The terminal addition intermediate can further yield different products among which the reaction paths abstracting the aldehyde hydrogen atom and the methyl hydrogen atom are dominant reaction exits. The minimum reaction path for the direct aldehydic hydrogen atom abstraction is also obtained. The reaction kinetics was calculated by the variational transition state theory in conjunction with the master equation method. From the theoretical model we predicted that the overall rate constant of the Cl + methacrolein reaction at 297 K and atmospheric pressure is koverall = 2.3× 10(-10) cm(3) molecule(-1) s(-1), and the branching ratio of the aldehydic hydrogen abstraction is about 12%. The reaction is pressure dependent at P pressure limit at about 100 Torr. The calculated results could well account for the experimental observations.

  9. Quantum dynamics of hydrogen atoms on graphene. II. Sticking

    Energy Technology Data Exchange (ETDEWEB)

    Bonfanti, Matteo, E-mail: matteo.bonfanti@unimi.it [Dipartimento di Chimica, Università degli Studi di Milano, v. Golgi 19, 20133 Milano (Italy); Jackson, Bret [Department of Chemistry, University of Massachusetts, Amherst, Massachusetts 01003 (United States); Hughes, Keith H. [School of Chemistry, Bangor University, Bangor, Gwynedd LL57 2UW (United Kingdom); Burghardt, Irene [Institute of Physical and Theoretical Chemistry, Goethe University Frankfurt, Max-von-Laue-Str. 7, 60438 Frankfurt/Main (Germany); Martinazzo, Rocco, E-mail: rocco.martinazzo@unimi.it [Dipartimento di Chimica, Università degli Studi di Milano, v. Golgi 19, 20133 Milano (Italy); Istituto di Scienze e Tecnologie Molecolari, Consiglio Nazionale delle Richerche, v. Golgi 19, 20133 Milano (Italy)

    2015-09-28

    Following our recent system-bath modeling of the interaction between a hydrogen atom and a graphene surface [Bonfanti et al., J. Chem. Phys. 143, 124703 (2015)], we present the results of converged quantum scattering calculations on the activated sticking dynamics. The focus of this study is the collinear scattering on a surface at zero temperature, which is treated with high-dimensional wavepacket propagations with the multi-configuration time-dependent Hartree method. At low collision energies, barrier-crossing dominates the sticking and any projectile that overcomes the barrier gets trapped in the chemisorption well. However, at high collision energies, energy transfer to the surface is a limiting factor, and fast H atoms hardly dissipate their excess energy and stick on the surface. As a consequence, the sticking coefficient is maximum (∼0.65) at an energy which is about one and half larger than the barrier height. Comparison of the results with classical and quasi-classical calculations shows that quantum fluctuations of the lattice play a primary role in the dynamics. A simple impulsive model describing the collision of a classical projectile with a quantum surface is developed which reproduces the quantum results remarkably well for all but the lowest energies, thereby capturing the essential physics of the activated sticking dynamics investigated.

  10. Transient absorption spectra of the laser-dressed hydrogen atom

    Science.gov (United States)

    Murakami, Mitsuko; Chu, Shih-I.

    2013-10-01

    We present a theoretical study of transient absorption spectra of laser-dressed hydrogen atoms, based on numerical solutions of the time-dependent Schrödinger equation. The timing of absorption is controlled by the delay between an extreme ultra violet (XUV) pulse and an infrared (IR) laser field. The XUV pulse is isolated and several hundred attoseconds in duration, which acts as a pump to drive the ground-state electron to excited p states. The subsequent interaction with the IR field produces dressed states, which manifest as sidebands between the 1s-np absorption spectra separated by one IR-photon energy. We demonstrate that the population of dressed states is maximized when the timing of the XUV pulse coincides with the zero crossing of the IR field, and that their energies can be manipulated in a subcycle time scale by adding a chirp to the IR field. An alternative perspective to the problem is to think of the XUV pulse as a probe to detect the dynamical ac Stark shifts. Our results indicate that the accidental degeneracy of the hydrogen excited states is removed while they are dressed by the IR field, leading to large ac Stark shifts. Furthermore, we observe the Autler-Townes doublets for the n=2 and 3 levels using the 656 nm dressing field, but their separation does not agree with the prediction by the conventional three-level model that neglects the dynamical ac Stark shifts.

  11. Understanding kinetic solvent effects on hydrogen abstraction reactions from carbon by the cumyloxyl radical.

    Science.gov (United States)

    Bietti, Massimo; Martella, Roberto; Salamone, Michela

    2011-11-18

    A kinetic study of the hydrogen abstraction reactions from tetrahydrofuran (THF) and cyclohexane (CHX) by the cumyloxyl radical was carried out in different solvents. With THF, a 4.5-fold decrease in rate constant (k(H)) was observed on going from isooctane to 2,2,2-trifluoroethanol. An opposite behavior was observed with CHX, where k(H) increased by a factor 4 on going from isooctane to 2,2,2-trifluoroethanol. The important role of substrate structure and of the solvent hydrogen bond donor ability is discussed.

  12. Exchange of carbon-bound hydrogen atoms ortho to the hydroxyl group in tyrosine.

    Science.gov (United States)

    Martin, R B; Morlino, V J

    1965-10-22

    The carbon-bound hydrogen atoms of tyrosine that exchange with solvent protons in strongly acid solutions at about 100 degrees C are not the methylene hydrogen atoms but a pair on the aromatic ring. Of the two pairs of protons on the aromatic ring, observed in the proton magnetic resonance spectra, the pair at higher field undergoes exchange in 2.4N DCI at 100 degrees C. Other hydrogen atoms, attached either to aliphatic or aromatic carbon atoms, exhibit no noticeable exchange under the same conditions. From a chemicalshift analysis the exchanging protons are assigned as those ortho to the hydroxyl group on the aromatic ring.

  13. Hydrogen atom addition to the surface of graphene nanoflakes: A density functional theory study

    Science.gov (United States)

    Tachikawa, Hiroto

    2017-02-01

    Polycyclic aromatic hydrocarbons (PAHs) provide a 2-dimensional (2D) reaction surface in 3-dimensional (3D) interstellar space and have been utilized as a model of graphene surfaces. In the present study, the reaction of PAHs with atomic hydrogen was investigated by means of density functional theory (DFT) to systematically elucidate the binding nature of atomic hydrogen to graphene nanoflakes. PAHs with n = 4-37 were chosen, where n indicates the number of benzene rings. Activation energies of hydrogen addition to the graphene surface were calculated to be 5.2-7.0 kcal/mol at the CAM-B3LYP/6-311G(d,p) level, which is almost constant for all PAHs. The binding energies of hydrogen atom were slightly dependent on the size (n): 14.8-28.5 kcal/mol. The absorption spectra showed that a long tail is generated at the low-energy region after hydrogen addition to the graphene surface. The electronic states of hydrogenated graphenes were discussed on the basis of theoretical results.

  14. Hyperfine splitting in non-relativistic QED: uniqueness of the dressed hydrogen atom ground state

    CERN Document Server

    Amour, Laurent

    2011-01-01

    We consider a free hydrogen atom composed of a spin-1/2 nucleus and a spin-1/2 electron in the standard model of non-relativistic QED. We study the Pauli-Fierz Hamiltonian associated with this system at a fixed total momentum. For small enough values of the fine-structure constant, we prove that the ground state is unique. This result reflects the hyperfine structure of the hydrogen atom ground state.

  15. Halogen-abstraction reactions from chloromethane and bromomethane molecules by alkaline-earth monocations.

    Science.gov (United States)

    Redondo, Pilar; Largo, Antonio; Rayón, Víctor Manuel; Molpeceres, Germán; Sordo, José Ángel; Barrientos, Carmen

    2014-08-14

    The reactions, in the gas phase, between alkali-earth monocations (Mg(+), Ca(+), Sr(+), Ba(+)) and CH3X (X = Cl, Br) have been theoretically studied. The stationary points on the potential energy surfaces were characterized at the Density Functional Theory level on the framework of the mPW1K functional with the QZVPP Ahlrichs's basis sets. A complementary kinetics study has also been performed using conventional/variational microcanonical transition state theory. In the reactions of Mg(+) with either chloro- or bromomethane the transition structure lies in energy clearly above the reactants rendering thermal activation of CH3Cl or CH3Br extremely improbable. The remaining reactions are exothermic and barrierless processes; thus carbon-halogen bonds in chloro- or bromomethane can be activated by calcium, strontium or barium monocations to obtain the metal halogen cation and the methyl radical. The Mulliken population analysis for the stationary points of the potential energy surfaces supports a "harpoon"-like mechanism for the halogen-atom abstraction processes. An analysis of the bonding situation for the stationary points on the potential energy surface has also been performed in the framework of the quantum theory of atoms in molecules.

  16. Which hydrogen atom of toluene protonates PAH molecules in (+)-mode APPI MS analysis?

    Science.gov (United States)

    Ahmed, Arif; Ghosh, Manik Kumer; Choi, Myung Chul; Choi, Cheol Ho; Kim, Sunghwan

    2013-03-01

    A previous study (Ahmed, A. et al., Anal. Chem. 84, 1146-1151( 2012) reported that toluene used as a solvent was the proton source for polyaromatic hydrocarbon compounds (PAHs) that were subjected to (+)-mode atmospheric-pressure photoionization. In the current study, the exact position of the hydrogen atom in the toluene molecule (either a methyl hydrogen or an aromatic ring hydrogen) involved in the formation of protonated PAH ions was investigated. Experimental analyses of benzene and anisole demonstrated that although the aromatic hydrogen atom of toluene did not contribute to the formation of protonated anthracene, it did contribute to the formation of protonated acridine. Thermochemical data and quantum mechanical calculations showed that the protonation of anthracene by an aromatic ring hydrogen atom of toluene is endothermic, while protonation by a methyl hydrogen atom is exothermic. However, protonation of acridine by either an aromatic ring hydrogen or a methyl hydrogen atom of toluene is exothermic. The different behavior of acridine and anthracene was attributed to differences in gas-phase basicity. It was concluded that both types of hydrogen in toluene can be used for protonation of PAH compounds, but a methyl hydrogen atom is preferred, especially for non-basic compounds.

  17. Water mediated hydrogen abstraction mechanism in the radical reaction between HOSO and NO2

    Science.gov (United States)

    Lesar, Antonija; Tušar, Simona

    2016-05-01

    The effect of water molecules on the direct hydrogen abstraction from HOSO by NO2 was investigated for the first time. Stationary points were located at the B3LYP/6-311+G(2df,2pd) and CCSD/aug-cc-pVDZ levels of theory whereas energetics was further improved by CBS-QB3 and G4 composite methods. The fractions of hydrated radical complexes were estimated in order to assess atmospheric relevance of the title reaction. The energy barrier of the water mediated process becomes negligible. The formations of post-reactive complexes from pre-reactive complexes are energetically very favorable and the processes are spontaneous suggesting that they should be very feasible under atmospheric conditions.

  18. Investigation of the Mechanism of Electron Capture and Electron Transfer Dissociation of Peptides with a Covalently Attached Free Radical Hydrogen Atom Scavenger.

    Science.gov (United States)

    Sohn, Chang Ho; Yin, Sheng; Peng, Ivory; Loo, Joseph A; Beauchamp, J L

    2015-11-15

    The mechanisms of electron capture and electron transfer dissociation (ECD and ETD) are investigated by covalently attaching a free-radical hydrogen atom scavenger to a peptide. The 2,2,6,6-tetramethylpiperidin-l-oxyl (TEMPO) radical was chosen as the scavenger due to its high hydrogen atom affinity (ca. 280 kJ/mol) and low electron affinity (ca. 0.45 ev), and was derivatized to the model peptide, FQX(TEMPO)EEQQQTEDELQDK. The X(TEMPO) residue represents a cysteinyl residue derivatized with an acetamido-TEMPO group. The acetamide group without TEMPO was also examined as a control. The gas phase proton affinity (882 kJ/mol) of TEMPO is similar to backbone amide carbonyls (889 kJ/mol), minimizing perturbation to internal solvation and sites of protonation of the derivatized peptides. Collision induced dissociation (CID) of the TEMPO tagged peptide dication generated stable odd-electron b and y type ions without indication of any TEMPO radical induced fragmentation initiated by hydrogen abstraction. The type and abundance of fragment ions observed in the CID spectra of the TEMPO and acetamide tagged peptides are very similar. However, ECD of the TEMPO labeled peptide dication yielded no backbone cleavage. We propose that a labile hydrogen atom in the charge reduced radical ions is scavenged by the TEMPO radical moiety, resulting in inhibition of N-Cα backbone cleavage processes. Supplemental activation after electron attachment (ETcaD) and CID of the charge-reduced precursor ion generated by electron transfer of the TEMPO tagged peptide dication produced a series of b + H (b(H)) and y + H (y(H)) ions along with some c ions having suppressed intensities, consistent with stable O-H bond formation at the TEMPO group. In summary, the results indicate that ECD and ETD backbone cleavage processes are inhibited by scavenging of a labile hydrogen atom by the localized TEMPO radical moiety. This observation supports the conjecture that ECD and ETD processes involve long

  19. Determination of thermodynamic affinities of various polar olefins as hydride, hydrogen atom, and electron acceptors in acetonitrile.

    Science.gov (United States)

    Cao, Ying; Zhang, Song-Chen; Zhang, Min; Shen, Guang-Bin; Zhu, Xiao-Qing

    2013-07-19

    A series of 69 polar olefins with various typical structures (X) were synthesized and the thermodynamic affinities (defined in terms of the molar enthalpy changes or the standard redox potentials in this work) of the polar olefins obtaining hydride anions, hydrogen atoms, and electrons, the thermodynamic affinities of the radical anions of the polar olefins (X(•-)) obtaining protons and hydrogen atoms, and the thermodynamic affinities of the hydrogen adducts of the polar olefins (XH(•)) obtaining electrons in acetonitrile were determined using titration calorimetry and electrochemical methods. The pure C═C π-bond heterolytic and homolytic dissociation energies of the polar olefins (X) in acetonitrile and the pure C═C π-bond homolytic dissociation energies of the radical anions of the polar olefins (X(•-)) in acetonitrile were estimated. The remote substituent effects on the six thermodynamic affinities of the polar olefins and their related reaction intermediates were examined using the Hammett linear free-energy relationships; the results show that the Hammett linear free-energy relationships all hold in the six chemical and electrochemical processes. The information disclosed in this work could not only supply a gap of the chemical thermodynamics of olefins as one class of very important organic unsaturated compounds but also strongly promote the fast development of the chemistry and applications of olefins.

  20. Vocal reaction times to unilaterally presented concrete and abstract words: towards a theory of differential right hemispheric semantic processing.

    Science.gov (United States)

    Rastatter, M; Dell, C W; McGuire, R A; Loren, C

    1987-03-01

    Previous studies investigating hemispheric organization for processing concrete and abstract nouns have provided conflicting results. Using manual reaction time tasks some studies have shown that the right hemisphere is capable of analyzing concrete words but not abstract. Others, however, have inferred that the left hemisphere is the sole analyzer of both types of lexicon. The present study tested these issues further by measuring vocal reaction times of normal subjects to unilaterally presented concrete and abstract items. Results were consistent with a model of functional localization which suggests that the minor hemisphere is capable of differentially processing both types of lexicon in the presence of a dominant left hemisphere.

  1. Hydrogen atoms can be located accurately and precisely by x-ray crystallography.

    Science.gov (United States)

    Woińska, Magdalena; Grabowsky, Simon; Dominiak, Paulina M; Woźniak, Krzysztof; Jayatilaka, Dylan

    2016-05-01

    Precise and accurate structural information on hydrogen atoms is crucial to the study of energies of interactions important for crystal engineering, materials science, medicine, and pharmacy, and to the estimation of physical and chemical properties in solids. However, hydrogen atoms only scatter x-radiation weakly, so x-rays have not been used routinely to locate them accurately. Textbooks and teaching classes still emphasize that hydrogen atoms cannot be located with x-rays close to heavy elements; instead, neutron diffraction is needed. We show that, contrary to widespread expectation, hydrogen atoms can be located very accurately using x-ray diffraction, yielding bond lengths involving hydrogen atoms (A-H) that are in agreement with results from neutron diffraction mostly within a single standard deviation. The precision of the determination is also comparable between x-ray and neutron diffraction results. This has been achieved at resolutions as low as 0.8 Å using Hirshfeld atom refinement (HAR). We have applied HAR to 81 crystal structures of organic molecules and compared the A-H bond lengths with those from neutron measurements for A-H bonds sorted into bonds of the same class. We further show in a selection of inorganic compounds that hydrogen atoms can be located in bridging positions and close to heavy transition metals accurately and precisely. We anticipate that, in the future, conventional x-radiation sources at in-house diffractometers can be used routinely for locating hydrogen atoms in small molecules accurately instead of large-scale facilities such as spallation sources or nuclear reactors.

  2. Lewis‐Acid‐assisted Hydrogen Atom Transfer to Manganese(V)‐Oxo Corrole through Valence Tautomerization

    OpenAIRE

    Bougher, Curt J.; Abu‐Omar, Mahdi M.

    2016-01-01

    Abstract The kinetics of formation of the valence tautomers (tpfc⋅)MnIV(O−LA)] n+ [where LA=ZnII, CaII, ScIII, YbIII, B(C6F5)3, and trifluoroacetic acid (TFA); tpfc=5,10,15‐tris(pentafluorophenyl) corrole] from (tpfc)MnV(O) were followed by UV/Vis spectroscopy, giving second‐order rate constants ranging over five orders of magnitude from 10−2 for Ca to 103  m −1 s−1 for Sc. Hydrogen atom transfer (HAT) rates from 2,4‐di‐tert‐butyl phenol (2,4‐DTBP) to the various Lewis acid valence tautomers ...

  3. Does God Play Dice with Universe The Hydrogen Atomic Model of Bohr and de Broglie

    CERN Document Server

    Kamenov, P S

    1999-01-01

    In this paper it is shown that if one accept assumption of de Broglie that "unitary wave-particle" exists simultaneously and this coexistence is real, then one can find the mean life time of the hydrogen atom of Bohr (intensities). Something more, the acceptance of de Broglie's ideas show that a single excited hydrogen atom decays at exactly predictable moment (after excitation). The natural width of excited hydrogen atoms are found using the Bohr's model of this atom and de Broglie's ideas. The mean life time of the excited states is a characteristic only of a statistical ensemble of many atoms and coincide exactly with experimental data and can be used for analytical applications. It is shown also that resonant Mossbauer absorption in time domain provides a qualitative evidence of the existence of "own lifetime" for first excited states of the nuclei.

  4. Semiclassical Szego limit of resonance clusters for the hydrogen atom Stark Hamiltonian

    CERN Document Server

    Hislop, Peter D

    2011-01-01

    We study the weighted averages of resonance clusters for the hydrogen atom with a Stark electric field in the weak field limit. We prove a semiclassical Szego-type theorem for resonance clusters showing that the limiting distribution of the resonance shifts concentrates on the classical energy surface corresponding to a rescaled eigenvalue of the hydrogen atom Hamiltonian. This result extends Szego-type results on eigenvalue clusters to resonance clusters. There are two new features in this work: first, the study of resonance clusters requires the use of non self-adjoint operators, and second, the Stark perturbation is unbounded so control of the perturbation is achieved using localization properties of coherent states corresponding to hydrogen atom eigenvalues.

  5. Hydrogen atom wave function and eigen energy in the Rindler space

    CERN Document Server

    Dai, De-Chang

    2016-01-01

    We study the hydrogen atom eigenstate energy and wave function in the Rindler space. The probability distribution is tilted because the electric field of the nucleus is no longer spherically symmetric. The hydrogen atom therefore cannot be treated exactly in the same way as what it is in an inertial frame. We also find that if the external force accelerates only the nucleus and then the nucleus accelerates its surrounding electrons through electromagnetic force, the electrons can tunnel through the local energy gap and split the hydrogen atom into an ion. This is similar to what one expects from the Stark effect. However, the critical acceleration is about $3\\times 10^{22} m/s^2$. It is well beyond the gravitational acceleration on a regular star surface.

  6. Diffusion mobility of the hydrogen atom with allowance for the anharmonic attenuation of migrating atom state

    Energy Technology Data Exchange (ETDEWEB)

    Kashlev, Y.A., E-mail: yakashlev@yandex.ru

    2017-04-15

    Evolution of vibration relaxation of hydrogen atoms in metals with the close-packed lattice at high and medium temperatures is investigated based on non-equilibrium statistical thermodynamics, in that number on using the retarded two-time Green function method. In accordance with main kinetic equation – the generalized Fokker- Plank- Kolmogorov equation, anharmonism of hydrogen atoms vibration in potential wells does not make any contribution to collision effects. It influences the relaxation processes at the expense of interference of fourth order anharmonism with single-phonon scattering on impurity hydrogen atoms. Therefore, the total relaxation time of vibration energy of system metal-hydrogen is written as a product of two factors: relaxation time of system in harmonic approximation and dimensionless anharmonic attenuation of quantum hydrogen state.

  7. Hydrogen atom wave function and eigen energy in the Rindler space

    Science.gov (United States)

    Dai, De-Chang

    2016-10-01

    We study the hydrogen atom eigenstate energy and wave function in the Rindler space. The probability distribution is tilted because the electric field of the nucleus is no longer spherically symmetric. The hydrogen atom therefore cannot be treated exactly in the same way as what it is in an inertial frame. We also find that if the external force accelerates only the nucleus and then the nucleus accelerates its surrounding electrons through electromagnetic force, the electrons can tunnel through the local energy gap and split the hydrogen atom into an ion. This is similar to what one expects from the Stark effect. However, the critical acceleration is about 3 ×1022 m /s2. It is well beyond the gravitational acceleration on a regular star surface.

  8. Diffusion mobility of the hydrogen atom with allowance for the anharmonic attenuation of migrating atom state

    Science.gov (United States)

    Kashlev, Y. A.

    2017-04-01

    Evolution of vibration relaxation of hydrogen atoms in metals with the close-packed lattice at high and medium temperatures is investigated based on non-equilibrium statistical thermodynamics, in that number on using the retarded two-time Green function method. In accordance with main kinetic equation - the generalized Fokker- Plank- Kolmogorov equation, anharmonism of hydrogen atoms vibration in potential wells does not make any contribution to collision effects. It influences the relaxation processes at the expense of interference of fourth order anharmonism with single-phonon scattering on impurity hydrogen atoms. Therefore, the total relaxation time of vibration energy of system metal-hydrogen is written as a product of two factors: relaxation time of system in harmonic approximation and dimensionless anharmonic attenuation of quantum hydrogen state.

  9. Allylic H-Abstraction Mechanism:  The Potential Energy Surface of the Reaction of Propene with OH Radical.

    Science.gov (United States)

    Szori, Milan; Fittschen, Christa; Csizmadia, Imre G; Viskolcz, Bela

    2006-11-01

    The allylic H-atom abstraction reaction plays a more dominant role, especially at lower temperature, than addition reactions in the case of the CH2 [Formula: see text] CH-CH3 + •OH system. Different computational methods including ab initio as well as density functional methods have been used to examine allylic H-abstraction. Both the energetically less favorable direct H-abstraction and the more favorable indirect H-abstractions have been investigated. Using first principles computations, for the indirect abstraction, a stable π- or reactantlike as well as a late productlike complex were found on the potential energy surface. Based on higher level single point calculations (QCISD(T)/6-311+G(3df,2p)), a new activation enthalpy value, Δ(⧧)H° = 0.3 ± 2 kJ/mol, is suggested for the title reaction. The computed reaction enthalpy ΔrH° = -124.7 ± 2 kJ/mol is in good agreement with the experimental value. The stability of the initial π-complex was found to be ΔH°π-complex = -7.1 kJ/mol. The product complex between the transition state and the product was found with the stability of -127.2 kJ/mol.

  10. Tunable Adsorption and Desorption of Hydrogen Atoms on Single-Walled Carbon Nanotubes

    Institute of Scientific and Technical Information of China (English)

    赵明文; 夏日源; 马玉臣; 英敏菊; 刘向东; 梅良模

    2002-01-01

    Chemical adsorption and desorption of hydrogen atoms on single-walled carbon nanotubes (SWNTs) are investi-gated by using molecular dynamics simulations. It is found that the adsorption and desorption energy of hydrogenatoms depend on the hydrogen coverage and the diameter of the SWNTs. Hydrogen-adsorption geometry at thecoverage of 1.0 is more energetically stable. The adsorption energy decreases with the increasing diameter ofthe armchair tubes. The adsorption and desorption energy of hydrogen atoms can be modified reversibly byexternally radial deformation. The averaged C-H bond energy on the high curvature sites of the deformed tubeincreases with increasing radial deformation, while that on the low curvature sites decreases.

  11. Quantum spacetime fluctuations: Lamb Shift and hyperfine structure of the hydrogen atom

    CERN Document Server

    Rivas, Juan Israel; Goeklue, Ertan

    2011-01-01

    We consider the consequences of the presence of metric fluctuations upon the properties of a hydrogen atom. Particularly, we introduce these metric fluctuations in the corresponding effective Schroedinger equation and deduce the modifications that they entail upon the hyperfine structure related to a hydrogen atom. We will find the change that these effects imply for the ground state energy of the system and obtain a bound for its size comparing our theoretical predictions against the experimental uncertainty reported in the literature. In addition, we analyze the corresponding Lamb shift effect emerging from these fluctuations of spacetime. Once again, we will set a bound to these oscillations resorting to the current experimental outcomes

  12. Existence of a ground state for the confined hydrogen atom in non-relativistic QED

    DEFF Research Database (Denmark)

    Amour, Laurent; Faupin, Jeremy

    2008-01-01

    We consider a system of a hydrogen atom interacting with the quantized electromagnetic field. Instead of fixing the nucleus, we assume that the system is confined by its center of mass. This model is used in theoretical physics to explain the Lamb-Dicke effect. After a brief review of the literat......We consider a system of a hydrogen atom interacting with the quantized electromagnetic field. Instead of fixing the nucleus, we assume that the system is confined by its center of mass. This model is used in theoretical physics to explain the Lamb-Dicke effect. After a brief review...

  13. Kinetic study on the H + SiH4 abstraction reaction using an ab initio potential energy surface.

    Science.gov (United States)

    Cao, Jianwei; Zhang, Zhijun; Zhang, Chunfang; Bian, Wensheng; Guo, Yin

    2011-01-14

    Variational transition state theory calculations with the correction of multidimensional tunneling are performed on a 12-dimensional ab initio potential energy surface for the H + SiH(4) abstraction reaction. The surface is constructed using a dual-level strategy. For the temperature range 200-1600 K, thermal rate constants are calculated and kinetic isotope effects for various isotopic species of the title reaction are investigated. The results are in very good agreement with available experimental data.

  14. Conformer-specific hydrogen atom tunnelling in trifluoromethylhydroxycarbene

    Science.gov (United States)

    Mardyukov, Artur; Quanz, Henrik; Schreiner, Peter R.

    2017-01-01

    Conformational control of organic reactions is at the heart of the biomolecular sciences. To achieve a particular reactivity, one of many conformers may be selected, for instance, by a (bio)catalyst, as the geometrically most suited and appropriately reactive species. The equilibration of energetically close-lying conformers is typically assumed to be facile and less energetically taxing than the reaction under consideration itself: this is termed the 'Curtin-Hammett principle'. Here, we show that the trans conformer of trifluoromethylhydroxycarbene preferentially rearranges through a facile quantum-mechanical hydrogen tunnelling pathway, while its cis conformer is entirely unreactive. Hence, this presents the first example of a conformer-specific hydrogen tunnelling reaction. The Curtin-Hammett principle is not applicable, due to the high barrier between the two conformers.

  15. Continuous vs. discrete models for the quantum harmonic oscillator and the hydrogen atom

    CERN Document Server

    Lorente, M

    2001-01-01

    The Kravchuk and Meixner polynomials of discrete variable are introduced for the discrete models of the harmonic oscillator and hydrogen atom. Starting from Rodrigues formula we construct raising and lowering operators, commutation and anticommutation relations. The physical properties of discrete models are figured out through the equivalence with the continuous models obtained by limit process.

  16. Continuous vs. discrete models for the quantum harmonic oscillator and the hydrogen atom

    Science.gov (United States)

    Lorente, Miguel

    2001-07-01

    The Kravchuk and Meixner polynomials of discrete variable are introduced for the discrete models of the harmonic oscillator and hydrogen atom. Starting from Rodrigues formula we construct raising and lowering operators, commutation and anticommutation relations. The physical properties of discrete models are figured out through the equivalence with the continuous models obtained by limit process.

  17. Continuous vs. discrete models for the quantum harmonic oscillator and the hydrogen atom

    OpenAIRE

    Lorente, M.

    2004-01-01

    The Kravchuk and Meixner polynomials of discrete variable are introduced for the discrete models of the harmonic oscillator and hydrogen atom. Starting from Rodrigues formula we construct raising and lowering operators, commutation and anticommutation relations. The physical properties of discrete models are figured out through the equivalence with the continuous models obtained by limit process.

  18. Resonant Scattering of Muonic Hydrogen Atoms and Dynamics of Muonic Molecular Complex

    CERN Document Server

    Fujiwara, M C; Bailey, J M; Beer, G A; Beveridge, J L; Faifman, M P; Huber, T M; Kammel, P; Kim, S K; Knowles, P E; Kunselman, A R; Maier, M; Markushin, V E; Marshall, G M; Martoff, C J; Mason, G R; Mulhauser, F; Olin, A; Petitjean, C; Porcelli, T A; Wozniak, J; Zmeskal, J

    2001-01-01

    Resonant scattering of muonic hydrogen atoms via back decay of molecular complex, a key process in the understanding of epithermal muonic molecular formation, is analyzed. The limitations of the effective rate approximation are discussed and the importance of the explicit treatment of the back decay is stressed. An expression of the energy distribution for the back-decayed atoms is given.

  19. Effect of vacuum polarization on the excitation of hydrogen atom by electron impact

    Directory of Open Access Journals (Sweden)

    Sujata Bhattacharyya

    1981-01-01

    for 1S−2S excitation of the hydrogen atom by electron impact. The excitation amplitude calculated field theoretically is found to be lowered by 0.47t2/(t2+93 where t2=4|P−Q|2, P and Q being the momenta of the incident and scattered electrons respectively.

  20. Resonant three-photon ionization of hydrogenic atoms by a non-monochromatic laser field

    NARCIS (Netherlands)

    Yakhontov, V.; Santra, R.; Jungmann, K.

    1999-01-01

    We present ionization probability and lineshape calculations for the two-step three- photon ionization process, 1S (2(h)over-bar-omega)under-right-arrow, 2S ((h)over-bar-omega)under-right-arrow epsilon P, of the ground state of hydrogenic atoms in a non-monochromatic laser field with a time-dependen

  1. Resonant three-photon ionization of hydrogenic atoms by a non-monochromatic laser field

    NARCIS (Netherlands)

    Yakhontov, V.; Santra, R.; Jungmann, K.

    1999-01-01

    We present ionization probability and lineshape calculations for a specifed two-step three-photon ionization process of the ground state of hydrogenic atoms in a non-monochromatic laser field with a time-dependent amplitude. Within the framework of a three-level model, the AC Stark shifts and non-ze

  2. Most Typical 12 Resonant Perturbation of the Hydrogen Atom by Weak Electric and Magnetic Fields

    NARCIS (Netherlands)

    Efstathiou, K.; Lukina, O. V.; Sadovskii, D. A.

    2008-01-01

    We study a perturbation of the hydrogen atom by small homogeneous static electric and magnetic fields in a specific mutual alignment with angle approximately pi/3 which results in the 12 resonance of the linearized Keplerian n-shell approximation. The bifurcation diagram of the classical integrable

  3. Relativistic Approach to the Hydrogen Atom in a Minimal Length Scenario

    Energy Technology Data Exchange (ETDEWEB)

    Francisco, Ronald Oliveira; Oakes, Thiago Luiz Antonacci; Fabris, Julio Cesar; Nogueira, Jose Alexandre, E-mail: jose.nogueira@ufes.br [Universidade Federal do Espirito Santo (UFES), Vitoria, ES (Brazil). Departamento de Fisica

    2014-07-01

    We show that relativistic contributions to the ground-state energy of the hydrogen atom from a minimal length introduced by a Lorentz-covariant algebra are more important than non-relativistic contributions; the nonrelativistic approach is therefore unsuitable. We compare our result with experimental data to estimate an upper bound of the order 10{sup -20}m for the minimal length. (author)

  4. Four kinds of raising and lowering operators of n-dimensional hydrogen atom and isotropic harmonic oscillator

    Institute of Scientific and Technical Information of China (English)

    刘宇峰; 曾谨言

    1997-01-01

    The factorization of the radial Schrodinger equation of n-dimensional (n≥2) hydrogen atoms and isotropic harmonic oscillators was investigated and four kinds of raising and lowering operators were derived.The relation between n -dimensional (n≥2) and one-dimensional hydrogen atoms and harmonic oscillators was discussed.

  5. Hydrogen atom temperature measured with wavelength-modulated laser absorption spectroscopy in large scale filament arc negative hydrogen ion source

    Energy Technology Data Exchange (ETDEWEB)

    Nakano, H., E-mail: nakano@nifs.ac.jp; Goto, M.; Tsumori, K.; Kisaki, M.; Ikeda, K.; Nagaoka, K.; Osakabe, M.; Takeiri, Y.; Kaneko, O. [National Institute for Fusion Science, 322-6 Oroshi-cho, Toki 5095292 (Japan); Nishiyama, S.; Sasaki, K. [Graduate school of Engineering, Hokkaido University, Kita 13, Nishi 8, Kita-ku, Sapporo 0608628 (Japan)

    2015-04-08

    The velocity distribution function of hydrogen atoms is one of the useful parameters to understand particle dynamics from negative hydrogen production to extraction in a negative hydrogen ion source. Hydrogen atom temperature is one of the indicators of the velocity distribution function. To find a feasibility of hydrogen atom temperature measurement in large scale filament arc negative hydrogen ion source for fusion, a model calculation of wavelength-modulated laser absorption spectroscopy of the hydrogen Balmer alpha line was performed. By utilizing a wide range tunable diode laser, we successfully obtained the hydrogen atom temperature of ∼3000 K in the vicinity of the plasma grid electrode. The hydrogen atom temperature increases as well as the arc power, and becomes constant after decreasing with the filling of hydrogen gas pressure.

  6. Ph(i-PrO)SiH2: An Exceptional Reductant for Metal-Catalyzed Hydrogen Atom Transfers.

    Science.gov (United States)

    Obradors, Carla; Martinez, Ruben M; Shenvi, Ryan A

    2016-04-13

    We report the discovery of an outstanding reductant for metal-catalyzed radical hydrofunctionalization reactions. Observations of unexpected silane solvolysis distributions in the HAT-initiated hydrogenation of alkenes reveal that phenylsilane is not the kinetically preferred reductant in many of these transformations. Instead, isopropoxy(phenyl)silane forms under the reaction conditions, suggesting that alcohols function as important silane ligands to promote the formation of metal hydrides. Study of its reactivity showed that isopropoxy(phenyl)silane is an exceptionally efficient stoichiometric reductant, and it is now possible to significantly decrease catalyst loadings, lower reaction temperatures, broaden functional group tolerance, and use diverse, aprotic solvents in iron- and manganese-catalyzed hydrofunctionalizations. As representative examples, we have improved the yields and rates of alkene reduction, hydration, hydroamination, and conjugate addition. Discovery of this broadly applicable, chemoselective, and solvent-versatile reagent should allow an easier interface with existing radical reactions. Finally, isotope-labeling experiments rule out the alternative hypothesis of hydrogen atom transfer from a redox-active β-diketonate ligand in the HAT step. Instead, initial HAT from a metal hydride to directly generate a carbon-centered radical appears to be the most reasonable hypothesis.

  7. Absolute rate constants for hydrogen atom transfer from tertiary amides to the cumyloxyl radical: evaluating the role of stereoelectronic effects.

    Science.gov (United States)

    Salamone, Michela; Milan, Michela; DiLabio, Gino A; Bietti, Massimo

    2014-08-01

    A time-resolved kinetic study of the hydrogen atom transfer (HAT) reactions from a series of alkanamides to the cumyloxyl radical (CumO(•)) was carried out. With N,N-dialkylformamides HAT preferentially occurs from the formyl C-H bond, while in N-formylpyrrolidine HAT mostly occurs from the ring α-C-H bonds. With the acetamides and the alkanamides almost exclusive HAT from the C-H bonds that are α to nitrogen was observed. The results obtained show that alignment between the C-H bond being broken and the amide π-system can lead to significant increases in the HAT rate constant (kH). This finding points toward the important role of stereoelectronic effects on the HAT reactivity and selectivity. The highest kH values were measured for the reactions of CumO(•) with N-acylpyrrolidines. These substrates have ring α-C-H bonds that are held in a conformation that is optimally aligned with the amide π-system, thus allowing for the relatively facile HAT reaction. The lowest kH value was measured for the reaction of N,N-diisobutylacetamide, wherein the steric bulk associated with the N-isobutyl groups increases the energy barrier required to reach the most suitable conformation for HAT. The experimental results are well supported by the computed BDEs for the C-H bonds of the most representative substrates.

  8. Mechanistic aspects of gas-phase hydrogen-atom transfer from methane to [CO](·+) and [SiO](·+) : why do they differ?

    Science.gov (United States)

    Dietl, Nicolas; Troiani, Anna; Schlangen, Maria; Ursini, Ornella; Angelini, Giancarlo; Apeloig, Yitzhak; de Petris, Giulia; Schwarz, Helmut

    2013-05-17

    The reactivity of the two diatomic congeneric systems [CO](·+) and [SiO](·+) towards methane has been investigated by means of mass spectrometry and quantum-chemical calculations. While [CO](·+) gives rise to three different reaction channels, [SiO](·+) reacts only by hydrogen-atom transfer (HAT) from methane under thermal conditions. A theoretical analysis of the respective HAT processes reveals two distinctly different mechanistic pathways for [CO](·+) and [SiO](·+), and a comparison to the higher metal oxides of Group 14 emphasizes the particular role of carbon as a second-row p element.

  9. Hydrogen Abstraction from Hydrocarbons by NH2.

    Science.gov (United States)

    Siddique, Kamal; Altarawneh, Mohammednoor; Gore, Jeff; Westmoreland, Phillip R; Dlugogorski, Bogdan Z

    2017-03-23

    This contribution investigates thermokinetic parameters of bimolecular gas-phase reactions involving the amine (NH2) radical and a large number of saturated and unsaturated hydrocarbons. These reactions play an important role in combustion and pyrolysis of nitrogen-rich fuels, most notably biomass. Computations performed at the CBS-QB3 level and based on the conventional transition-state theory yield potential-energy surfaces and reaction rate constants, accounting for tunnelling effects and the presence of hindered rotors. In an analogy to other H abstraction systems, we demonstrate only a small influence of variational effects on the rate constants for selected reaction. The studied reactions cover the abstraction of hydrogen atoms by the NH2 radical from the C-H bonds in C1-C4 species, and four C5 hydrocarbons of 2-methylbutane, 2-methyl-1-butene, 3-methyl-1-butene, 3-methyl-2-butene, and 3-methyl-1-butyne. For the abstraction of H from methane, in the temperature windows 300-500 and 1600-2000 K, the calculated reaction rate constants concur with the available experimental measurements, i.e., kcalculated/kexperimetal = 0.3-2.5 and 1.1-1.4, and the previous theoretical estimates. Abstraction of H atom from ethane attains the ratio of kcalculated/kexperimetal equal to 0.10-1.2 and 1.3-1.5 over the temperature windows of available experimental measurements, i.e., 300-900 K and 1500-2000 K, respectively. For the remaining alkanes (propane and n-butane), the average kexperimental/kcalculated ratio remains 2.6 and 1.3 over the temperature range of experimental data. Also, comparing the calculated standard enthalpy of reaction (ΔrH°298) with the available experimental measurements for alkanes, we found the mean unsigned error of computations as 3.7 kJ mol(-1). This agreement provides an accuracy benchmark of our methodology, affording the estimation of the unreported kinetic parameters for H abstractions from alkenes and alkynes. On the basis of the Evans

  10. Abstracts of International Conference on Diffusion and Reactions: From Basis to Applications

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1994-12-31

    The conference has been devoted to diffusion of corrosion agents and chemical reactions (sulfidation and oxidation) in metals, alloys and composite materials from the view point of their corrosion mechanism and material resistance in different conditions.The three main topics have been broadly represented at the conference sessions: heterogeneous reactions; high temperature diffusion and corrosion mechanism and current problems and trends in development and characterization of materials.

  11. Infrared absorption on a complex comprising three equivalent hydrogen atoms in ZnO

    Science.gov (United States)

    Herklotz, F.; Hupfer, A.; Johansen, K. M.; Svensson, B. G.; Koch, S. G.; Lavrov, E. V.

    2015-10-01

    A hydrogen-related defect in ZnO which causes two broad IR absorption bands at 3303 and 3321 cm-1 is studied by means of infrared absorption spectroscopy and first-principles theory. In deuterated samples, the defect reveals two sharp absorption lines at 2466 and 2488 cm-1 accompanied by weaker sidebands at 2462 and 2480 cm-1. Isotope substitution experiments with varying concentrations of H and D together with polarization-sensitive measurements strongly suggest that these IR absorption lines are due to stretch local vibrational modes of a defect comprising three equivalent hydrogen atoms. The zinc vacancy decorated by three hydrogen atoms, VZnH3 , and ammonia trapped at the zinc vacancy, (NH3)Zn, are discussed as a possible origin for the complex.

  12. Hydrogen atom in space with a compactified extra dimension and potential defined by Gauss' law

    CERN Document Server

    Bureš, Martin

    2014-01-01

    We investigate the consequences of one extra spatial dimension for the stability and energy spectrum of the non-relativistic hydrogen atom with a potential defined by Gauss' law, i.e. proportional to $1/|x|^2$. The additional spatial dimension is considered to be either infinite or curled-up in a circle of radius $R$. In both cases, the energy spectrum is bounded from below for charges smaller than the same critical value and unbounded from below otherwise. As a consequence of compactification, negative energy eigenstates appear: if $R$ is smaller than a quarter of the Bohr radius, the corresponding Hamiltonian possesses an infinite number of bound states with minimal energy extending at least to the ground state of the hydrogen atom.

  13. Hydrogen atom in space with a compactified extra dimension and potential defined by Gauss' law

    Science.gov (United States)

    Bureš, Martin; Siegl, Petr

    2015-03-01

    We investigate the consequences of one extra spatial dimension for the stability and energy spectrum of the non-relativistic hydrogen atom with a potential defined by Gauss' law, i.e. proportional to 1 /| x | 2. The additional spatial dimension is considered to be either infinite or curled-up in a circle of radius R. In both cases, the energy spectrum is bounded from below for charges smaller than the same critical value and unbounded from below otherwise. As a consequence of compactification, negative energy eigenstates appear: if R is smaller than a quarter of the Bohr radius, the corresponding Hamiltonian possesses an infinite number of bound states with minimal energy extending at least to the ground state of the hydrogen atom.

  14. Hydrogen and muonic-Hydrogen Atomic Spectra in Non-commutative Space-Time

    CERN Document Server

    Haghighat, M

    2014-01-01

    Comparing electronic Hydrogen with muonic Hydrogen shows that the discrepancy in measurement of the Lamb shift in the both systems are relatively of order of $(\\frac{m_\\mu}{m_e})^{4-5}$. We explore the spectrum of Hydrogen atom in noncommutative $QED$ to compare the noncommutative effects on the both bound states. We show that in the Lorentz violating noncommutative QED the ratio of NC-corrections is $(\\frac{m_\\mu}{m_e})^3$ while in the Lorentz conserving NCQED is $(\\frac{m_\\mu}{m_e})^5$. An uncertainty about $1 \\,Hz\\ll 3\\,kHz$ in the Lamb shift of Hydrogen atom leads to an NC correction about $10 \\,MHz$ in the Lorentz violating noncommutative QED and about $400 \\,GHz$ in the Lorentz conserving noncommutative QED.

  15. Al13H-: Hydrogen atom site selectivity and the shell model

    Science.gov (United States)

    Grubisic, A.; Li, X.; Stokes, S. T.; Vetter, K.; Ganteför, G. F.; Bowen, K. H.; Jena, P.; Kiran, B.; Burgert, R.; Schnöckel, H.

    2009-09-01

    Using a combination of anion photoelectron spectroscopy and density functional theory calculations, we explored the influence of the shell model on H atom site selectivity in Al13H-. Photoelectron spectra revealed that Al13H- has two anionic isomers and for both of them provided vertical detachment energies (VDEs). Theoretical calculations found that the structures of these anionic isomers differ by the position of the hydrogen atom. In one, the hydrogen atom is radially bonded, while in the other, hydrogen caps a triangular face. VDEs for both anionic isomers as well as other energetic relationships were also calculated. Comparison of the measured versus calculated VDE values permitted the structure of each isomer to be confirmed and correlated with its observed photoelectron spectrum. Shell model, electron-counting considerations correctly predicted the relative stabilities of the anionic isomers and identified the stable structure of neutral Al13H.

  16. Emission of fast non-Maxwellian hydrogen atoms in low-density laboratory plasma

    Science.gov (United States)

    Brandt, Christian; Marchuk, Oleksandr; Pospieszczyk, Albrecht; Dickheuer, Sven

    2017-03-01

    The source of strong and broad emission of the Balmer-α line in mixed plasmas of hydrogen (or deuterium) and noble gases in front of metallic surfaces is a subject of controversial discussion of many plasma types. In this work the excitation source of the Balmer lines is investigated by means of optical emission spectroscopy in the plasma device PSI-2. Neutral fast non-Maxwellian hydrogen atoms are produced by acceleration of hydrogen ions towards an electrode immersed into the plasma. By variation of the electrode potential the energy of ions and in turn of reflected fast atoms can be varied in the range of 40-300 eV. The fast atoms in front of the electrode are observed simultaneously by an Echelle spectrometer (0.001 nm/channel) and by an imaging spectrometer (0.01 nm/channel) up to few cm in the plasma. Intense excitation channels of the Balmer lines are observed when hydrogen is mixed with argon or with krypton. Especially in Ar-H and Ar-D mixed plasmas the emission of fast hydrogen atoms is very strong. Intermixing hydrogen with other noble gases (He, Ne or Xe) one observes the same effect however the emission is one order of magnitude less compared to Kr-H or Kr-D plasmas. It is shown, that the key process, impacting this emission, is the binary collision between the fast neutral hydrogen atom and the noble gas atom. Two possible sources of excitation are discussed in details: one is the excitation of hydrogen atoms by argon atoms in the ground state and the second one is the process of the so-called excitation transfer between the metastable states of noble gases and hydrogen. In the latter case the atomic data for excitation of Balmer lines are still not available in literature. Further experimental investigations are required to conclude on the source process of fast atom emission.

  17. Trends in substrate hydroxylation reactions by heme and nonheme iron(IV)-oxo oxidants give correlations between intrinsic properties of the oxidant with barrier height.

    Science.gov (United States)

    de Visser, Sam P

    2010-01-27

    Iron(IV)-oxo species have been characterized in several nonheme enzymes and biomimetic systems and are efficient oxidants of aliphatic hydroxylation reactions. However, there appears to be a large variation in substrate hydroxylation ability by different iron(IV)-oxo oxidants due to the effect of the ligands bound to the metal. In this work, we have studied these indirect effects of ligands perpendicular (cis or equatorial) and opposite (trans or axial) to the iron(IV)-oxo group in heme and nonheme oxidants on the oxygenation capability of the oxidant. To this end, we have done a series of density functional theory calculations on the hydrogen atom abstraction of propene by a range of different iron(IV)-oxo oxidants that include heme and nonheme iron(IV)-oxo oxidants. We show that the hydrogen atom abstraction barrier of substrate hydroxylation correlates linearly with the strength of the Fe(III)O-H bond that is formed, i.e., BDE(OH), and that this value ranges by at least 20 kcal mol(-1) dependent on the cis- and trans-ligands attached to the metal. Thus, our studies show that ligands bound to the metal are noninnocent and influence the catalytic properties of the metal-oxo group dramatically due to involvement into the high-lying occupied and virtual orbitals. A general valence bond curve crossing model is set up that explains how the rate constant of hydrogen atom abstraction is proportional to the difference in energy of the C-H bond of the substrate that is broken and the O-H bond of the Fe(III)O-H complex that is formed, i.e., proportional to BDE(CH) - BDE(OH) or the reaction enthalpy. In addition, we show a correlation between the polarizability change and barrier height for the hydrogen atom abstraction reaction.

  18. Quantum states of hydrogen atom on Pd(1 1 0) surface

    Science.gov (United States)

    Padama, Allan Abraham B.; Nakanishi, Hiroshi; Kasai, Hideaki

    2015-12-01

    The quantum states of adsorbed hydrogen atom on Pd(1 1 0) surface are investigated in this work. From the calculated potential energy surface (PES) of hydrogen atom on Pd(1 1 0), the wave functions and eigenenergies in the ground and few excited states of protium (H) and deuterium (D) are calculated. Localized wave functions of hydrogen atom exist on pseudo-threefold and long bridge sites of Pd(1 1 0). The short bridge site is a local minimum from the result of PES, however, quantum behavior of hydrogen revealed that its vibration would allow it to hop to other pseudo-threefold site (that crosses the short bridge site) than to stay on the short bridge site. Exchange of ordering of the wave functions between H and D is attributed to the difference in their masses. The calculated eigenenergies are found to be in fair agreement with experimental data based from the identified vibrations of hydrogen with component perpendicular to the surface. The activation barriers measured from the eigenenergies are in better agreement with experimental findings in comparison to the data gathered from PES.

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

    Energy Technology Data Exchange (ETDEWEB)

    Bonfanti, Matteo, E-mail: matteo.bonfanti@unimi.it [Dipartimento di Chimica, Università degli Studi di Milano, v. Golgi 19, 20133 Milano (Italy); Jackson, Bret [Department of Chemistry, University of Massachusetts, Amherst, Massachusetts 01003 (United States); Hughes, Keith H. [School of Chemistry, Bangor University, Bangor, Gwynedd LL57 2UW (United Kingdom); Burghardt, Irene [Institute of Physical and Theoretical Chemistry, Goethe University Frankfurt, Max-von-Laue-Str. 7, 60438 Frankfurt/Main (Germany); Martinazzo, Rocco, E-mail: rocco.martinazzo@unimi.it [Dipartimento di Chimica, Università degli Studi di Milano, v. Golgi 19, 20133 Milano (Italy); Istituto di Scienze e Tecnologie Molecolari, Consiglio Nazionale delle Richerche, v. Golgi 19, 20133 Milano (Italy)

    2015-09-28

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

  20. Strain field of interstitial hydrogen atom in body-centered cubic iron and its effect on hydrogen-dislocation interaction

    OpenAIRE

    Wang, Shuai; Takahashi, Keisuke; Hashimoto, Naoyuki; Isobe, Shigehito; Ohnuki, Somei

    2013-01-01

    Effect of hydrogen in body-centered cubic iron is explored by using the density function theory. Hydrogen atoms increase the concentration of free electrons in the simulation cell and have bonding interaction with Fe atom. Caused by anisotropic strain components of hydrogen atoms in the tetrahedral sites, elastic interaction for hydrogen with screw dislocation has been found. The dependence of hydrogen-screw dislocation interaction on hydrogen concentration is confirmed by repeated stress rel...

  1. 氢原子斯塔克效应的结构平衡模型仿真%Structural Equation Modeling Simulation of Hydrogen Atom Stark Effect

    Institute of Scientific and Technical Information of China (English)

    周志祥

    2015-01-01

    斯塔克效应常应用于原子分子结构的研究,对氢原子进行结构平衡模型数学建模和仿真,可以准确分析氢原子在外电场作用下能级和光谱特性.传统的氢原子斯塔克效应结构平衡采用双线间隔分离模型,对原始读数和测量值的等价分析具有随机性,不能有效实现结构平衡.提出一种基于固有电偶极矩外电场分析的氢原子斯塔克效应的结构平衡模型.首先分析氢原子的原子特性,进行斯塔克效应数学建模,分析氢原子的晶体反应谱线分裂特征模型,光谱的发射是由于价电子的跃迁形成,电场一定会改变原子内部电荷的分布,得出斯塔克效应下的结构平衡和模型的能级分裂,其裂距与电场强度成正比,采用固有电偶极矩外电场分析,实现数学模型构建,并通过Matlab进行仿真实现.实验结果表明,模型能有效反映氢原子斯塔库克效应下的光谱特征,基于固有电偶极矩外电场分析,外电场能耗降低,性能稳定.%The study of Stark effect applied to atomic and molecular structure, structural balance model for mathematical modeling and Simulation of the hydrogen atom, can accurate analysis of the hydrogen atom in the level in the external elec-tric field and spectral characteristics. The traditional hydrogen atomic Stark effect structure equilibrium separation model adopts double spaced, randomness is equivalent to the original reading and analysis of the measured value, can not effec-tively to achieve structural balance. Put forward a kind of intrinsic electric dipole moment equilibrium structure analysis of external electric field of the hydrogen atom Stark effect model based on. The first atomic properties analysis of atomic and hydrogen, Stark effect on mathematical modeling, analysis of crystal reaction of hydrogen atomic spectral line splitting fea-ture model, spectral emission is due to transition of the valence electron, electric field distribution will

  2. Stability of Titanium Nitride and Titanium Carbide When Exposed to Hydrogen Atoms from 298 to 1950 K

    Science.gov (United States)

    Philipp, Warren H.

    1961-01-01

    Titanium nitride and titanium carbide deposited on tungsten wires were exposed to hydrogen atoms (10(exp -4) atm pressure) produced by the action of microwave radiation on molecular hydrogen. The results of these experiments in the temperature range 298 to 1950 K indicate that no appreciable reaction takes place between atomic hydrogen and TiN or TiC. The formation of reaction products (NH3, CH4, C2H2) should be favored at lower temperatures. However, because of the high catalytic activity of Ti for H atom recombination, the rate of such reactions with H atoms is controlled by the rate of evaporation of Ti from the surface, this rate being low at temperatures below 1200 K. In order to interpret the stability of TiN and TiC in H atoms more fully, the stability of TiN and TiC in vacuum and H2 gas was also studied. The thermodynamic computations conform in order of magnitude to the experimentally found rates of decomposition of TiN and TiC in vacuum and are also consistent with the fact that no appreciable reaction is found with these compounds in molecular H2 at a pressure of 10(exp -3) atmosphere in the temperature range 2980 to 2060 K. When TiN or TiC was heated in atomic H or molecular H2, no reaction products other than those obtained from the simple decomposition of the nitride and carbide were observed. The gaseous products were analyzed in a mass spectrometer.

  3. Kinetic solvent effects on hydrogen abstraction reactions from carbon by the cumyloxyl radical. The role of hydrogen bonding.

    Science.gov (United States)

    Bietti, Massimo; Salamone, Michela

    2010-08-20

    A kinetic study of the H-atom abstraction reactions from 1,4-cyclohexadiene and triethylamine by the cumyloxyl radical has been carried out in different solvents. Negligible effects are observed with 1,4-cyclohexadiene, whereas with triethylamine a significant decrease in rate constant (k(H)) is observed on going from benzene to MeOH. A good correlation between log k(H) and the solvent hydrogen bond donor parameter alpha is observed, indicative of an H-bonding interaction between the amine lone pair and the solvent.

  4. Labile sleep promotes awareness of abstract knowledge in a serial reaction time task

    Directory of Open Access Journals (Sweden)

    Roumen eKirov

    2015-09-01

    Full Text Available Sleep has been identified as a critical brain state enhancing the probability of gaining insight into covert task regularities. Both non-rapid eye movement (NREM and REM sleep have been implicated with offline re-activation and reorganization of memories supporting explicit knowledge generation. According to two-stage models of sleep function, offline processing of information during sleep is sequential requiring multiple cycles of NREM and REM sleep stages. However, the role of overnight dynamic sleep macrostructure for insightfulness has not been studied so far. In the present study, we test the hypothesis that the frequency of interactions between NREM and REM sleep stages might be critical for awareness after sleep. For that aim, the rate of sleep stage transitions was evaluated in 53 participants who learned implicitly a serial reaction time task (SRTT in which a determined sequence was inserted. The amount of explicit knowledge about the sequence was established by verbal recall after a night of sleep following SRTT learning. Polysomnography was recorded in this night and in a control night before and was analyzed to compare the rate of sleep-stage transitions between participants who did or did not gain awareness of task regularity after sleep. Indeed, individual ability of explicit knowledge generation was strongly associated with increased rate of transitions between NREM and REM sleep stages and between light sleep stages and slow wave sleep. However, the rate of NREM-REM transitions specifically predicted the amount of explicit knowledge after sleep in a trait-dependent way. These results demonstrate that enhanced lability of sleep goes along with individual ability of knowledge awareness. Observations suggest that facilitated dynamic interactions between sleep stages, particularly between NREM and REM sleep stages play a role for offline processing which promotes rule extraction and awareness.

  5. Labile sleep promotes awareness of abstract knowledge in a serial reaction time task.

    Science.gov (United States)

    Kirov, Roumen; Kolev, Vasil; Verleger, Rolf; Yordanova, Juliana

    2015-01-01

    Sleep has been identified as a critical brain state enhancing the probability of gaining insight into covert task regularities. Both non-rapid eye movement (NREM) and rapid eye movement (REM) sleep have been implicated with offline re-activation and reorganization of memories supporting explicit knowledge generation. According to two-stage models of sleep function, offline processing of information during sleep is sequential requiring multiple cycles of NREM and REM sleep stages. However, the role of overnight dynamic sleep macrostructure for insightfulness has not been studied so far. In the present study, we test the hypothesis that the frequency of interactions between NREM and REM sleep stages might be critical for awareness after sleep. For that aim, the rate of sleep stage transitions was evaluated in 53 participants who learned implicitly a serial reaction time task (SRTT) in which a determined sequence was inserted. The amount of explicit knowledge about the sequence was established by verbal recall after a night of sleep following SRTT learning. Polysomnography was recorded in this night and in a control night before and was analyzed to compare the rate of sleep-stage transitions between participants who did or did not gain awareness of task regularity after sleep. Indeed, individual ability of explicit knowledge generation was strongly associated with increased rate of transitions between NREM and REM sleep stages and between light sleep stages and slow wave sleep. However, the rate of NREM-REM transitions specifically predicted the amount of explicit knowledge after sleep in a trait-dependent way. These results demonstrate that enhanced lability of sleep goes along with individual ability of knowledge awareness. Observations suggest that facilitated dynamic interactions between sleep stages, particularly between NREM and REM sleep stages play a role for offline processing which promotes rule extraction and awareness.

  6. Modeling of hydrogen atom diffusion and response behavior of hydrogen sensors in Pd–Y alloy nanofilm

    Science.gov (United States)

    Liu, Yi; Li, Yanli; Huang, Pengcheng; Song, Han; Zhang, Gang

    2016-11-01

    To detect hydrogen gas leakage rapidly, many types of hydrogen sensors containing palladium alloy film have been proposed and fabricated to date. However, the mechanisms and factors that determine the response rate of such hydrogen sensor have not been established theoretically. The manners in which response time is forecasted and sensitive film is designed are key issues in developing hydrogen sensors with nanometer film. In this paper, a unilateral diffusion model of hydrogen atoms in Pd alloy based on Fick’s second law is proposed to describe the Pd–H reaction process. Model simulation shows that the hydrogen sensor response time with Pd alloy film is dominated by two factors (film thickness and hydrogen diffusion coefficient). Finally, a series of response rate experiments with varying thicknesses of Pd–Y (yttrium) alloy film are implemented to verify model validity. Our proposed model can help researchers in the precise optimization of film thickness to realize a simultaneously speedy and sensitive hydrogen sensor. This study also aids in evaluating the influence of manufacturing errors on performances and comparing the performances of sensors with different thicknesses.

  7. Modeling of hydrogen atom diffusion and response behavior of hydrogen sensors in Pd-Y alloy nanofilm.

    Science.gov (United States)

    Liu, Yi; Li, Yanli; Huang, Pengcheng; Song, Han; Zhang, Gang

    2016-11-15

    To detect hydrogen gas leakage rapidly, many types of hydrogen sensors containing palladium alloy film have been proposed and fabricated to date. However, the mechanisms and factors that determine the response rate of such hydrogen sensor have not been established theoretically. The manners in which response time is forecasted and sensitive film is designed are key issues in developing hydrogen sensors with nanometer film. In this paper, a unilateral diffusion model of hydrogen atoms in Pd alloy based on Fick's second law is proposed to describe the Pd-H reaction process. Model simulation shows that the hydrogen sensor response time with Pd alloy film is dominated by two factors (film thickness and hydrogen diffusion coefficient). Finally, a series of response rate experiments with varying thicknesses of Pd-Y (yttrium) alloy film are implemented to verify model validity. Our proposed model can help researchers in the precise optimization of film thickness to realize a simultaneously speedy and sensitive hydrogen sensor. This study also aids in evaluating the influence of manufacturing errors on performances and comparing the performances of sensors with different thicknesses.

  8. Electronic and optical properties of BxNyCz monolayers with adsorption of hydrogen atoms

    Science.gov (United States)

    Leite, L.; Azevedo, S.; de Lima Bernardo, B.

    2017-03-01

    We apply first-principles calculations, using density functional theory, to analyze the electronic and optical properties of monolayers of graphene with a nanodomain of 2D hexagonal boron nitrite (h-BN). It also investigated the effects of the adsorption of hydrogen atoms in different atoms at the edge of the h-BN nanodomain. We calculate the electronic band structure, the complex dielectric function and the optical conductivity. For such systems, the calculations demonstrate that the compounds exhibit a prominent excitement in the visible and near-infrared regions. In this form, the present study provides physical basis for potential applications of the considered materials in optoelectronic devices at the nanoscale.

  9. The Hydrogen Atom: a Review on the Birth of Modern Quantum Mechanics

    CERN Document Server

    Nanni, Luca

    2015-01-01

    The purpose of this work is to retrace the steps that were made by scientists of XIX century, like Bohr, Schrodinger, Heisenberg, Pauli, Dirac, for the formulation of what today represents the modern quantum mechanics and that, within two decades, put in question the classical physics. In this context, the study of the electronic structure of hydrogen atom has been the main starting point for the formulation of the theory and, till now, remains the only real case for which the quantum equation of motion can be solved exactly. The results obtained by each theory will be discussed critically, highlighting limits and potentials that allowed the further development of the quantum theory.

  10. Interference Dynamics of Hydrogen Atoms in High-Frequency Dichromatic Laser Fields

    Science.gov (United States)

    Cheng, Tai-Wang; Li, Xiao-Feng; Fu, Pan-Ming; Chen, Shi-Gang

    2002-08-01

    We investigate the ionization and high-order harmonic generation of a hydrogen atom in high-frequency (several atomic units) super strong (up to several tens of atomic units) dichromatic laser fields. An effective iterative method in the framework of high-frequency Floquet theory is used in the calculations. We have considered two kinds of dichromatic laser field, i.e. 1ω-2ω and 1ω-3ω. We find that, in both the cases, the ionization and high-order harmonic generation show evident dependence on the relative phase and strength of the additional harmonic field. The dynamical origin of these interference effects is also discussed.

  11. Interference Dynamics of Hydrogen Atoms in High-Frequency Dichromatic Laser Fields

    Institute of Scientific and Technical Information of China (English)

    程太旺; 李晓峰; 傅盘铭; 陈式刚

    2002-01-01

    We investigate the ionization and high-order harmonic generation of a hydrogen atom in high-frequency (several atomic units) super strong (up to several tens of atomic units) dichromatic laser fields. An effective iterative method in the framework of high-frequency Floquet theory is used in the calculations. We have considered two kinds of dichromatic laser field, i.e. 1ω - 2ω and lω - 3ω. We find that, in both the cases, the ionization and high-order harmonic generation show evident dependence on the relative phase and strength of the additional harmonic field. The dynamical origin of these interference effects is also discussed.

  12. Computation for High Excited Stark Levels of hydrogen Atoms in Uniform Electric Fields

    Institute of Scientific and Technical Information of China (English)

    田人和

    2003-01-01

    We present a new method for the numerical calculation of exact complex eigenvalues of Schrodinger equations for a hydrogen atom in a uniform electric field. This method allows a direct calculation for complex eigenvalues without using any auxiliary treatment, such as the Breit-Wigner parametrization and the complex scale transformation,etc. The characteristics of high excited atoms in electric field have attracted extensive interest in experimental aspect, however, the existing theoretical calculation is only up to n = 40. Here we present the computation results ranging from n = 1 to 100. The data for n(<,_ ) 40 are in agreement with the results of other researchers.

  13. Interbasis expansion and SO(3) symmetry in the two-dimensional hydrogen atom.

    Energy Technology Data Exchange (ETDEWEB)

    Torres del Castillo, G.F.; Lopez Villanueva, A. [Universidad Autonoma de Puebla, Puebla (Mexico)

    2001-04-01

    Making use of the SO(3) symmetry of the two-dimensional hydrogen atom, each of the bases for the bound states formed by the separable solutions of the Schroedinger equation in polar and parabolic coordinates are expressed in terms of the other. [Spanish] Usando la simetria SO(3) del atomo de hidrogeno en dos dimensiones, cada una de las bases para los estados ligados formadas por las soluciones separables de la ecuacion de Schroedinger en coordenadas polares y parabolicas se expresan en terminos de la otra.

  14. Relativistic spectrum of hydrogen atom in the space-time non-commutativity

    Energy Technology Data Exchange (ETDEWEB)

    Moumni, Mustafa; BenSlama, Achour; Zaim, Slimane [Matter Sciences Department, Faculty of SE and SNV, University of Biskra (Algeria); Laboratoire de Physique Mathematique et Subatomique, Mentouri University, Constantine (Algeria); Matter Sciences Department, Faculty of Sciences, University of Batna (Algeria)

    2012-06-27

    We study space-time non-commutativity applied to the hydrogen atom and its phenomenological effects. We find that it modifies the Coulomb potential in the Hamiltonian and add an r{sup -3} part. By calculating the energies from Dirac equation using perturbation theory, we study the modifications to the hydrogen spectrum. We find that it removes the degeneracy with respect to the total angular momentum quantum number and acts like a Lamb shift. Comparing the results with experimental values from spectroscopy, we get a new bound for the space-time non-commutative parameter.

  15. Angular momentum in non-relativistic QED and photon contribution to spin of hydrogen atom

    Energy Technology Data Exchange (ETDEWEB)

    Chen Panying, E-mail: pychen@umd.ed [Maryland Center for Fundamental Physics, Department of Physics, University of Maryland, College Park, MD 20742 (United States); Ji Xiangdong [Maryland Center for Fundamental Physics, Department of Physics, University of Maryland, College Park, MD 20742 (United States); Institute of Particle Physics and Cosmology, Department of Physics, Shanghai Jiao Tong University, Shanghai, 200240 (China); Center for High-Energy Physics and Institute of Theoretical Physics, Peking University, Beijing, 100080 (China); Xu Yang [Center for High-Energy Physics and Institute of Theoretical Physics, Peking University, Beijing, 100080 (China); Zhang Yue [Maryland Center for Fundamental Physics, Department of Physics, University of Maryland, College Park, MD 20742 (United States); Center for High-Energy Physics and Institute of Theoretical Physics, Peking University, Beijing, 100080 (China)

    2010-04-26

    We study angular momentum in non-relativistic quantum electrodynamics (NRQED). We construct the effective total angular momentum operator by applying Noether's theorem to the NRQED lagrangian. We calculate the NRQED matching for the individual components of the QED angular momentum up to one loop. We illustrate an application of our results by the first calculation of the angular momentum of the ground state hydrogen atom carried in radiative photons, alpha{sub em}{sup 3}/18pi, which might be measurable in future atomic experiments.

  16. Traces of Lorentz symmetry breaking in a hydrogen atom at ground state

    Science.gov (United States)

    Borges, L. H. C.; Barone, F. A.

    2016-02-01

    Some traces of a specific Lorentz symmetry breaking scenario in the ground state of the hydrogen atom are investigated. We use standard Rayleigh-Schrödinger perturbation theory in order to obtain the corrections to the ground state energy and the wave function. It is shown that an induced four-pole moment arises, due to the Lorentz symmetry breaking. The model considered is the one studied in Borges et al. (Eur Phys J C 74:2937, 2014), where the Lorentz symmetry is broken in the electromagnetic sector.

  17. Quantum Spectra of Hydrogen Atoms in Various Magnetic Fields with the Closed Orbit Theory

    Institute of Scientific and Technical Information of China (English)

    彭良友; 张现周; 饶建国

    2002-01-01

    The quantum spectra of hydrogen atoms in various magnetic fields have been calculated with the closed orbit theory. The magnitude of the magnetic field decreases from 5.96 T to 0.56 T with a step of 0. 6 T. We demonstrate schematically that the closed orbits disappear with the decrease of the magnitude of the magnetic field when the corresponding finite resolution of experiment is fixed. This may give us a good way to control the shape and the number of the closed orbits in the system, and thus to control where a peak should exist in the Fourier transformation of the quantum spectra.

  18. Traces of Lorentz symmetry breaking in a Hydrogen atom at ground state

    CERN Document Server

    Borges, Luiz Henrique de Campos

    2016-01-01

    Some traces of a specific Lorentz symmetry breaking scenario in the ground state of the Hydrogen atom are investigated. It is used standard Rayleigh-Schr\\"odinger perturbation theory in order to obtain the corrections to the the ground state energy and wave function. It is shown that an induced four-pole moment arises, due to the Lorentz symmetry breaking. The model considered is the one studied in reference Eur. Phys. J. C {\\bf 74}, 2937 (2014), where the Lorentz symmetry is broken in the electromagnetic sector.

  19. Multiphoton resonant ionization of hydrogen atom exposed to two-colour laser pulses

    Institute of Scientific and Technical Information of China (English)

    Wang Pei-Jie; Fang Yan

    2008-01-01

    This paper studies the multiphoton resonant ionization by two-colour laser pulses in the hydrogen atom by solving the time-dependent Schr(o)dinger equation.By fixing the parameters of fundamental laser field and scanning the frequency of second laser field,it finds that the ionization probability shows several resonance peaks and is also much larger than the linear superposition of probabilities by applying two lasers separately.The enhancement of the ionization happens when the system is resonantly pumped to the excited states by absorbing two or more colour photons non-sequentially.

  20. Variational treatment of the confined hydrogen atom with a moving nucleus

    Energy Technology Data Exchange (ETDEWEB)

    Fernandez, Francisco M, E-mail: fernande@quimica.unlp.edu.a [INIFTA (UNLP, CCT La Plata-CONICET), Division Quimica Teorica, Blvd. 113 S/N, Sucursal 4, Casilla de Correo 16, 1900 La Plata (Argentina)

    2010-05-15

    We solve the Schroedinger equation for a hydrogen atom within a spherical box approximately by means of the variational method. We propose two simple trial functions for the case in which both the nucleus and the electron move within the box. Present results are sufficiently accurate for all values of the box radius and therefore an improvement on an earlier calculation based on perturbation theory. We compare the energies of three alternative approaches for the moving-nucleus model with that of the nucleus clamped at origin. We also outline some physical applications of the model.

  1. Extremely high reflection of solar wind protons as neutral hydrogen atoms from regolith in space

    CERN Document Server

    Wieser, Martin; Futaana, Yoshifumi; Holmström, Mats; Bhardwaj, Anil; Sridharan, R; Dhanya, MB; Wurz, Peter; Schaufelberger, Audrey; Asamura, Kazushi; 10.1016/j.pss.2009.09.012

    2010-01-01

    We report on measurements of extremely high reflection rates of solar wind particles from regolith-covered lunar surfaces. Measurements by the Sub-keV Atom Reflecting Analyzer (SARA) instrument on the Indian Chandrayaan-1 spacecraft in orbit around the Moon show that up to 20% of the impinging solar wind protons are reflected from the lunar surface back to space as neutral hydrogen atoms. This finding, generally applicable to regolith-covered atmosphereless bodies, invalidates the widely accepted assumption that regolith almost completely absorbs the impinging solar wind.

  2. Adiabatic Floquet Picture for Hydrogen Atom in an Intense Laser Field

    CERN Document Server

    Wang, Yujun; Esry, B D

    2010-01-01

    We develop an adiabatic Floquet picture in the length gauge to describe the dynamics of a hydrogen atom in an intense laser field. In this picture, we discuss the roles played by frequency and intensity in terms of adiabatic potentials and the couplings between them, which gives a physical and intuitive picture for quantum systems exposed to a laser field. For simplicity, analyze hydrogen and give the adiabatic potential curves as well as some physical quantities that can be readily calculated for the ground state. Both linearly and circularly polarized laser fields are discussed.

  3. Traces of Lorentz symmetry breaking in a hydrogen atom at ground state

    Energy Technology Data Exchange (ETDEWEB)

    Borges, L.H.C. [Universidade Federal do ABC, Centro de Ciencias Naturais e Humanas, Santo Andre, SP (Brazil); Barone, F.A. [IFQ-Universidade Federal de Itajuba, Itajuba, MG (Brazil)

    2016-02-15

    Some traces of a specific Lorentz symmetry breaking scenario in the ground state of the hydrogen atom are investigated. We use standard Rayleigh-Schroedinger perturbation theory in order to obtain the corrections to the ground state energy and the wave function. It is shown that an induced four-pole moment arises, due to the Lorentz symmetry breaking. The model considered is the one studied in Borges et al. (Eur Phys J C 74:2937, 2014), where the Lorentz symmetry is broken in the electromagnetic sector. (orig.)

  4. Reaction rate constants of H-abstraction by OH from large ketones: Measurements and site-specific rate rules

    KAUST Repository

    Badra, Jihad

    2014-01-01

    Reaction rate constants of the reaction of four large ketones with hydroxyl (OH) are investigated behind reflected shock waves using OH laser absorption. The studied ketones are isomers of hexanone and include 2-hexanone, 3-hexanone, 3-methyl-2-pentanone, and 4-methl-2-pentanone. Rate constants are measured under pseudo-first-order kinetics at temperatures ranging from 866 K to 1375 K and pressures near 1.5 atm. The reported high-temperature rate constant measurements are the first direct measurements for these ketones under combustion-relevant conditions. The effects of the position of the carbonyl group (CO) and methyl (CH3) branching on the overall rate constant with OH are examined. Using previously published data, rate constant expressions covering, low-to-high temperatures, are developed for acetone, 2-butanone, 3-pentanone, and the hexanone isomers studied here. These Arrhenius expressions are used to devise rate rules for H-abstraction from various sites. Specifically, the current scheme is applied with good success to H-abstraction by OH from a series of n-ketones. Finally, general expressions for primary and secondary site-specific H-abstraction by OH from ketones are proposed as follows (the subscript numbers indicate the number of carbon atoms bonded to the next-nearest-neighbor carbon atom, the subscript CO indicates that the abstraction is from a site next to the carbonyl group (CO), and the prime is used to differentiate different neighboring environments of a methylene group):P1,CO = 7.38 × 10-14 exp(-274 K/T) + 9.17 × 10-12 exp(-2499 K/T) (285-1355 K)S10,CO = 1.20 × 10-11 exp(-2046 K/T) + 2.20 × 10-13 exp(160 K/T) (222-1464 K)S11,CO = 4.50 × 10-11 exp(-3000 K/T) + 8.50 × 10-15 exp(1440 K/T) (248-1302 K)S11′,CO = 3.80 × 10-11 exp(-2500 K/T) + 8.50 × 10-15 exp(1550 K/T) (263-1370 K)S 21,CO = 5.00 × 10-11 exp(-2500 K/T) + 4.00 × 10-13 exp(775 K/T) (297-1376 K) © 2014 the Partner Organisations.

  5. Polarization dependence in inelastic scattering of electrons by hydrogen atoms in a circularly polarized laser field

    Science.gov (United States)

    Buică, Gabriela

    2017-01-01

    We theoretically study the influence of laser polarization in inelastic scattering of electrons by hydrogen atoms in the presence of a circularly polarized laser field in the domain of field strengths below 107 V/cm and high projectile energies. A semi-perturbative approach is used in which the interaction of the projectile electrons with the laser field is described by Gordon-Volkov wave functions, while the interaction of the hydrogen atom with the laser field is described by first-order time-dependent perturbation theory. A closed analytical solution is derived in laser-assisted inelastic electron-hydrogen scattering for the 1 s → nl excitation cross section which is valid for both circular and linear polarizations. For the excitation of the n=2 levels simple analytical expressions of differential cross section are derived for laser-assisted inelastic scattering in the perturbative domain, and the differential cross sections by the circularly and linearly polarized laser fields and their ratios for one- and two-photon absorption are calculated as a function of the scattering angle. Detailed numerical results for the angular dependence and the resonance structure of the differential cross sections are discussed for the 1 s → 4 l excitations of hydrogen in a circularly polarized laser field.

  6. Electrochemical removal of hydrogen atoms in Mg-doped GaN epitaxial layers

    Energy Technology Data Exchange (ETDEWEB)

    Lee, June Key, E-mail: junekey@jnu.ac.kr, E-mail: hskim7@jbnu.ac.kr; Hyeon, Gil Yong; Tawfik, Wael Z.; Choi, Hee Seok [Department of Materials Science and Engineering, and Optoelectronics Convergence Research Center, Chonnam National University, Gwangju 500-757 (Korea, Republic of); Ryu, Sang-Wan [Department of Physics and Optoelectronics Convergence Research Center, Chonnam National University, Gwangju 500-757 (Korea, Republic of); Jeong, Tak [Korea Photonics Technology Institute, Gwangju 500-460 (Korea, Republic of); Jung, Eunjin; Kim, Hyunsoo, E-mail: junekey@jnu.ac.kr, E-mail: hskim7@jbnu.ac.kr [School of Semiconductor and Chemical Engineering, Semiconductor Physics Research Center, Chonbuk National University, Jeonju 561-756 (Korea, Republic of)

    2015-05-14

    Hydrogen atoms inside of an Mg-doped GaN epitaxial layer were effectively removed by the electrochemical potentiostatic activation (EPA) method. The role of hydrogen was investigated in terms of the device performance of light-emitting diodes (LEDs). The effect of the main process parameters for EPA such as solution type, voltage, and time was studied and optimized for application to LED fabrication. In optimized conditions, the light output of 385-nm LEDs was improved by about 26% at 30 mA, which was caused by the reduction of the hydrogen concentration by ∼35%. Further removal of hydrogen seems to be involved in the breaking of Ga-H bonds that passivate the nitrogen vacancies. An EPA process with high voltage breaks not only Mg-H bonds that generate hole carriers but also Ga-H bonds that generate electron carriers, thus causing compensation that impedes the practical increase of hole concentration, regardless of the drastic removal of hydrogen atoms. A decrease in hydrogen concentration affects the current-voltage characteristics, reducing the reverse current by about one order and altering the forward current behavior in the low voltage region.

  7. A molecular dynamics simulation of hydrogen atoms collisions on an H-preadsorbed silica surface

    Science.gov (United States)

    Rutigliano, M.; Gamallo, P.; Sayós, R.; Orlandini, S.; Cacciatore, M.

    2014-08-01

    The interaction of hydrogen atoms and molecules with a silica surface is relevant for many research and technological areas. Here, the dynamics of hydrogen atoms colliding with an H-preadsorbed β-cristobalite (0 0 1) surface has been studied using a semiclassical collisional method in conjunction with a recently developed analytical potential energy surface based on density functional theory (DFT) calculations. The atomic recombination probability via an Eley-Rideal (E-R) mechanism, as well as the probabilities for other competitive surface processes, have been determined in a broad range of collision energies (0.04-3.0 eV) for off-normal (θv = 45°) and normal (θv = 0°) incidence and for two different surface temperatures (TS = 300 and 1000 K). H2,gas molecules form in roto-vibrational excited levels while the energy transferred to the solid surface is below 10% for all simulated conditions. Finally, the global atomic recombination coefficient (γE-R) and vibrational state resolved recombination coefficients (γ(v)) were calculated and compared with the available experimental values. The calculated collisional data are of interest in chemical kinetics studies and fluid dynamics simulations of silica surface processes in H-based low-temperature, low-pressure plasmas.

  8. Dynamics of a Rydberg hydrogen atom near a metal surface in the electron-extraction scheme

    Energy Technology Data Exchange (ETDEWEB)

    Iñarrea, Manuel [Área de Física Aplicada, Universidad de La Rioja, Logroño (Spain); Lanchares, Víctor [Departamento de Matemáticas y Computación, Universidad de La Rioja, Logroño, La Rioja (Spain); Palacián, Jesús [Departamento de Ingeniería Matemática e Informática, Universidad Pública de Navarra, Pamplona (Spain); Pascual, Ana I. [Departamento de Matemáticas y Computación, Universidad de La Rioja, Logroño, La Rioja (Spain); Salas, J. Pablo, E-mail: josepablo.salas@unirioja.es [Área de Física Aplicada, Universidad de La Rioja, Logroño (Spain); Yanguas, Patricia [Departamento de Ingeniería Matemática e Informática, Universidad Pública de Navarra, Pamplona (Spain)

    2015-01-23

    We study the classical dynamics of a Rydberg hydrogen atom near a metal surface in the presence of a constant electric field in the electron-extraction situation [1], e.g., when the field attracts the electron to the vacuum. From a dynamical point of view, this field configuration provides a dynamics richer than in the usual ion-extraction scheme, because, depending on the values of field and the atom–surface distance, the atom can be ionized only towards the metal surface, only to the vacuum or to the both sides. The evolution of the phase space structure as a function of the atom–surface distance is explored in the bound regime of the atom. In the high energy regime, the ionization mechanism is also investigated. We find that the classical results of this work are in good agreement with the results obtained in the wave-packet propagation study carried out by So et al. [1]. - Highlights: • We study a classical hydrogen atom near a metal surface plus a electric field. • We explore the phase space structure as a function of the field strength. • We find most of the electronic orbits are oriented along the field direction. • We study the ionization of the atom for several atom–surface distances. • This classical study is in good agreement with the quantum results.

  9. The dynamical properties of Rydberg hydrogen atom near a metal surface

    Institute of Scientific and Technical Information of China (English)

    GE Meihua; ZHANG Yanhui; WANG Dehua; DU Mengli; LIN Shenglu

    2005-01-01

    The dynamical properties of Rydberg hydrogen atom near a metal surface are presented by using the methods of phase space analysis and closed orbit theory. Transforming the coordinates of the Hamiltonian, we find that the phase space of the system is divided into vibrational and rotational region. Both the Poincaré surface of section and the closed orbit theory verify the same conclusion clearly. In this paper we choose the atomic principal quantum number as n = 20. The dynamical character of the exited hydrogen atom depends sensitively on the atom-surface distance d. When d is sufficiently large, the atom-surface potential can be expressed by the traditional van der Waals force and the system is integrable. When d becomes smaller, there exists a critical value dc. For d > dc, the system is near-integrable and the motion is regular. While chaotic motion appears for d < dc, and the system tends to be non-integrable. The trajectories become unstable and the electron might be captured onto the metal surface.

  10. Time-resolved Absorption Spectra of the Laser-dressed Hydrogen Atom

    Science.gov (United States)

    Murakami, Mitsuko; Chu, Shih-I.

    2013-05-01

    A theoretical study of the transient absorption spectra for the laser-dressed hydrogen atom based on the accurate numerical solution of the time-dependent Schrödinger equation is presented. The timing of absorption is controlled by the time delay between an isolated extreme ultraviolet (XUV) pulse and a dressing infrared (IR) field. We identify two different kinds of physical processes in the spectra. One is the formation of dressed states, signified by the appearance of sidebands between the XUV absorption lines separated by one IR-photon energy. We show that their population is maximized when the XUV pulse coincides with the zero-crossing of the IR field, and that their energy can be manipulated by using a chirped IR field. The other process is the dynamical AC Stark shift induced by the IR field and probed by the XUV pulse. Our calculations indicate that the accidental degeneracy of the hydrogen atom leads to the multiple splittings of each XUV absorption line whose separations change in response to a slowly-varying IR envelope. Furthermore, we observe the Autler-Townes doublets for the n=2 and 3 states using the 656 nm dressing field, but their separation does not agree with the prediction by the conventional 3-level model that neglects the dynamical AC Stark effects.

  11. Observations and Interpretations of Energetic Neutral Hydrogen Atoms from the December 5, 2006 Solar Event

    Science.gov (United States)

    Mewaldt, R. A.; Leske, R. A.; Shih, A. Y.; Stone, E. C.; Barghouty, A. f.; Cohen, C. M. S.; Cummings, A. c.; Labrador, A. W.; vonRosenvinge, T. T.

    2009-01-01

    We discuss recently reported observations of energetic neutral hydrogen atoms (ENAs) from an X9 solar flare/coronal mass ejection event on 5 December 2006, located at E79. The observations were made by the Low Energy Telescopes (LETs) on STEREO A and B. Prior to the arrival of the main solar energetic particle (SEP) event at Earth, both LETs observed a sudden burst of 1.6 to 15 MeV energetic neutral hydrogen atoms produced by either flare or shock-accelerated protons. RHESSI measurements of the 2.2-MeV gamma-ray line provide an estimate of the number of interacting flare-accelerated protons in this event, which leads to an improved estimate of ENA production by flare-accelerated protons. Taking into account ENA losses, we find that the observed ENAs must have been produced in the high corona at heliocentric distances > or equal to 2 solar radii. Although there are no CME images from this event, it is shown that CME-shock-accelerated protons can, in principle, produce a time-history consistent with the observations.

  12. Hydrogen atom abstraction of 3,5-disubstituted analogues of paracetamol by horseradish peroxidase and cytochrome P450

    NARCIS (Netherlands)

    Bessems, J.G.M.; Groot, M.J. de; Baede, E.J.; Koppele, J.M. te; Vermeulen, N.P.E.

    1998-01-01

    1. The formation of free radicals during enzyme catalysed oxidation of eight 3,5-disubstituted analogues of paracetamol (PAR) has been studied. A simple peroxidase system as well as cytochrome P450-containing systems were used. Radicals were detected by electron spin resonance (ESR) on incubation of

  13. Insights into the Electronic Structure of Ozone and Sulfur Dioxide from Generalized Valence Bond Theory: Addition of Hydrogen Atoms.

    Science.gov (United States)

    Lindquist, Beth A; Takeshita, Tyler Y; Dunning, Thom H

    2016-05-05

    Ozone (O3) and sulfur dioxide (SO2) are valence isoelectronic species, yet their properties and reactivities differ dramatically. In particular, O3 is highly reactive, whereas SO2 is chemically relatively stable. In this paper, we investigate serial addition of hydrogen atoms to both the terminal atoms of O3 and SO2 and to the central atom of these species. It is well-known that the terminal atoms of O3 are much more amenable to bond formation than those of SO2. We show that the differences in the electronic structure of the π systems in the parent triatomic species account for the differences in the addition of hydrogen atoms to the terminal atoms of O3 and SO2. Further, we find that the π system in SO2, which is a recoupled pair bond dyad, facilitates the addition of hydrogen atoms to the sulfur atom, resulting in stable HSO2 and H2SO2 species.

  14. Engaging unactivated alkyl, alkenyl and aryl iodides in visible-light-mediated free radical reactions.

    Science.gov (United States)

    Nguyen, John D; D'Amato, Erica M; Narayanam, Jagan M R; Stephenson, Corey R J

    2012-10-01

    Radical reactions are a powerful class of chemical transformations. However, the formation of radical species to initiate these reactions has often required the use of stoichiometric amounts of toxic reagents, such as tributyltin hydride. Recently, the use of visible-light-mediated photoredox catalysis to generate radical species has become popular, but the scope of these radical precursors has been limited. Here, we describe the identification of reaction conditions under which photocatalysts such as fac-Ir(ppy)3 can be utilized to form radicals from unactivated alkyl, alkenyl and aryl iodides. The generated radicals undergo reduction via hydrogen atom abstraction or reductive cyclization. The reaction protocol utilizes only inexpensive reagents, occurs under mild reaction conditions, and shows exceptional functional group tolerance. Reaction efficiency is maintained upon scale-up and decreased catalyst loading, and the reaction time can be significantly shortened when the reaction is performed in a flow reactor.

  15. Importance of tunneling in H-abstraction reactions by OH radicals. The case of CH4 + OH studied through isotope-substituted analogs

    Science.gov (United States)

    Lamberts, T.; Fedoseev, G.; Kästner, J.; Ioppolo, S.; Linnartz, H.

    2017-03-01

    We present a combined experimental and theoretical study focussing on the quantum tunneling of atoms in the reaction between CH4 and OH. The importance of this reaction pathway is derived by investigating isotope substituted analogs. Quantitative reaction rates needed for astrochemical models at low temperature are currently unavailable both in the solid state and in the gas phase. Here, we study tunneling effects upon hydrogen abstraction in CH4 + OH by focusing on two reactions: CH4 + OD → CH3 + HDO and CD4 + OH → CD3 + HDO. The experimental study shows that the solid-state reaction rate RCH4 + OD is higher than RCD4 + OH at 15 K. Experimental results are accompanied by calculations of the corresponding unimolecular and bimolecular reaction rate constants using instanton theory taking into account surface effects. For the work presented here, the unimolecular reactions are particularly interesting as these provide insight into reactions following a Langmuir-Hinshelwood process. The resulting ratio of the rate constants shows that the H abstraction (kCH4 + OD) is approximately ten times faster than D-abstraction (kCD4 + OH) at 65 K. We conclude that tunneling is involved at low temperatures in the abstraction reactions studied here. The unimolecular rate constants can be used by the modeling community as a first approach to describe OH-mediated abstraction reactions in the solid phase. For this reason we provide fits of our calculated rate constants that allow the inclusion of these reactions in models in a straightforward fashion.

  16. Effect of hydrogen atoms on the structures of trinuclear metal carbonyl clusters: trinuclear manganese carbonyl hydrides.

    Science.gov (United States)

    Liu, Xian-mei; Wang, Chao-yang; Li, Qian-shu; Xie, Yaoming; King, R Bruce; Schaefer, Henry F

    2009-05-18

    The structures of the trinuclear manganese carbonyl hydrides H(3)Mn(3)(CO)(n) (n = 12, 11, 10, 9) have been investigated by density functional theory (DFT). Optimization of H(3)Mn(3)(CO)(12) gives the experimentally known structure in which all carbonyl groups are terminal and each edge of a central Mn(3) equilateral triangle is bridged by a single hydrogen atom. This structure establishes the canonical distance 3.11 A for the Mn-Mn single bond satisfying the 18-electron rule. The central triangular (mu-H)(3)Mn(3) unit is retained in the lowest energy structure of H(3)Mn(3)(CO)(11), which may thus be derived from the H(3)Mn(3)(CO)(12) structure by removal of a carbonyl group with concurrent conversion of one of the remaining carbonyl groups into a semibridging carbonyl group to fill the resulting hole. The potential energy surface of H(3)Mn(3)(CO)(10) is relatively complicated with six singlet and five triplet structures. One of the lower energy H(3)Mn(3)(CO)(10) structures has one of the hydrogen atoms bridging the entire Mn(3) triangle and the other two hydrogen atoms bridging Mn-Mn edges. This H(3)Mn(3)(CO)(10) structure achieves the favored 18-electron configuration with a very short MnMn triple bond of 2.36 A. The other low energy H(3)Mn(3)(CO)(10) structure retains the (mu-H)(3)Mn(3) core of H(3)Mn(3)(CO)(12) but has a unique six-electron donor eta(2)-mu(3) carbonyl group bridging the entire Mn(3) triangle similar to the unique carbonyl group in the known compound Cp(3)Nb(3)(CO)(6)(eta(2)-mu(3)-CO). For H(3)Mn(3)(CO)(9) a structure with a central (mu(3)-H)(2)Mn(3) trigonal bipyramid lies >20 kcal/mol below any of the other structures. Triplet structures were found for the unsaturated H(3)Mn(3)(CO)(n) (n = 11, 10, 9) systems but at significantly higher energies than the lowest lying singlet structures.

  17. Resonances of a hydrogen atom in strong parallel electric and magnetic fields using B-spline basis sets

    Institute of Scientific and Technical Information of China (English)

    Zhang Yue-Xia; Meng Hui-Yan; Shi Ting-Yun

    2008-01-01

    The B-spline basis set plus complex scaling method is applied to the numerical calculation of the exact resonance parameters Er and I/2 of a hydrogen atom in parallel electric and magnetic fields.The method can calculate the ground and higher excited resonances accurately and efficiently.The resonance parameters with accuracies of 10-9 - 10-12 for hydrogen atom in parallel fields with different field strengths and symmetries are presented and compared with previous ones.Extension to the calculation of Rydberg atom in crossed electric and magnetic fields and of atomic double excited states in external electric fields is discussed.

  18. The hydrogen atom in strong electric fields summation of the weak field series expansion

    CERN Document Server

    Ohshima, Y; Ohshima, Yoshihisa; Suzuki, Hiroshi

    1995-01-01

    The order dependent mapping method, its convergence has recently been proven for the energy eigenvalue of the anharmonic oscillator, is applied to re-sum the standard perturbation series for Stark effect of the hydrogen atom. We perform a numerical experiment up to the fiftieth order of the perturbation expansion. A simple mapping suggested by the analytic structure and the strong field behavior gives an excellent agreement with the exact value for an intermediate range of the electric field, 0.03\\leq E\\leq0.25. The imaginary part of the energy (the decay width) as well as the real part of the energy is reproduced from the standard perturbation series.

  19. THE INFRARED SPECTRA OF POLYCYCLIC AROMATIC HYDROCARBONS WITH SOME OR ALL HYDROGEN ATOMS REMOVED

    Energy Technology Data Exchange (ETDEWEB)

    Bauschlicher, Charles W. Jr. [Entry Systems and Technology Division, Mail Stop 230-3, NASA Ames Research Center, Moffett Field, CA 94035 (United States); Ricca, Alessandra, E-mail: Charles.W.Bauschlicher@nasa.gov, E-mail: Alessandra.Ricca-1@nasa.gov [Carl Sagan Center, SETI Institute, 189 Bernardo Avenue, Mountain View, CA 94043 (United States)

    2013-10-20

    The loss of one hydrogen from C{sub 96}H{sub 24} does not significantly affect the infrared spectra of the neutral, cation, or anion. Excluding a very weak C-C stretching band at 5.1 μm, the loss of two adjacent duo hydrogens does not significantly affect the spectra compared with the parent. Removing all of the hydrogen atoms significantly increases the intensity of the new C-C stretching band, and, for the cation, shifts it to a longer (5.2 μm) wavelength. Observations show a feature near 5.25 μm, which has been attributed to overtone and combination bands from polycyclic aromatic hydrocarbons (PAHs). This current work suggests that dehydrogenated PAHs might also contribute to this band, but its weakness implies that fully dehydrogenated cationic or dicationic species are very rare.

  20. Relativistic Spectrum of Hydrogen Atom in Space-Time Non-Commutativity

    CERN Document Server

    Moumni, Mustafa; Zaim, Slimane; 10.1063/1.4715429

    2012-01-01

    We study space-time non-commutativity applied to the hydrogen atom via the Seiberg-Witten map and its phenomenological effects. We find that it modifies the Coulomb potential in the Hamiltonian and add an r-3 part. By calculating the energies from Dirac equation using perturbation theory, we study the modifications to the hydrogen spectrum. We find that it removes the degeneracy with respect to the total angular momentum quantum number and acts like a Lamb shift. Comparing the results with experimental values from spectroscopy, we get a new bound for the space-time non-commutative parameter. N.B: In precedent works (arXiv:0907.1904, arXiv:1003.5732 and arXiv:1006.4590), we have used the Bopp Shift formulation of non-commutativity but here use it \\`a la Seiberg-Witten in the Relativistic case.

  1. Chemisorption of hydrogen atoms and hydroxyl groups on stretched graphene: A coupled QM/QM study

    Science.gov (United States)

    Katin, Konstantin P.; Prudkovskiy, Vladimir S.; Maslov, Mikhail M.

    2017-09-01

    Using the density functional theory coupled with the nonorthogonal tight-binding model, we analyze the chemisorption of hydrogen atoms and hydroxyl groups on the unstrained and stretched graphene sheets. Drawback of finite cluster model of graphene for the chemisorption energy calculation in comparison with the QM/QM approach applied is discussed. It is shown that the chemisorption energy for the hydroxyl group is sufficiently lower than for hydrogen at stretching up to 7.5%. The simultaneous paired chemisorption of hydrogen and hydroxyl groups on the same hexagon has also been examined. Adsorption of two radicals in ortho and para positions is found to be more energetically favorable than those in meta position at any stretching considered. In addition the energy difference between adsorbent pairs in ortho and para positions decreases as the stretching rises. It could be concluded that the graphene stretching leads to the loss of preferred mutual arrangement of two radicals on its surface.

  2. Semiclassical Calculation of Recurrence Spectra of Rydberg Hydrogen Atom Near a Metal Surface

    Institute of Scientific and Technical Information of China (English)

    WANG De-Hua

    2009-01-01

    Using closed orbit theory, we give a clear physical picture description of the Rydberg hydrogen atom near a metal surface and calculate the Fourier transformed recurrence spectra of this system at different scaled energies below ionization threshold.The results show that with the increase of the scaled energy, the number of the closed orbit increases greatly.Some of the orbits are created by the bifurcation of the perpendicular orbit.This case is quite similar to the Rydberg atom in an electric field.When the scaled energy increases furthermore, chaotic orbits appear.This study provides a different perspective on the dynamical behavior of the Rydberg atom near a metal surface.

  3. A unified numerical model of collisional depolarization and broadening rates due to hydrogen atom collisions

    CERN Document Server

    Derouich, M; Barklem, P S

    2015-01-01

    Interpretation of solar polarization spectra accounting for partial or complete frequency redistribution requires data on various collisional processes. Data for depolarization and polarization transfer are needed but often missing, while data for collisional broadening are usually more readily available. Recent work by Sahal-Br\\'echot and Bommier concluded that despite underlying similarities in the physics of collisional broadening and depolarization processes, relationships between them are not possible to derive purely analytically. We aim to derive accurate numerical relationships between the collisional broadening rates and the collisional depolarization and polarization transfer rates due to hydrogen atom collisions. Such relationships would enable accurate and efficient estimation of collisional data for solar applications. Using earlier results for broadening and depolarization processes based on general (i.e. not specific to a given atom), semi-classical calculations employing interaction potentials...

  4. Variational-integral perturbation corrections of some lower excited states for hydrogen atoms in magnetic fields

    Institute of Scientific and Technical Information of China (English)

    Yuan Lin; Zhao Yun-Hui; Xu Jun; Zhou Ben-Hu; Hai Wen-Hua

    2012-01-01

    A variational-integral perturbation method (VIPM) is established by combining the variational perturbation with the integral perturbation.The first-order corrected wave functions are constructed,and the second-order energy corrections for the ground state and several lower excited states are calculated by applying the VIPM to the hydrogen atom in a strong uniform magnetic field.Our calculations demonstrated that the energy calculated by the VIPM only shows a negative value,which indicates that the VIPM method is more accurate than the other methods.Our study indicated that the VIPM can not only increase the accuracy of the results but also keep the convergence of the wave functions.

  5. Non-dipole effects in multiphoton ionization of hydrogen atom in short superintense laser fields

    Energy Technology Data Exchange (ETDEWEB)

    Jobunga, Eric O. [AG Moderne Optik, Institut fuer Physik, Humboldt-Universitaet zu Berlin, Newtonstr. 15, D-12489 Berlin (Germany); Department of Mathematics and Physics, Technical University of Mombasa, P. O. Box 90420-80100, Mombasa (Kenya); Saenz, Alejandro [AG Moderne Optik, Institut fuer Physik, Humboldt-Universitaet zu Berlin, Newtonstr. 15, D-12489 Berlin (Germany)

    2014-07-01

    The development of novel light sources has enabled the realization of high-precision experiments investigating various non-linear processes in the dynamics of atomic, molecular, and ionic systems interacting with high intense laser pulses. At high intensities or short wavelengths, the analysis of these experiments would definitely require a reliable non-perturbative solution of the time-dependent Schroedinger or Dirac equation. These solutions should consider both the temporal and the spatial intensity variations of the laser pulse.We have solved the non-relativistic time dependent Schroedinger equation for a ground state hydrogen atom interacting with short intense spatially and temporally resolved laser fields corresponding to the multiphoton ATI regime for a monochromatic source with λ= 800 nm. We shall analyse the effects of the A{sup 2} term and the corresponding orders of the multipolar expansion of the transition matrix.

  6. Hidden momentum in a hydrogen atom and the Lorentz-force law

    Science.gov (United States)

    Filho, J. S. Oliveira; Saldanha, Pablo L.

    2015-11-01

    By using perturbation theory, we show that a hydrogen atom with magnetic moment due to the orbital angular momentum of the electron has so-called hidden momentum in the presence of an external electric field. This means that the atomic electronic cloud has a nonzero linear momentum in its center-of-mass rest frame due to a relativistic effect. This is completely analogous to the hidden momentum that a classical current loop has in the presence of an external electric field. We discuss how this effect is essential for the validity of the Lorentz-force law in quantum systems. We also connect our results to the long-standing Abraham-Minkowski debate about the momentum of light in material media.

  7. Hidden momentum in a hydrogen atom and the Lorentz force law

    CERN Document Server

    Filho, J S Oliveira

    2015-01-01

    By using perturbation theory, we show that an hydrogen atom with magnetic moment due to the orbital angular momentum of the electron has hidden momentum in the presence of an external electric field. This means that the atomic electronic cloud has a nonzero linear momentum in its center of mass rest frame due to a relativistic effect. This is completely analogous to the hidden momentum that a classical current loop has in the presence of an external electric field. We discuss that this effect is essential for the validity of the Lorentz force law in quantum systems. We also connect our results to the secular Abraham-Minkowski debate about the momentum of light in material media.

  8. Dirac equation, hydrogen atom spectrum and the Lamb shift in dynamical non-commutative spaces

    Indian Academy of Sciences (India)

    S A ALAVI; N REZAEI

    2017-05-01

    We derive the relativistic Hamiltonian of hydrogen atom in dynamical non-commutative spaces (DNCS or $\\tau$ -space). Using this Hamiltonian we calculate the energy shift of the ground state as well the $2P_{1/2}$, $2S_{1/2}$levels. In all the cases, the energy shift depends on the dynamical non-commutative parameter $\\tau$. Using the accuracy of the energy measurement, we obtain an upper bound for $\\tau$. We also study the Lamb shift in DNCS. Both $2P_{1/2}$ and $2S_{1/2}$ levels receive corrections due to dynamical non-commutativity of space which is in contrast with the non-dynamical non-commutative spaces (NDNCS or $\\theta$-space) in which the $2S_{1/2}$ level receives no correction.

  9. Hydrogen atom in strong magnetic field: a high accurate calculation in spheroidal coordinates

    Institute of Scientific and Technical Information of China (English)

    LIU Qiang; KANG Shuai; ZHANG Xian-zhou; SHI Ting-yun

    2006-01-01

    A B-spline-type basis set method for the calculation of hydrogen atom in strong magnetic fields in the frame of spheroidal coordinates has been introduced.High accurate energy levels of hydrogen in the magnetic field,with strength ranging from 0 to 1000 a.u.,have been obtained.For the ground state,ls0,energies with at least 11 significant digits have been obtained.For the low-lying excited state,2p-1,energies with at least 9 significant digits are obtained.The method has also been applied to the calculation of hydrogen Rydberg states in laboratory magnetic fields.Energy spectra with at least 10 significant digits are presented.A comparison with other results in the literatures has been performed.Our results are comparable to the most accurate one up to date.A possible extension to the cases of parallel and crossed electric and magnetic fields have been discussed.

  10. Kinetic solvent effects on hydrogen abstraction from phenol by the cumyloxyl radical. Toward an understanding of the role of protic solvents.

    Science.gov (United States)

    Bietti, Massimo; Salamone, Michela; DiLabio, Gino A; Jockusch, Steffen; Turro, Nicholas J

    2012-02-03

    A time-resolved kinetic study of the hydrogen atom abstraction reactions from phenol by the cumyloxyl radical (CumO(•)) was carried out in different solvents. The hydrogen atom abstraction rate constant (k(H)) was observed to decrease by almost 3 orders of magnitude on going from isooctane to MeOH. In TFE, MeCN/H(2)O 2:1, and MeOH, the measured k(H) values were lower than expected on the basis of the Snelgrove-Ingold (SI) equation that correlates log k(H) to the solvent hydrogen bond acceptor (HBA) ability parameter β(2)(H). As these solvents also act as hydrogen bond donors (HBDs), we explored the notion that a more thorough description of solvent effects could be provided by including a solvent HBD ability term, α(2)(H), into the SI equation via β(2)(H)(1 + α(2)(H)). The inclusion of such a term greatly improves the fitting for TFE, MeCN/H(2)O 2:1, and MeOH but at the expense of that for tertiary alkanols. This finding suggests that, for the reaction of CumO(•) with phenol, the HBA and HBD abilities of both the solvent and the substrate could be responsible for the observed KSEs. but this requires that primary and tertiary alkanols exhibit different solvation behaviors. Possible explanations for this different behavior are explored.

  11. Presolvated Electron Reactions with Methyl Acetoacetate: Electron Localization, Proton-Deuteron Exchange, and H-Atom Abstraction

    Directory of Open Access Journals (Sweden)

    Alex Petrovici

    2014-09-01

    Full Text Available Radiation-produced electrons initiate various reaction processes that are important to radiation damage to biomolecules. In this work, the site of attachment of the prehydrated electrons with methyl acetoacetate (MAA, CH3-CO-CH2-COOCH3 at 77 K and subsequent reactions of the anion radical (CH3-CO•−-CH2-COOCH3 in the 77 to ca. 170 K temperature range have been investigated in homogeneous H2O and D2O aqueous glasses by electron spin resonance (ESR spectroscopy. At 77 K, the prehydrated electron attaches to MAA forming the anion radical in which the electron is delocalized over the two carbonyl groups. This species readily protonates to produce the protonated electron adduct radical CH3-C(•OH-CH2-COOCH3. The ESR spectrum of CH3-C(•OH-CH2-COOCH3 in H2O shows line components due to proton hyperfine couplings of the methyl and methylene groups. Whereas, the ESR spectrum of CH3-C(•OH-CH2-COOCH3 in D2O glass shows only the line components due to proton hyperfine couplings of CH3 group. This is expected since the methylene protons in MAA are readily exchangeable in D2O. On stepwise annealing to higher temperatures (ca. 150 to 170 K, CH3-C(•OH-CH2-COOCH3 undergoes bimolecular H-atom abstraction from MAA to form the more stable radical, CH3-CO-CH•-COOCH3. Theoretical calculations using density functional theory (DFT support the radical assignments.

  12. Bifurcations in the hydrogen atom in the presence of a circularly polarized microwave field and a static magnetic field

    Energy Technology Data Exchange (ETDEWEB)

    Lanchares, V. [Departamento de Matematicas y Computacion, Universidad de La Rioja, 26004 Logrono (Spain); Inarrea, M.; Salas, J.P. [Area de Fisica Aplicada, Universidad de La Rioja, 26004 Logrono (Spain)

    1997-09-01

    In a classical model, the dynamics of the hydrogen atom subjected to a circularly polarized microwave field and a magnetic field is shown to belong to the family of so-called biparametric quadratic Hamiltonians. The energy-level structure is studied in terms of the parametric bifurcations. {copyright} {ital 1997} {ital The American Physical Society}

  13. Use of a PhET Interactive Simulation in General Chemistry Laboratory: Models of the Hydrogen Atom

    Science.gov (United States)

    Clark, Ted M.; Chamberlain, Julia M.

    2014-01-01

    An activity supporting the PhET interactive simulation, Models of the Hydrogen Atom, has been designed and used in the laboratory portion of a general chemistry course. This article describes the framework used to successfully accomplish implementation on a large scale. The activity guides students through a comparison and analysis of the six…

  14. Single crystal to single crystal transformation and hydrogen-atom transfer upon oxidation of a cerium coordination compound.

    Science.gov (United States)

    Williams, Ursula J; Mahoney, Brian D; Lewis, Andrew J; DeGregorio, Patrick T; Carroll, Patrick J; Schelter, Eric J

    2013-04-15

    Trivalent and tetravalent cerium compounds of the octamethyltetraazaannulene (H2omtaa) ligand have been synthesized. Electrochemical analysis shows a strong thermodynamic preference for the formal cerium(IV) oxidation state. Oxidation of the cerium(III) congener Ce(Homtaa)(omtaa) occurs by hydrogen-atom transfer that includes a single crystal to single crystal transformation upon exposure to an ambient atmosphere.

  15. A Guided-Inquiry Lab for the Analysis of the Balmer Series of the Hydrogen Atomic Spectrum

    Science.gov (United States)

    Bopegedera, A. M. R. P.

    2011-01-01

    A guided-inquiry lab was developed to analyze the Balmer series of the hydrogen atomic spectrum. The emission spectrum of hydrogen was recorded with a homemade benchtop spectrophotometer. By drawing graphs and a trial-and-error approach, students discover the linear relationship presented in the Rydberg formula and connect it with the Bohr model…

  16. Use of a PhET Interactive Simulation in General Chemistry Laboratory: Models of the Hydrogen Atom

    Science.gov (United States)

    Clark, Ted M.; Chamberlain, Julia M.

    2014-01-01

    An activity supporting the PhET interactive simulation, Models of the Hydrogen Atom, has been designed and used in the laboratory portion of a general chemistry course. This article describes the framework used to successfully accomplish implementation on a large scale. The activity guides students through a comparison and analysis of the six…

  17. Symmetry-resolved spectroscopy by detection of a metastable hydrogen atom for investigating the doubly excited states of molecular hydrogen

    Energy Technology Data Exchange (ETDEWEB)

    Odagiri, Takeshi; Kumagai, Yoshiaki; Tanabe, Takehiko; Nakano, Motoyoshi; Kouchi, Noriyuki [Department of Chemistry, Tokyo Institute of Technology, Meguro-ku, Tokyo 152-8551 (Japan); Suzuki, Isao H, E-mail: joe@chem.titech.ac.j [Photon Factory, IMSS, KEK, Tsukuba, Ibaraki 305-0801 (Japan)

    2009-11-01

    Symmetry-resolved spectroscopy for investigating the doubly excited states of molecular hydrogen has been newly developed, where a metastable hydrogen atom dissociating in a direction parallel and perpendicular to the electric vector of the linearly polarized incident light is detected.

  18. Corrigendum: "Extracting Closed Classical Orbits from Quantum Recurrence Spectra of a Non-Hydrogenic Atom in Parallel Electric and Magnetic Fields"

    Institute of Scientific and Technical Information of China (English)

    WANG De-Hua

    2010-01-01

    @@ In a paper published by us,[1] we studied how to extract the closed orbit of the non-hydrogenic atom in parallel electric and magnetic fields. However, there was another paper published in 1996 by Courtney,[2] which studied the initial conditions of closed classical orbits from quantum spectra of hydrogen atom in magnetic field.

  19. Reactions of the cumyloxyl and benzyloxyl radicals with tertiary amides. Hydrogen abstraction selectivity and the role of specific substrate-radical hydrogen bonding.

    Science.gov (United States)

    Salamone, Michela; Milan, Michela; DiLabio, Gino A; Bietti, Massimo

    2013-06-21

    A time-resolved kinetic study in acetonitrile and a theoretical investigation of hydrogen abstraction reactions from N,N-dimethylformamide (DMF) and N,N-dimethylacetamide (DMA) by the cumyloxyl (CumO(•)) and benzyloxyl (BnO(•)) radicals was carried out. CumO(•) reacts with both substrates by direct hydrogen abstraction. With DMF, abstraction occurs from the formyl and N-methyl C-H bonds, with the formyl being the preferred abstraction site, as indicated by the measured kH/kD ratios and by theory. With DMA, abstraction preferentially occurs from the N-methyl groups, whereas abstraction from the acetyl group represents a minor pathway, in line with the computed C-H BDEs and the kH/kD ratios. The reactions of BnO(•) with both substrates were best described by the rate-limiting formation of hydrogen-bonded prereaction complexes between the BnO(•) α-C-H and the amide oxygen, followed by intramolecular hydrogen abstraction. This mechanism is consistent with the very large increases in reactivity measured on going from CumO(•) to BnO(•) and with the observation of kH/kD ratios close to unity in the reactions of BnO(•). Our modeling supports the different mechanisms proposed for the reactions of CumO(•) and BnO(•) and the importance of specific substrate/radical hydrogen bond interactions, moreover providing information on the hydrogen abstraction selectivity.

  20. Hydrogen abstraction from cyclic amines by the cumyloxyl and benzyloxyl radicals. The role of stereoelectronic effects and of substrate/radical hydrogen bonding.

    Science.gov (United States)

    Salamone, Michela; Martella, Roberto; Bietti, Massimo

    2012-10-05

    A kinetic study on the hydrogen abstraction reactions from cyclic amines and diamines (pyrrolidines, piperidines, morpholines, and piperazines) by the cumyloxyl (CumO(•)) and benzyloxyl (BnO(•)) radicals was carried out. The reactions with CumO(•) were described in all cases as direct hydrogen abstractions. The differences in the hydrogen abstraction rate constant (k(H)) were explained in terms of the different number of abstractable hydrogen atoms, the operation of stereoelectronic effects, and, with the morpholines, on the basis of polar effects. Significantly higher k(H) values were measured for the reactions of the amines with BnO(•). This behavior was explained on the basis of a mechanism that proceeds through the rate-determining formation of a hydrogen bonded pre-reaction complex between the radical α-C-H and the nitrogen lone pair followed by hydrogen abstraction within the complex. A decrease in k(H) was observed going from secondary to tertiary amines and, with tertiary amines, on increasing steric hindrance at nitrogen, pointing toward the important role of steric and electronic effects on pre-reaction complex formation. These results expand previous findings contributing to a detailed mechanistic description of the reactions of alkoxyl radicals with amines, showing that structural effects in both the substrate and the radical can play a dramatic role and providing new information on the role of substrate/radical interactions on these processes.

  1. ChemInform Abstract: The Palladium-Catalyzed Aerobic Kinetic Resolution of Secondary Alcohols: Reaction Development, Scope, and Applications.

    KAUST Repository

    Ebner, David C.

    2010-03-30

    ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

  2. Theoretical study of the reactivity trends in the Cl-abstraction reactions of CHCl3 + CHX·−/CX$_{2}^{·−}$ (X = Cl, Br and I)

    Indian Academy of Sciences (India)

    Jun Xi Liang; Zhi Yuan Geng; Yong Cheng Wang

    2011-09-01

    To better understand how and to what extent the halosubstituted carbene radical anions effect the chlorine abstraction of CHCl3, a detailed theoretical investigation has been performed at the UMP2/6-311++G (d, p)/RECP level of theory. The model system CHCl3+CHX·−/CX$^{·−}_{2}$ (X = Cl, Br, and I) has been chosen for the present study. According to the detailed discussions of geometries and energetics of the optimized stationary points, our theoretical findings suggest that the Cl-abstraction reactions by CHX·− are energetically favourable, indicating the less massive substitution X in CHX·− the easier abstraction reaction, as compared to those by CX$^{·−}_{2}$, which are energetically unfavourable and would be endothermic.

  3. Revisiting the inelastic electron tunneling spectroscopy of single hydrogen atom adsorbed on the Cu(100) surface

    Energy Technology Data Exchange (ETDEWEB)

    Jiang, Zhuoling; Wang, Hao [Centre for Nanoscale Science and Technology, Key Laboratory for the Physics and Chemistry of Nanodevices, Department of Electronics, Peking University, Beijing 100871 (China); Sanvito, Stefano [School of Physics, AMBER and CRANN Institute, Trinity College, Dublin 2 (Ireland); Hou, Shimin, E-mail: smhou@pku.edu.cn [Centre for Nanoscale Science and Technology, Key Laboratory for the Physics and Chemistry of Nanodevices, Department of Electronics, Peking University, Beijing 100871 (China); Beida Information Research (BIR), Tianjin 300457 (China)

    2015-12-21

    Inelastic electron tunneling spectroscopy (IETS) of a single hydrogen atom on the Cu(100) surface in a scanning tunneling microscopy (STM) configuration has been investigated by employing the non-equilibrium Green’s function formalism combined with density functional theory. The electron-vibration interaction is treated at the level of lowest order expansion. Our calculations show that the single peak observed in the previous STM-IETS experiments is dominated by the perpendicular mode of the adsorbed H atom, while the parallel one only makes a negligible contribution even when the STM tip is laterally displaced from the top position of the H atom. This propensity of the IETS is deeply rooted in the symmetry of the vibrational modes and the characteristics of the conduction channel of the Cu-H-Cu tunneling junction, which is mainly composed of the 4s and 4p{sub z} atomic orbitals of the Cu apex atom and the 1s orbital of the adsorbed H atom. These findings are helpful for deepening our understanding of the propensity rules for IETS and promoting IETS as a more popular spectroscopic tool for molecular devices.

  4. Revisiting the inelastic electron tunneling spectroscopy of single hydrogen atom adsorbed on the Cu(100) surface.

    Science.gov (United States)

    Jiang, Zhuoling; Wang, Hao; Sanvito, Stefano; Hou, Shimin

    2015-12-21

    Inelastic electron tunneling spectroscopy (IETS) of a single hydrogen atom on the Cu(100) surface in a scanning tunneling microscopy (STM) configuration has been investigated by employing the non-equilibrium Green's function formalism combined with density functional theory. The electron-vibration interaction is treated at the level of lowest order expansion. Our calculations show that the single peak observed in the previous STM-IETS experiments is dominated by the perpendicular mode of the adsorbed H atom, while the parallel one only makes a negligible contribution even when the STM tip is laterally displaced from the top position of the H atom. This propensity of the IETS is deeply rooted in the symmetry of the vibrational modes and the characteristics of the conduction channel of the Cu-H-Cu tunneling junction, which is mainly composed of the 4s and 4pz atomic orbitals of the Cu apex atom and the 1s orbital of the adsorbed H atom. These findings are helpful for deepening our understanding of the propensity rules for IETS and promoting IETS as a more popular spectroscopic tool for molecular devices.

  5. Photoionization microscopy of Rydberg hydrogen atom in a non-uniform electrical field

    Science.gov (United States)

    Shao-Hao, Cheng; De-Hua, Wang; Zhao-Hang, Chen; Qiang, Chen

    2016-06-01

    In this paper, we investigate the photoionization microscopy of the Rydberg hydrogen atom in a gradient electric field for the first time. The observed oscillatory patterns in the photoionization microscopy are explained within the framework of the semiclassical theory, which can be considered as a manifestation of interference between various electron trajectories arriving at a given point on the detector plane. In contrast with the photoionization microscopy in the uniform electric field, the trajectories of the ionized electron in the gradient electric field will become chaotic. An infinite set of different electron trajectories can arrive at a given point on the detector plane, which makes the interference pattern of the electron probability density distribution extremely complicated. Our calculation results suggest that the oscillatory pattern in the electron probability density distribution depends sensitively on the electric field gradient, the scaled energy and the position of the detector plane. Through our research, we predict that the interference pattern in the electron probability density distribution can be observed in an actual photoionization microscopy experiment once the external electric field strength and the position of the electron detector plane are reasonable. This study provides some references for the future experimental research on the photoionization microscopy of the Rydberg atom in the non-uniform external fields. Project supported by the National Natural Science Foundation of China (Grant No. 11374133) and the Project of Shandong Provincial Higher Educational Science and Technology Program, China (Grant No. J13LJ04).

  6. Excited states of two-dimensional hydrogen atom in tilted magnetic field: Quantum chaos

    Science.gov (United States)

    Koval, Eugene A.; Koval, Oksana A.

    2017-09-01

    The aim of the current work is the research of the influence of a tilted magnetic field direction on the spectrum and the energy level spacing distribution of a two-dimensional (2D) hydrogen atom and of an exciton in GaAs/Al0.33Ga0.67As quantum well. It was discovered that the quantum chaos (QC) is initiated with an increasing angle α between the magnetic field direction and the normal to the atomic plane. It is characterized by the repulsion of levels leading to the eliminating of the shell structure and by changing the spectrum statistical properties. The statement about the initiation of chaos and its dominance over regular motion with increasing angle α is confirmed by the results of our calculations of the classical dynamics presented in this paper. The evolution of the spatial distribution of the square of the absolute value of the wave function at an increasing angle α was observed. The differences of calculated dependencies of energies for various excited states on the tilt angle at a wide range of the magnetic field strength were described.

  7. Observation and Interpretation of Energetic Neutral Hydrogen Atoms from the December 5, 2006 Solar Flare

    Science.gov (United States)

    Barghouty, A. F.; Mewaldt, R. A.; Leske, R. A.; Shih, A. Y.; Stone, E. C.; Cohen, C. M. S.; Cummings, A. C.; Labrador, A. W.; vonRosenvinge, T. T.; Wiedenbeck, M. E.

    2009-01-01

    We discuss observations of energetic neutral hydrogen atoms (ENAs) from a solar flare/coronal mass ejection event reported by Mewaldt et al. (2009). The observations were made during the 5 December 2006 X9 solar flare, located at E79, by the Low Energy Telescopes (LETs) on STEREO A and B. Prior to the arrival of the main solar energetic particle (SEP) event at Earth, both LETs observed a sudden burst of 1.6 to 15 MeV particles arriving from the Sun. The derived solar emission profile, arrival directions, and energy spectrum all show that the atoms produced by either flare or shock-accelerated protons. RHESSI measurements of the 2.2-MeV gamma-ray line provide an estimate of the number of interacting flare-accelerated protons in this event, which leads to an improved estimate of ENA production by flare-accelerated protons. CME-driven shock acceleration is also considered. Taking into account ENA losses, we conclude that the observed ENAs must have been produced in the high corona at heliocentric distances .2 solar radii.

  8. Ab initio dynamics of the cytochrome P450 hydroxylation reaction

    Energy Technology Data Exchange (ETDEWEB)

    Elenewski, Justin E.; Hackett, John C, E-mail: jchackett@vcu.edu [Department of Physiology and Biophysics and The Massey Cancer Center, School of Medicine, Virginia Commonwealth University, 401 College Street, Richmond, Virginia 23219-1540 (United States)

    2015-02-14

    The iron(IV)-oxo porphyrin π-cation radical known as Compound I is the primary oxidant within the cytochromes P450, allowing these enzymes to affect the substrate hydroxylation. In the course of this reaction, a hydrogen atom is abstracted from the substrate to generate hydroxyiron(IV) porphyrin and a substrate-centered radical. The hydroxy radical then rebounds from the iron to the substrate, yielding the hydroxylated product. While Compound I has succumbed to theoretical and spectroscopic characterization, the associated hydroxyiron species is elusive as a consequence of its very short lifetime, for which there are no quantitative estimates. To ascertain the physical mechanism underlying substrate hydroxylation and probe this timescale, ab initio molecular dynamics simulations and free energy calculations are performed for a model of Compound I catalysis. Semiclassical estimates based on these calculations reveal the hydrogen atom abstraction step to be extremely fast, kinetically comparable to enzymes such as carbonic anhydrase. Using an ensemble of ab initio simulations, the resultant hydroxyiron species is found to have a similarly short lifetime, ranging between 300 fs and 3600 fs, putatively depending on the enzyme active site architecture. The addition of tunneling corrections to these rates suggests a strong contribution from nuclear quantum effects, which should accelerate every step of substrate hydroxylation by an order of magnitude. These observations have strong implications for the detection of individual hydroxylation intermediates during P450 catalysis.

  9. The closed-orbit and the photoabsorption spectra of the Rydberg hydrogen atom between two parallel metallic surfaces

    Institute of Scientific and Technical Information of China (English)

    Wang De-Hua

    2007-01-01

    Using the closed orbit theory,we study the classical motion and calculate the photoabsorption spectra of Rydberg hydrogen atom between two parallel metallic surfaces.The results show that the metallic surfaces have a significant effect on the photoabsorption process.When the distances between the hydrogen atom and the two metallic surfaces are close to a critical value dc,the number of the closed orbits is the greatest.When the distance larger or smaller than dc,the number of the closed orbits decreases and the absorption spectra are shown to exhibit a damping oscillation.This work is an interesting new application of closed-orbit theory and is of potential experimental interest.

  10. Hydrogen atom in a quantum plasma environment under the influence of Aharonov-Bohm flux and electric and magnetic fields

    CERN Document Server

    Falaye, Babatunde James; Silva-Ortigoza, Ramón; Dong, Shi-Hai

    2016-01-01

    This study presents the confinement influences of Aharonov-Bohm-flux (AB-flux), electric and magnetic fields directed along $z$-axis and encircled by quantum plasmas, on the hydrogen atom. The all-inclusive effects result to a strongly attractive system while the localizations of quantum levels change and the eigenvalues decrease. We find that, the combined effect of the fields is stronger than solitary effect and consequently, there is a substantial shift in the bound state energy of the system. We also find that to perpetuate a low-energy medium for hydrogen atom in quantum plasmas, strong electric field and weak magnetic field are required, where AB-flux field can be used as a regulator. The application of perturbation technique utilized in this paper is not restricted to plasma physics, it can also be applied in molecular physics.

  11. Three-dimensional simulation on explosions of hydrogen atomic clusters irradiated by an intense femtosecond laser pulse

    Institute of Scientific and Technical Information of China (English)

    Xia Yong; Liu Jian-Sheng; Ni Guo-Quan; Xu Zhi-Zhan

    2004-01-01

    Using classic particle dynamics simulations, the interaction process between an intense femtosecond laser pulse and icosahedral hydrogen atomic clusters H13, H55 and H147 has been studied. It is revealed that with increasing number of atoms in the cluster, the kinetic energy of ions generated in the Coulomb explosion of the ionized hydrogen clusters increases. The expansion process of the clusters after laser irradiation has also been examined, showing that the expansion scale decreases with increasing cluster size.

  12. Single and double hydrogen atom migrations in substituted alkyl benzoates: a study on the substituent effect using MIKE spectrometry

    Science.gov (United States)

    Tobita, Seiji; Tajima, Susumu; Ishihara, Yasuko; Kojima, Masahiro; Shigihara, Atsushi

    1994-03-01

    The substituent effect on the single and double hydrogen atom migrations is ionized ortho-, meta-, and para-substituted isobutyl (XC6H4COOC4H9) and isopropyl (XC6H4COOC3H7) benzoates is investigated by mass-analyzed ion kinetic energy spectrometry. The observed product ion ratios [XC6H4COOH]+/[XC6H4COOH2]+ show a general tendency: the compounds with an electron-donating substituent favour the formation of [XC6H4COOH]+ by single hydrogen atom migration (McLafferty rearrangement), while those with an electron-withdrawing substituent produce preferentially [XC6H4COOH2]+ through double hydrogen atom migration (McLaffery + 1 rearrangement). The thermochemical considerations combined with MO calculations show that the substituent effects observed are rationalized by the effects of substituent on the ionization energy (IE) and proton affinity (PA) of XC6H4COOH, i.e. the product ratios are determined by the difference of the product thermochemical stabilities which can be evaluated as IE(XC6H4COOH) + PA(XC6H4COOH).

  13. Reactions of the cumyloxyl and benzyloxyl radicals with strong hydrogen bond acceptors. Large enhancements in hydrogen abstraction reactivity determined by substrate/radical hydrogen bonding.

    Science.gov (United States)

    Salamone, Michela; DiLabio, Gino A; Bietti, Massimo

    2012-12-07

    A kinetic study on hydrogen abstraction from strong hydrogen bond acceptors such as DMSO, HMPA, and tributylphosphine oxide (TBPO) by the cumyloxyl (CumO(•)) and benzyloxyl (BnO(•)) radicals was carried out in acetonitrile. The reactions with CumO(•) were described in terms of a direct hydrogen abstraction mechanism, in line with the kinetic deuterium isotope effects, k(H)/k(D), of 2.0 and 3.1 measured for reaction of this radical with DMSO/DMSO-d(6) and HMPA/HMPA-d(18). Very large increases in reactivity were observed on going from CumO(•) to BnO(•), as evidenced by k(H)(BnO(•))/k(H)(CumO(•)) ratios of 86, 4.8 × 10(3), and 1.6 × 10(4) for the reactions with HMPA, TBPO, and DMSO, respectively. The k(H)/k(D) of 0.91 and 1.0 measured for the reactions of BnO(•) with DMSO/DMSO-d(6) and HMPA/HMPA-d(18), together with the k(H)(BnO(•))/k(H)(CumO(•)) ratios, were explained on the basis of the formation of a hydrogen-bonded prereaction complex between the benzyloxyl α-C-H and the oxygen atom of the substrates followed by hydrogen abstraction. This is supported by theoretical calculations that show the formation of relatively strong prereaction complexes. These observations confirm that in alkoxyl radical reactions specific hydrogen bond interactions can dramatically influence the hydrogen abstraction reactivity, pointing toward the important role played by structural and electronic effects.

  14. An ab Initio/Rice-Ramsperger-Kassel-Marcus Study of the Reactions of Propenols with OH. Mechanism and Kinetics of H Abstraction Channels

    Science.gov (United States)

    Zhou, Chong-Wen; Mebel, Alexander M.; Li, Xiang-Yuan

    2009-09-01

    Propenols have been found to be common intermediates in the hydrocarbon combustion and they are present in substantial concentrations in a wide range of flames. However, the kinetics properties of these species in combustion flames have not received much attention. In this work, the mechanism and kinetics of the OH hydrogen abstraction from propenols are investigated. Three stable conformations of propenols, (E)-1-propenol, (Z)-1-propenol, and syn-propen-2-ol, are taken into consideration. The potential energy profiles for the three reaction systems have been first investigated by the CCSD(T) method. The geometric parameters and relative energies of the reactants, reactant complexes, transition states, product complexes, and products have been investigated theoretically. The rate constants are calculated in the temperature range of 200-3000 K by the Variflex code based on the weak collision master equation/microcanonical variational RRKM theory. For all considered reactions, our results support a stepwise mechanism involving the formation of a reactant complex in the entrance channel and a product complex in the exit channel. In the reaction of OH with (E)-1-propenol, the hydrogen abstractions from the -CH3 and -OH sites are dominant and competitive with each other in the temperature range from 500 to 2000 K. Above 2000 K, the hydrogen abstraction from the -CH group bonded to O atom becomes dominant with a relative yield of 51.1% at 3000 K. In the reaction of OH with (Z)-1-propenol, the hydrogen abstractions from -CH3, -CH bonded to O atom, and -OH are preferable in the temperature range from 500 to 1800 K, with the first two channels being competitive with each other. Above 1800 K, the hydrogen abstraction reaction from the CH group bonded to the CH3 group becomes dominant with the branching ratio of 90.3% at 3000 K. In the reaction of OH with syn-propen-2-ol, the abstractions from the -CH3 and -OH sites are competitive with each other when the temperature is

  15. Different catalytic effects of a single water molecule: the gas-phase reaction of formic acid with hydroxyl radical in water vapor.

    Science.gov (United States)

    Anglada, Josep M; Gonzalez, Javier

    2009-12-07

    The effect of a single water molecule on the reaction mechanism of the gas-phase reaction between formic acid and the hydroxyl radical was investigated with high-level quantum mechanical calculations using DFT-B3LYP, MP2 and CCSD(T) theoretical approaches in concert with the 6-311+G(2df,2p) and aug-cc-pVTZ basis sets. The reaction between HCOOH and HO has a very complex mechanism involving a proton-coupled electron transfer process (pcet), two hydrogen-atom transfer reactions (hat) and a double proton transfer process (dpt). The hydroxyl radical predominantly abstracts the acidic hydrogen of formic acid through a pcet mechanism. A single water molecule affects each one of these reaction mechanisms in different ways, depending on the way the water interacts. Very interesting is also the fact that our calculations predict that the participation of a single water molecule results in the abstraction of the formyl hydrogen of formic acid through a hydrogen atom transfer process (hat).

  16. The role of hydrogen atoms in interactions involving imidazolium-based ionic liquids

    Science.gov (United States)

    Kempter, V.; Kirchner, B.

    2010-05-01

    In the first part of this report experimental results are discussed which focus onto the importance of hydrogen atoms in the interaction of imidazolium-based ionic liquids. These include examples for the cation-anion interaction in neat ionic liquids as well as the interactions between ionic liquids and their molecular environment, water in particular. Most of the studies emphasize the importance of the C(2)-H group of the imidazolium ring for the intra- and intermolecular interactions; commonly, the interactions of the type C-H … X (X =: O, halide) are attributed to "hydrogen bonding". In the second part it is analyzed whether these interactions and their consequences fulfill the criteria set by standard definitions of hydrogen bonding. Two cation-anion co-conformations at the C(2)-H group are found. One co-conformer (in-plane) often resembles a hydrogen bond while the other one (on-top) points to a non-hydrogen bonding behavior. Furthermore, the degree of hydrogen bonding for the in-plane structure is very dependent on the anion. Spatial distribution functions show that, in general, both co-conformations are occupied. However, the question of how long a particular co-conformer is populated in the liquid state has yet to be answered. Therefore, it is concluded that the term "hydrogen bond" should, at present, be treated with care to characterize the cation-anion contacts, because of the above-mentioned difficulties. Once more it must be stressed that oversimplifications and generalizations, even for this subclass of ionic liquids have to be avoided, because these liquids are more complicated than it appears from first sight.

  17. Rate coefficients for hydrogen abstraction reaction of pinonaldehyde C10H16O2 with Cl atoms between 200 and 400 K: A DFT study

    Indian Academy of Sciences (India)

    G SRINIVASULU; B RAJAKUMAR

    2016-06-01

    The kinetics of the reaction between pinonaldehyde C10H16O2 and Cl atom were studied usinghigh level ab initio G3(MP2) and DFT based MPWB1K/6-31+G(d) and MPW1K/6-31+G(d) levels of theoriescoupled with Conventional Transition State Theory in the temperature range between 200 and 400 K. Thenegative temperature dependent rate expression for the title reaction obtained with Wigner’s and Eckart’s symmetricaltunneling corrections are k(T)=(5.1 ± 0.56) × 10−19T2.35exp[(2098 ± 2)/T] cm3 molecule-1 s-1, and k(T)=(0.92 ± 0.18) × 10-19T2.60exp[(2204 ± 4)/T] cm3 molecule-1 s-1, respectively, at G3(MP2)//MPWB1Kmethod. The H abstraction reaction from the –CHO group was found to be the most dominant reaction channelamong all the possible reaction pathways and its corresponding rate coefficient at 300 K is kEckart’s unsymmetrical= 3.86 ×10-10 cm3 molecule-1 s-1. Whereas the channel with immediate lower activation energy is the H-abstraction from –CH- group (Tertiary H-abstraction site, Cg). The rate coefficient for this channel is kCg(Eckart’s unsymmetrical) = 1.83 ×10-15 cm3 molecule-1 s-1 which is smaller than the dominant channel byfive orders of magnitude. The atmospherically relevant parameters such as lifetimes were computed in thisinvestigation of its reaction with Cl atom.

  18. Enhanced Reactivity in Hydrogen Atom Transfer from Tertiary Sites of Cyclohexanes and Decalins via Strain Release: Equatorial C-H Activation vs Axial C-H Deactivation.

    Science.gov (United States)

    Salamone, Michela; Ortega, Vanesa B; Bietti, Massimo

    2015-05-01

    Absolute rate constants for hydrogen atom transfer (HAT) from cycloalkanes and decalins to the cumyloxyl radical (CumO(•)) were measured by laser flash photolysis. Very similar reactivities were observed for the C-H bonds of cyclopentane and cyclohexane, while the tertiary C-H bond of methylcyclopentane was found to be 6 times more reactive than the tertiary axial C-H bond of methylcyclohexane, pointing toward a certain extent of tertiary axial C-H bond deactivation. Comparison between the cis and trans isomers of 1,2-dimethylcyclohexane, 1,4-dimethylcyclohexane and decalin provides a quantitative evaluation of the role played by strain release in these reactions. kH values for HAT from tertiary equatorial C-H bonds were found to be at least 1 order of magnitude higher than those for HAT from the corresponding tertiary axial C-H bonds (kH(eq)/kH(ax) = 10-14). The higher reactivity of tertiary equatorial C-H bonds was explained in terms of 1,3-diaxial strain release in the HAT transition state. Increase in torsional strain in the HAT transition state accounts instead for tertiary axial C-H bond deactivation. The results are compared with those obtained for the corresponding C-H functionalization reactions by dioxiranes and nonheme metal-oxo species indicating that CumO(•) can represent a convenient model for the reactivity patterns of these oxidants.

  19. Hydrogen atom transfer from 1,n-alkanediamines to the cumyloxyl radical. Modulating C-H deactivation through acid-base interactions and solvent effects.

    Science.gov (United States)

    Milan, Michela; Salamone, Michela; Bietti, Massimo

    2014-06-20

    A time-resolved kinetic study on the effect of trifluoroacetic acid (TFA) on the hydrogen atom transfer (HAT) reactions from 1,n-alkanediamines (R2N(CH2)nNR2, R = H, CH3; n = 1-4), piperazine, and 1,4-dimethylpiperazine to the cumyloxyl radical (CumO(•)), has been carried out in MeCN and DMSO. Very strong deactivation of the α-C-H bonds has been observed following nitrogen protonation and the results obtained have been explained in terms of substrate basicity, of the distance between the two basic centers and of the solvent hydrogen bond acceptor ability. At [substrate] ≤ 1/2 [TFA] the substrates exist in the doubly protonated form HR2N(+)(CH2)nN(+)R2H, and no reaction with CumO(•) is observed. At 1/2 [TFA] [TFA], HAT occurs from the α-C-H bonds of R2N(CH2)nNR2, and the mesured kH values are very close to those obtained in the absence of TFA. Comparison between MeCN and DMSO clearly shows that in the monoprotonated diamines R2N(CH2)nN(+)R2H remote C-H deactivation can be modulated through solvent hydrogen bonding.

  20. Influence of the heterogeneous reaction HCl + HOCl on an ozone hole model with hydrocarbon additions

    Science.gov (United States)

    Elliott, Scott; Cicerone, Ralph J.; Turco, Richard P.; Drdla, Katja; Tabazadeh, Azadeh

    1994-02-01

    Injection of ethane or propane has been suggested as a means for reducing ozone loss within the Antarctic vortex because alkanes can convert active chlorine radicals into hydrochloric acid. In kinetic models of vortex chemistry including as heterogeneous processes only the hydrolysis and HCl reactions of ClONO2 and N2O5, parts per billion by volume levels of the light alkanes counteract ozone depletion by sequestering chlorine atoms. Introduction of the surface reaction of HCl with HOCl causes ethane to deepen baseline ozone holes and generally works to impede any mitigation by hydrocarbons. The increased depletion occurs because HCl + HOCl can be driven by HOx radicals released during organic oxidation. Following initial hydrogen abstraction by chlorine, alkane breakdown leads to a net hydrochloric acid activation as the remaining hydrogen atoms enter the photochemical system. Lowering the rate constant for reactions of organic peroxy radicals with ClO to 10-13 cm3 molecule-1 s-1 does not alter results, and the major conclusions are insensitive to the timing of the ethane additions. Ignoring the organic peroxy radical plus ClO reactions entirely restores remediation capabilities by allowing HOx removal independent of HCl. Remediation also returns if early evaporation of polar stratospheric clouds leaves hydrogen atoms trapped in aldehyde intermediates, but real ozone losses are small in such cases.

  1. HYDROGEN ATOM BOND INCREMENTS (HBI) FOR CALCULATION OF THERMODYNAMIC PROPERTIES OF HYDROCARBON RADICAL SPECIES. (R824970)

    Science.gov (United States)

    The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...

  2. HYDROGEN ATOM BOND INCREMENTS (HBI) FOR CALCULATION OF THERMODYNAMIC PROPERTIES OF HYDROCARBON RADICAL SPECIES. (R824970)

    Science.gov (United States)

    The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...

  3. A full-dimensional quantum dynamics study of the mode specificity in the H + HOD abstraction reaction

    Science.gov (United States)

    Fu, Bina; Zhang, Dong H.

    2015-02-01

    We employ the initial state-selected time-dependent wave packet approach to an atom-triatom reaction to study the H + HOD → OH + HD/OD + H2 reaction without the centrifugal sudden approximation, based on an accurate potential energy surface which was recently developed by neural network fitting to high level ab initio energy points. The total reaction probabilities and integral cross sections, which are the exact coupled-channel results, are calculated for the HOD reactant initially in the ground and several vibrationally excited states, including the bending excited state, OD stretching excited states, OH stretching excited states, and combined excitations of them. The reactivity enhancements from different initial states of HOD are presented, which feature strong bond-selective effects of the reaction dynamics. The current results for the product branching ratios, reactivity enhancements, and relative cross sections are largely improved over the previous calculations, in quantitatively good agreement with experiment. The thermal rate constant for the title reaction and the contributions from individual vibrational states of HOD are also obtained.

  4. An investigation of one- versus two-dimensional semiclassical transition state theory for H atom abstraction and exchange reactions

    Science.gov (United States)

    Greene, Samuel M.; Shan, Xiao; Clary, David C.

    2016-02-01

    We investigate which terms in Reduced-Dimensionality Semiclassical Transition State Theory (RD SCTST) contribute most significantly in rate constant calculations of hydrogen extraction and exchange reactions of hydrocarbons. We also investigate the importance of deep tunneling corrections to the theory. In addition, we introduce a novel formulation of the theory in Jacobi coordinates. For the reactions of H atoms with methane, ethane, and cyclopropane, we find that a one-dimensional (1-D) version of the theory without deep tunneling corrections compares well with 2-D SCTST results and accurate quantum scattering results. For the "heavy-light-heavy" H atom exchange reaction between CH3 and CH4, deep tunneling corrections are needed to yield 1-D results that compare well with 2-D results. The finding that accurate rate constants can be obtained from derivatives of the potential along only one dimension further validates RD SCTST as a computationally efficient yet accurate rate constant theory.

  5. Stimulated Raman scattering of an ultrashort XUV radiation pulse by a hydrogen atom

    Science.gov (United States)

    Dondera, Mihai; Florescu, Viorica; Bachau, Henri

    2017-02-01

    We consider the hydrogen atom H (1 s ) exposed to an ultrashort laser pulse with a central frequency ω0 ranging from several hundreds of eV to 1.5 keV (≈55 a.u.) and a peak intensity of 3.51 ×1016W /cm2 . We study the excitation of the atom by stimulated Raman scattering, a process involving pairs of frequencies (ω1,ω2 ). These frequencies are non-negligible components of the pulse Fourier transform and they satisfy the condition Eg+ℏ ω1=Eb+ℏ ω2,Eg and Eb≡En being the ground-state and the excited-state energy, respectively. The numerical results obtained by integrating the time-dependent Schrödinger equation (TDSE) are compared with calculations in lowest order perturbation theory (LOPT). In LOPT we consider, in the second order of PT, the contribution of the term A .P in the dipole approximation and, in first order of PT, the expression of A2 taken for first-order retardation effects. (A denotes the vector potential of the field and P is the momentum operator.) We focus on the Raman excitation of bound states with principal quantum numbers n up to n =13 . The evaluation in perturbation theory of the A .P contribution to 1 s -n s and 1 s -n d transition probabilities uses analytic expressions of the corresponding Kramers-Heisenberg matrix elements. At fixed pulse duration τ =6 π a.u. (≈0.48 fs), we find that the retardation effects play an important role at high frequencies: they progressively diminish as the frequency decreases until the contribution of A .P dominates over the A2 contribution for ω0 values of a few a.u. We also study the dependence of the Raman process on the pulse duration for several values of ω0. In the case ω0=13 a .u .(≈354 eV ) where dipole and nondipole contributions are of the same order of magnitude, we present the Raman excitation probability as a function of the pulse duration for excited n s ,n p , and n d states.

  6. Pronounced non-Arrhenius behaviour of hydrogen-abstractions from toluene and derivatives by phthalimide-N-oxyl radicals: a theoretical study.

    Science.gov (United States)

    Hermans, Ive; Jacobs, Pierre; Peeters, Jozef

    2008-02-28

    Abstraction of hydrogen atoms by pthalimide-N-oxyl radicals is an important step in the N-hydroxyphthalimide catalyzed autoxidation of hydrocarbons. In this contribution, the temperature dependency of this reaction is evaluated by a detailed transition state theory based kinetic analysis for the case of toluene. Tunneling was found to play a very important role, enhancing the rate constant by a factor of 20 at room temperature. As a result, tunneling, in combination with the existence of two distinct rotamers of the transition state, causes a pronounced temperature dependency of the pre-exponential frequency factor, and, as a consequence, marked curvature of the Arrhenius plot. This explains why earlier experimental studies over a limited temperature range around 300 K found formal Arrhenius activation energies and pre-factors that are 4 kcal mol(-1) and three orders of magnitude smaller than the actual energy barrier and the corresponding frequency factor, respectively. Also as a consequence of tunneling, substitution of a deuterium atom for a hydrogen atom causes a large decrease in the rate constant, in agreement with the measured kinetic isotope effects. The present theoretical analysis, complementary to the experimental rate coefficient data, allows for a reliable prediction of the rate coefficient at higher temperatures, relevant for actual autoxidation processes.

  7. Ab initio based potential energy surface and kinetics study of the OH + NH3 hydrogen abstraction reaction.

    Science.gov (United States)

    Monge-Palacios, M; Rangel, C; Espinosa-Garcia, J

    2013-02-28

    A full-dimensional analytical potential energy surface (PES) for the OH + NH3 → H2O + NH2 gas-phase reaction was developed based exclusively on high-level ab initio calculations. This reaction presents a very complicated shape with wells along the reaction path. Using a wide spectrum of properties of the reactive system (equilibrium geometries, vibrational frequencies, and relative energies of the stationary points, topology of the reaction path, and points on the reaction swath) as reference, the resulting analytical PES reproduces reasonably well the input ab initio information obtained at the coupled-cluster single double triple (CCSD(T)) = FULL/aug-cc-pVTZ//CCSD(T) = FC/cc-pVTZ single point level, which represents a severe test of the new surface. As a first application, on this analytical PES we perform an extensive kinetics study using variational transition-state theory with semiclassical transmission coefficients over a wide temperature range, 200-2000 K. The forward rate constants reproduce the experimental measurements, while the reverse ones are slightly underestimated. However, the detailed analysis of the experimental equilibrium constants (from which the reverse rate constants are obtained) permits us to conclude that the experimental reverse rate constants must be re-evaluated. Another severe test of the new surface is the analysis of the kinetic isotope effects (KIEs), which were not included in the fitting procedure. The KIEs reproduce the values obtained from ab initio calculations in the common temperature range, although unfortunately no experimental information is available for comparison.

  8. Differential steric effects in Cl reactions with aligned CHD3(v1 = 1) by the R(0) and Q(1) transitions. II. Abstracting the unexcited D-atoms

    Science.gov (United States)

    Wang, Fengyan; Liu, Kopin

    2016-10-01

    A complete set of four polarization-dependent differential cross sections in the reactions of Cl + aligned-CHD 3 ( v 1 = 1 , |" separators=" jK > ) → DCl ( v = 0 ) + CHD 2 ( v 1 = 1 ) is reported here for two different, rotationally polarized states with j = 1: specifically the |" separators=" jK > = |" separators=" 10 > state prepared via the R(0) excitation and the |" separators=" 1 ± 1 > state via Q(1). In stark contrast to the complicated situation of the HCl(v) + CD3(v = 0) channel reported in Paper-I, the stereo-requirement of this isotopic channel for both polarized reactants appears quite straightforward and consistent with a direct rebound mechanism. The extent of steric effects is moderate and relatively smaller than the alternative H-atom abstraction channel. All major findings reported here can qualitatively be understood by first noting that the present reaction invokes abstracting a D-atom, which is the spectator in the IR-excitation process. Next, it is recognized that the directional properties of two polarized states of CHD 3 ( v 1 = 1 , |" separators=" jK > ) should manifest primarily in the IR-excited C-H bond, leaving secondary imprints in the unexcited CD3-moiety. The stereo-specificity of the DCl + CHD2 product channel is further reduced by the fact that the abstraction can occur with any one of the three spatially distinct D-atoms.

  9. Complex mechanism of the gas phase reaction between formic acid and hydroxyl radical. Proton coupled electron transfer versus radical hydrogen abstraction mechanisms.

    Science.gov (United States)

    Anglada, Josep M

    2004-08-11

    The gas phase reaction between formic acid and hydroxyl radical has been investigated with high level quantum mechanical calculations using DFT-B3LYP, MP2, CASSCF, QCISD, and CCSD(T) theoretical approaches in connection with the 6-311+G(2df,2p) and aug-cc-pVTZ basis sets. The reaction has a very complex mechanism involving several elementary processes, which begin with the formation of a reactant complex before the hydrogen abstraction by hydroxyl radical. The results obtained in this investigation explain the unexpected experimental fact that hydroxyl radical extracts predominantly the acidic hydrogen of formic acid. This is due to a mechanism involving a proton coupled electron-transfer process. The calculations show also that the abstraction of formyl hydrogen has an increased contribution at higher temperatures, which is due to a conventional hydrogen abstraction radical type mechanism. The overall rate constant computed at 298 K is 6.24 x 10(-13) cm3 molecules(-1) s(-1), and compares quite well with the range from 3.2 +/- 1 to 4.9 +/- 1.2 x 10(-13) cm3 molecules(-1) s(-1), reported experimentally.

  10. Effects of the interaction between the magnetic moments of the proton and electron on the energy states of hydrogen atom

    CERN Document Server

    Dolocan, Voicu

    2014-01-01

    We make a comparison between the energy levels of the hydrogen atom, calculated by using standard methods, and that by using a modified Coulomb potential due to the interaction between the magnetic moments of the proton and electron. In this later method we use to ways. One is that in which we solve the Schroedinger equation with the modified Coulomb potential and some constraint conditions. The other is that in which we expand the modified Coulomb potential in Taylor series. The obtained results show that the first way gives a better agreement with experimental data.

  11. Metal-Free Hydrogen Atom Transfer from Water: Expeditious Hydrogenation of N-Heterocycles Mediated by Diboronic Acid.

    Science.gov (United States)

    Xia, Yun-Tao; Sun, Xiao-Tao; Zhang, Ling; Luo, Kai; Wu, Lei

    2016-11-21

    A hydrogenation of N-heterocycles mediated by diboronic acid with water as the hydrogen atom source is reported. A variety of N-heterocycles can be hydrogenated with medium to excellent yields within 10 min. Complete deuterium incorporation from stoichiometric D2 O onto substrates further exemplifies the H/D atom sources. Mechanism studies reveal that the reduction proceeds with initial 1,2-addition, in which diboronic acid synergistically activates substrates and water via a six-membered ring transition state.

  12. Energy spectrum of the hydrogen atom in a space with one compactified extra dimension, R3 ×S1

    Science.gov (United States)

    Bureš, Martin

    2015-12-01

    We investigate the consequences of one extra compactified dimension for the energy spectrum of the non-relativistic hydrogen atom with a potential defined by Gauss' law, i.e. proportional to 1 /| x | 2 in non-compactified 4d space. The calculations were performed numerically by diagonalizing the Hamiltonian in two different sets of basis vectors. The energy levels and electron probability density are plotted as a function of the compactification radius. The occurrence of several physical effects is discussed and interpreted.

  13. Toroidal configuration of the orbit of the electron of the hydrogen atom under strong external magnetic fields

    OpenAIRE

    Aringazin, A. K.

    2002-01-01

    In this paper we overview some results on the hydrogen atom in external static uniform magnetic fields. We focus on the case of very strong magnetic field, B>>B_0=2.3x10^9 Gauss, use various approximate models and, particularly, in the adiabatic approximation have calculated exactly the integral defining the effective potential. This potential appears to be finite at z=0. Our consideration of the problem of highly magnetized atoms and molecules is motivated by the recently developed MagneGas ...

  14. Collisions of electrons with hydrogen atoms I. Package outline and high energy code

    Science.gov (United States)

    Benda, Jakub; Houfek, Karel

    2014-11-01

    Being motivated by the applied researchers’ persisting need for accurate scattering data for the collisions of electrons with hydrogen atoms, we developed a computer package-Hex-that is designed to provide trustworthy results for all basic discrete and continuous processes within non-relativistic framework. The package consists of several computational modules that implement different methods, valid for specific energy regimes. Results of the modules are kept in a common database in the unified form of low-level scattering data (partial-wave T-matrices) and accessed by an interface program which is able to produce various derived quantities like e.g. differential and integral cross sections. This article is the first one of a series of articles that are concerned with the implementation and testing of the modules. Here we give an overview of their structure and present (a) the command-line interface program hex-db that can be also easily compiled into a derived code or used as a backend for a web-page form and (b) simple illustrative module specialized for high energies, hex-dwba, that implements distorted and plane wave Born approximation. Catalogue identifier: AETH_v1_0 Program summary URL:http://cpc.cs.qub.ac.uk/summaries/AETH_v1_0.html Program obtainable from: CPC Program library, Queen’s University, Belfast, N. Ireland Licensing provisions: Standard CPC licence, http://cpc.cs.qub.ac.uk/licence/licence.html No. of lines in distributed program, including test data etc.: 30367 No. of bytes in distributed program, including test data etc.: 232032 Distribution format: tar.gz Programming language: C++11 Operating system: Any system with a C++11 compiler (e.g. GCC 4.8.1; tested on OpenSUSE 13.1 and Windows 8). RAM: Test run 3 MiB. CPC Library Classification: 2.4 Electron scattering External libraries:GSL [49], FFTW3[52], SQLite3 [46]. All of the libraries are open-source and maintained. Nature of problem: Extraction of derived (observable) quantities from partial

  15. Excitation and charge transfer in low-energy hydrogen atom collisions with neutral atoms: Theory, comparisons, and application to Ca

    CERN Document Server

    Barklem, Paul S

    2016-01-01

    A theoretical method for the estimation of cross sections and rates for excitation and charge transfer processes in low-energy hydrogen atom collisions with neutral atoms, based on an asymptotic two-electron model of ionic-covalent interactions in the neutral atom-hydrogen atom system, is presented. The calculation of potentials and non-adiabatic radial couplings using the method is demonstrated. The potentials are used together with the multi-channel Landau-Zener model to calculate cross sections and rate coefficients. The main feature of the method is that it employs asymptotically exact atomic wavefunctions, which can be determined from known atomic parameters. The method is applied to Li+H, Na+H, and Mg+H collisions, and the results compare well with existing detailed full-quantum calculations. The method is applied to the astrophysically important problem of Ca+H collisions, and rate coefficients are calculated for temperatures in the range 1000-20000 K.

  16. Electrical and mechanical controlling of the kinetic and magnetic properties of hydrogen atoms on free-standing silicene

    Science.gov (United States)

    Podsiadły-Paszkowska, Agata; Krawiec, Mariusz

    2016-07-01

    Effects of strain, charge doping and external electric field on kinetic and magnetic properties of hydrogen atoms on a free-standing silicene layer are investigated by first-principles density functional theory. It was found that the charge doping and strain are the most effective ways of changing the hydrogen-silicene binding energy, but they can only raise its value. The perpendicular external electric field can also lower it albeit in a narrower range. The strain has also the strongest impact on diffusion processes, and the diffusion barrier can be modified up to 50% of its unstrained value. The adsorption of hydrogen atoms results in a locally antiferromagnetic ground state with the effective exchange constant of approximately 1 eV. The system can easily be driven into a nonmagnetic phase by the charge doping and strain. The obtained results are very promising in view of the silicene functionalization and potential applications of silicene in fields of modern nanoelectronics and spintronics.

  17. Inner hydrogen atom transfer in benzo-fused low symmetrical metal-free tetraazaporphyrin and phthalocyanine analogues: density functional theory studies.

    Science.gov (United States)

    Qi, Dongdong; Zhang, Yuexing; Cai, Xue; Jiang, Jianzhuang; Bai, Ming

    2009-02-01

    Density functional theory (DFT) calculations were carried out to study the inner hydrogen atom transfer in low symmetrical metal-free tetrapyrrole analogues ranging from tetraazaporphyrin H(2)TAP (A(0)B(0)C(0)D(0)) to naphthalocyanine H(2)Nc (A(2)B(2)C(2)D(2)) via phthalocyanine H(2)Pc (A(1)B(1)C(1)D(1)). All the transition paths of sixteen different compounds (A(0)B(0)C(0)D(0)-A(2)B(2)C(2)D(2) and A(0)B(0)C(m)D(n), m rings onto the TAP skeleton have significant effect on the potential energy barrier of the inner hydrogen atom transfer. Introducing fused benzene rings onto the hydrogen-releasing pyrrole rings can increase the transitivity of inner hydrogen atom and thus lower the transfer barrier of this inner hydrogen atom while fusing benzene rings onto the hydrogen-accepting pyrrole rings will increase the hydrogen transfer barrier to this pyrrole ring. The transient cis-isomer intermediate with hydrogen atoms joined to the two adjacent pyrrole rings with less fused benzene rings is much stable than the others. It is also found that the benzene rings fused directly onto pyrrole rings have more effect on the inner hydrogen atom transfer than the outer benzene rings fused onto the periphery of isoindole rings. The present work, representing the first effort towards systematically understanding the effect of ring enlargement through asymmetrical peripheral fusion of benzene ring(s) onto the TAP skeleton on the inner hydrogen transfer of tetrapyrrole derivatives, will be helpful in clarifying the N-H tautomerization phenomenon and detecting the cis-porphyrin isomer in bio-systems.

  18. Theoretical study of H-abstraction reactions from CH3Cl and CH3Br molecules by ClO and BrO radicals.

    Science.gov (United States)

    Canneaux, Sébastien; Hammaecher, Catherine; Cours, Thibaud; Louis, Florent; Ribaucour, Marc

    2012-05-03

    The rate constants of the H-abstraction reactions from CH(3)Cl and CH(3)Br molecules by ClO and BrO radicals have been estimated over the temperature range of 300-2500 K using four different levels of theory. Calculations of optimized geometrical parameters and vibrational frequencies are performed using B3LYP and MP2 methods combined with the cc-pVTZ basis set. Single-point energy calculations have been carried out with the highly correlated ab initio coupled cluster method in the space of single, double, and triple (perturbatively) electron excitations CCSD(T) using the cc-pVTZ and cc-pVQZ basis sets. Canonical transition-state theory combined with an Eckart tunneling correction has been used to predict the rate constants as a function of temperature. In order to choose the appropriate levels of theory with chlorine- and bromine-containing species, the reference reaction Cl ((2)P(3/2)) + CH(3)Cl → HCl + CH(2)Cl (R(ref)) was first theoretically studied because its kinetic parameters are well-established from numerous experiments, evaluation data, and theoretical studies. The kinetic parameters of the reaction R(ref) have been determined accurately using the CCSD(T)/cc-pVQZ//MP2/cc-pVTZ level of theory. This level of theory has been used for the rate constant estimation of the reactions ClO + CH(3)Cl (R(1)), ClO + CH(3)Br (R(2)), BrO + CH(3)Cl (R(3)), and BrO + CH(3)Br (R(4)). Six-parameter Arrhenius expressions have been obtained by fitting to the computed rate constants of these four reactions (including cis and trans pathways) over the temperature range of 300-2500 K.

  19. Hydride, hydrogen, proton, and electron affinities of imines and their reaction intermediates in acetonitrile and construction of thermodynamic characteristic graphs (TCGs) of imines as a "molecule ID card".

    Science.gov (United States)

    Zhu, Xiao-Qing; Liu, Qiao-Yun; Chen, Qiang; Mei, Lian-Rui

    2010-02-01

    A series of 61 imines with various typical structures were synthesized, and the thermodynamic affinities (defined as enthalpy changes or redox potentials in this work) of the imines to abstract hydride anions, hydrogen atoms, and electrons, the thermodynamic affinities of the radical anions of the imines to abstract hydrogen atoms and protons, and the thermodynamic affinities of the hydrogen adducts of the imines to abstract electrons in acetonitrile were determined by using titration calorimetry and electrochemical methods. The pure heterolytic and homolytic dissociation energies of the C=N pi-bond in the imines were estimated. The polarity of the C=N double bond in the imines was examined using a linear free-energy relationship. The idea of a thermodynamic characteristic graph (TCG) of imines as an efficient "Molecule ID Card" was introduced. The TCG can be used to quantitatively diagnose and predict the characteristic chemical properties of imines and their various reaction intermediates as well as the reduction mechanism of the imines. The information disclosed in this work could not only supply a gap of thermodynamics for the chemistry of imines but also strongly promote the fast development of the applications of imines.

  20. Van der Waals interaction between microparticle and uniaxial crystal with application to hydrogen atoms and multiwall carbon nanotubes

    CERN Document Server

    Blagov, E V; Mostepanenko, V M

    2005-01-01

    The Lifshitz theory of the van der Waals force is extended for the case of an atom (molecule) interacting with a plane surface of an uniaxial crystal or with a long solid cylinder or cylindrical shell made of isotropic material or uniaxial crystal. For a microparticle near a semispace or flat plate made of an uniaxial crystal the exact expressions for the free energy of the van der Waals and Casimir-Polder interaction are presented. An approximate expression for the free energy of microparticle- cylinder interaction is obtained which becomes precise for microparticle-cylinder separations much smaller than cylinder radius. The obtained expressions are used to investigate the van der Waals interaction between hydrogen atoms (molecules) and graphite plates or multiwall carbon nanotubes. To accomplish this the behavior of graphite dielectric permittivities along the imaginary frequency axis is found using the optical data for the complex refractive index of graphite for the ordinary and extraordinary rays. It is ...

  1. The gravitational analogue to the hydrogen atom (A summer study at the borders of quantum mechanics and general relativity)

    CERN Document Server

    Kober, M; Koch, B; Bleicher, Marcus; Kober, Martin; Koch, Ben

    2007-01-01

    This article reports on a student summer project performed in 2006 at the University of Frankfurt. It is addressed to undergraduate students familiar with the basic principles of relativistic quantum mechanics and general relativity. The aim of the project was to study the Dirac equation in curved space time. To obtain the general relativistic Dirac equation we use the formulation of gravity as a gauge theory in the first part. After these general considerations we restrict the further discussion to the special case of the Schwarzschild metric. This setting corresponds to the hydrogen atom, with the electromagnetic field replaced by gravity. Although there is a singularity at the event horizon it turns out that a regular solution of the time independent Dirac equation exists. Finally the Dirac equation is solved numerically using suitable boundary conditions.

  2. Complete classification of qualitatively different perturbations of the hydrogen atom in weak near-orthogonal electric and magnetic fields

    Energy Technology Data Exchange (ETDEWEB)

    Efstathiou, K; Lukina, O V [Department of Mathematics, University of Groningen, Groningen 9700 AK (Netherlands); SadovskiI, D A [Departement de physique, Universite du Littoral, 59140 Dunkerque (France)], E-mail: K.Efstathiou@rug.nl, E-mail: O.Lukina@math.rug.nl, E-mail: sadovski@univ-littoral.fr

    2009-02-06

    We consider perturbations of the hydrogen atom by sufficiently small homogeneous static electric and magnetic fields in near-orthogonal configurations. Normalization of the Keplerian symmetry reveals that in the parameter space such systems belong in a 'zone' of systems close to the 1:1 resonance, the latter corresponding to the exactly orthogonal configuration. Integrable approximations obtained from second normalization of systems in the 1:1 zone are classified into several different qualitative types, many of which possess nontrivial monodromy. We compute monodromy of the complete three-dimensional energy-momentum map, compare the joint quantum spectrum to classical bifurcation diagrams, and show the effect of second normalization to the joint spectrum.

  3. Extracting Closed Classical Orbits from Quantum Recurrence Spectra of a Non-Hydrogenic Atom in Parallel Electric and Magnetic Fields

    Institute of Scientific and Technical Information of China (English)

    WANG De-Hua; LIN Sheng-Lu

    2004-01-01

    @@ We show how to extract the closed orbits from the quantum spectra data. According to the closed orbit theory,each closed orbit produces a sharp peak in the recurrence spectra of a non-hydrogenic atom in parallel electric and magnetic fields. For a given initial state, closed-orbit theory gives the dependence of this recurrence amplitude on the initial angle of an orbit. By comparing the recurrence amplitude for different initial states, we can determine the initial angles of the closed classical orbits from the quantum recurrence spectra. Therefore, by integrating the Hamiltonian motion equations, we can obtain the closed orbits directly. This method can also be used to extract the closed orbits from the experimental data.

  4. Kinetics study of the CN + CH4 hydrogen abstraction reaction based on a new ab initio analytical full-dimensional potential energy surface.

    Science.gov (United States)

    Espinosa-Garcia, Joaquin; Rangel, Cipriano; Suleimanov, Yury V

    2017-07-26

    We have developed an analytical full-dimensional potential energy surface, named PES-2017, for the gas-phase hydrogen abstraction reaction between the cyano radical and methane. This surface is fitted using high-level ab initio information as input. Using the PES-2017 surface, a kinetics study was performed via two theoretical approaches: variational transition-state theory with multidimensional tunnelling (VTST-MT) and ring polymer molecular dynamics (RPMD). The results are compared with the experimental data. In the whole temperature range analysed, 300-1500 K, both theories agree within a factor of kinetic isotope effects are important, reproducing the scarce experimental evidence. The good agreement with the ab initio information used in the fitting process (self-consistency test) and with the kinetic behaviour in a wide temperature range gives confidence and strength to the new surface.

  5. Accurate ab initio potential energy surface, thermochemistry, and dynamics of the F(-) + CH3F SN2 and proton-abstraction reactions.

    Science.gov (United States)

    Szabó, István; Telekes, Hajnalka; Czakó, Gábor

    2015-06-28

    We develop a full-dimensional global analytical potential energy surface (PES) for the F(-) + CH3F reaction by fitting about 50 000 energy points obtained by an explicitly correlated composite method based on the second-order Møller-Plesset perturbation-F12 and coupled-cluster singles, doubles, and perturbative triples-F12a methods and the cc-pVnZ-F12 [n = D, T] basis sets. The PES accurately describes the (a) back-side attack Walden inversion mechanism involving the pre- and post-reaction (b) ion-dipole and (c) hydrogen-bonded complexes, the configuration-retaining (d) front-side attack and (e) double-inversion substitution pathways, as well as (f) the proton-abstraction channel. The benchmark quality relative energies of all the important stationary points are computed using the focal-point analysis (FPA) approach considering electron correlation up to coupled-cluster singles, doubles, triples, and perturbative quadruples method, extrapolation to the complete basis set limit, core-valence correlation, and scalar relativistic effects. The FPA classical(adiabatic) barrier heights of (a), (d), and (e) are -0.45(-0.61), 46.07(45.16), and 29.18(26.07) kcal mol(-1), respectively, the dissociation energies of (b) and (c) are 13.81(13.56) and 13.73(13.52) kcal mol(-1), respectively, and the endothermicity of (f) is 42.54(38.11) kcal mol(-1). Quasiclassical trajectory computations of cross sections, scattering (θ) and initial attack (α) angle distributions, as well as translational and internal energy distributions are performed for the F(-) + CH3F(v = 0) reaction using the new PES. Apart from low collision energies (Ecoll), the SN2 excitation function is nearly constant, the abstraction cross sections rapidly increase with Ecoll from a threshold of ∼40 kcal mol(-1), and retention trajectories via double inversion are found above Ecoll = ∼ 30 kcal mol(-1), and at Ecoll = ∼ 50 kcal mol(-1), the front-side attack cross sections start to increase very rapidly. At

  6. Accurate ab initio potential energy surface, thermochemistry, and dynamics of the F- + CH3F SN2 and proton-abstraction reactions

    Science.gov (United States)

    Szabó, István; Telekes, Hajnalka; Czakó, Gábor

    2015-06-01

    We develop a full-dimensional global analytical potential energy surface (PES) for the F- + CH3F reaction by fitting about 50 000 energy points obtained by an explicitly correlated composite method based on the second-order Møller-Plesset perturbation-F12 and coupled-cluster singles, doubles, and perturbative triples-F12a methods and the cc-pVnZ-F12 [n = D, T] basis sets. The PES accurately describes the (a) back-side attack Walden inversion mechanism involving the pre- and post-reaction (b) ion-dipole and (c) hydrogen-bonded complexes, the configuration-retaining (d) front-side attack and (e) double-inversion substitution pathways, as well as (f) the proton-abstraction channel. The benchmark quality relative energies of all the important stationary points are computed using the focal-point analysis (FPA) approach considering electron correlation up to coupled-cluster singles, doubles, triples, and perturbative quadruples method, extrapolation to the complete basis set limit, core-valence correlation, and scalar relativistic effects. The FPA classical(adiabatic) barrier heights of (a), (d), and (e) are -0.45(-0.61), 46.07(45.16), and 29.18(26.07) kcal mol-1, respectively, the dissociation energies of (b) and (c) are 13.81(13.56) and 13.73(13.52) kcal mol-1, respectively, and the endothermicity of (f) is 42.54(38.11) kcal mol-1. Quasiclassical trajectory computations of cross sections, scattering (θ) and initial attack (α) angle distributions, as well as translational and internal energy distributions are performed for the F- + CH3F(v = 0) reaction using the new PES. Apart from low collision energies (Ecoll), the SN2 excitation function is nearly constant, the abstraction cross sections rapidly increase with Ecoll from a threshold of ˜40 kcal mol-1, and retention trajectories via double inversion are found above Ecoll = ˜ 30 kcal mol-1, and at Ecoll = ˜ 50 kcal mol-1, the front-side attack cross sections start to increase very rapidly. At low Ecoll, the

  7. Electronic Origins of the Variable Efficiency of Room-Temperature Methane Activation by Homo- and Heteronuclear Cluster Oxide Cations [XYO2](+) (X, Y = Al, Si, Mg): Competition between Proton-Coupled Electron Transfer and Hydrogen-Atom Transfer.

    Science.gov (United States)

    Li, Jilai; Zhou, Shaodong; Zhang, Jun; Schlangen, Maria; Weiske, Thomas; Usharani, Dandamudi; Shaik, Sason; Schwarz, Helmut

    2016-06-29

    The reactivity of the homo- and heteronuclear oxide clusters [XYO2](+) (X, Y = Al, Si, Mg) toward methane was studied using Fourier transform ion cyclotron resonance mass spectrometry, in conjunction with high-level quantum mechanical calculations. The most reactive cluster by both experiment and theory is [Al2O2](•+). In its favorable pathway, this cluster abstracts a hydrogen atom by means of proton-coupled electron transfer (PCET) instead of following the conventional hydrogen-atom transfer (HAT) route. This mechanistic choice originates in the strong Lewis acidity of the aluminum site of [Al2O2](•+), which cleaves the C-H bond heterolytically to form an Al-CH3 entity, while the proton is transferred to the bridging oxygen atom of the cluster ion. In addition, a comparison of the reactivity of heteronuclear and homonuclear oxide clusters [XYO2](+) (X, Y = Al, Si, Mg) reveals a striking doping effect by aluminum. Thus, the vacant s-p hybrid orbital on Al acts as an acceptor of the electron pair from methyl anion (CH3(-)) and is therefore eminently important for bringing about thermal methane activation by PCET. For the Al-doped cluster ions, the spin density at an oxygen atom, which is crucial for the HAT mechanism, acts here as a spectator during the course of the PCET mediated C-H bond cleavage. A diagnostic plot of the deformation energy vis-à-vis the barrier shows the different HAT/PCET reactivity map for the entire series. This is a strong connection to the recently discussed mechanism of oxidative coupling of methane on magnesium oxide surfaces proceeding through Grignard-type intermediates.

  8. Methane Formation by Flame-Generated Hydrogen Atoms in the Flame Ionization Detector

    DEFF Research Database (Denmark)

    Holm, Torkil; Madsen, Jørgen Øgaard

    1996-01-01

    The precombustion degradation of organic compounds in the flame ionization detector has been studied (1) by heating the additives in hydrogen in a quartz capillary and analyzing the reaction products by GC and (2) by following the degradation of the additives in a hydrogen flame, by means of a th...

  9. New experimental results on the interference of the states of the hydrogen atom due to long-range interaction with the metal surface

    NARCIS (Netherlands)

    Kucheryaev, YA; Pal'chikov, VG; Pchelin, YA; Sokolov, YL; Yakovlev, VP

    2005-01-01

    The interference of the 2P state of the hydrogen atom due to unknown long-range interaction with the metal surface (Sokolov effect) has been studied by an atomic interferometer. In contrast to previous experiments, where an atomic beam passed through slits in metal plates, a beam in the presented ex

  10. Porphyrin Cobalt(III) "Nitrene Radical" Reactivity; Hydrogen Atom Transfer from Ortho-YH Substituents to the Nitrene Moiety of Cobalt-Bound Aryl Nitrene Intermediates (Y = O, NH).

    Science.gov (United States)

    Goswami, Monalisa; Rebreyend, Christophe; de Bruin, Bas

    2016-02-20

    In the field of cobalt(II) porphyrin-catalyzed metallo-radical reactions, organic azides have emerged as successful nitrene transfer reagents. In the pursuit of employing ortho-YH substituted (Y = O, NH) aryl azides in Co(II) porphyrin-catalyzed nitrene transfer reactions, unexpected hydrogen atom transfer (HAT) from the OH or NH₂ group in the ortho-position to the nitrene moiety of the key radical-intermediate was observed. This leads to formation of reactive ortho-iminoquinonoid (Y = O) and phenylene diimine (Y = NH) species. These intermediates convert to subsequent products in non-catalyzed reactions, as is typical for these free organic compounds. As such, the observed reactions prevent the anticipated cobalt-mediated catalytic radical-type coupling of the nitrene radical intermediates to alkynes or alkenes. Nonetheless, the observed reactions provide valuable insights into the reactivity of transition metal nitrene-radical intermediates, and give access to ortho-iminoquinonoid and phenylene diimine intermediates from ortho-YH substituted aryl azides in a catalytic manner. The latter can be employed as intermediates in one-pot catalytic transformations. From the ortho-hydroxy aryl azide substrates both phenoxizinones and benzoxazines could be synthesized in high yields. From the ortho-amino aryl azide substrates azabenzene compounds were obtained as the main products. Computational studies support these observations, and reveal that HAT from the neighboring OH and NH₂ moiety to the nitrene radical moiety has a low energy barrier.

  11. A computational study on the adsorption configurations and reactions of SiHx(x = 1-4) on clean and H-covered Si(100) surfaces

    Science.gov (United States)

    Le, Thong N.-M.; Raghunath, P.; Huynh, Lam K.; Lin, M. C.

    2016-11-01

    Possible adsorption configurations of H and SiHx (x = 1 - 4) on clean and H-covered Si(100) surfaces are determined by using spin-polarized DFT calculations. The results show that, on the clean surface, the gas-phase hydrogen atom and SiH3 radicals effectively adsorb on the top sites, while SiH and SiH2 prefer the bridge sites of the first layer. Another possibility for SiH is to reside on the hollow sites with a triple-bond configuration. For a partially H-coverd Si(100) surface, the mechanism is similar but with higher adsorption energies in most cases. This suggests that the surface species become more stable in the presence of surface hydrogens. The minimum energy paths for the adsorption/migration and reactions of H/SiHx species on the surfaces are explored using the climbing image-nudged elastic band method. The competitive surface processes for Si thin-film formation from SiHx precursors are also predicted. The study reveals that the migration of hydrogen adatom is unimportant with respect to leaving open surface sites because of its high barriers (>29.0 kcal/mol). Alternatively, the abstraction of hydrogen adatoms by H/SiHx radicals is more favorable. Moreover, the removal of hydrogen atoms from adsorbed SiHx, an essential step for forming Si layers, is dominated by abstraction rather than the decomposition processes.

  12. Selected Abstracts

    Institute of Scientific and Technical Information of China (English)

    2012-01-01

    The Three - Stage Interaction Model of Lexicon - Syntax Interface Liu Yuhong (80) The Three -Stage Interaction Model maintains that the interactions at the lexicon -syntax interface are divisible into three levels, namely, the interaction between lexical meaning and lexical grammar that determines syntactic items, the interaction among lexical items that determines syntactic structure, and the interaction between abstract syntactic structure (i. e. construction) and temporary syntactic combinations that determines and coerces grammaticality of the latter. The Three - Stage Interaction Model is hierarchical, complete and bidirectional in language comprehension. It also testifies to the varying abstractness between grammar (syntax) and semantics, and between the five grammatical cases. According to this model, temporary syntactic combination is sanctioned by abstract syntactic structure, therefore the conventional linguistic significance of P600 is maintained without coining contradictory new terms.

  13. H-atom addition and abstraction reactions in mixed CO, H2CO and CH3OH ices: an extended view on complex organic molecule formation

    CERN Document Server

    Chuang, K -J; Ioppolo, S; van Dishoeck, E F; Linnartz, H

    2016-01-01

    Complex organic molecules (COMs) have been observed not only in the hot cores surrounding low- and high- mass protostars, but also in cold dark clouds. Therefore, it is interesting to understand how such species can be formed without the presence of embedded energy sources. We present new laboratory experiments on the low-temperature solid state formation of three complex molecules: methyl formate (HC(O)OCH3), glycolaldehyde (HC(O)CH2OH) and ethylene glycol (H2C(OH)CH2OH), through recombination of free radicals formed via H-atom addition and abstraction reactions at different stages in the CO-H2CO-CH3OH hydrogenation network at 15 K. The experiments extend previous CO hydrogenation studies and aim at resembling the physical&chemical conditions typical of the CO freeze-out stage in dark molecular clouds, when H2CO and CH3OH form by recombination of accreting CO molecules and H-atoms on ice grains. We confirm that H2CO, once formed through CO hydrogenation, not only yields CH3OH through ongoing H-atom addit...

  14. Abstract algebra

    CERN Document Server

    Garrett, Paul B

    2007-01-01

    Designed for an advanced undergraduate- or graduate-level course, Abstract Algebra provides an example-oriented, less heavily symbolic approach to abstract algebra. The text emphasizes specifics such as basic number theory, polynomials, finite fields, as well as linear and multilinear algebra. This classroom-tested, how-to manual takes a more narrative approach than the stiff formalism of many other textbooks, presenting coherent storylines to convey crucial ideas in a student-friendly, accessible manner. An unusual feature of the text is the systematic characterization of objects by universal

  15. Formation of Cu, Ag and Au nanofiims under the influence of hydrogen atoms

    Directory of Open Access Journals (Sweden)

    Zhavzharov E. L.

    2015-12-01

    Full Text Available Due to their electrical properties, thin metallic films are widely used in modern micro- and nanoelectronics. These properties allow solving fundamental problems of surface and solid state physics. Up-to-date methods of producing thin films involve high vacuum or multi-stage processes, which calls for complicated equipment. The authors propose an alternative method of producing thin metallic films using atomic hydrogen. Exothermal reaction of atoms recombination in a molecule (about 4.5 eV / recombination act initiated on the solid surface by atomic hydrogen may stimulate local heating, spraying and surface atoms transfer. We investigated the process of atomic hydrogen treatment of Cu, Ag and Au metal films, obtained by thermal vacuum evaporation. There are two methods of obtaining nanofilms using atomic hydrogen treatment: sputtering and vapor-phase epitaxy. In the first method, a film is formed by reducing the thickness of the starting film. This method allows obtaining a film as thick as the monolayer. In the second method, a nanofilm is formed by deposition of metal atoms from the vapor phase. This method allows obtaining a film thickness from monolayer to ~10 nm. These methods allow creating nanofilms with controlled parameters and metal thickness. Such films would be technologically pure and have good adhesion.

  16. Influence of Steric Hindrance Between Hydrogen Atoms of Linkage Groups and Adjacent Phenyls on Properties of Polyimide

    Institute of Scientific and Technical Information of China (English)

    PANG Yu-wei; LUO Long-bo; CHEN Yi; ZHANG Peng; WANG Xu; PENG Chao-rong; LIU Xiang-yang

    2012-01-01

    A diamine monomer 4,4'-methylenedianiline(MDA) was introduced to modify the polyimide of pyromellitic dianhydride(PMDA) and 4,4'-oxydianiline(ODA) by polycondensation.A series of polyamic acids was synthesized from MDA and ODA of different molar ratios with PMDA of sum mole of moles of MDA and ODA,and polyimide films were obtained by thermal imidization.Polyimide(PI) films were characterized by tensile testing,dynamic mechanical analysis(DMA),thermal gravimetry analysis(TGA),Fourier transform infrared spectroscopy (FTIR),wide X-ray diffraction(WAXD) and molecular simulation.With the increase of MDA content,the tensile strength and thermal decomposition temperature remained generally stable compared with those of PMDA/ODA polyimide.Unexpectedly,the glass transition temperature(Tg) and Young's modulus increased from 388.7 ℃ and 2.37 GPa to 408.3 ℃ and 5.74 GPa,respectively.The results of WAXD and molecular simulation indicate the steric hindrance among hydrogen atoms of the linkage groups and adjacent phenyls enhanced the properties of the polyimide modified with MDA.

  17. Effect of the coupling channel on the excitation of hydrogenic atoms by the impact of protons and antiprotons

    Science.gov (United States)

    Tantawi, Reda S.

    2014-02-01

    Excitation of hydrogenic atoms H, He+ and Li++ initially in the 2p excited state to the n = 3 states by impact of protons and antiprotons is studied using the single-center atomic orbital close-coupling formalism in its impact parameter approach. The calculations cover the incident energy range from 1 to 1000 keV, in which the straight-line trajectory description of nuclear motion is applicable and the inertial confinement plasma research is of main interest. The influences of couplings between the n = 2 states, as well as the back coupling to the 2p initial state, on the excitation processes are investigated. Including the back couplings is found to be more important in the case of proton scattering than in the case of antiproton, and neglecting couplings between the n = 2 states is found to increase the effect of the sign of the projectile's charge. The calculated cross sections for the H atom are compared with those obtained by previous theoretical calculations.

  18. Long-range interactions of hydrogen atoms in excited states. II. Hyperfine-resolved (2 S -2 S ) systems

    Science.gov (United States)

    Jentschura, U. D.; Debierre, V.; Adhikari, C. M.; Matveev, A.; Kolachevsky, N.

    2017-02-01

    The interaction of two excited hydrogen atoms in metastable states constitutes a theoretically interesting problem because of the quasidegenerate 2 P1 /2 levels that are removed from the 2 S states only by the Lamb shift. The total Hamiltonian of the system is composed of the van der Waals Hamiltonian, the Lamb shift, and the hyperfine effects. The van der Waals shift becomes commensurate with the 2 S -2 P3 /2 fine-structure splitting only for close approach (R Hamiltonian matrix a priori is of dimension 64. A careful analysis of the symmetries of the the problem allows one to reduce the dimensionality of the most involved irreducible submatrix to 12. We determine the Hamiltonian matrices and the leading-order van der Waals shifts for states that are degenerate under the action of the unperturbed Hamiltonian (Lamb shift plus hyperfine structure). The leading first- and second-order van der Waals shifts lead to interaction energies proportional to 1 /R3 and 1 /R6 and are evaluated within the hyperfine manifolds. When both atoms are metastable 2 S states, we find an interaction energy of order Ehχ (a0/R ) 6 , where Eh and L are the Hartree and Lamb shift energies, respectively, and χ =Eh/L ≈6.22 ×106 is their ratio.

  19. Fine Control over Site and Substrate Selectivity in Hydrogen Atom Transfer-Based Functionalization of Aliphatic C-H Bonds.

    Science.gov (United States)

    Salamone, Michela; Carboni, Giulia; Bietti, Massimo

    2016-10-07

    The selective functionalization of unactivated aliphatic C-H bonds over intrinsically more reactive ones represents an ongoing challenge of synthetic chemistry. Here we show that in hydrogen atom transfer (HAT) from the aliphatic C-H bonds of alkane, ether, alcohol, amide, and amine substrates to the cumyloxyl radical (CumO(•)) fine control over site and substrate selectivity is achieved by means of acid-base interactions. Protonation of the amines and metal ion binding to amines and amides strongly deactivates the C-H bonds of these substrates toward HAT to CumO(•), providing a powerful method for selective functionalization of unactivated or intrinsically less reactive C-H bonds. With 5-amino-1-pentanol, site-selectivity has been drastically changed through protonation of the strongly activating NH2 group, with HAT that shifts to the C-H bonds that are adjacent to the OH group. In the intermolecular selectivity studies, trifluoroacetic acid, Mg(ClO4)2, and LiClO4 have been employed in a orthogonal fashion for selective functionalization of alkane, ether, alcohol, and amide (or amine) substrates in the presence of an amine (or amide) one. Ca(ClO4)2, that promotes deactivation of amines and amides by Ca(2+) binding, offers, moreover, the opportunity to selectively functionalize the C-H bonds of alkane, ether, and alcohol substrates in the presence of both amines and amides.

  20. Observation and Interpretation of Energetic Neutral Hydrogen Atoms from the December 5, 2006 Solar Event

    Science.gov (United States)

    Mewaldt, R. A.; Leske, R. A.; Stone, E. C.; Barghouty, A. F.; Shih, A. Y.; von Rosenvinge, T. T.; Labrador, A. W.; Cohen, C. M. S.; Cummings, A. C.; Cummings, A. C.

    2009-01-01

    We report the first observations of energetic neutral atoms (ENAs) from a solar flare/coronal mass ejection event. The observations were made during the December 5, 2006 X9 solar flare, located at E79, by the Low Energy Telescopes (LETs) on the STEREO A and B spacecraft. Within 1-2 hours of the flare onset, both LETs observed a sudden burst of 1.6 to 15 MeV protons arriving hours before the onset of the main solar energetic particle (SEP) event at Earth. More than 70% of these particles arrived from a longitude within +-10 degrees of the Sun. The derived emission profile at the Sun lasted for more than an hour and had a profile remarkably similar to the GOES soft X-ray profile. The observed arrival directions and energy spectrum argue strongly that the particle events atoms that were stripped of their electrons upon entering the LET sensor. To our knowledge, this is the first reported observation of ENA emission from a solar flare/coronal mass ejection. We discuss possible origins for the production of ENAs in solar events, including charge-transfer reactions involving both flare and shock-accelerated protons. Assuming isotropic emission, we find that 2 x 10E28 ENAs escaped from the Sun in the upper hemisphere. Based on the 2.2 MeV gamma-ray emission observed by RHESSI in this event, and using measured and theoretical cross sections, we estimate that 3 x 10E31 ENAs with 1.8 - 5 MeV could be produced by protons accelerated in the flare. CME-driven shock acceleration is also a possible ENA source, but unfortunately there were no CME observations available from this event. Taking into account ENA losses, we conclude that the observed ENAs were most likely produced in the high corona at heliocentric distances 1.6 solar radii.

  1. *H atom and *OH radical reactions with 5-methylcytosine.

    Science.gov (United States)

    Grand, A; Morell, C; Labet, V; Cadet, J; Eriksson, L A

    2007-09-20

    The reactions between either a hydrogen atom or a hydroxyl radical and 5-methylcytosine (5-MeCyt) are studied by using the hybrid kinetic energy meta-GGA functional MPW1B95. *H atom and *OH radical addition to positions C5 and C6 of 5-MeCyt, or *OH radical induced H-abstraction from the C5 methyl group, are explored. All systems are optimized in bulk solvent. The data presented show that the barriers to reaction are very low: ca. 7 kcal/mol for the *H atom additions and 1 kcal/mol for the reactions involving the *OH radical. Thermodynamically, the two C6 radical adducts and the *H-abstraction product are the most stable ones. The proton hyperfine coupling constants (HFCC), computed at the IEFPCM/MPW1B95/6-311++G(2d,2p) level, agree well with B3LYP results and available experimental and theoretical data on related thymine and cytosine radicals.

  2. MAIN ABSTRACTS

    Institute of Scientific and Technical Information of China (English)

    2011-01-01

    Ideological Critique of Marx and Philosophical Transformation This paper addresses a tendency today that tries to reinterpret the Marxist transformation in philosophy with a "non-ideological" perspective. It explicates the leap that Marx achieved from abstract human spirit and state reason to the proletariat world view, as well as the overall withdrawal from the abstract universalism. Such a leap and withdrawal is not only the key to the materialistic inversion of the Hegelian dialectics, but also the foundation for sticking to and enriching the Marxist philosophy. Without sticking to this direction, we will not be able to clearly understand Marxism as the successor and promoter of the magnificent cultural achievements of mankind, including the enlightenment thoughts and classical German philosophy, nor will we fully understand the value and strength of Marxist philosophy today.

  3. Tuning reactivity and selectivity in hydrogen atom transfer from aliphatic C-H bonds to alkoxyl radicals: role of structural and medium effects.

    Science.gov (United States)

    Salamone, Michela; Bietti, Massimo

    2015-11-17

    Hydrogen atom transfer (HAT) is a fundamental reaction that takes part in a wide variety of chemical and biological processes, with relevant examples that include the action of antioxidants, damage to biomolecules and polymers, and enzymatic and biomimetic reactions. Moreover, great attention is currently devoted to the selective functionalization of unactivated aliphatic C-H bonds, where HAT based procedures have been shown to play an important role. In this Account, we describe the results of our recent studies on the role of structural and medium effects on HAT from aliphatic C-H bonds to the cumyloxyl radical (CumO(•)). Quantitative information on the reactivity and selectivity patterns observed in these reactions has been obtained by time-resolved kinetic studies, providing a deeper understanding of the factors that govern HAT from carbon and leading to the definition of useful guidelines for the activation or deactivation of aliphatic C-H bonds toward HAT. In keeping with the electrophilic character of alkoxyl radicals, polar effects can play an important role in the reactions of CumO(•). Electron-rich C-H bonds are activated whereas those that are α to electron withdrawing groups are deactivated toward HAT, with these effects being able to override the thermodynamic preference for HAT from the weakest C-H bond. Stereoelectronic effects can also influence the reactivity of the C-H bonds of ethers, amines, and amides. HAT is most rapid when these bonds can be eclipsed with a lone pair on an adjacent heteroatom or with the π-system of an amide functionality, thus allowing for optimal orbital overlap. In HAT from cyclohexane derivatives, tertiary axial C-H bond deactivation and tertiary equatorial C-H bond activation have been observed. These effects have been explained on the basis of an increase in torsional strain or a release in 1,3-diaxial strain in the HAT transition states, with kH(eq)/kH(ax) ratios that have been shown to exceed one order of

  4. Spectroscopic determination of highly nonequilibrium velocity spectra of hydrogen atoms in H{sub 2} + Ne, Ar, Kr hollow-cathode discharges

    Energy Technology Data Exchange (ETDEWEB)

    Lavrov, B.P.; Mel`nikov, A.S. [St. Petersburg State Univ., Peterhof (Russian Federation)

    1995-12-01

    Energy distribution functions of excited (into the state with principal quantum number n = 3) and normal hydrogen atoms in plasma of a hollow-cathode discharge in an H{sub 2} + Ar mixture are determined in the range of 0-120 eV from Doppler profiles of spectral lines of the Balmer series. The distribution functions are found to be substantially nonequilibrium. The analysis of spectral profiles of H{sub {alpha}}lines in plasma of a high-volt-age hollow-cathode discharge in pure hydrogen shows that a part of the high-velocity excited hydrogen atoms is formed through charge exchange of negative H{sup {minus}} ions. Estimates show that the concentration of high-velocity H{sup {minus}} ions does not exceed several percent of the concentration of positive ions and increases with hydrogen pressure. Estimates of relative cross sections for excitation of hydrogen atoms to levels with n = 3, 4, and 5 in collisions of H atorns with H{sub 2} molecules are made. 18 refs., 3 figs., 1 tab.

  5. Intermolecula transfer and elimination of molecular hydrogen in thermal reactions of unsaturated organic compounds

    Energy Technology Data Exchange (ETDEWEB)

    Suria, Sabartanty [Iowa State Univ., Ames, IA (United States)

    1995-02-10

    Two reactions which are important to coal liquefaction include intermolecular transfer and the elimination of two hydrogen atoms. We have designed several model reactions to probe the viability of several hydrogen transfer and elimination pathways. This report described studies on these reactions using organic model compounds.

  6. Inventory Abstraction

    Energy Technology Data Exchange (ETDEWEB)

    C. Leigh

    2000-11-03

    The purpose of the inventory abstraction as directed by the development plan (CRWMS M&O 1999b) is to: (1) Interpret the results of a series of relative dose calculations (CRWMS M&O 1999c, 1999d). (2) Recommend, including a basis thereof, a set of radionuclides that should be modeled in the Total System Performance Assessment in Support of the Site Recommendation (TSPA-SR) and the Total System Performance Assessment in Support of the Final Environmental Impact Statement (TSPA-FEIS). (3) Provide initial radionuclide inventories for the TSPA-SR and TSPA-FEIS models. (4) Answer the U.S. Nuclear Regulatory Commission (NRC)'s Issue Resolution Status Report ''Key Technical Issue: Container Life and Source Term'' (CLST IRSR) (NRC 1999) key technical issue (KTI): ''The rate at which radionuclides in SNF [Spent Nuclear Fuel] are released from the EBS [Engineered Barrier System] through the oxidation and dissolution of spent fuel'' (Subissue 3). The scope of the radionuclide screening analysis encompasses the period from 100 years to 10,000 years after the potential repository at Yucca Mountain is sealed for scenarios involving the breach of a waste package and subsequent degradation of the waste form as required for the TSPA-SR calculations. By extending the time period considered to one million years after repository closure, recommendations are made for the TSPA-FEIS. The waste forms included in the inventory abstraction are Commercial Spent Nuclear Fuel (CSNF), DOE Spent Nuclear Fuel (DSNF), High-Level Waste (HLW), naval Spent Nuclear Fuel (SNF), and U.S. Department of Energy (DOE) plutonium waste. The intended use of this analysis is in TSPA-SR and TSPA-FEIS. Based on the recommendations made here, models for release, transport, and possibly exposure will be developed for the isotopes that would be the highest contributors to the dose given a release to the accessible environment. The inventory abstraction is important in

  7. INVENTORY ABSTRACTION

    Energy Technology Data Exchange (ETDEWEB)

    G. Ragan

    2001-12-19

    The purpose of the inventory abstraction, which has been prepared in accordance with a technical work plan (CRWMS M&O 2000e for ICN 02 of the present analysis, and BSC 2001e for ICN 03 of the present analysis), is to: (1) Interpret the results of a series of relative dose calculations (CRWMS M&O 2000c, 2000f). (2) Recommend, including a basis thereof, a set of radionuclides that should be modeled in the Total System Performance Assessment in Support of the Site Recommendation (TSPA-SR) and the Total System Performance Assessment in Support of the Final Environmental Impact Statement (TSPA-FEIS). (3) Provide initial radionuclide inventories for the TSPA-SR and TSPA-FEIS models. (4) Answer the U.S. Nuclear Regulatory Commission (NRC)'s Issue Resolution Status Report ''Key Technical Issue: Container Life and Source Term'' (CLST IRSR) key technical issue (KTI): ''The rate at which radionuclides in SNF [spent nuclear fuel] are released from the EBS [engineered barrier system] through the oxidation and dissolution of spent fuel'' (NRC 1999, Subissue 3). The scope of the radionuclide screening analysis encompasses the period from 100 years to 10,000 years after the potential repository at Yucca Mountain is sealed for scenarios involving the breach of a waste package and subsequent degradation of the waste form as required for the TSPA-SR calculations. By extending the time period considered to one million years after repository closure, recommendations are made for the TSPA-FEIS. The waste forms included in the inventory abstraction are Commercial Spent Nuclear Fuel (CSNF), DOE Spent Nuclear Fuel (DSNF), High-Level Waste (HLW), naval Spent Nuclear Fuel (SNF), and U.S. Department of Energy (DOE) plutonium waste. The intended use of this analysis is in TSPA-SR and TSPA-FEIS. Based on the recommendations made here, models for release, transport, and possibly exposure will be developed for the isotopes that would be the highest

  8. Kinetic Study of the Aroxyl-Radical-Scavenging Activity of Five Fatty Acid Esters and Six Carotenoids in Toluene Solution: Structure-Activity Relationship for the Hydrogen Abstraction Reaction.

    Science.gov (United States)

    Mukai, Kazuo; Yoshimoto, Maya; Ishikura, Masaharu; Nagaoka, Shin-Ichi

    2017-08-17

    A kinetic study of the reaction between an aroxyl radical (ArO(•)) and fatty acid esters (LHs 1-5, ethyl stearate 1, ethyl oleate 2, ethyl linoleate 3, ethyl linolenate 4, and ethyl arachidonate 5) has been undertaken. The second-order rate constants (ks) for the reaction of ArO(•) with LHs 1-5 in toluene at 25.0 °C have been determined spectrophotometrically. The ks values obtained increased in the order of LH 1 hydrogen abstraction reaction. A similar kinetic study was performed for the reaction of ArO(•) with six carotenoids (Car-Hs 1-6, astaxanthin 1, β-carotene 2, lycopene 3, capsanthin 4, zeaxanthin 5, and lutein 6). The ks values obtained increased in the order of Car-H 1 Car-H 6 was 8.4 × 10(-4) M(-1) s(-1). The ks values obtained for Car-Hs 1-6 are in the same order as that of the values for LHs 1-5. The results of detailed analyses of the ks values for the above reaction indicated that the reaction was also explained by an allylic hydrogen abstraction reaction. Furthermore, the structure-activity relationship for the reaction was discussed by taking the result of density functional theory calculation reported by Martinez and Barbosa into account.

  9. Evaluated kinetics of terminal and non-terminal addition of hydrogen atoms to 1-alkenes: a shock tube study of H + 1-butene.

    Science.gov (United States)

    Manion, Jeffrey A; Awan, Iftikhar A

    2015-01-22

    Single-pulse shock tube methods have been used to thermally generate hydrogen atoms and investigate the kinetics of their addition reactions with 1-butene at temperatures of 880 to 1120 K and pressures of 145 to 245 kPa. Rate parameters for the unimolecular decomposition of 1-butene are also reported. Addition of H atoms to the π bond of 1-butene results in displacement of either methyl or ethyl depending on whether addition occurs at the terminal or nonterminal position. Postshock monitoring of the initial alkene products has been used to determine the relative and absolute reaction rates. Absolute rate constants have been derived relative to the reference reaction of displacement of methyl from 1,3,5-trimethylbenzene (135TMB). With k(H + 135TMB → m-xylene + CH3) = 6.7 × 10(13) exp(-3255/T) cm(3) mol(-1) s(-1), we find the following: k(H + 1-butene → propene + CH3) = k10 = 3.93 × 10(13) exp(-1152 K/T) cm(3) mol(-1) s(-1), [880-1120 K; 145-245 kPa]; k(H + 1-butene → ethene + C2H5) = k11 = 3.44 × 10(13) exp(-1971 K/T) cm(3) mol(-1) s(-1), [971-1120 K; 145-245 kPa]; k10/k11 = 10((0.058±0.059)) exp [(818 ± 141) K/T), 971-1120 K. Uncertainties (2σ) in the absolute rate constants are about a factor of 1.5, while the relative rate constants should be accurate to within ±15%. The displacement rate constants are shown to be very close to the high pressure limiting rate constants for addition of H, and the present measurements are the first direct determination of the branching ratio for 1-olefins at high temperatures. At 1000 K, addition to the terminal site is favored over the nonterminal position by a factor of 2.59 ± 0.39, where the uncertainty is 2σ and includes possible systematic errors. Combining the present results with evaluated data from the literature pertaining to temperatures of <440 K leads us to recommend the following: k∞(H + 1-butene → 2-butyl) = 1.05 × 10(9)T(1.40) exp(-366/T) cm(3) mol(-1) s(-1), [220-2000 K]; k∞(H + 1-butene → 1

  10. Selected Abstracts

    Institute of Scientific and Technical Information of China (English)

    2012-01-01

    The Elasticity of Vague Language Abstract:This paper develops an overarching theoretical framework for dealing with the strategic elastic- ity of vague language. Employing the metaphor of a slingshot, it describes how the vague language (VL) is stretched to meet the needs of communication. Drawing attention to the positive and effective role played by VL, the study further looks into how the VL theory is derived from real - life data of ten- sion -prone encounters. The empirical evidence validates the theory~ main maxim and its four specific maxims, and lends support to the following findings: 1 ) the pragmatic functions which VL performs, their linguistic realizations, and the pragmatic maxims they conform to are interconnected; 2) the dom- inant factor in the functioning of VL is the communicative goal; and 3 ) stretching on a continuum of polarities, between soft and tough, firm and flexible, cooperative and uncooperative, shows the versa- tility and elasticity of VL. An important implication of this study is that while VL~ vagueness is context -governed and culture- denendent it~ nll A ~1.o~;.;~.. ; :

  11. TR-ESR Investigation on Reaction of Vitamin C with Excited Triplet of 9,10-phenanthrenequinone in Reversed Micelle Solutions

    Science.gov (United States)

    Xu, Xin-sheng; Shi, Lei; Liu, Yi; Ji, Xue-han; Cui, Zhi-feng

    2011-04-01

    Time-resolved electron spin resonance has been used to study quenching reactions between the antioxidant Vitamin C (VC) and the triplet excited states of 9,10-phenanthrenequinone (PAQ) in ethylene glycol-water (EG-H2O) homogeneous and inhomogeneous reversed micelle solutions. Reversed micelle solutions were used to be the models of physiological environment of biological cell and tissue. In PAQ/EG-H2O homogeneous solution, the excited triplet of PAQ (3PAQ*) abstracts hydrogen atom from solvent EG. In PAQ/VC/EG-H2O solution, 3PAQ* abstracts hydrogen atom not only from solvent EG but also from VC. The quenching rate constant of 3PAQ* by VC is close to the diffusion-controlled value of 1.41 × 108 L/(mol ·s). In hexadecyltrimethylammonium bromide (CTAB)/EG-H2O and aerosol OT (AOT)/EG-H2O reversed micelle solutions, 3PAQ* and VC react around the water-oil interface of the reversed micelle. Exit of 3PAQ* from the lipid phase slows down the quenching reaction. For Triton X-100 (TX-100)/EG-H2O reversed micelle solution, PAQ and VC coexist inside the hydrophilic polyethylene glycol core, and the quenching rate constant of 3PAQ* by VC is larger than those in AOT/EG-H2O and CTAB/EG-H2O reversed micelle solutions, even a little larger than that in EG-H2O homogeneous solution. The strong emissive chemically induced dynamic electron polarization of As.- resulted from the effective TM spin polarization transfer in hydrogen abstraction of 3PAQ* from VC.

  12. Binding to Redox-Inactive Alkali and Alkaline Earth Metal Ions Strongly Deactivates the C-H Bonds of Tertiary Amides toward Hydrogen Atom Transfer to Reactive Oxygen Centered Radicals.

    Science.gov (United States)

    Salamone, Michela; Carboni, Giulia; Mangiacapra, Livia; Bietti, Massimo

    2015-09-18

    The effect of alkali and alkaline earth metal ions on the reactions of the cumyloxyl radical (CumO(•)) with N,N-dimethylformamide (DMF) and N,N-dimethylacetamide (DMA) was studied by laser flash photolysis. In acetonitrile, a >2 order of magnitude decrease in the rate constant for hydrogen atom transfer (HAT) from the C-H bonds of these substrates (kH) was measured after addition of Li(+). This behavior was explained in terms of a strong interaction between Li(+) and the oxygen atom of both DMF and DMA that increases the extent of positive charge on the amide, leading to C-H bond deactivation toward HAT to the electrophilic radical CumO(•). Similar effects were observed after addition of Ca(2+), which was shown to strongly bind up to four equivalents of the amide substrates. With Mg(2+), weak C-H deactivation was observed for the first two substrate equivalents followed by stronger deactivation for two additional equivalents. No C-H deactivation was observed in DMSO after addition of Li(+) and Mg(2+). These results point toward the important role played by metal ion Lewis acidity and solvent Lewis basicity, indicating that C-H deactivation can be modulated by varying the nature of the metal cation and solvent and allowing for careful control over the HAT reactivity of amide substrates.

  13. Lowest Landau excited states of a hydrogen atom in magnetic fields up to 4.7 X 10 to the 12th gauss

    Science.gov (United States)

    Chu, M.-C.; Friedrich, H.

    1983-12-01

    Autoionization widths and energies of the lowest-lying Landau excited states of a hydrogen atom in strong magnetic fields are calculated for azimuthal quantum numbers /m/ = 0, 1, and 2. For fields ranging from below 10 to the 9th G, where these states lie close to the ionization threshold, up to 4.7 x 10 to the 12th G, the width of the lowest autoionizing state in each m subspace is, to within the accuracy of the calculation, inversely proportional to the fourth root of the field strength. A comparison with radiative widths is made.

  14. Electronic processes near kinematic threshold for grazing scattering of fast hydrogen atoms from a LiF(0 0 1) surface

    CERN Document Server

    Lederer, S; Winter, H; Aumayr, F; Winter, H P; Staemmler, V

    2003-01-01

    In coincident studies on projectile energy loss and number distributions of emitted electrons for scattering of hydrogen atoms from an atomically clean and flat LiF(0 0 1) surface we derive probabilities for emission of electrons and production of surface excitons near their respective kinematic thresholds. We analyze our data in terms of electron transfer in binary atomic collisions with one collision partner being embedded at the anion site of an ionic crystal and derive information on the energy defects in these collisions.

  15. Energy spectrum of the hydrogen atom in a space with one compactified extra dimension, $\\mathbb{R}^3 \\times S^1$

    CERN Document Server

    Bureš, Martin

    2015-01-01

    We investigate the consequences of one extra compactified dimension for the energy spectrum of the non-relativistic hydrogen atom with a potential defined by Gauss' law, i.e. proportional to $1/|x|^2$ in non-compactified 4d space. The calculations were performed numerically by diagonalizing the Hamiltonian in two different sets of basis vectors. The energy levels and electron probability density are plotted as a function of the compactification radius. The occurrence of several physical effects is discussed and interpreted.

  16. Triple differential cross-sections for the ionization of metastable 2P-state hydrogen atoms by electrons with exchange effects

    Indian Academy of Sciences (India)

    SUNIL DHAR; NURUN NAHAR

    2016-11-01

    In this paper, triple differential cross-sections for the ionization of metastable 2P-state hydrogen atoms by 250 eV electron energy with exchange effects for various kinematic conditions are calculated. Multiple scattering theory proposed by Das and Seal in {\\it Phys. Rev.} A 47, 2978 (1993) is utilized here. The computational results provide significant peak features that show good qualitative agreement with the hydrogenic ground-state experimental data and theoretical results and the present first Born results. In addition, physical origin of the peaks of the cross-section curves is investigated.

  17. High-level direct-dynamics variational transition state theory calculations including multidimensional tunneling of the thermal rate constants, branching ratios, and kinetic isotope effects of the hydrogen abstraction reactions from methanol by atomic hydrogen.

    Science.gov (United States)

    Meana-Pañeda, Rubén; Truhlar, Donald G; Fernández-Ramos, Antonio

    2011-03-07

    We report a detailed theoretical study of the hydrogen abstraction reaction from methanol by atomic hydrogen. The study includes the analysis of thermal rate constants, branching ratios, and kinetic isotope effects. Specifically, we have performed high-level computations at the MC3BB level together with direct dynamics calculations by canonical variational transition state theory (CVT) with the microcanonically optimized multidimensional tunneling (μOMT) transmission coefficient (CVT/μOMT) to study both the CH(3)OH+H→CH(2)OH+H(2) (R1) reaction and the CH(3)OH+H→CH(3)O+H(2) (R2) reaction. The CVT/μOMT calculations show that reaction R1 dominates in the whole range 298≤T (K)≤2500 and that anharmonic effects on the torsional mode about the C-O bond are important, mainly at high temperatures. The activation energy for the total reaction sum of R1 and R2 reactions changes substantially with temperature and, therefore, the use of straight-line Arrhenius plots is not valid. We recommend the use of new expressions for the total R1 + R2 reaction and for the R1 and R2 individual reactions.

  18. A computational study on the adsorption configurations and reactions of SiH{sub x}(x = 1-4) on clean and H-covered Si(100) surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Le, Thong N-M [Molecular Science and Nano-Materials Laboratory, Institute for Computational Science and Technology, Quang Trung Software Park, Dist. 12, Ho Chi Minh City (Viet Nam); Raghunath, P. [Center for Interdisciplinary Molecular Science, Department of Applied Chemistry, National Chiao Tung University, Hsinchu 300, Taiwan (China); Huynh, Lam K., E-mail: lamhuynh.us@gmail.com [Department of Applied Chemistry, School of Biotechnology,International University, VNU-HCMC, Quarter 6, Linh Trung, Thu Duc District, Ho Chi Minh City (Viet Nam); Lin, M.C., E-mail: chemmcl@emory.edu [Center for Interdisciplinary Molecular Science, Department of Applied Chemistry, National Chiao Tung University, Hsinchu 300, Taiwan (China)

    2016-11-30

    Highlights: • Possible adsorption configurations of all adsorbates on Si(100) surface are systematically explored. • The mechanisms leading to the formation of silicon adatoms on the surface are proposed. • The barriers for hydrogen abstractions from the surface are negligible comparing to the barriers for the hydrogen migrations. • The barriers for hydrogen abstractions from the adsorbed speices are negligible comparing to the barriers for the decompositions. - Abstract: Possible adsorption configurations of H and SiH{sub x} (x = 1 − 4) on clean and H-covered Si(100) surfaces are determined by using spin-polarized DFT calculations. The results show that, on the clean surface, the gas-phase hydrogen atom and SiH{sub 3} radicals effectively adsorb on the top sites, while SiH and SiH{sub 2} prefer the bridge sites of the first layer. Another possibility for SiH is to reside on the hollow sites with a triple-bond configuration. For a partially H-coverd Si(100) surface, the mechanism is similar but with higher adsorption energies in most cases. This suggests that the surface species become more stable in the presence of surface hydrogens. The minimum energy paths for the adsorption/migration and reactions of H/SiH{sub x} species on the surfaces are explored using the climbing image-nudged elastic band method. The competitive surface processes for Si thin-film formation from SiH{sub x} precursors are also predicted. The study reveals that the migration of hydrogen adatom is unimportant with respect to leaving open surface sites because of its high barriers (>29.0 kcal/mol). Alternatively, the abstraction of hydrogen adatoms by H/SiH{sub x} radicals is more favorable. Moreover, the removal of hydrogen atoms from adsorbed SiH{sub x}, an essential step for forming Si layers, is dominated by abstraction rather than the decomposition processes.

  19. Ab initio study on the paths of oxygen abstraction of hydrogen trioxide (HO3) molecule in the HO3 + SO2 reaction

    Indian Academy of Sciences (India)

    R Bagherzadeh; Sattar Ebrahimi; Moein Goodarzi

    2013-07-01

    The reaction paths of hydrogen trioxide (HO3) with sulphur dioxide (SO2) have been investigated on the doublet potential energy surface, theoretically. All species of the title reaction have been optimized at the PMP2(FC)/cc-pVDZ computational level. Energetic data have been obtained at the CCSD(T)//PMP2 level employing the cc-pVDZ basis set. No stable collision complexes have been found between the SO2 and HO3 molecules. Therefore, the SO2 + HO3 reaction starts without initial associations. The four possible paths, P1 through P4, have been obtained for the formation of SO3 (D3h) + HOO$^{\\bullet}$ product. Our results show that these four paths include relatively high energy barriers to produce the final product of the SO3 (D3h) + HOO$^{\\bullet}$. Therefore, the SO2 + HO3 → SO3(D3h) + HOO$^{\\bullet}$ reaction is difficult to perform under atmospheric conditions. This means that the importance of SO2 + HO3 → SO3 (D3h) + HOO$^{\\bullet}$ reaction increases with increasing temperature and, this reaction plays an important role in the SO3(D3h) production as the main molecule of the formation of acid rain at high temperatures.

  20. Collisions of electrons with hydrogen atoms II. Low-energy program using the method of the exterior complex scaling

    Science.gov (United States)

    Benda, Jakub; Houfek, Karel

    2014-11-01

    While collisions of electrons with hydrogen atoms pose a well studied and in some sense closed problem, there is still no free computer code ready for “production use”, that would enable applied researchers to generate necessary data for arbitrary impact energies and scattering transitions directly if absent in on-line scattering databases. This is the second article on the Hex program package, which describes a new computer code that is, with a little setup, capable of solving the scattering equations for energies ranging from a fraction of the ionization threshold to approximately 100 eV or more, depending on the available computational resources. The program implements the exterior complex scaling method in the B-spline basis. Catalogue identifier: AETI_v1_0 Program summary URL:http://cpc.cs.qub.ac.uk/summaries/AETI_v1_0.html Program obtainable from: CPC Program Library, Queen’s University, Belfast, N. Ireland Licensing provisions: Standard CPC licence, http://cpc.cs.qub.ac.uk/licence/licence.html No. of lines in distributed program, including test data, etc.: 44 440 No. of bytes in distributed program, including test data, etc.: 322 643 Distribution format: tar.gz Programming language: C++11. Computer: Any. Operating system: Any system with a C++11 compiler (e.g. GCC 4.8.1; tested on OpenSUSE 13.1 and Windows 8). Has the code been vectorized or parallelized?: Parallelized by OpenMP and MPI. RAM: Depending on input; 4.9 GiB for the test run. Classification: 2.4. External routines: GSL [1], HDF5 [2], UMFPACK [3], FFTW3 [4], optionally with OpenBLAS [5]. Nature of problem: Solution of the two-particle Schrödinger equation in central field. Solution method: The two-electron states are expanded into angular momentum eigenstates, which gives rise to the coupled bi-radial equations. The bi-radially dependent solution is then represented in a B-spline basis, which transforms the set of equations into a large matrix equation in this basis. The boundary condition

  1. The influence hydrogen atom addition has on charge switching during motion of the metal atom in endohedral Ca@C60H4 isomers.

    Science.gov (United States)

    Raggi, G; Besley, E; Stace, A J

    2016-09-13

    Density functional theory has been applied in a study of charge transfer between an endohedral calcium atom and the fullerene cage in Ca@C60H4 and [Ca@C60H4](+) isomers. Previous calculations on Ca@C60 have shown that the motion of calcium within a fullerene is accompanied by large changes in electron density on the carbon cage. Based on this observation, it has been proposed that a tethered endohedral fullerene might form the bases of a nanoswitch. Through the addition of hydrogen atoms to one hemisphere of the cage it is shown that, when compared with Ca@C60, asymmetric and significantly reduced energy barriers can be generated with respect to motion of the calcium atom. It is proposed that hydrogen atom addition to a fullerene might offer a route for creating a bi-stable nanoswitch that can be fine-tuned through the selection of an appropriate isomer and number of atoms attached to the cage of an endohedral fullerene.This article is part of the themed issue 'Fullerenes: past, present and future, celebrating the 30th anniversary of Buckminster Fullerene'.

  2. A probable vacuum state containing a large number of hydrogen atom of excited state or ground state K, Rb or Cs atom

    CERN Document Server

    You, Pei-Lin

    2008-01-01

    The linear Stark effect shows that the first excited state of hydrogen atom has large permanent electric dipole moment (EDM), d(H)=3eao (ao is Bohr radius). Using special capacitors our experiments discovered that the ground state K, Rb or Cs atom is polar atom with a large EDM of the order of eao as hydrogen atom of excited state. Their capacitance(C) at different voltage (V) was measured. The C-V curve shows that the saturation polarization of K, Rb or Cs vapor has be observed when the field E more than ten to the fifth power V/m. When the saturation polarization appeared, nearly all K, Rb or Cs atoms(more than 98 percent) turned toward the direction of the field, and C is approximately equal to Co (Co is vacuum capacitance) or their dielectric constant is nearly the same as vacuum! K, Rb or Cs vapor just exist in the lowest energy state, so we see the vacuum state containing a large number of atoms! Due to the saturation polarization of hydrogen vapor of excited state is easily appears, we conjecture that ...

  3. H{sup .} atom and OH{sup .} radical reactions with 5-methyl-cytosine

    Energy Technology Data Exchange (ETDEWEB)

    Grand, A.; Morell, C.; Labet, V.; Cadet, J. [CEA Grenoble, Lab Les Acides Nucl, DRFMC/SCIB, UMR-E 3, CEA-UJF, F-38054 Grenoble, (France); Eriksson, L.A. [Univ Orebro, Dept Nat Sci and Orebro Life Sci Ctr, S-70182 Orebro, (Sweden)

    2007-07-01

    The reactions between either a hydrogen atom or a hydroxyl radical and 5-methyl-cytosine (5-MeCyt) are studied by using the hybrid kinetic energy meta-GGA functional MPW1B95. H{sup .} atom and OH{sup .} radical addition to positions C5 and C6 of 5-MeCyt, or OH{sup .} radical induced H-abstraction from the C5 methyl group, are explored. All systems are optimized in bulk solvent. The data presented show that the barriers to reaction are very low: ca. 7 kCal/mol for the H{sup .} atom additions and 1 kCal/mol for the reactions involving the OH{sup .} radical. Thermodynamically, the two C6 radical adducts and the H{sup .}- abstraction product are the most stable ones. The proton hyperfine coupling constants (HFCC), computed at the IEFPCM/MPW1B95/6-311++G(2d,2p) level, agree well with B3LYP results and available experimental and theoretical data on related thymine and cytosine radicals. (authors)

  4. Time-dependent wave packet state-to-state quantum dynamics study of the abstraction reaction S({sup 3}P) + H{sub 2}(v = 0, j = 0) on 1{sup 3}A″ electronic state

    Energy Technology Data Exchange (ETDEWEB)

    Wu, Hui [State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, University of Chinese Academy of Sciences, Dalian 116023 (China); Liang, Dongyue [Department of Modern Physics, University of Science and Technology of China, Hefei 230026 (China); Zhang, Pei-Yu, E-mail: pyzhang@dicp.ac.cn [State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, University of Chinese Academy of Sciences, Dalian 116023 (China)

    2015-05-12

    Highlights: • The reaction probabilities, characteristic ICS and DCS are presented. • The features of ICS and DCS are explained. • Different mechanisms relevant to several sets of J partial waves lead to the maxima in the DCS in the collision process. - Abstract: The state-to-state quantum dynamics of the abstraction channel of S({sup 3}P) + H{sub 2}(v = 0, j = 0) reaction is studied on the potential energy surface (PES) constructed by Lv et al. (2012), utilizing the product Jacobi coordinate based time-dependent wave packet method. Reaction probabilities and total integral cross section (ICS) agree well with previous results (Lv et al., 2012) for collision energies ranging from 0.8 to 1.4 eV. Results show that total differential cross sections (DCSs) for small collision energies have backward structures, whereas those for large collision energies are sideways peaked. Although the summed-over-all-final-state DCS for single collision energy is smoothly varied, the DCS of the product HS of a selected final state shows strong oscillations. For the selected final state, the opacity function derived by reaction probability multiplied by (2J + 1), shows that different mechanisms relevant to several sets of J partial waves lead to the maxima in the differential cross section in the collision process.

  5. An improved treatment of spectator mode vibrations in reduced dimensional quantum dynamics: application to the hydrogen abstraction reactions mu + CH4, H + CH4, D + CH4, and CH3 + CH4.

    Science.gov (United States)

    Banks, Simon T; Tautermann, Christofer S; Remmert, Sarah M; Clary, David C

    2009-07-28

    A method for projecting chemical reaction surface coordinates from a Hessian in curvilinear internal coordinates has recently been developed. Here we introduce a modification to this approach which allows for analytical evaluation of the necessary coordinate derivatives, thus reducing the number of ab initio calculations required. We apply this method to the determination of spectator mode frequencies and zero-point energies for the series of hydrogen abstraction reactions X + CH(4) --> XH + CH(3), X = muonium (mu), H, D, CH(3). Comparison of these frequencies with those obtained using rectilinear coordinates allows us to examine how the mass of X affects the coordinate sensitivity of the spectator modes. We carry out two-dimensional quantum reactive scattering calculations for these reactions to highlight instances where the choice of coordinates may have a significant impact on the evaluated thermal rate constants.

  6. Product spin-orbit state resolved dynamics of the H+H2O and H+D2O abstraction reactions.

    Science.gov (United States)

    Brouard, M; Burak, I; Marinakis, S; Rubio Lago, L; Tampkins, P; Vallance, C

    2004-12-01

    The product state-resolved dynamics of the reactions H+H(2)O/D(2)O-->OH/OD((2)Pi(Omega);v',N',f )+H(2)/HD have been explored at center-of-mass collision energies around 1.2, 1.4, and 2.5 eV. The experiments employ pulsed laser photolysis coupled with polarized Doppler-resolved laser induced fluorescence detection of the OH/OD radical products. The populations in the OH spin-orbit states at a collision energy of 1.2 eV have been determined for the H+H(2)O reaction, and for low rotational levels they are shown to deviate from the statistical limit. For the H+D(2)O reaction at the highest collision energy studied the OD((2)Pi(3/2),v'=0,N'=1,A') angular distributions show scattering over a wide range of angles with a preference towards the forward direction. The kinetic energy release distributions obtained at 2.5 eV also indicate that the HD coproducts are born with significantly more internal excitation than at 1.4 eV. The OD((2)Pi(3/2),v'=0,N'=1,A') angular and kinetic energy release distributions are almost identical to those of their spin-orbit excited OD((2)Pi(1/2),v'=0,N'=1,A') counterpart. The data are compared with previous experimental measurements at similar collision energies, and with the results of previously published quasiclassical trajectory and quantum mechanical calculations employing the most recently developed potential energy surface. Product OH/OD spin-orbit effects in the reaction are discussed with reference to simple models.

  7. An ab initio/Rice-Ramsperger-Kassel-Marcus study of the hydrogen-abstraction reactions of methyl ethers, H(3)COCH(3-x)(CH(3))(x), x = 0-2, by OH; mechanism and kinetics.

    Science.gov (United States)

    Zhou, Chong-Wen; Simmie, John M; Curran, Henry J

    2010-07-14

    A theoretical study of the mechanism and kinetics of the H-abstraction reaction from dimethyl (DME), ethylmethyl (EME) and iso-propylmethyl (IPME) ethers by the OH radical has been carried out using the high-level methods CCSD(T)/CBS, G3 and G3MP2BH&H. The computationally less-expensive methods of G3 and G3MP2BH&H yield results for DME within 0.2-0.6 and 0.7-0.9 kcal mol(-1), respectively, of the coupled cluster, CCSD(T), values extrapolated to the basis set limit. So the G3 and G3MP2BH&H methods can be confidently used for the reactions of the higher ethers. A distinction is made between the two different kinds of H-atoms, classified as in/out-of the symmetry plane, and it is found that abstraction from the out-of-plane H-atoms proceeds through a stepwise mechanism involving the formation of a reactant complex in the entrance channel and product complex in the exit channel. The in-plane H-atom abstractions take place through a more direct mechanism and are less competitive. Rate constants of the three reactions have been calculated in the temperature range of 500-3000 K using the Variflex code, based on the weak collision, master equation/microcanonical variational RRKM theory including tunneling corrections. The computed total rate constants (cm(3) mol(-1) s(-1)) have been fitted as follows: k(DME) = 2.74 xT(3.94) exp (1534.2/T), k(EME) = 20.93 xT(3.61) exp (2060.1/T) and k(IPME) = 0.55 xT(3.93) exp (2826.1/T). Expressions of the group rate constants for the three different carbon sites are also provided.

  8. NMR study of the FH⋯F hydrogen bond. Relation between hydrogen atom position and FH⋯F bond length

    Science.gov (United States)

    Panich, A. M.

    1995-07-01

    1H and 19F NMR study of (NH 4) 3BiBr 6NH 4Br·2NH 4HF 2 shows the bifluoride ion in this compound to be asymmetric with distances r( HF) = 1.042 ± 0.002 and R( FF) = 2.373 ± 0.008 Å. Existing NMR and neutron diffraction data for the FH⋯F hydrogen bond in solids have been studied to find a relation between the position of the hydrogen atom and FH⋯F bond length. Such a relation has been established and explained in the framework of the two-dimensional dynamic model of the hydrogen bond. The dependencies of r(AH) on R(AB) for the OH⋯O and FH⋯F bonds are shown to be similar.

  9. Fine splits of photon emission spectrum of hydrogen atom caused by transitions between different dressed states in intense high frequency laser field

    Institute of Scientific and Technical Information of China (English)

    Zhou Zhao-Yan; Yuan Jian-Min

    2008-01-01

    The photon emission spectrum of the hydrogen atoms in an intense high-frequency laser pulse is simulated by using one-dimensional soft Coulomb potential. Regular fine structures appear on the two sides of both the odd and even multiples of photon energy of the laser field besides the ordinary odd harmonic peaks. It is proved that the splits of the fine structures are responsible for hyper-Raman lines and the energy spacing between the odd harmonic lines is equal to the difference in energy between the eigenstates with the same parity of the time averaged Krameters-Henneberger (KH) potential. By analysing the features of the fine structures, we also verify that the so-called even order harmonics under the stabilization condition are indeed hyper-Raman lines caused by the transitions between the dressed atomic states with different values of parity.

  10. Development of a high dynamic range spectroscopic system for observation of neutral hydrogen atom density distribution in Large Helical Device core plasma

    Energy Technology Data Exchange (ETDEWEB)

    Fujii, K., E-mail: fujii@me.kyoto-u.ac.jp; Atsumi, S.; Watanabe, S.; Shikama, T.; Hasuo, M. [Department of Mechanical Engineering and Science, Graduate School of Engineering, Kyoto University, Kyoto 606-8540 (Japan); Goto, M.; Morita, S. [National Institute for Fusion Science, Toki 509-5292 (Japan)

    2014-02-15

    We report development of a high dynamic range spectroscopic system comprising a spectrometer with 30% throughput and a camera with a low-noise fast-readout complementary metal-oxide semiconductor sensor. The system achieves a 10{sup 6} dynamic range (∼20 bit resolution) and an instrumental function approximated by a Voigt profile with Gauss and Lorentz widths of 31 and 0.31 pm, respectively, for 656 nm light. The application of the system for line profile observations of the Balmer-α emissions from high temperature plasmas generated in the Large Helical Device is also presented. In the observed line profiles, emissions are detected in far wings more than 1.0 nm away from the line center, equivalent to neutral hydrogen atom kinetic energies above 1 keV. We evaluate atom density distributions in the core plasma by analyzing the line profiles.

  11. Energy partitioning in polyatomic chemical reactions: Quantum state resolved studies of highly exothermic atom abstraction reactions from molecules in the gas phase and at the gas-liquid interface

    Science.gov (United States)

    Zolot, Alexander M.

    This thesis recounts a series of experiments that interrogate the dynamics of elementary chemical reactions using quantum state resolved measurements of gas-phase products. The gas-phase reactions F + HCl → HF + Cl and F + H2O → HF + OH are studied using crossed supersonic jets under single collision conditions. Infrared (IR) laser absorption probes HF product with near shot-noise limited sensitivity and high resolution, capable of resolving rovibrational states and Doppler lineshapes. Both reactions yield inverted vibrational populations. For the HCl reaction, strongly bimodal rotational distributions are observed, suggesting microscopic branching of the reaction mechanism. Alternatively, such structure may result from a quantum-resonance mediated reaction similar to those found in the well-characterized F + HD system. For the H2O reaction, a small, but significant, branching into v = 2 is particularly remarkable because this manifold is accessible only via the additional center of mass collision energy in the crossed jets. Rotationally hyperthermal HF is also observed. Ab initio calculations of the transition state geometry suggest mechanisms for both rotational and vibrational excitation. Exothermic chemical reaction dynamics at the gas-liquid interface have been investigated by colliding a supersonic jet of F atoms with liquid squalane (C30H62), a low vapor pressure hydrocarbon compatible with the high vacuum environment. IR spectroscopy provides absolute HF( v,J) product densities and Doppler resolved velocity component distributions perpendicular to the surface normal. Compared to analogous gas-phase F + hydrocarbon reactions, the liquid surface is a more effective "heat sink," yet vibrationally excited populations reveal incomplete thermal accommodation with the surface. Non-Boltzmann J-state populations and hot Doppler lineshapes that broaden with HF excitation indicate two competing scattering mechanisms: (i) a direct reactive scattering channel

  12. Markovnikov free radical addition reactions, a sleeping beauty kissed to life.

    Science.gov (United States)

    Hoffmann, Reinhard W

    2016-02-01

    This review covers free radical additions, which are initiated by the formal addition of a hydrogen atom to a C[double bond, length as m-dash]C double bond. These reactions originated in the realms of inorganic chemistry, polymer chemistry, and organic chemistry, whereby barriers between these disciplines impeded the rapid implementation of the findings.

  13. TR-ESR Investigation on Reaction of Vitamin C with Excited Triplet of 9,10-phenanthrenequinone in Reversed Micelle Solutions%维生素C对菲醌三重激发态的淬灭机理及动力学研究

    Institute of Scientific and Technical Information of China (English)

    许新胜; 史蕾; 刘毅; 季学韩; 崔执凤

    2011-01-01

    Time-resolved electron spin resonance has been used to study quenching reactions between the antioxidant Vitamin C (VC) and the triplet excited states of 9,10-phenanthrenequinone (PAQ) in ethylene glycol-water (EG-H2O) homogeneous and inhomogeneous reversed micelle solutions. Reversed micelle solutions were used to be the models of physiological environment of biological cell and tissue. In PAQ/EG-H2O homogeneous solution, the excited triplet of PAQ (3PAQ*) abstracts hydrogen atom from solvent EG. In PAQ/VC/EG-H2O solution,3PAQ* abstracts hydrogen atom not only from solvent EG but also from VC. The quenching rate constant of 3PAQ* by VC is close to the diffusion-controlled value of 1.41 × 108 L/(mol.s).In hexadecyltrimethylammonium bromide (CTAB)/EG-H2O and aerosol OT (AOT)/EGH2O reversed micelle solutions; 3PAQ* and VC react around the water-oil interface of the reversed micelle. Exit of 3PAQ* from the lipid phase slows down the quenching reaction.For Triton X-100 (TX-100)/EG-H2O reversed micelle solution, PAQ and VC coexist inside the hydrophilic polyethylene glycol core, and the quenching rate constant of 3PAQ* by VC is larger than those in AOT/EG-H2O and CTAB/EG-H2O reversed micetle solutions, even a little larger than that in EG-H2O homogeneous solution. The strong emissive chemically induced dynamic electron polarization of As- resulted from the effective TM spin polarization transfer in hydrogen abstraction of 3PAQ* from VC.

  14. The su(1, 1) dynamical algebra from the Schroedinger ladder operators for N-dimensional systems: hydrogen atom, Mie-type potential, harmonic oscillator and pseudo-harmonic oscillator

    Energy Technology Data Exchange (ETDEWEB)

    Martinez, D [Universidad Autonoma de la Ciudad de Mexico, Plantel Cuautepec, Av. La Corona 320, Col. Loma la Palma, Delegacion Gustavo A. Madero, 07160, Mexico DF (Mexico); Flores-Urbina, J C; Mota, R D [Unidad Profesional Interdisciplinaria de Ingenieria y Tecnologias Avanzadas, IPN. Av. Instituto Politecnico Nacional 2580, Col. La Laguna Ticoman, Delegacion Gustavo A. Madero, 07340 Mexico DF (Mexico); Granados, V D [Escuela Superior de Fisica y Matematicas, Instituto Politecnico Nacional, Ed. 9, Unidad Profesional Adolfo Lopez Mateos, 07738 Mexico DF (Mexico)], E-mail: dmartinezs77@yahoo.com.mx

    2010-04-02

    We apply the Schroedinger factorization to construct the ladder operators for the hydrogen atom, Mie-type potential, harmonic oscillator and pseudo-harmonic oscillator in arbitrary dimensions. By generalizing these operators we show that the dynamical algebra for these problems is the su(1, 1) Lie algebra.

  15. Carbon-sulfur bond-forming reaction catalysed by the radical SAM enzyme HydE

    Science.gov (United States)

    Rohac, Roman; Amara, Patricia; Benjdia, Alhosna; Martin, Lydie; Ruffié, Pauline; Favier, Adrien; Berteau, Olivier; Mouesca, Jean-Marie; Fontecilla-Camps, Juan C.; Nicolet, Yvain

    2016-05-01

    Carbon-sulfur bond formation at aliphatic positions is a challenging reaction that is performed efficiently by radical S-adenosyl-L-methionine (SAM) enzymes. Here we report that 1,3-thiazolidines can act as ligands and substrates for the radical SAM enzyme HydE, which is involved in the assembly of the active site of [FeFe]-hydrogenase. Using X-ray crystallography, in vitro assays and NMR spectroscopy we identified a radical-based reaction mechanism that is best described as the formation of a C-centred radical that concomitantly attacks the sulfur atom of a thioether. To the best of our knowledge, this is the first example of a radical SAM enzyme that reacts directly on a sulfur atom instead of abstracting a hydrogen atom. Using theoretical calculations based on our high-resolution structures we followed the evolution of the electronic structure from SAM through to the formation of S-adenosyl-L-cysteine. Our results suggest that, at least in this case, the widely proposed and highly reactive 5‧-deoxyadenosyl radical species that triggers the reaction in radical SAM enzymes is not an isolable intermediate.

  16. Time-dependent wave packet state-to-state quantum dynamics study of the abstraction reaction S(3P) + H2(v = 0, j = 0) on 13A″ electronic state

    Science.gov (United States)

    Wu, Hui; Liang, Dongyue; Zhang, Pei-Yu

    2015-05-01

    The state-to-state quantum dynamics of the abstraction channel of S(3P) + H2(v = 0, j = 0) reaction is studied on the potential energy surface (PES) constructed by Lv et al. (2012), utilizing the product Jacobi coordinate based time-dependent wave packet method. Reaction probabilities and total integral cross section (ICS) agree well with previous results (Lv et al., 2012) for collision energies ranging from 0.8 to 1.4 eV. Results show that total differential cross sections (DCSs) for small collision energies have backward structures, whereas those for large collision energies are sideways peaked. Although the summed-over-all-final-state DCS for single collision energy is smoothly varied, the DCS of the product HS of a selected final state shows strong oscillations. For the selected final state, the opacity function derived by reaction probability multiplied by (2J + 1), shows that different mechanisms relevant to several sets of J partial waves lead to the maxima in the differential cross section in the collision process.

  17. Nonheme Fe(IV) Oxo Complexes of Two New Pentadentate Ligands and Their Hydrogen-Atom and Oxygen-Atom Transfer Reactions

    NARCIS (Netherlands)

    Mitra, Mainak; Nimir, Hassan; Demeshko, Serhiy; Bhat, Satish S; Malinkin, Sergey O; Haukka, Matti; Lloret-Fillol, Julio; Lisensky, George C; Meyer, Franc; Shteinman, Albert A; Browne, Wesley R; Hrovat, David A; Richmond, Michael G; Costas, Miquel; Nordlander, Ebbe

    2015-01-01

    Two new pentadentate {N5} donor ligands based on the N4Py (N4Py = N,N-bis(2-pyridylmethyl)-N-bis(2-pyridyl)methylamine) framework have been synthesized, viz. [N-(1-methyl-2-benzimidazolyl)methyl-N-(2-pyridyl)methyl-N-(bis-2-pyridyl methyl)amine] (L(1)) and [N-bis(1-methyl-2-benzimidazolyl)methyl-N-(

  18. From Abstract Art to Abstracted Artists

    Directory of Open Access Journals (Sweden)

    Romi Mikulinsky

    2016-11-01

    Full Text Available What lineage connects early abstract films and machine-generated YouTube videos? Hans Richter’s famous piece Rhythmus 21 is considered to be the first abstract film in the experimental tradition. The Webdriver Torso YouTube channel is composed of hundreds of thousands of machine-generated test patterns designed to check frequency signals on YouTube. This article discusses geometric abstraction vis-à-vis new vision, conceptual art and algorithmic art. It argues that the Webdriver Torso is an artistic marvel indicative of a form we call mathematical abstraction, which is art performed by computers and, quite possibly, for computers.

  19. Theoretical study of the oxidation mechanisms of naphthalene initiated by hydroxyl radicals: the H abstraction pathway.

    Science.gov (United States)

    Shiroudi, Abolfazl; Deleuze, Michael S

    2014-05-22

    Reaction mechanisms for the initial stages of naphthalene oxidation at high temperatures (T ≥ 600 K) have been studied theoretically using density functional theory along with various exchange-correlation functionals, as well as the benchmark CBS-QB3 quantum chemical approach. These stages correspond to the removal of hydrogen atoms by hydroxyl radical and the formation thereby of 1- and 2-naphthyl radicals. Bimolecular kinetic rate constants were estimated by means of transition state theory. The excellent agreement with the available experimental kinetic rate constants demonstrates that a two-step reaction scheme prevails. Comparison with results obtained with density functional theory in conjunction with various exchange-correlation functionals also shows that DFT remains unsuited for quantitative insights into kinetic rate constants. Analysis of the computed structures, bond orders, and free energy profiles demonstrates that the reaction steps involved in the removal of hydrogen atoms by OH radicals satisfy Hammond's principle. Computations of branching ratios also show that these reactions do not exhibit a particularly pronounced site-selectivity.

  20. Intermediate Q from soluble methane monooxygenase hydroxylates the mechanistic substrate probe norcarane: evidence for a stepwise reaction.

    Science.gov (United States)

    Brazeau, B J; Austin, R N; Tarr, C; Groves, J T; Lipscomb, J D

    2001-12-05

    Norcarane is a valuable mechanistic probe for enzyme-catalyzed hydrocarbon oxidation reactions because different products or product distributions result from concerted, radical, and cation based reactions. Soluble methane monooxygenase (sMMO) from Methylosinus trichosporium OB3b catalyzes the oxidation of norcarane to afford 3-hydroxymethylcyclohexene and 3-cycloheptenol, compounds characteristic of radical and cationic intermediates, respectively, in addition to 2- and 3-norcaranols. Past single turnover transient kinetic studies have identified several optically distinct intermediates from the catalytic cycle of the hydroxylase component of sMMO. Thus, the reaction between norcarane and key reaction intermediates can be directly monitored. The presence of norcarane increases the rate of decay of only one intermediate, the high-valent bis-mu-oxo Fe(IV)(2) cluster-containing species compound Q, showing that it is responsible for the majority of the oxidation chemistry. The observation of products from both radical and cationic intermediates from norcarane oxidation catalyzed by sMMO is consistent with a mechanism in which an initial substrate radical intermediate is formed by hydrogen atom abstraction. This intermediate then undergoes either oxygen rebound, intramolecular rearrangement followed by oxygen rebound, or loss of a second electron to yield a cationic intermediate to which OH(-) is transferred. The estimated lower limit of 20 ps for the lifetime of the putative radical intermediate is in accord with values determined from previous studies of sterically hindered sMMO probes.

  1. Influence of inelastic collisions with hydrogen atoms on the formation of AlI and SiI lines in stellar spectra

    Science.gov (United States)

    Mashonkina, L. I.; Belyaev, A. K.; Shi, J.-R.

    2016-06-01

    We have performed calculations by abandoning the assumption of local thermodynamic equilibrium (within the so-called non-LTE approach) for Al I and Si I with model atmospheres corresponding to stars of spectral types F-G-Kwith differentmetal abundances. To take into account inelastic collisions with hydrogen atoms, for the first time we have applied the cross sections calculated by Belyaev et al. using model approaches within the formalism of the Born-Oppenheimer quantum theory. We show that for Al I non-LTE leads to higher ionization (overionization) than in LTE in the spectral line formation region and to a weakening of spectral lines, which is consistent with earlier non-LTE studies. However, our results, especially for the subordinate lines, differ quantitatively from the results of predecessors. Owing to their large cross sections, the ion-pair production and mutual neutralization processes Al I( nl) + HI(1 s) ↔ Al II(3 s 2) + H- provide a close coupling of highly excited Al I levels with the Al II ground state, which causes the deviations from the equilibrium level population to decrease compared to the calculations where the collisions only with electrons are taken into account. For three moderately metal-deficient dwarf stars, the aluminum abundance has been determined from seven Al I lines in different models of their formation. Under the assumption of LTE and in non-LTE calculations including the collisions only with electrons, the Al I 3961 ˚A resonance line gives a systematically lower abundance than the mean abundance from the subordinate lines, by 0.25-0.45 dex. The difference for each star is removed by taking into account the collisions with hydrogen atoms, and the rms error of the abundance derived from all seven Al I lines decreases by a factor of 1.5-3 compared to the LTE analysis. We have calculated the non- LTE corrections to the abundance for six subordinate Al I lines as a function of the effective temperature (4500 K ≤ T eff ≤ 6500 K

  2. Anti-oxidant activity of 6-gingerol as a hydroxyl radical scavenger by hydrogen atom transfer, radical addition and electron transfer mechanisms

    Indian Academy of Sciences (India)

    MANISH K TIWARI; P C MISHRA

    2016-08-01

    Mechanisms of anti-oxidant action of 6-gingerol as a hydroxyl radical scavenger have been investigated using the transition state theory within the framework of density functional theory. Hydrogen abstraction by a hydroxyl radical from the different sites of 6-gingerol and addition of the former to the different sites ofthe latter were studied. Electron transfer from 6-gingerol to a hydroxyl radical was also studied. Solvent effect in aqueous media was treated using the integral equation formalism of the polarizable continuum model (IEFPCM). Reaction rate constants in aqueous media were generally found to be larger than those in gas phase. The tunneling contributions to rate constants were found to be appreciable. Our results show that 6-gingerol is an excellent anti-oxidant and would scavenge hydroxyl radicals efficiently.

  3. PRISMA for Abstracts

    DEFF Research Database (Denmark)

    Beller, Elaine M; Glasziou, Paul P; Altman, Douglas G;

    2013-01-01

    Elaine Beller and colleagues from the PRISMA for Abstracts group provide a reporting guidelines for reporting abstracts of systematic reviews in journals and at conferences.......Elaine Beller and colleagues from the PRISMA for Abstracts group provide a reporting guidelines for reporting abstracts of systematic reviews in journals and at conferences....

  4. The stereochemistry and dynamics of the introduction of hydrogen atoms onto FeMo-co, the active site of nitrogenase.

    Science.gov (United States)

    Dance, Ian

    2013-11-18

    The catalyzed hydrogenations effected at the active site FeMo-co of nitrogenase have been proposed to involve serial supply of the required multiple protons along a proton wire terminating at sulfur atom S3B of FeMo-co. In conjunction with serial electron transfer to FeMo-co, these protons become H atoms, and then are able to migrate from S3B to other Fe and S atoms of FeMo-co, and to transfer to bound substrate and intermediates. This general model, which can account for all reactions of nitrogenase, involves a preparatory stage in which each incoming H atom is required to move from the proton delivery side of S3B to the opposite migration side of S3B. This report examines the mechanism of this reconfiguration of S3B-H, finding four stable configurations in which S3B-H has pyramidal-trigonal coordination, with one elongated Fe-S3B interaction. The transition states and energies for reconfiguration are described. Pseudotetrahedral four coordination and planar-trigonal coordination for S3B-H are less stable than pyramidal-trigonal coordination. Results are presented for FeMo-co with one, two, three, and four H atoms (the E1H1, E2H2, E3H3, and E4H4 Thorneley-Lowe stages), and the general principles are defined, for application in the various chemical mechanisms of nitrogenase.

  5. High-energy tail of the linear momentum distribution in the ground state of hydrogen atoms or hydrogen-like ions

    Energy Technology Data Exchange (ETDEWEB)

    Oks, E. [Physics Department, Auburn University, Auburn, AL (United States)

    2001-06-14

    A long-standing dispute concerning the high-energy tail of the linear momentum distribution (HTMD) in the ground state of hydrogen atoms/hydrogen-like ions (GSHA) has been unresolved up to now. A possible resolution of the above dispute might be connected to the problem of the role of singular solutions of quantal equations, which is a fundamental problem in its own right. The paradigm is that, even allowing for finite nuclear sizes, singular solutions of the Dirac equation for the Coulomb problem should be rejected for nuclear charges Z<1/{alpha}{approx}137. In this paper we break this paradigm. First, we derive a general condition for matching a regular interior solution with a singular exterior solution of the Dirac equation for arbitrary interior and exterior potentials. Then we find explicit forms of several classes of potentials that allow such a match. Finally, we show that, as an outcome, the HTMD for the GSHA acquires terms falling off much slower than the 1/p{sup 6}-law prescribed by the previously adopted quantal result. Our results open up a unique way to test intimate details of the nuclear structure by performing atomic (rather than nuclear) experiments and calculations. (author)

  6. Photoionization of hydrogen atom by coherent intense high-frequency short laser pulses: Direct propagation of electron wave packets on enormous spatial grids

    CERN Document Server

    Demekhin, Philipp V; Cederbaum, Lorenz S

    2013-01-01

    The time-dependent Schr\\"{o}dinger equation for the hydrogen atom and its interaction with coherent intense high-frequency short laser pulses is solved numerically exactly by employing the code implemented for the multi-configurational time-dependent Hartree-Fock (MCTDHF) method. Thereby, the wavefunction is followed in space and time for times longer than the pulse duration. Results are explicitly shown for 3 and 10 fs pulses. Particular attention is paid to identifying the effect of dynamic interference of photoelectrons emitted with the same kinetic energy at different times during the rising and falling sides of the pulse predicted in [\\emph{Ph.V. Demekhin and L.S. Cederbaum}, Phys. Rev. Lett. \\textbf{108}, 253001 (2012)]. In order to be able to see the dynamic interference pattern in the computed electron spectra, the photoelectron wave packet has to be propagated over long distances. Clearly, complex absorption potentials often employed to compute spectra of emitted particles cannot be used to detect dy...

  7. Solid H2 versus solid noble-gas environment: Influence on photoinduced hydrogen-atom transfer in matrix-isolated 4(3H)-pyrimidinone

    Science.gov (United States)

    Lapinski, Leszek; Nowak, Maciej J.; Rostkowska, Hanna

    2017-03-01

    UV-induced transformations have been studied for 4(3H)-pyrimidinone monomers isolated in low-temperature Ar, Ne, n-D2, and n-H2 matrices. The observed photochemical behavior of the compound drastically depended on the solid matrix environment. For 4(3H)-pyrimidinone isolated in solid Ar, the UV-induced phototautomeric transformation was clearly the dominating process, leading to a nearly quantitative conversion of the oxo reactant into the hydroxy product. For solid Ne environment, the oxo → hydroxy transformation was still the major photoprocess, but yielding less of the hydroxy product (ca. 64% of the yield in solid Ar). For 4(3H)-pyrimidinone isolated in solid n-H2, the oxo → hydroxy phototautomeric conversion did not occur (or occurred at a very tiny scale). Also for deuterated 4(3D)-pyrimidinone isolated in solid hydrogen, the analogous oxo → deuteroxy phototransformation was not observed. Finally, for the compound trapped in solid n-D2, the oxo → hydroxy phototautomerism clearly occurred, but the yield of the hydroxy tautomer was small (ca. 18% of the yield in solid Ar). Apart from hydrogen-atom-transfer processes, two other phototransformations: generation of open-ring conjugated ketene and valence Dewar isomer were observed for the compound isolated in Ar, Ne, n-D2, and n-H2 matrices.

  8. Towards high-level theoretical studies of large biodiesel molecules: an ONIOM [QCISD(T)/CBS:DFT] study of hydrogen abstraction reactions of C(n)H(2n+1)COOC(m)H(2m+1) + H.

    Science.gov (United States)

    Zhang, Lidong; Zhang, Peng

    2015-01-07

    Recent interest in biodiesel combustion urges the need for the theoretical chemical kinetics of large alkyl ester molecules. This is, however, computationally challenging for prevalent high-level electronic structure theory based methods. The hydrogen abstraction reactions of alky esters CnH2n+1COOCmH2m+1 (n = 1-5, 9, 15; m = 1, 2) by a hydrogen radical were investigated by a computational technique based on a two-layer ONIOM method, employing a QCISD(T)/CBS method for the high layer and a DFT method for the low layer. The calculated energy barriers and heats of reaction, using the ONIOM method with a minimum of the required chemically active portion, are in very good agreement with those obtained using the widely accepted high-level QCISD(T)/CBS theory because the computational errors were less than 0.1 kcal mol(-1) for all the tested cases. The ONIOM[QCISD(T)/CBS:DFT] method provides a computationally accurate and affordable approach to the high-level theoretical chemical kinetics of large biodiesel molecules.

  9. Intramolecular proton or hydrogen-atom transfer in the ground- and excited-states of 2-hydroxybenzophenone: A theoretical study

    Energy Technology Data Exchange (ETDEWEB)

    Yi, Ping G. [School of Chemistry and Chemical Engineering, Hunan University of Science and Technology, Xiangtan 411201 (China); Liang, Yong H. [School of Chemistry and Chemical Engineering, Hunan University of Science and Technology, Xiangtan 411201 (China)], E-mail: kaixgl@sina.com.cn; Cao, Chen Z. [School of Chemistry and Chemical Engineering, Hunan University of Science and Technology, Xiangtan 411201 (China)

    2005-08-29

    The internal rotational motion and the ground- and excited-state intramolecular proton transfer (GISPT, EISPT) reaction of 2-hydroxybenzophenone (HBP) are studied at the B3LYP/6-31G**, CIS/6-31G** and TD B3LYP/6-31++G** level. The calculated results show that there is only one minimum at the S{sub 0} and S{sub 1} state, the enol form (E) is the single minimum at the S{sub 0} state, and its rotamers and tautomers are with more than 8.24 and 10.43 kcal/mol less stable, respectively, however, the keto tautomer (K*) is the single minimum at the S{sub 1} state. Therefore, the ground- and excited-state intramolecular proton transfer reacts without a barrier between E and K or E* and K*. The energy gap between the first excited electronic state S{sub 1} 1({pi}, {pi}*){sup 1} and the second excited electronic state S{sub 2} 2(n, {pi}*){sup 1} of E is only 0.019 eV at CIS/6-31G** level. So the S{sub 0} {yields} S{sub 1} and S{sub 0} {yields} S{sub 2} excitation may occur at the same time, and the S{sub 1} state may occur the EISPT process and result a large Stokes shifted fluorescence. And the S{sub 2} state may through internal conversion to the S{sub 1} state or intersystem crossing to the T{sub 2} state. These theoretical results contrast with the conclusion of Nakayama and his coworkers [M. Hagiri, N. Ichinose, J. Kinugasa, T. Iwasa, T. Nakayama, Chem. Lett. 33 (2004) 326] stating the present of two ground-state conformers of HBP.

  10. Introduction to abstract algebra

    CERN Document Server

    Nicholson, W Keith

    2012-01-01

    Praise for the Third Edition ". . . an expository masterpiece of the highest didactic value that has gained additional attractivity through the various improvements . . ."-Zentralblatt MATH The Fourth Edition of Introduction to Abstract Algebra continues to provide an accessible approach to the basic structures of abstract algebra: groups, rings, and fields. The book's unique presentation helps readers advance to abstract theory by presenting concrete examples of induction, number theory, integers modulo n, and permutations before the abstract structures are defined. Readers can immediately be

  11. Abstraction and Consolidation

    Science.gov (United States)

    Monaghan, John; Ozmantar, Mehmet Fatih

    2006-01-01

    The framework for this paper is a recently developed theory of abstraction in context. The paper reports on data collected from one student working on tasks concerned with absolute value functions. It examines the relationship between mathematical constructions and abstractions. It argues that an abstraction is a consolidated construction that can…

  12. Accurate ab initio potential energy surface, thermochemistry, and dynamics of the F{sup −} + CH{sub 3}F S{sub N}2 and proton-abstraction reactions

    Energy Technology Data Exchange (ETDEWEB)

    Szabó, István; Telekes, Hajnalka; Czakó, Gábor, E-mail: czako@chem.elte.hu [Laboratory of Molecular Structure and Dynamics, Institute of Chemistry, Eötvös University, H-1518 Budapest 112, P.O. Box 32 (Hungary)

    2015-06-28

    We develop a full-dimensional global analytical potential energy surface (PES) for the F{sup −} + CH{sub 3}F reaction by fitting about 50 000 energy points obtained by an explicitly correlated composite method based on the second-order Møller–Plesset perturbation-F12 and coupled-cluster singles, doubles, and perturbative triples-F12a methods and the cc-pVnZ-F12 [n = D, T] basis sets. The PES accurately describes the (a) back-side attack Walden inversion mechanism involving the pre- and post-reaction (b) ion-dipole and (c) hydrogen-bonded complexes, the configuration-retaining (d) front-side attack and (e) double-inversion substitution pathways, as well as (f) the proton-abstraction channel. The benchmark quality relative energies of all the important stationary points are computed using the focal-point analysis (FPA) approach considering electron correlation up to coupled-cluster singles, doubles, triples, and perturbative quadruples method, extrapolation to the complete basis set limit, core-valence correlation, and scalar relativistic effects. The FPA classical(adiabatic) barrier heights of (a), (d), and (e) are −0.45(−0.61), 46.07(45.16), and 29.18(26.07) kcal mol{sup −1}, respectively, the dissociation energies of (b) and (c) are 13.81(13.56) and 13.73(13.52) kcal mol{sup −1}, respectively, and the endothermicity of (f) is 42.54(38.11) kcal mol{sup −1}. Quasiclassical trajectory computations of cross sections, scattering (θ) and initial attack (α) angle distributions, as well as translational and internal energy distributions are performed for the F{sup −} + CH{sub 3}F(v = 0) reaction using the new PES. Apart from low collision energies (E{sub coll}), the S{sub N}2 excitation function is nearly constant, the abstraction cross sections rapidly increase with E{sub coll} from a threshold of ∼40 kcal mol{sup −1}, and retention trajectories via double inversion are found above E{sub coll} = ∼ 30 kcal mol{sup −1}, and at E{sub coll} =

  13. Water-Soluble Iron(IV)-Oxo Complexes Supported by Pentapyridine Ligands: Axial Ligand Effects on Hydrogen Atom and Oxygen Atom Transfer Reactivity.

    Science.gov (United States)

    Chantarojsiri, Teera; Sun, Yujie; Long, Jeffrey R; Chang, Christopher J

    2015-06-15

    We report the photochemical generation and study of a family of water-soluble iron(IV)-oxo complexes supported by pentapyridine PY5Me2-X ligands (PY5Me2 = 2,6-bis(1,1-bis(2-pyridyl)ethyl)pyridine; X = CF3, H, Me, or NMe2), in which the oxidative reactivity of these ferryl species correlates with the electronic properties of the axial pyridine ligand. Synthesis of a systematic series of [Fe(II)(L)(PY5Me2-X)](2+) complexes, where L = CH3CN or H2O, and characterizations by several methods, including X-ray crystallography, cyclic voltammetry, and Mössbauer spectroscopy, show that increasing the electron-donating ability of the axial pyridine ligand tracks with less positive Fe(III)/Fe(II) reduction potentials and quadrupole splitting parameters. The Fe(II) precursors are readily oxidized to their Fe(IV)-oxo counterparts using either chemical outer-sphere oxidants such as CAN (ceric ammonium nitrate) or flash-quench photochemical oxidation with [Ru(bpy)3](2+) as a photosensitizer and K2S2O8 as a quencher. The Fe(IV)-oxo complexes are capable of oxidizing the C-H bonds of alkane (4-ethylbenzenesulfonate) and alcohol (benzyl alcohol) substrates via hydrogen atom transfer (HAT) and an olefin (4-styrenesulfonate) substrate by oxygen atom transfer (OAT). The [Fe(IV)(O)(PY5Me2-X)](2+) derivatives with electron-poor axial ligands show faster rates of HAT and OAT compared to their counterparts supported by electron-rich axial donors, but the magnitudes of these differences are relatively modest.

  14. The role of Rydberg and continuum levels in computing high harmonic generation spectra of the hydrogen atom using time-dependent configuration interaction.

    Science.gov (United States)

    Luppi, Eleonora; Head-Gordon, Martin

    2013-10-28

    We study the role of Rydberg bound-states and continuum levels in the field-induced electronic dynamics associated with the High-Harmonic Generation (HHG) spectroscopy of the hydrogen atom. Time-dependent configuration-interaction (TD-CI) is used with very large atomic orbital (AO) expansions (up to L = 4 with sextuple augmentation and off-center functions) to describe the bound Rydberg levels, and some continuum levels. To address the lack of ionization losses in TD-CI with finite AO basis sets, we employed a heuristic lifetime for energy levels above the ionization potential. The heuristic lifetime model is compared against the conventional atomic orbital treatment (infinite lifetimes), and a third approximation which is TD-CI using only the bound levels (continuum lifetimes go to zero). The results suggest that spectra calculated using conventional TD-CI do not converge with increasing AO basis set size, while the zero lifetime and heuristic lifetime models converge to qualitatively similar spectra, with implications for how best to apply bound state electronic structure methods to simulate HHG. The origin of HHG spectral features including the cutoff and extent of interference between peaks is uncovered by separating field-induced coupling between different types of levels (ground state, bound Rydberg levels, and continuum) in the simulated electronic dynamics. Thus the origin of deviations between the predictions of the semi-classical three step model and the full simulation can be associated with particular physical contributions, which helps to explain both the successes and the limitations of the three step model.

  15. Abstraction and Problem Reformulation

    Science.gov (United States)

    Giunchiglia, Fausto

    1992-01-01

    In work done jointly with Toby Walsh, the author has provided a sound theoretical foundation to the process of reasoning with abstraction (GW90c, GWS9, GW9Ob, GW90a). The notion of abstraction formalized in this work can be informally described as: (property 1), the process of mapping a representation of a problem, called (following historical convention (Sac74)) the 'ground' representation, onto a new representation, called the 'abstract' representation, which, (property 2) helps deal with the problem in the original search space by preserving certain desirable properties and (property 3) is simpler to handle as it is constructed from the ground representation by "throwing away details". One desirable property preserved by an abstraction is provability; often there is a relationship between provability in the ground representation and provability in the abstract representation. Another can be deduction or, possibly inconsistency. By 'throwing away details' we usually mean that the problem is described in a language with a smaller search space (for instance a propositional language or a language without variables) in which formulae of the abstract representation are obtained from the formulae of the ground representation by the use of some terminating rewriting technique. Often we require that the use of abstraction results in more efficient .reasoning. However, it might simply increase the number of facts asserted (eg. by allowing, in practice, the exploration of deeper search spaces or by implementing some form of learning). Among all abstractions, three very important classes have been identified. They relate the set of facts provable in the ground space to those provable in the abstract space. We call: TI abstractions all those abstractions where the abstractions of all the provable facts of the ground space are provable in the abstract space; TD abstractions all those abstractions wllere the 'unabstractions' of all the provable facts of the abstract space are

  16. Abstracts--Citations

    Science.gov (United States)

    Occupational Mental Health, 1972

    1972-01-01

    Provides abstracts and citations of journal articles and reports dealing with aspects of mental health. Topics include absenteeism, alcoholism, drug abuse, leisure, disadvantaged, job satisfaction, and others. (SB)

  17. Computational Abstraction Steps

    DEFF Research Database (Denmark)

    Thomsen, Lone Leth; Thomsen, Bent; Nørmark, Kurt

    2010-01-01

    and class instantiations. Our teaching experience shows that many novice programmers find it difficult to write programs with abstractions that materialise to concrete objects later in the development process. The contribution of this paper is the idea of initiating a programming process by creating......In this paper we discuss computational abstraction steps as a way to create class abstractions from concrete objects, and from examples. Computational abstraction steps are regarded as symmetric counterparts to computational concretisation steps, which are well-known in terms of function calls...

  18. On the calculation of line strengths, oscillator strengths and lifetimes for very large principal quantum numbers in hydrogenic atoms and ions by the McLean-Watson formula

    Science.gov (United States)

    Hey, J. D.

    2014-08-01

    As a sequel to an earlier study (Hey 2009 J. Phys. B: At. Mol. Opt. Phys. 42 125701), we consider further the application of the line strength formula derived by Watson (2006 J. Phys. B: At. Mol. Opt. Phys. 39 L291) to transitions arising from states of very high principal quantum number in hydrogenic atoms and ions (Rydberg-Rydberg transitions, n > 1000). It is shown how apparent difficulties associated with the use of recurrence relations, derived (Hey 2006 J. Phys. B: At. Mol. Opt. Phys. 39 2641) by the ladder operator technique of Infeld and Hull (1951 Rev. Mod. Phys. 23 21), may be eliminated by a very simple numerical device, whereby this method may readily be applied up to n ≈ 10 000. Beyond this range, programming of the method may entail greater care and complexity. The use of the numerically efficient McLean-Watson formula for such cases is again illustrated by the determination of radiative lifetimes and comparison of present results with those from an asymptotic formula. The question of the influence on the results of the omission or inclusion of fine structure is considered by comparison with calculations based on the standard Condon-Shortley line strength formula. Interest in this work on the radial matrix elements for large n and n‧ is related to measurements of radio recombination lines from tenuous space plasmas, e.g. Stepkin et al (2007 Mon. Not. R. Astron. Soc. 374 852), Bell et al (2011 Astrophys. Space Sci. 333 377), to the calculation of electron impact broadening parameters for such spectra (Watson 2006 J. Phys. B: At. Mol. Opt. Phys. 39 1889) and comparison with other theoretical methods (Peach 2014 Adv. Space Res. in press), to the modelling of physical processes in H II regions (Roshi et al 2012 Astrophys. J. 749 49), and the evaluation bound-bound transitions from states of high n during primordial cosmological recombination (Grin and Hirata 2010 Phys. Rev. D 81 083005, Ali-Haïmoud and Hirata 2010 Phys. Rev. D 82 063521, Ali

  19. Truthful Monadic Abstractions

    DEFF Research Database (Denmark)

    Brock-Nannestad, Taus; Schürmann, Carsten

    2012-01-01

    indefinitely, finding neither a proof nor a disproof of a given subgoal. In this paper we characterize a family of truth-preserving abstractions from intuitionistic first-order logic to the monadic fragment of classical first-order logic. Because they are truthful, these abstractions can be used to disprove...

  20. Completeness of Lyapunov Abstraction

    DEFF Research Database (Denmark)

    Wisniewski, Rafal; Sloth, Christoffer

    2013-01-01

    This paper addresses the generation of complete abstractions of polynomial dynamical systems by timed automata. For the proposed abstraction, the state space is divided into cells by sublevel sets of functions. We identify a relation between these functions and their directional derivatives along...

  1. Knowledge-Based Abstracting.

    Science.gov (United States)

    Black, William J.

    1990-01-01

    Discussion of automatic abstracting of technical papers focuses on a knowledge-based method that uses two sets of rules. Topics discussed include anaphora; text structure and discourse; abstracting techniques, including the keyword method and the indicator phrase method; and tools for text skimming. (27 references) (LRW)

  2. Completeness of Lyapunov Abstraction

    Directory of Open Access Journals (Sweden)

    Rafael Wisniewski

    2013-08-01

    Full Text Available In this work, we continue our study on discrete abstractions of dynamical systems. To this end, we use a family of partitioning functions to generate an abstraction. The intersection of sub-level sets of the partitioning functions defines cells, which are regarded as discrete objects. The union of cells makes up the state space of the dynamical systems. Our construction gives rise to a combinatorial object - a timed automaton. We examine sound and complete abstractions. An abstraction is said to be sound when the flow of the time automata covers the flow lines of the dynamical systems. If the dynamics of the dynamical system and the time automaton are equivalent, the abstraction is complete. The commonly accepted paradigm for partitioning functions is that they ought to be transversal to the studied vector field. We show that there is no complete partitioning with transversal functions, even for particular dynamical systems whose critical sets are isolated critical points. Therefore, we allow the directional derivative along the vector field to be non-positive in this work. This considerably complicates the abstraction technique. For understanding dynamical systems, it is vital to study stable and unstable manifolds and their intersections. These objects appear naturally in this work. Indeed, we show that for an abstraction to be complete, the set of critical points of an abstraction function shall contain either the stable or unstable manifold of the dynamical system.

  3. Designing for Mathematical Abstraction

    Science.gov (United States)

    Pratt, Dave; Noss, Richard

    2010-01-01

    Our focus is on the design of systems (pedagogical, technical, social) that encourage mathematical abstraction, a process we refer to as "designing for abstraction." In this paper, we draw on detailed design experiments from our research on children's understanding about chance and distribution to re-present this work as a case study in designing…

  4. Completeness of Lyapunov Abstraction

    DEFF Research Database (Denmark)

    Wisniewski, Rafal; Sloth, Christoffer

    2013-01-01

    This paper addresses the generation of complete abstractions of polynomial dynamical systems by timed automata. For the proposed abstraction, the state space is divided into cells by sublevel sets of functions. We identify a relation between these functions and their directional derivatives along...

  5. Data Abstraction in GLISP.

    Science.gov (United States)

    Novak, Gordon S., Jr.

    GLISP is a high-level computer language (based on Lisp and including Lisp as a sublanguage) which is compiled into Lisp. GLISP programs are compiled relative to a knowledge base of object descriptions, a form of abstract datatypes. A primary goal of the use of abstract datatypes in GLISP is to allow program code to be written in terms of objects,…

  6. Nuclear medicine. Abstracts; Nuklearmedizin 2000. Abstracts

    Energy Technology Data Exchange (ETDEWEB)

    Anon.

    2000-07-01

    This issue of the journal contains the abstracts of the 183 conference papers as well as 266 posters presented at the conference. Subject fields covered are: Neurology, psychology, oncology, pediatrics, radiopharmacy, endocrinology, EDP, measuring equipment and methods, radiological protection, cardiology, and therapy. (orig./CB) [German] Die vorliegende Zeitschrift enthaelt die Kurzfassungen der 183 auf der Tagung gehaltenen Vortraege sowie der 226 praesentierten Poster, die sich mit den folgenden Themen befassten: Neurologie, Psychiatrie, Onkologie, Paediatrie, Radiopharmazie, Endokrinologie, EDV, Messtechnik, Strahlenschutz, Kardiologie sowie Therapie. (MG)

  7. Low energy ion-molecule reactions

    Energy Technology Data Exchange (ETDEWEB)

    Farrar, J.M. [Univ. of Rochester, NY (United States)

    1993-12-01

    This project is concerned with elucidating the dynamics of elementary ion-molecule reactions at collision energies near and below 1 eV. From measurements of the angular and energy distributions of the reaction products, one can infer intimathe details about the nature of collisions leading to chemical reaction, the geometries and lifetimes of intermediate complexes that govern the reaction dynamics, and the collision energy dependence of these dynamical features. The author employs crossed-beam low energy mass spectrometry technology developed over the last several years, with the focus of current research on proton transfer and hydrogen atom transfer reactions of te O{sup {minus}} ion with species such as HF, H{sub 2}O, and NH{sub 3}.

  8. Abstracts of SIG Sessions.

    Science.gov (United States)

    Proceedings of the ASIS Annual Meeting, 1997

    1997-01-01

    Presents abstracts of SIG Sessions. Highlights include digital collections; information retrieval methods; public interest/fair use; classification and indexing; electronic publication; funding; globalization; information technology projects; interface design; networking in developing countries; metadata; multilingual databases; networked…

  9. Computational Abstraction Steps

    DEFF Research Database (Denmark)

    Thomsen, Lone Leth; Thomsen, Bent; Nørmark, Kurt

    2010-01-01

    and class instantiations. Our teaching experience shows that many novice programmers find it difficult to write programs with abstractions that materialise to concrete objects later in the development process. The contribution of this paper is the idea of initiating a programming process by creating......In this paper we discuss computational abstraction steps as a way to create class abstractions from concrete objects, and from examples. Computational abstraction steps are regarded as symmetric counterparts to computational concretisation steps, which are well-known in terms of function calls...... or capturing concrete values, objects, or actions. As the next step, some of these are lifted to a higher level by computational means. In the object-oriented paradigm the target of such steps is classes. We hypothesise that the proposed approach primarily will be beneficial to novice programmers or during...

  10. Mathematical games, abstract games

    CERN Document Server

    Neto, Joao Pedro

    2013-01-01

    User-friendly, visually appealing collection offers both new and classic strategic board games. Includes abstract games for two and three players and mathematical games such as Nim and games on graphs.

  11. Abstract sectional category

    CERN Document Server

    Diaz, F; Garcia, P; Murillo, A; Remedios, J

    2011-01-01

    We study, in an abstract axiomatic setting, the notion of sectional category of a morphism. From this, we unify and generalize known results about this invariant in different settings as well as we deduce new applications.

  12. Abstracts of contributed papers

    Energy Technology Data Exchange (ETDEWEB)

    1994-08-01

    This volume contains 571 abstracts of contributed papers to be presented during the Twelfth US National Congress of Applied Mechanics. Abstracts are arranged in the order in which they fall in the program -- the main sessions are listed chronologically in the Table of Contents. The Author Index is in alphabetical order and lists each paper number (matching the schedule in the Final Program) with its corresponding page number in the book.

  13. Metacognition and abstract reasoning.

    Science.gov (United States)

    Markovits, Henry; Thompson, Valerie A; Brisson, Janie

    2015-05-01

    The nature of people's meta-representations of deductive reasoning is critical to understanding how people control their own reasoning processes. We conducted two studies to examine whether people have a metacognitive representation of abstract validity and whether familiarity alone acts as a separate metacognitive cue. In Study 1, participants were asked to make a series of (1) abstract conditional inferences, (2) concrete conditional inferences with premises having many potential alternative antecedents and thus specifically conducive to the production of responses consistent with conditional logic, or (3) concrete problems with premises having relatively few potential alternative antecedents. Participants gave confidence ratings after each inference. Results show that confidence ratings were positively correlated with logical performance on abstract problems and concrete problems with many potential alternatives, but not with concrete problems with content less conducive to normative responses. Confidence ratings were higher with few alternatives than for abstract content. Study 2 used a generation of contrary-to-fact alternatives task to improve levels of abstract logical performance. The resulting increase in logical performance was mirrored by increases in mean confidence ratings. Results provide evidence for a metacognitive representation based on logical validity, and show that familiarity acts as a separate metacognitive cue.

  14. Monadic abstract interpreters

    DEFF Research Database (Denmark)

    Sergey, Ilya; Devriese, Dominique; Might, Matthew;

    2013-01-01

    -bounding to be independent of any particular semantics. Monads become the unifying agent between these concepts and between semantics. For instance, by plugging the same “context-insensitivity monad” into a monadicallyparameterized semantics for Java or for the lambda calculus, it yields the expected context......-insensitive analysis. To achieve this unification, we develop a systematic method for transforming a concrete semantics into a monadically-parameterized abstract machine. Changing the monad changes the behavior of the machine. By changing the monad, we recover a spectrum of machines—from the original concrete...... semantics to a monovariant, flow- and context-insensitive static analysis with a singly-threaded heap and weak updates. The monadic parameterization also suggests an abstraction over the ubiquitous monotone fixed-point computation found in static analysis. This abstraction makes it straightforward...

  15. Monadic abstract interpreters

    DEFF Research Database (Denmark)

    Sergey, Ilya; Devriese, Dominique; Might, Matthew

    2013-01-01

    -bounding to be independent of any particular semantics. Monads become the unifying agent between these concepts and between semantics. For instance, by plugging the same “context-insensitivity monad” into a monadicallyparameterized semantics for Java or for the lambda calculus, it yields the expected context...... semantics to a monovariant, flow- and context-insensitive static analysis with a singly-threaded heap and weak updates. The monadic parameterization also suggests an abstraction over the ubiquitous monotone fixed-point computation found in static analysis. This abstraction makes it straightforward...... to instrument an analysis with high-level strategies for improving precision and performance, such as abstract garbage collection and widening. While the paper itself runs the development for continuationpassing style, our generic implementation replays it for direct-style lambda-calculus and Featherweight Java...

  16. Structure of Naegleria Tet-like dioxygenase (NgTet1) in complexes with a reaction intermediate 5-hydroxymethylcytosine DNA.

    Science.gov (United States)

    Hashimoto, Hideharu; Pais, June E; Dai, Nan; Corrêa, Ivan R; Zhang, Xing; Zheng, Yu; Cheng, Xiaodong

    2015-12-15

    The family of ten-eleven translocation (Tet) dioxygenases is widely distributed across the eukaryotic tree of life, from mammals to the amoeboflagellate Naegleria gruberi. Like mammalian Tet proteins, the Naegleria Tet-like protein, NgTet1, acts on 5-methylcytosine (5mC) and generates 5-hydroxymethylcytosine (5hmC), 5-formylcytosine (5fC) and 5-carboxylcytosine (5caC) in three consecutive, Fe(II)- and α-ketoglutarate-dependent oxidation reactions. The two intermediates, 5hmC and 5fC, could be considered either as the reaction product of the previous enzymatic cycle or the substrate for the next cycle. Here we present a new crystal structure of NgTet1 in complex with DNA containing a 5hmC. Along with the previously solved NgTet1-5mC structure, the two complexes offer a detailed picture of the active site at individual stages of the reaction cycle. In the crystal, the hydroxymethyl (OH-CH2-) moiety of 5hmC points to the metal center, representing the reaction product of 5mC hydroxylation. The hydroxyl oxygen atom could be rotated away from the metal center, to a hydrophobic pocket formed by Ala212, Val293 and Phe295. Such rotation turns the hydroxyl oxygen atom away from the product conformation, and exposes the target CH2 towards the metal-ligand water molecule, where a dioxygen O2 molecule would occupy to initiate the next round of reaction by abstracting a hydrogen atom from the substrate. The Ala212-to-Val (A212V) mutant profoundly limits the product to 5hmC, probably because the reduced hydrophobic pocket size restricts the binding of 5hmC as a substrate. © The Author(s) 2015. Published by Oxford University Press on behalf of Nucleic Acids Research.

  17. The deleuzian abstract machines

    DEFF Research Database (Denmark)

    Werner Petersen, Erik

    2005-01-01

    production. In Kafka: Toward a Minor Literature, Deleuze and Guatari gave the most comprehensive explanation to the abstract machine in the work of art. Like the war-machines of Virilio, the Kafka-machine operates in three gears or speeds. Furthermore, the machine is connected to spatial diagrams...

  18. ARM : abstract rewriting machine

    NARCIS (Netherlands)

    J.F.T. Kamperman; H.R. Walters (Pum)

    1993-01-01

    textabstractTerm rewriting is frequently used as implementation technique for algebraic specifications. In this paper we present the abstract term rewriting machine (ARM), which has an extremely compact instruction set and imposes no restrictions on the implemented TRSs. Apart from standard

  19. Abstraction and art.

    Science.gov (United States)

    Gortais, Bernard

    2003-01-01

    In a given social context, artistic creation comprises a set of processes, which relate to the activity of the artist and the activity of the spectator. Through these processes we see and understand that the world is vaster than it is said to be. Artistic processes are mediated experiences that open up the world. A successful work of art expresses a reality beyond actual reality: it suggests an unknown world using the means and the signs of the known world. Artistic practices incorporate the means of creation developed by science and technology and change forms as they change. Artists and the public follow different processes of abstraction at different levels, in the definition of the means of creation, of representation and of perception of a work of art. This paper examines how the processes of abstraction are used within the framework of the visual arts and abstract painting, which appeared during a period of growing importance for the processes of abstraction in science and technology, at the beginning of the twentieth century. The development of digital platforms and new man-machine interfaces allow multimedia creations. This is performed under the constraint of phases of multidisciplinary conceptualization using generic representation languages, which tend to abolish traditional frontiers between the arts: visual arts, drama, dance and music. PMID:12903659

  20. SPR 2015. Abstracts

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    2015-04-01

    The volume contains the abstracts of the SPR (society for pediatric radiology) 2015 meeting covering the following issues: fetal imaging, muscoskeletal imaging, cardiac imaging, chest imaging, oncologic imaging, tools for process improvement, child abuse, contrast enhanced ultrasound, image gently - update of radiation dose recording/reporting/monitoring - meaningful or useless meaning?, pediatric thoracic imaging, ALARA.

  1. The Abstraction Engine

    DEFF Research Database (Denmark)

    Fortescue, Michael David

    The main thesis of this book is that abstraction, far from being confined to higher forms of cognition, language and logical reasoning, has actually been a major driving force throughout the evolution of creatures with brains. It is manifest in emotive as well as rational thought. Wending its way...

  2. ABSTRACTS AND KEY WORDS

    Institute of Scientific and Technical Information of China (English)

    2011-01-01

    Study on Optimization of Enzymic Preparation of Collagen Polypeptide from Skin of Gadous macrocephaius Liu Chun-e et al. (1) Abstract Enzymolysis was used to prepare collagen peptide. The optimum condition was determined based on one way ANOVA and orthogonal experimental design. The result indicated that use alkaline protease on the concentration of 4.5%,

  3. Parent Education: Abstract Bibliography.

    Science.gov (United States)

    Kremer, Barbara, Comp.

    This bibliography has been compiled to alert educators to parent education documents found in the ERIC microfiche collection and in journal literature. Abstracts of selected documents have been taken from "Research in Education (RIE)", and journal article citations from the "Current Index to Journals in Education (CIJE)". Included are published…

  4. ABSTRACTS AND KEY WORDS

    Institute of Scientific and Technical Information of China (English)

    2011-01-01

    Study on the Long-distance Transportation of Argopecten irridians concentricus ShenQin-long(1) Abstract The experiment was carried out in order to improve the survival rate of the scallop. The result indicated that keeping the water temperature at 4℃ was reasonable for the long-distance transportation of the scallop with oxygenated bags.

  5. Full Abstraction for HOPLA

    DEFF Research Database (Denmark)

    Nygaard, Mikkel; Winskel, Glynn

    2003-01-01

    A fully abstract denotational semantics for the higher-order process language HOPLA is presented. It characterises contextual and logical equivalence, the latter linking up with simulation. The semantics is a clean, domain-theoretic description of processes as downwards-closed sets of computation...

  6. Abstracts of SIG Sessions.

    Science.gov (United States)

    Proceedings of the ASIS Annual Meeting, 1995

    1995-01-01

    Presents abstracts of 15 special interest group (SIG) sessions. Topics include navigation and information utilization in the Internet, natural language processing, automatic indexing, image indexing, classification, users' models of database searching, online public access catalogs, education for information professions, information services,…

  7. Abstraction through Game Play

    Science.gov (United States)

    Avraamidou, Antri; Monaghan, John; Walker, Aisha

    2012-01-01

    This paper examines the computer game play of an 11-year-old boy. In the course of building a virtual house he developed and used, without assistance, an artefact and an accompanying strategy to ensure that his house was symmetric. We argue that the creation and use of this artefact-strategy is a mathematical abstraction. The discussion…

  8. Beyond the abstractions?

    DEFF Research Database (Denmark)

    Olesen, Henning Salling

    2006-01-01

      The anniversary of the International Journal of Lifelong Education takes place in the middle of a conceptual landslide from lifelong education to lifelong learning. Contemporary discourses of lifelong learning etc are however abstractions behind which new functions and agendas for adult education...

  9. Reasoning abstractly about resources

    Science.gov (United States)

    Clement, B.; Barrett, A.

    2001-01-01

    r describes a way to schedule high level activities before distributing them across multiple rovers in order to coordinate the resultant use of shared resources regardless of how each rover decides how to perform its activities. We present an algorithm for summarizing the metric resource requirements of an abstract activity based n the resource usages of its potential refinements.

  10. Incremental Bisimulation Abstraction Refinement

    DEFF Research Database (Denmark)

    Godskesen, Jens Christian; Song, Lei; Zhang, Lijun

    2013-01-01

    an abstraction refinement approach for the probabilistic computation tree logic (PCTL), which is based on incrementally computing a sequence of may- and must-quotient automata. These are induced by depth-bounded bisimulation equivalences of increasing depth. The approach is both sound and complete, since...

  11. Seismic Consequence Abstraction

    Energy Technology Data Exchange (ETDEWEB)

    M. Gross

    2004-10-25

    The primary purpose of this model report is to develop abstractions for the response of engineered barrier system (EBS) components to seismic hazards at a geologic repository at Yucca Mountain, Nevada, and to define the methodology for using these abstractions in a seismic scenario class for the Total System Performance Assessment - License Application (TSPA-LA). A secondary purpose of this model report is to provide information for criticality studies related to seismic hazards. The seismic hazards addressed herein are vibratory ground motion, fault displacement, and rockfall due to ground motion. The EBS components are the drip shield, the waste package, and the fuel cladding. The requirements for development of the abstractions and the associated algorithms for the seismic scenario class are defined in ''Technical Work Plan For: Regulatory Integration Modeling of Drift Degradation, Waste Package and Drip Shield Vibratory Motion and Seismic Consequences'' (BSC 2004 [DIRS 171520]). The development of these abstractions will provide a more complete representation of flow into and transport from the EBS under disruptive events. The results from this development will also address portions of integrated subissue ENG2, Mechanical Disruption of Engineered Barriers, including the acceptance criteria for this subissue defined in Section 2.2.1.3.2.3 of the ''Yucca Mountain Review Plan, Final Report'' (NRC 2003 [DIRS 163274]).

  12. ABSTRACTS AND KEY WORDS

    Institute of Scientific and Technical Information of China (English)

    2012-01-01

    Study on the Enrichment Regularity of Semicarbazide in Algae Tian Xiu-hui eta1. (1) Abstract Semicarbazide (SEM) in three kinds of representative algae (Nitzschia closterium, Tetraselmis chui and Dicrateria sp) and seawater was determined using ultra performance liquid chromatogram tandem mass spectrometry in this work. Accumulation of semicarbazide (SEM) in algae under laboratory conditions was studied.

  13. Metaphors in Abstract Thought

    NARCIS (Netherlands)

    I. Boot (Inge)

    2010-01-01

    textabstractThe aim of the dissertation was to investigate the Conceptual Metaphor Theory (CMT, Lakoff & Johnson, 1980, 1999).The CMT proposes that abstract concepts are partly structured by concrete concepts through the mechanism of metaphorical mapping. In Chapter 2 we wanted to investigate the

  14. 2002 NASPSA Conference Abstracts.

    Science.gov (United States)

    Journal of Sport & Exercise Psychology, 2002

    2002-01-01

    Contains abstracts from the 2002 conference of the North American Society for the Psychology of Sport and Physical Activity. The publication is divided into three sections: the preconference workshop, "Effective Teaching Methods in the Classroom;" symposia (motor development, motor learning and control, and sport psychology); and free…

  15. ESPR 2014. Abstracts

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    2014-06-15

    The Proceedings on ESPR 2014 include abstracts concerning the following topics: pediatric imaging: thorax, cardiovascular system, CT-technique, head and neck, perinatal imaging, molecular imaging; interventional imaging; specific focus: muscoskeletal imaging in juvenile idiopathic arthritis; radiation protection; oncology; molecular imaging - nuclear medicine; uroradiology and abdominal imaging.

  16. Cambridge Scientific Abstracts

    Institute of Scientific and Technical Information of China (English)

    2012-01-01

    正Meteorological and Environmental Research has been included by Cambridge Scientific Abstracts (CSA) since 2011. CSA is a retrieval system published by Cambridge Information Group. CSA was founded in the late 1950's,and became part of the CIG family in 1971. CSA's original mission was publishing secondary source materials relating to the physical sciences. Completely

  17. Cambridge Scientific Abstracts

    Institute of Scientific and Technical Information of China (English)

    2012-01-01

    Meteorological and Environmental Research has been included by Cambridge Scientific Abstracts (CSA) since 2011. CSA is a retrieval system published by Cambridge Information Group. CSA was founded in the late 1950’s,and became part of the CIG family in 1971. CSA’s original mission was publishing secondary source materials relating to the physical sciences. Completely

  18. Impredicative concurrent abstract predicates

    DEFF Research Database (Denmark)

    Svendsen, Kasper; Birkedal, Lars

    2014-01-01

    We present impredicative concurrent abstract predicates { iCAP { a program logic for modular reasoning about concurrent, higher- order, reentrant, imperative code. Building on earlier work, iCAP uses protocols to reason about shared mutable state. A key novel feature of iCAP is the ability to dene...

  19. Molecular Beam Studies of Hot Atom Chemical Reactions: Reactive Scattering of Energetic Deuterium Atoms

    Science.gov (United States)

    Continetti, R. E.; Balko, B. A.; Lee, Y. T.

    1989-02-01

    A brief review of the application of the crossed molecular beams technique to the study of hot atom chemical reactions in the last twenty years is given. Specific emphasis is placed on recent advances in the use of photolytically produced energetic deuterium atoms in the study of the fundamental elementary reactions D + H{sub 2} -> DH + H and the substitution reaction D + C{sub 2}H{sub 2} -> C{sub 2}HD + H. Recent advances in uv laser and pulsed molecular beam techniques have made the detailed study of hydrogen atom reactions under single collision conditions possible.

  20. EBS Radionuclide Transport Abstraction

    Energy Technology Data Exchange (ETDEWEB)

    R. Schreiner

    2001-06-27

    The purpose of this work is to develop the Engineered Barrier System (EBS) radionuclide transport abstraction model, as directed by a written development plan (CRWMS M&O 1999a). This abstraction is the conceptual model that will be used to determine the rate of release of radionuclides from the EBS to the unsaturated zone (UZ) in the total system performance assessment-license application (TSPA-LA). In particular, this model will be used to quantify the time-dependent radionuclide releases from a failed waste package (WP) and their subsequent transport through the EBS to the emplacement drift wall/UZ interface. The development of this conceptual model will allow Performance Assessment Operations (PAO) and its Engineered Barrier Performance Department to provide a more detailed and complete EBS flow and transport abstraction. The results from this conceptual model will allow PA0 to address portions of the key technical issues (KTIs) presented in three NRC Issue Resolution Status Reports (IRSRs): (1) the Evolution of the Near-Field Environment (ENFE), Revision 2 (NRC 1999a), (2) the Container Life and Source Term (CLST), Revision 2 (NRC 1999b), and (3) the Thermal Effects on Flow (TEF), Revision 1 (NRC 1998). The conceptual model for flow and transport in the EBS will be referred to as the ''EBS RT Abstraction'' in this analysis/modeling report (AMR). The scope of this abstraction and report is limited to flow and transport processes. More specifically, this AMR does not discuss elements of the TSPA-SR and TSPA-LA that relate to the EBS but are discussed in other AMRs. These elements include corrosion processes, radionuclide solubility limits, waste form dissolution rates and concentrations of colloidal particles that are generally represented as boundary conditions or input parameters for the EBS RT Abstraction. In effect, this AMR provides the algorithms for transporting radionuclides using the flow geometry and radionuclide concentrations

  1. Building Safe Concurrency Abstractions

    DEFF Research Database (Denmark)

    Madsen, Ole Lehrmann

    2014-01-01

    Concurrent object-oriented programming in Beta is based on semaphores and coroutines and the ability to define high-level concurrency abstractions like monitors, and rendezvous-based communication, and their associated schedulers. The coroutine mechanism of SIMULA has been generalized...... into the notions of concurrent and alternating objects. Alternating objects may be used to start a cooperative thread for each possible blocking communication and is thus an alternative to asynchronous messages and guarded commands. Beta like SIMULA, the first OO language, was designed as a language for modeling...... as well as programming, and we describe how this has had an impact on the design of the language. Although Beta supports the definition of high-level concurrency abstractions, the use of these rely on the discipline of the programmer as is the case for Java and other mainstream OO languages. We introduce...

  2. Abstracts of Main Essays

    Institute of Scientific and Technical Information of China (English)

    2012-01-01

    The Position of Capitalist Study in Marx's Social Formation Theory Yang Xue-gong Xi Da-min The orientation and achievements of Marx's study of Capitalism or bourgeois society is the foundation of his social formation theory. On the base of his scientific study of capitalism, Marx evolves his concept of eco- nomic social formation, the scientific methodology of researching other social formations or social forms, the clues of the development of social formations, the abstraction of the general laws as well as his reflection on this abstraction. A full evaluation and acknowledgement of the position of capitalist study in Marx's social formation theory is crucial for revising Marx's social formation theory in the new era and for solving some controversial issues in the research of social formation theory.

  3. An Abstract Data Interface

    Science.gov (United States)

    Allan, D. J.

    The Abstract Data Interface (ADI) is a system within which both abstract data models and their mappings on to file formats can be defined. The data model system is object-oriented and closely follows the Common Lisp Object System (CLOS) object model. Programming interfaces in both C and \\fortran are supplied, and are designed to be simple enough for use by users with limited software skills. The prototype system supports access to those FITS formats most commonly used in the X-ray community, as well as the Starlink NDF data format. New interfaces can be rapidly added to the system---these may communicate directly with the file system, other ADI objects or elsewhere (e.g., a network connection).

  4. Introduction to abstract analysis

    CERN Document Server

    Goldstein, Marvin E

    2015-01-01

    Developed from lectures delivered at NASA's Lewis Research Center, this concise text introduces scientists and engineers with backgrounds in applied mathematics to the concepts of abstract analysis. Rather than preparing readers for research in the field, this volume offers background necessary for reading the literature of pure mathematics. Starting with elementary set concepts, the treatment explores real numbers, vector and metric spaces, functions and relations, infinite collections of sets, and limits of sequences. Additional topics include continuity and function algebras, Cauchy complet

  5. DEGRO 2017. Abstracts

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    2017-06-15

    The volume includes abstracts of the Annual DEGRO Meeting 2017 covering lectures and poster sessions with the following issues: lymphoma, biology, physics, radioimmunotherapy, sarcomas and rare tumors, prostate carcinoma, lung tumors, benign lesions and new media, mamma carcinoma, gastrointestinal tumors, quality of life, care science and quality assurance, high-technology methods and palliative situation, head-and-neck tumors, brain tumors, central nervous system metastases, guidelines, radiation sensitivity, radiotherapy, radioimmunotherapy.

  6. SPR 2014. Abstracts

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    2014-05-15

    The proceedings of the SPR 2014 meeting include abstracts on the following topics: Body imaging techniques: practical advice for clinic work; thoracic imaging: focus on the lungs; gastrointestinal imaging: focus on the pancreas and bowel; genitourinary imaging: focus on gonadal radiology; muscoskeletal imaging; focus on oncology; child abuse and nor child abuse: focus on radiography; impact of NMR and CT imaging on management of CHD; education and communication: art and practice in pediatric radiology.

  7. Research Abstracts of 1982.

    Science.gov (United States)

    1982-12-01

    Activity in Hamsters (Abstract #667) 9. L. SIMONSON*, B. LAMBERTS, E. PEDERSON and D. REIHER’--*gEffect of Saliva and Sucrose on Adherence of S.. mutans to...presence of osteosclerosis and/or enlargement of periodontal ligament space; pain duration greater than one hour and spontaneous or severe pain; no...Unstimulated whole saliva was collected in chilled containers from 29 CF and 29 CA recruits, along with data on smoking habits. Flow rate, pH, OSCN

  8. Generalized Abstract Symbolic Summaries

    Science.gov (United States)

    Person, Suzette; Dwyer, Matthew B.

    2009-01-01

    Current techniques for validating and verifying program changes often consider the entire program, even for small changes, leading to enormous V&V costs over a program s lifetime. This is due, in large part, to the use of syntactic program techniques which are necessarily imprecise. Building on recent advances in symbolic execution of heap manipulating programs, in this paper, we develop techniques for performing abstract semantic differencing of program behaviors that offer the potential for improved precision.

  9. Towards Composable Concurrency Abstractions

    Directory of Open Access Journals (Sweden)

    Janwillem Swalens

    2014-06-01

    Full Text Available In the past decades, many different programming models for managing concurrency in applications have been proposed, such as the actor model, Communicating Sequential Processes, and Software Transactional Memory. The ubiquity of multi-core processors has made harnessing concurrency even more important. We observe that modern languages, such as Scala, Clojure, or F#, provide not one, but multiple concurrency models that help developers manage concurrency. Large end-user applications are rarely built using just a single concurrency model. Programmers need to manage a responsive UI, deal with file or network I/O, asynchronous workflows, and shared resources. Different concurrency models facilitate different requirements. This raises the issue of how these concurrency models interact, and whether they are composable. After all, combining different concurrency models may lead to subtle bugs or inconsistencies. In this paper, we perform an in-depth study of the concurrency abstractions provided by the Clojure language. We study all pairwise combinations of the abstractions, noting which ones compose without issues, and which do not. We make an attempt to abstract from the specifics of Clojure, identifying the general properties of concurrency models that facilitate or hinder composition.

  10. Product detection of the CH radical reaction with acetaldehyde.

    Science.gov (United States)

    Goulay, Fabien; Trevitt, Adam J; Savee, John D; Bouwman, Jordy; Osborn, David L; Taatjes, Craig A; Wilson, Kevin R; Leone, Stephen R

    2012-06-21

    The reaction of the methylidyne radical (CH) with acetaldehyde (CH(3)CHO) is studied at room temperature and at a pressure of 4 Torr (533.3 Pa) using a multiplexed photoionization mass spectrometer coupled to the tunable vacuum ultraviolet synchrotron radiation of the Advanced Light Source at Lawrence Berkeley National Laboratory. The CH radicals are generated by 248 nm multiphoton photolysis of CHBr(3) and react with acetaldehyde in an excess of helium and nitrogen gas flow. Five reaction exit channels are observed corresponding to elimination of methylene (CH(2)), elimination of a formyl radical (HCO), elimination of carbon monoxide (CO), elimination of a methyl radical (CH(3)), and elimination of a hydrogen atom. Analysis of the photoionization yields versus photon energy for the reaction of CH and CD radicals with acetaldehyde and CH radical with partially deuterated acetaldehyde (CD(3)CHO) provides fine details about the reaction mechanism. The CH(2) elimination channel is found to preferentially form the acetyl radical by removal of the aldehydic hydrogen. The insertion of the CH radical into a C-H bond of the methyl group of acetaldehyde is likely to lead to a C(3)H(5)O reaction intermediate that can isomerize by β-hydrogen transfer of the aldehydic hydrogen atom and dissociate to form acrolein + H or ketene + CH(3), which are observed directly. Cycloaddition of the radical onto the carbonyl group is likely to lead to the formation of the observed products, methylketene, methyleneoxirane, and acrolein.

  11. EBS Radionuclide Transport Abstraction

    Energy Technology Data Exchange (ETDEWEB)

    J. Prouty

    2006-07-14

    The purpose of this report is to develop and analyze the engineered barrier system (EBS) radionuclide transport abstraction model, consistent with Level I and Level II model validation, as identified in Technical Work Plan for: Near-Field Environment and Transport: Engineered Barrier System: Radionuclide Transport Abstraction Model Report Integration (BSC 2005 [DIRS 173617]). The EBS radionuclide transport abstraction (or EBS RT Abstraction) is the conceptual model used in the total system performance assessment (TSPA) to determine the rate of radionuclide releases from the EBS to the unsaturated zone (UZ). The EBS RT Abstraction conceptual model consists of two main components: a flow model and a transport model. Both models are developed mathematically from first principles in order to show explicitly what assumptions, simplifications, and approximations are incorporated into the models used in the TSPA. The flow model defines the pathways for water flow in the EBS and specifies how the flow rate is computed in each pathway. Input to this model includes the seepage flux into a drift. The seepage flux is potentially split by the drip shield, with some (or all) of the flux being diverted by the drip shield and some passing through breaches in the drip shield that might result from corrosion or seismic damage. The flux through drip shield breaches is potentially split by the waste package, with some (or all) of the flux being diverted by the waste package and some passing through waste package breaches that might result from corrosion or seismic damage. Neither the drip shield nor the waste package survives an igneous intrusion, so the flux splitting submodel is not used in the igneous scenario class. The flow model is validated in an independent model validation technical review. The drip shield and waste package flux splitting algorithms are developed and validated using experimental data. The transport model considers advective transport and diffusive transport

  12. IPR 2016. Abstracts

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    2016-05-15

    The volume on the meeting of pediatric radiology includes abstract on the following issues: chest, cardiovascular system, neuroradiology, CT radiation DRs (diagnostic reference levels) and dose reporting guidelines, genitourinary imaging, gastrointestinal radiology, oncology an nuclear medicine, whole body imaging, fetal/neonates imaging, child abuse, oncology and hybrid imaging, value added imaging, muscoskeletal imaging, dose and radiation safety, imaging children - immobilization and distraction techniques, information - education - QI and healthcare policy, ALARA, the knowledge skills and competences for a technologist/radiographer in pediatric radiology, full exploitation of new technological features in pediatric CT, image quality issues in pediatrics, abdominal imaging, interventional radiology, MR contrast agents, tumor - mass imaging, cardiothoracic imaging, ultrasonography.

  13. ESPR 2015. Abstracts

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    2015-05-10

    The volume includes the abstracts of the ESPR 2015 covering the following topics: PCG (post graduate courses): Radiography; fluoroscopy and general issue; nuclear medicine, interventional radiology and hybrid imaging, pediatric CT, pediatric ultrasound; MRI in childhood. Scientific sessions and task force sessions: International aspects; neuroradiology, neonatal imaging, engineering techniques to simulate injury in child abuse, CT - dose and quality, challenges in the chest, cardiovascular and chest, muscoskeletal, oncology, pediatric uroradiology and abdominal imaging, fetal and postmortem imaging, education and global challenges, neuroradiology - head and neck, gastrointestinal and genitourinary.

  14. ABSTRACTS AND KEY WORDS

    Institute of Scientific and Technical Information of China (English)

    2011-01-01

    Establishment of a Method for Content Determination of Polysaccharide in Membranous milkveteh root Applied in Fisheries Yu Xiao-qing et al. (1) Abstract Some chemical component in the traditional Chinese medicine Membranous milkvetch root can improve the ability of disease-prevention of animal and it can be applied in fisheries. In the paper, the method about content determination of polysaccharide in the root was established based on orthogonal experimental design Key words medicine; polysaccharide in Membranous milkvetch root; method of determination

  15. Abstracts of Major Articles

    Institute of Scientific and Technical Information of China (English)

    2012-01-01

    On Problems in Fujian's Present Health Insurance Professionals and Related Suggestions LIN Deng-hui,WU Xiao-nan (School of Public Health, Fujian Medical University, Fuzhou 350108, China) Abstract:Based on a statistical analysis of questionnaire survey data collected from practitioners in Fu- jian's medical insurance management system, the paper discusses the problems relevant to the staff's qua lity structure in this industry as well as mechanisms for continuing education and motivation. Finally, the authors advance such suggestions as increasing the levels of practitioner's expertise and working capacity by developing disciplinary education and continuing motivated with a well-established motivation system. education, and encouraging employees to get highly

  16. SPR 2017. Abstracts

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    2017-05-15

    The conference proceedings SPR 2017 include abstracts on the following issues: gastrointestinal radiography - inflammatory bowel diseases, cardiovascular CTA, general muscoskeletal radiology, muscoskeletal congenital development diseases, general pediatric radiology - chest, muscoskeletal imaging - marrow and infectious disorders, state-of-the-art body MR imaging, practical pediatric sonography, quality and professionalism, CT imaging in congenital heart diseases, radiographic courses, body MT techniques, contrast enhanced ultrasound, machine learning, forensic imaging, the radiation dos conundrum - reconciling imaging, imagining and managing, the practice of radiology, interventional radiology, neuroradiology, PET/MR.

  17. Elements of abstract algebra

    CERN Document Server

    Clark, Allan

    1984-01-01

    This concise, readable, college-level text treats basic abstract algebra in remarkable depth and detail. An antidote to the usual surveys of structure, the book presents group theory, Galois theory, and classical ideal theory in a framework emphasizing proof of important theorems.Chapter I (Set Theory) covers the basics of sets. Chapter II (Group Theory) is a rigorous introduction to groups. It contains all the results needed for Galois theory as well as the Sylow theorems, the Jordan-Holder theorem, and a complete treatment of the simplicity of alternating groups. Chapter III (Field Theory)

  18. Building Safe Concurrency Abstractions

    DEFF Research Database (Denmark)

    Madsen, Ole Lehrmann

    2014-01-01

    into the notions of concurrent and alternating objects. Alternating objects may be used to start a cooperative thread for each possible blocking communication and is thus an alternative to asynchronous messages and guarded commands. Beta like SIMULA, the first OO language, was designed as a language for modeling...... as well as programming, and we describe how this has had an impact on the design of the language. Although Beta supports the definition of high-level concurrency abstractions, the use of these rely on the discipline of the programmer as is the case for Java and other mainstream OO languages. We introduce...

  19. Hydrogen Atomic Positions of O-H···O Hydrogen Bonds in Solution and in the Solid State: The Synergy of Quantum Chemical Calculations with ¹H-NMR Chemical Shifts and X-ray Diffraction Methods.

    Science.gov (United States)

    Siskos, Michael G; Choudhary, M Iqbal; Gerothanassis, Ioannis P

    2017-03-07

    The exact knowledge of hydrogen atomic positions of O-H···O hydrogen bonds in solution and in the solid state has been a major challenge in structural and physical organic chemistry. The objective of this review article is to summarize recent developments in the refinement of labile hydrogen positions with the use of: (i) density functional theory (DFT) calculations after a structure has been determined by X-ray from single crystals or from powders; (ii) ¹H-NMR chemical shifts as constraints in DFT calculations, and (iii) use of root-mean-square deviation between experimentally determined and DFT calculated ¹H-NMR chemical shifts considering the great sensitivity of ¹H-NMR shielding to hydrogen bonding properties.

  20. Abstract Storage Devices

    CERN Document Server

    Koenig, Robert; Tessaro, Stefano

    2007-01-01

    A quantum storage device differs radically from a conventional physical storage device. Its state can be set to any value in a certain (infinite) state space, but in general every possible read operation yields only partial information about the stored state. The purpose of this paper is to initiate the study of a combinatorial abstraction, called abstract storage device (ASD), which models deterministic storage devices with the property that only partial information about the state can be read, but that there is a degree of freedom as to which partial information should be retrieved. This concept leads to a number of interesting problems which we address, like the reduction of one device to another device, the equivalence of devices, direct products of devices, as well as the factorization of a device into primitive devices. We prove that every ASD has an equivalent ASD with minimal number of states and of possible read operations. Also, we prove that the reducibility problem for ASD's is NP-complete, that t...

  1. EBS Radionuclide Transport Abstraction

    Energy Technology Data Exchange (ETDEWEB)

    J.D. Schreiber

    2005-08-25

    The purpose of this report is to develop and analyze the engineered barrier system (EBS) radionuclide transport abstraction model, consistent with Level I and Level II model validation, as identified in ''Technical Work Plan for: Near-Field Environment and Transport: Engineered Barrier System: Radionuclide Transport Abstraction Model Report Integration'' (BSC 2005 [DIRS 173617]). The EBS radionuclide transport abstraction (or EBS RT Abstraction) is the conceptual model used in the total system performance assessment for the license application (TSPA-LA) to determine the rate of radionuclide releases from the EBS to the unsaturated zone (UZ). The EBS RT Abstraction conceptual model consists of two main components: a flow model and a transport model. Both models are developed mathematically from first principles in order to show explicitly what assumptions, simplifications, and approximations are incorporated into the models used in the TSPA-LA. The flow model defines the pathways for water flow in the EBS and specifies how the flow rate is computed in each pathway. Input to this model includes the seepage flux into a drift. The seepage flux is potentially split by the drip shield, with some (or all) of the flux being diverted by the drip shield and some passing through breaches in the drip shield that might result from corrosion or seismic damage. The flux through drip shield breaches is potentially split by the waste package, with some (or all) of the flux being diverted by the waste package and some passing through waste package breaches that might result from corrosion or seismic damage. Neither the drip shield nor the waste package survives an igneous intrusion, so the flux splitting submodel is not used in the igneous scenario class. The flow model is validated in an independent model validation technical review. The drip shield and waste package flux splitting algorithms are developed and validated using experimental data. The transport

  2. Structure and Reactions of Carbon and Hydrogen on Ru(0001): A Scanning Tunneling Microscopy Study

    Energy Technology Data Exchange (ETDEWEB)

    Shimizu, Tomoko K.; Mugarza, Aitor; Cerda, Jorge; Salmeron, Miquel

    2008-09-09

    The interaction between carbon and hydrogen atoms on a Ru(0001) surface was studied using scanning tunneling microscopy (STM), Density Functional Theory (DFT) and STM image calculations. Formation of CH species by reaction between adsorbed H and C was observed to occur readily at 100 K. When the coverage of H increased new complexes of the form CH+nH (n = 1, 2 and 3) were observed. These complexes, never observed before, might be precursors for further hydrogenation reactions. DFT analysis reveals that a considerable energy barrier exists for the CH+H {yields} CH{sub 2} reaction.

  3. Writing a successful research abstract.

    Science.gov (United States)

    Bliss, Donna Z

    2012-01-01

    Writing and submitting a research abstract provides timely dissemination of the findings of a study and offers peer input for the subsequent development of a quality manuscript. Acceptance of abstracts is competitive. Understanding the expected content of an abstract, the abstract review process and tips for skillful writing will improve the chance of acceptance.

  4. ABSTRACTS AND KEY WORDS

    Institute of Scientific and Technical Information of China (English)

    2012-01-01

    Determination of the Estrogen Alkylphenols and Bisphenol A in Marine Sediments by Gas Chromatography-Mass Spectrometry Deng Xu-xiu et al. (1) Abstract Octylphenol, nonylphenol and bisphenol A are recognized environmental endocrine disruptors. A quantitative method was established for the simultaneous determination of octylphenol, nonylphenol and bisphenol A in marine sediments by gas chromatography-mass spectrometry. The test sample was extracted by methanol with ultrasonic technique, purified with copper powder and carbon solid phase extraction column, and derived with heptafluorobutyric anhydride. Then the analytes were separated on HP-5ms column and determined by gas chromatography-mass. The recovery of the method was between 84.3% and 94.5%, and the LOQ of 4-N- octylphenol, nonylphenol and bisphenol A was 0.25 g/kg, 0.15 g/kg and 0.15 g/kg. Key words octylphenol; nonylphenol; bisphenol A; gas chromatography-mass spectrometry

  5. A LARI Experience (Abstract)

    Science.gov (United States)

    Cook, M.

    2015-12-01

    (Abstract only) In 2012, Lowell Observatory launched The Lowell Amateur Research Initiative (LARI) to formally involve amateur astronomers in scientific research by bringing them to the attention of and helping professional astronomers with their astronomical research. One of the LARI projects is the BVRI photometric monitoring of Young Stellar Objects (YSOs), wherein amateurs obtain observations to search for new outburst events and characterize the colour evolution of previously identified outbursters. A summary of the scientific and organizational aspects of this LARI project, including its goals and science motivation, the process for getting involved with the project, a description of the team members, their equipment and methods of collaboration, and an overview of the programme stars, preliminary findings, and lessons learned is presented.

  6. ABSTRACTS AND KEY WORDS

    Institute of Scientific and Technical Information of China (English)

    2011-01-01

    Acute Toxicity Test of Four Drugs to Perch Fries Zhu You-fang et al(1) Abstract Acute toxicity test of four drugs to perch Lateolabrax maculates were studied. The results showed: (1)The LC50 values of perch to copper sulfate was 4.58 mg/L(24h), 2.93 mg/ L(48h), 1.81 mg/L(72h) and 0.78 mg/L (96h) respectively; to SHA CHONG WEI was 35.11 mg/ L(24h), 15.81 mg/L(48h), 11.20 mg/L(72h), 9.36 mg/ L (96h)respectively;

  7. Abstracts of Selected Papers

    Institute of Scientific and Technical Information of China (English)

    2012-01-01

    On the Social Solidarity of Organization An Empirical Analysis Li Hanlin Abstract: Based on the 2002 survey data, this paper tries to measure solidarity in organization. The operationalization for this measurement goes from two points of view. One is from the degree of cohesion and another one is from the degree of vulnerability. To observe and measure the degree of cohesion three subscales like social support, vertical integration and organizational identity have been used. To observe and measure the degree of vulnerability other three subscales like dissatisfaction, relative deprivation and anomie have been used. The paper tries to explore finally under which condition the organization behavior and behavior orientation could go to the similarity or make some difference. Key words: Organization Cohesion Vulnerability Organization Behavior

  8. Contents and Abstracts

    Institute of Scientific and Technical Information of China (English)

    2012-01-01

    [Ancient Mediterranean Civilizations] Title: On Poseidon's Image in Homeric Epics Author: Zhu Yizhang, Lecturer, School of History and Culture, Shandong University, Jinan, Shandong, 250100, China. Abstract: Poseidon was an important role in religion, myth and literature of ancient Greece. His religious functions, and status in mythical image in literature were mainly established by Homeric Epics. Poseidon doesn't only appear frequently in the Homeric Epics but also influences the development of the plots directly; therefore, he could be seen as one of the most important gods in the Epics. But Homeric Epics do not introduce his basic image clearly. In Homeric Epics, Poseidon carries the deity and humanity aspect of the figure, and the latter was emphasized, which implied his archetype was a mortal wanax.

  9. Problems in abstract algebra

    CERN Document Server

    Wadsworth, A R

    2017-01-01

    This is a book of problems in abstract algebra for strong undergraduates or beginning graduate students. It can be used as a supplement to a course or for self-study. The book provides more variety and more challenging problems than are found in most algebra textbooks. It is intended for students wanting to enrich their learning of mathematics by tackling problems that take some thought and effort to solve. The book contains problems on groups (including the Sylow Theorems, solvable groups, presentation of groups by generators and relations, and structure and duality for finite abelian groups); rings (including basic ideal theory and factorization in integral domains and Gauss's Theorem); linear algebra (emphasizing linear transformations, including canonical forms); and fields (including Galois theory). Hints to many problems are also included.

  10. Stellar Presentations (Abstract)

    Science.gov (United States)

    Young, D.

    2015-12-01

    (Abstract only) The AAVSO is in the process of expanding its education, outreach and speakers bureau program. powerpoint presentations prepared for specific target audiences such as AAVSO members, educators, students, the general public, and Science Olympiad teams, coaches, event supervisors, and state directors will be available online for members to use. The presentations range from specific and general content relating to stellar evolution and variable stars to specific activities for a workshop environment. A presentation—even with a general topic—that works for high school students will not work for educators, Science Olympiad teams, or the general public. Each audience is unique and requires a different approach. The current environment necessitates presentations that are captivating for a younger generation that is embedded in a highly visual and sound-bite world of social media, twitter and U-Tube, and mobile devices. For educators, presentations and workshops for themselves and their students must support the Next Generation Science Standards (NGSS), the Common Core Content Standards, and the Science Technology, Engineering and Mathematics (STEM) initiative. Current best practices for developing relevant and engaging powerpoint presentations to deliver information to a variety of targeted audiences will be presented along with several examples.

  11. Exoplanets and Multiverses (Abstract)

    Science.gov (United States)

    Trimble, V.

    2016-12-01

    (Abstract only) To the ancients, the Earth was the Universe, of a size to be crossed by a god in a day, by boat or chariot, and by humans in a lifetime. Thus an exoplanet would have been a multiverse. The ideas gradually separated over centuries, with gradual acceptance of a sun-centered solar system, the stars as suns likely to have their own planets, other galaxies beyond the Milky Way, and so forth. And whenever the community divided between "just one' of anything versus "many," the "manies" have won. Discoveries beginning in 1991 and 1995 have gradually led to a battalion or two of planets orbiting other stars, very few like our own little family, and to moderately serious consideration of even larger numbers of other universes, again very few like our own. I'm betting, however, on habitable (though not necessarily inhabited) exoplanets to be found, and habitable (though again not necessarily inhabited) universes. Only the former will yield pretty pictures.

  12. Automated Supernova Discovery (Abstract)

    Science.gov (United States)

    Post, R. S.

    2015-12-01

    (Abstract only) We are developing a system of robotic telescopes for automatic recognition of Supernovas as well as other transient events in collaboration with the Puckett Supernova Search Team. At the SAS2014 meeting, the discovery program, SNARE, was first described. Since then, it has been continuously improved to handle searches under a wide variety of atmospheric conditions. Currently, two telescopes are used to build a reference library while searching for PSN with a partial library. Since data is taken every night without clouds, we must deal with varying atmospheric and high background illumination from the moon. Software is configured to identify a PSN, reshoot for verification with options to change the run plan to acquire photometric or spectrographic data. The telescopes are 24-inch CDK24, with Alta U230 cameras, one in CA and one in NM. Images and run plans are sent between sites so the CA telescope can search while photometry is done in NM. Our goal is to find bright PSNs with magnitude 17.5 or less which is the limit of our planned spectroscopy. We present results from our first automated PSN discoveries and plans for PSN data acquisition.

  13. Judgement of abstract paintings

    Directory of Open Access Journals (Sweden)

    Dakulović Sandra

    2006-01-01

    Full Text Available In two experiments the judgement of twenty one abstract paintings was investigated. In Experiment 1, subjects were asked to make similarity judgements of 210 pairs of paintings on a 7 step bipolar scale (similar-dissimilar. The Multi-dimensional scaling (MDS method was used for data analysis. The distribution of paintings within MDS 2-D space suggested two grouping criteria: colorfullness (e.g. from Klee to Kline and geometrization (e.g. from Vasarely to Kandinsky. In Experiment 2, subjects were asked to judge the same paintings on three factors of the instrument SDF 9 (Marković et al., 2002b: Evaluation, Arousal and Regularity. The purpose of this experiment was to specify the subjective criteria on which the (dissimilarity judgements were based. In the regression analysis the three factors of SDF 9 were defined as predictors, whereas the x and y coordinates of MDS 2-D space were defined as dependent variables. The results have shown that the dimension x was reducible to the Evaluation factor, and dimension y is reducible to the Regularity factor.

  14. Abstraction of Drift Seepage

    Energy Technology Data Exchange (ETDEWEB)

    J.T. Birkholzer

    2004-11-01

    This model report documents the abstraction of drift seepage, conducted to provide seepage-relevant parameters and their probability distributions for use in Total System Performance Assessment for License Application (TSPA-LA). Drift seepage refers to the flow of liquid water into waste emplacement drifts. Water that seeps into drifts may contact waste packages and potentially mobilize radionuclides, and may result in advective transport of radionuclides through breached waste packages [''Risk Information to Support Prioritization of Performance Assessment Models'' (BSC 2003 [DIRS 168796], Section 3.3.2)]. The unsaturated rock layers overlying and hosting the repository form a natural barrier that reduces the amount of water entering emplacement drifts by natural subsurface processes. For example, drift seepage is limited by the capillary barrier forming at the drift crown, which decreases or even eliminates water flow from the unsaturated fractured rock into the drift. During the first few hundred years after waste emplacement, when above-boiling rock temperatures will develop as a result of heat generated by the decay of the radioactive waste, vaporization of percolation water is an additional factor limiting seepage. Estimating the effectiveness of these natural barrier capabilities and predicting the amount of seepage into drifts is an important aspect of assessing the performance of the repository. The TSPA-LA therefore includes a seepage component that calculates the amount of seepage into drifts [''Total System Performance Assessment (TSPA) Model/Analysis for the License Application'' (BSC 2004 [DIRS 168504], Section 6.3.3.1)]. The TSPA-LA calculation is performed with a probabilistic approach that accounts for the spatial and temporal variability and inherent uncertainty of seepage-relevant properties and processes. Results are used for subsequent TSPA-LA components that may handle, for example, waste package

  15. Hydroxyl radical (OH•) reaction with guanine in an aqueous environment: a DFT study.

    Science.gov (United States)

    Kumar, Anil; Pottiboyina, Venkata; Sevilla, Michael D

    2011-12-22

    The reaction of hydroxyl radical (OH(•)) with DNA accounts for about half of radiation-induced DNA damage in living systems. Previous literature reports point out that the reaction of OH(•) with DNA proceeds mainly through the addition of OH(•) to the C═C bonds of the DNA bases. However, recently it has been reported that the principal reaction of OH(•) with dGuo (deoxyguanosine) is the direct hydrogen atom abstraction from its exocyclic amine group rather than addition of OH(•) to the C═C bonds. In the present work, these two reaction pathways of OH(•) attack on guanine (G) in the presence of water molecules (aqueous environment) are investigated using the density functional theory (DFT) B3LYP method with 6-31G* and 6-31++G** basis sets. The calculations show that the initial addition of the OH(•) at C(4)═C(5) double bond of guanine is barrier free and the adduct radical (G-OH(•)) has only a small activation barrier of ca. 1-6 kcal/mol leading to the formation of a metastable ion-pair intermediate (G(•+)---OH(-)). The formation of ion-pair is a result of the highly oxidizing nature of the OH(•) in aqueous media. The resulting ion-pair (G(•+)---OH(-)) deprotonates to form H(2)O and neutral G radicals favoring G(N(1)-H)(•) with an activation barrier of ca. 5 kcal/mol. The overall process from the G(C(4))-OH(•) (adduct) to G(N(1)-H)(•) and water is found to be exothermic in nature by more than 13 kcal/mol. (G-OH(•)), (G(•+)---OH(-)), and G(N(1)-H)(•) were further characterized by the CAM-B3LYP calculations of their UV-vis spectra and good agreement between theory and experiment is achieved. Our calculations for the direct hydrogen abstraction pathway from N(1) and N(2) sites of guanine by the OH(•) show that this is also a competitive route to produce G(N(2)-H)(•), G(N(1)-H)(•) and H(2)O.

  16. Summer 2015 Internship Abstract

    Science.gov (United States)

    Smith, Courtney

    2015-01-01

    Green fluorescent protein (GFP) visually shows the expression of proteins by fluorescing when exposed to certain wavelengths of light. The GFP in this experiment was used to identify cells actively releasing viruses. The experiment focused on the effect of microgravity on the GFP expression of Akata B-cells infected with Epstein Barr Virus (EBV). Two flasks were prepared with 30 million cells each and two bioreactors were prepared with 50 million cells each. All four cultures were incubated for 16 days and fed every four days. Cellometer readings were taken on the feeding days to find cell size, viability, and GFP expression. In addition, the cells were treated with Propodium monoazide (PMA) and run through real time PCR to determine viral load on the feeding days. On the International Space Station air samples are taken to analyze the bacterial and fungal organisms in the air. The Sartorius Portable Airport is being investigated for potential use on the ISS to analyze for viral content in the air. Multiple samples were taken around Johnson Space Center building 37 and in Clear Lake Pediatric Clinic. The filter used was the gelatin membrane filter and the DNA was extracted directly from the filter. The DNA was then run through real time PCR for Varicella Zoster Virus (VZV) and EBV as well as GAPDH to test for the presence of DNA. The results so far have shown low DNA yield and no positive results for VZV or EBV. Further inquiry involves accurately replicating an atmosphere with high viral load from saliva as would be found on the ISS to run the air sampler in. Another line of research is stress hormones that may be correlated to the reactivation of latent viruses. The stress hormones from saliva samples are analyzed rather than blood samples. The quantity found in saliva shows the quantity of the hormones actually attached to cells and causing a reaction, whereas in the blood the quantity of hormones is the total amount released to cause a reaction. The particular

  17. Interaction of interstitial hydrogen atoms within h.c.p. metals and distribution of diffuse radiation-scattering intensity in reciprocal space

    Energy Technology Data Exchange (ETDEWEB)

    Tatarenko, V.A. [G.V. Kurdyumov Inst. for Metal Physics, Kyyiv (Ukraine). Dept. of Soilid State Theory

    2001-05-01

    A microscopic model for the strain-controlled atomic ordering of interstitial impurity atoms and for the strain-induced decomposition reaction in their solid solutions based on host crystals with a polyatomic basis is used. It takes into account the 'blocking' and static-displacements' effects in interactions between impurity atoms arranged on different-type interstices, in order to explain the salient features of distribution of the diffuse-scattering intensity in reciprocal space for such interstitial solid solutions based on some hexagonal close-packed (h.c.p.) transition and rare-earth metals. (Author)

  18. Consultation document: risk management measure for benzenamine, N-phenyl-, reaction products with styrene and 2,4, 4-trimethylpentene (BNST)[Chemical Abstracts Service Registry Number (CAS RN): 68921-45-9

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    2010-10-15

    The Benzenamine, N-phenyl-, reaction products with styrene and 2,4,4-Trimethylpentene, also known as BNST, is a chemical substance that has been analysed by the Government of Canada in order to determine if the substance could generate harmful effects on the environment. The main use of BNST, according to industry information, is as an antioxidant in vehicle engine oils. The analysis concluded that BNST is persistent, bioaccumulative and may have harmful effects on aquatic organisms. In August 2009, considering the results of the examination, the Government of Canada suggested in a consultation paper to add BNST to the Prohibition of Certain Toxic Substances Regulations, 2005. The report provides elements to promote discussion and allow interested stakeholders to give their opinion and provide data regarding the addition of BNST to these regulations. 4 refs.

  19. Gas-Phase Intercluster Thiyl-Radical Induced C-H Bond Homolysis Selectively Forms Sugar C2-Radical Cations of Methyl D-Glucopyranoside: Isotopic Labeling Studies and Cleavage Reactions

    Science.gov (United States)

    Osburn, Sandra; Speciale, Gaetano; Williams, Spencer J.; O'Hair, Richard A. J.

    2017-07-01

    A suite of isotopologues of methyl D-glucopyranosides is used in conjunction with multistage mass spectrometry experiments to determine the radical site and cleavage reactions of sugar radical cations formed via a recently developed `bio-inspired' method. In the first stage of CID (MS2), collision-induced dissociation (CID) of a protonated noncovalent complex between the sugar and S-nitrosocysteamine, [H3NCH2CH2SNO + M]+, unleashes a thiyl radical via bond homolysis to give the noncovalent radical cation, [H3NCH2CH2S• + M]+. CID (MS3) of this radical cation complex results in dissociation of the noncovalent complex to generate the sugar radical cation. Replacement of all exchangeable OH and NH protons with deuterons reveals that the sugar radical cation is formed in a process involving abstraction of a hydrogen atom from a C-H bond of the sugar coupled with proton transfer to the sugar, to form [M - H• + D+]. Investigation of this process using individual C-D labeled sugars reveals that the main site of H/D abstraction is the C2 position, since only the C2-deuterium labeled sugar yields a dominant [M - D• + H+] product ion. The fragmentation reactions of the distonic sugar radical cation, [M - H•+ H+], were studied by another stage of CID (MS4). 13C-labeling studies revealed that a series of three related fragment ions each contain the C1-C3 atoms; these arise from cross-ring cleavage reactions of the sugar.

  20. Using abstract language signals power.

    Science.gov (United States)

    Wakslak, Cheryl J; Smith, Pamela K; Han, Albert

    2014-07-01

    Power can be gained through appearances: People who exhibit behavioral signals of power are often treated in a way that allows them to actually achieve such power (Ridgeway, Berger, & Smith, 1985; Smith & Galinsky, 2010). In the current article, we examine power signals within interpersonal communication, exploring whether use of concrete versus abstract language is seen as a signal of power. Because power activates abstraction (e.g., Smith & Trope, 2006), perceivers may expect higher power individuals to speak more abstractly and therefore will infer that speakers who use more abstract language have a higher degree of power. Across a variety of contexts and conversational subjects in 7 experiments, participants perceived respondents as more powerful when they used more abstract language (vs. more concrete language). Abstract language use appears to affect perceived power because it seems to reflect both a willingness to judge and a general style of abstract thinking.

  1. The effects of surface temperature on the gas-liquid interfacial reaction dynamics of O(3P)+squalane

    Science.gov (United States)

    Köhler, Sven P. K.; Allan, Mhairi; Kelso, Hailey; Henderson, David A.; McKendrick, Kenneth G.

    2005-01-01

    OH/OD product state distributions arising from the reaction of gas-phase O(3P) atoms at the surface of the liquid hydrocarbon squalane C30H62/C30D62 have been measured. The O(3P) atoms were generated by 355 nm laser photolysis of NO2 at a low pressure above the continually refreshed liquid. It has been shown unambiguously that the hydroxyl radicals detected by laser-induced fluorescence originate from the squalane surface. The gas-phase OH/OD rotational populations are found to be partially sensitive to the liquid temperature, but do not adapt to it completely. In addition, rotational temperatures for OH/OD(v'=1) are consistently colder (by 34±5 K) than those for OH/OD(v'=0). This is reminiscent of, but less pronounced than, a similar effect in the well-studied homogeneous gas-phase reaction of O(3P) with smaller hydrocarbons. We conclude that the rotational distributions are composed of two different components. One originates from a direct abstraction mechanism with product characteristics similar to those in the gas phase. The other is a trapping-desorption process yielding a thermal, Boltzmann-like distribution close to the surface temperature. This conclusion is consistent with that reached previously from independent measurements of OH product velocity distributions in complementary molecular-beam scattering experiments. It is further supported by the temporal profiles of OH/OD laser-induced fluorescence signals as a function of distance from the surface observed in the current experiments. The vibrational branching ratios for (v'=1)/(v'=0) for OH and OD have been found to be (0.07±0.02) and (0.30±0.10), respectively. The detection of vibrationally excited hydroxyl radicals suggests that secondary and/or tertiary hydrogen atoms may be accessible to the attacking oxygen atoms.

  2. Selective Oxygenation of Cyclohexene by Dioxygen via an Iron(V)-Oxo Complex-Autocatalyzed Reaction.

    Science.gov (United States)

    Sankaralingam, Muniyandi; Lee, Yong-Min; Nam, Wonwoo; Fukuzumi, Shunichi

    2017-05-01

    An iron complex with a tetraamido macrocyclic ligand, [(TAML)Fe(III)](-), was found to be an efficient and selective catalyst for allylic oxidation of cyclohexene by dioxygen (O2); cyclohex-2-enone was obtained as the major product along with cyclohexene oxide as the minor product. An iron(V)-oxo complex, [(TAML)Fe(V)(O)](-), which was formed by activating O2 in the presence of cyclohexene, initiated the autoxidation of cyclohexene with O2 to produce cyclohexenyl hydroperoxide, which reacted with [(TAML)Fe(III)](-) to produce [(TAML)Fe(V)(O)](-) by autocatalysis. Then, [(TAML)Fe(V)(O)](-) reacted rapidly with [(TAML)Fe(III)](-) to produce a μ-oxo dimer, [(TAML)Fe(IV)(O)Fe(IV)(TAML)](2-), which was ultimately converted to [(TAML)Fe(V)(O)](-) when [(TAML)Fe(III)](-) was not present in the reaction solution. An induction period was observed in the autocatalytic production of [(TAML)Fe(V)(O)](-). The induction period was shortened with increasing catalytic amounts of [(TAML)Fe(V)(O)](-) and cyclohexenyl hydroperoxide, whereas the induction period was prolonged by adding catalytic amounts of a spin trapping reagent such as 5,5-dimethyl-1-pyrroline N-oxide (DMPO). The allylic oxidation of cycloalkenes was also found to depend on the allylic C-H bond dissociation energies, suggesting that the hydrogen atom abstraction from the allylic C-H bonds of cycloalkenes is the rate-determining radical chain initiation step. In this study, we have shown that an iron(III) complex with a tetraamido macrocyclic ligand is an efficient catalyst for the allylic oxidation of cyclohexene via an autocatalytic radical chain mechanism and that [(TAML)Fe(V)(O)](-) acts as a reactive intermediate for the selective oxygenation of cyclohexene with O2 to produce cyclohex-2-enone predominantly.

  3. 氢原子电多极动态极化率的解析表达式及其应用%Analytical Multipole Dynamic Polarizabilities of Hydrogen Atoms and its Application

    Institute of Scientific and Technical Information of China (English)

    黄时中; 李增

    2012-01-01

    在Tang和Chan所给出的氢原子的2l-极动态极化率的微分表达式的基础上,进一步导出了氢原子电多极动态极化率的解析表达式,从而完全解决了氢原子动态极化率的计算问题.应用此解析表达式,首次计算了氢原子H(2s)-H(2s)-H(2s)体系的三体相互作用系数.%An analytic expression for the 2l-pole dynamic polarizability of hydrogen atom in an arbitrary state is derived from a differential expression obtained by Tang and Chan,and the problem of calculating the 2l-pole dynamic polarizability of hydrogen is solved.As an application,new three-body van der Waals dispersion coefficients for the H (2s)-H(2s)-H (2s) system are calculated from integrals of products of the dynamic polarizabilities of the interacting atoms.

  4. 氢原子能级与碱金属原子能级的比较研究%Comparative Studying of Hydrogen Atomic Energy Level and Alkali Metal Atomic Energy Level

    Institute of Scientific and Technical Information of China (English)

    王建伟; 蒲小芹

    2014-01-01

    The article by Bohr theory and The analysis of forces method, considered the interaction of different sit-uation, hydrogen atoms with alkali metal atomic energy level structure have been analyzed, and the numerical cal-culation, energy level diagram have been drawn out., Hydrogen energy and alkali metal atomic energy level were compared, by using the method of comparative study on the similarities and differences are found out.%运用玻尔理论及受力分析的方法,考虑相互作用的不同情况,分析了氢原子与碱金属原子能级结构,并进行了数值计算,画出了能级结构图。再运用比较研究的方法对氢原子能级与碱金属原子能级进行比较,找出其相同点及不同点。

  5. Reaction rate constant of CH2O + H = HCO + H2 revisited: a combined study of direct shock tube measurement and transition state theory calculation.

    Science.gov (United States)

    Wang, Shengkai; Dames, Enoch E; Davidson, David F; Hanson, Ronald K

    2014-11-06

    The rate constant of the H-abstraction reaction of formaldehyde (CH2O) by hydrogen atoms (H), CH2O + H = H2 + HCO, has been studied behind reflected shock waves with use of a sensitive mid-IR laser absorption diagnostic for CO, over temperatures of 1304-2006 K and at pressures near 1 atm. C2H5I was used as an H atom precursor and 1,3,5-trioxane as the CH2O precursor, to generate a well-controlled CH2O/H reacting system. By designing the experiments to maintain relatively constant H atom concentrations, the current study significantly boosted the measurement sensitivity of the target reaction and suppressed the influence of interfering reactions. The measured CH2O + H rate constant can be expressed in modified Arrhenius from as kCH2O+H(1304-2006 K, 1 atm) = 1.97 × 10(11)(T/K)(1.06) exp(-3818 K/T) cm(3) mol(-1)s(-1), with uncertainty limits estimated to be +18%/-26%. A transition-state-theory (TST) calculation, using the CCSD(T)-F12/VTZ-F12 level of theory, is in good agreement with the shock tube measurement and extended the temperature range of the current study to 200-3000 K, over which a modified Arrhenius fit of the rate constant can be expressed as kCH2O+H(200-3000 K) = 5.86 × 10(3)(T/K)(3.13) exp(-762 K/T) cm(3) mol(-1)s(-1).

  6. Modal abstractions of concurrent behavior

    DEFF Research Database (Denmark)

    Nielson, Flemming; Nanz, Sebastian; Nielson, Hanne Riis

    2011-01-01

    We present an effective algorithm for the automatic construction of finite modal transition systems as abstractions of potentially infinite concurrent processes. Modal transition systems are recognized as valuable abstractions for model checking because they allow for the validation as well...... as refutation of safety and liveness properties. However, the algorithmic construction of finite abstractions from potentially infinite concurrent processes is a missing link that prevents their more widespread usage for model checking of concurrent systems. Our algorithm is a worklist algorithm using concepts...

  7. Mechanical Engineering Department technical abstracts

    Energy Technology Data Exchange (ETDEWEB)

    Denney, R.M. (ed.)

    1982-07-01

    The Mechanical Engineering Department publishes listings of technical abstracts twice a year to inform readers of the broad range of technical activities in the Department, and to promote an exchange of ideas. Details of the work covered by an abstract may be obtained by contacting the author(s). Overall information about current activities of each of the Department's seven divisions precedes the technical abstracts.

  8. Hedonism in Abstract Art: Minimalist digital abstract photography

    Directory of Open Access Journals (Sweden)

    Srdjan Jovanović

    2009-06-01

    Full Text Available In this piece of writing the writer/artist puts forward the view that art can be understood and taken in as sometimes purely hedonistic. By drawing upon the theories pertaining to hedonism, he applies this view to minimalist digital abstract photography and tries to justify his point of view with the help of three abstract photographs.

  9. Potential energy surfaces and reaction dynamics of polyatomic molecules

    Energy Technology Data Exchange (ETDEWEB)

    Chang, Yan-Tyng.

    1991-11-01

    A simple empirical valence bond (EVB) model approach is suggested for constructing global potential energy surfaces for reactions of polyatomic molecular systems. This approach produces smooth and continuous potential surfaces which can be directly utilized in a dynamical study. Two types of reactions are of special interest, the unimolecular dissociation and the unimolecular isomerization. For the first type, the molecular dissociation dynamics of formaldehyde on the ground electronic surface is investigated through classical trajectory calculations on EVB surfaces. The product state distributions and vector correlations obtained from this study suggest very similar behaviors seen in the experiments. The intramolecular hydrogen atom transfer in the formic acid dimer is an example of the isomerization reaction. High level ab initio quantum chemistry calculations are performed to obtain optimized equilibrium and transition state dimer geometries and also the harmonic frequencies.

  10. Abstract concepts in grounded cognition

    NARCIS (Netherlands)

    Lakens, D.

    2010-01-01

    When people think about highly abstract concepts, they draw upon concrete experiences to structure their thoughts. For example, black knights in fairytales are evil, and knights in shining armor are good. The sensory experiences black and white are used to represent the abstract concepts of good and

  11. Modal abstractions of concurrent behavior

    DEFF Research Database (Denmark)

    Nielson, Flemming; Nanz, Sebastian; Nielson, Hanne Riis

    2011-01-01

    We present an effective algorithm for the automatic construction of finite modal transition systems as abstractions of potentially infinite concurrent processes. Modal transition systems are recognized as valuable abstractions for model checking because they allow for the validation as well as re...

  12. Vague Language in Conference Abstracts

    Science.gov (United States)

    Cutting, Joan

    2012-01-01

    This study examined abstracts for a British Association for Applied Linguistics conference and a Sociolinguistics Symposium, to define the genre of conference abstracts in terms of vague language, specifically universal general nouns (e.g. people) and research general nouns (e.g. results), and to discover if the language used reflected the level…

  13. Food Science and Technology Abstracts.

    Science.gov (United States)

    Cohen, Elinor; Federman, Joan

    1979-01-01

    Introduces the reader to the Food Science and Technology Abstracts, a data file that covers worldwide literature on human food commodities and aspects of food processing. Topics include scope, subject index, thesaurus, searching online, and abstracts; tables provide a comparison of ORBIT and DIALOG versions of the file. (JD)

  14. Abstract models of transfinite reductions

    DEFF Research Database (Denmark)

    Bahr, Patrick

    2010-01-01

    We investigate transfinite reductions in abstract reduction systems. To this end, we study two abstract models for transfinite reductions: a metric model generalising the usual metric approach to infinitary term rewriting and a novel partial order model. For both models we distinguish between...

  15. Technical abstracts: Mechanical engineering, 1990

    Energy Technology Data Exchange (ETDEWEB)

    Broesius, J.Y. (comp.)

    1991-03-01

    This document is a compilation of the published, unclassified abstracts produced by mechanical engineers at Lawrence Livermore National Laboratory (LLNL) during the calendar year 1990. Many abstracts summarize work completed and published in report form. These are UCRL-JC series documents, which include the full text of articles to be published in journals and of papers to be presented at meetings, and UCID reports, which are informal documents. Not all UCIDs contain abstracts: short summaries were generated when abstracts were not included. Technical Abstracts also provides descriptions of those documents assigned to the UCRL-MI (miscellaneous) category. These are generally viewgraphs or photographs presented at meetings. An author index is provided at the back of this volume for cross referencing.

  16. Abstract algebra structure and application

    CERN Document Server

    Finston, David R

    2014-01-01

    This text seeks to generate interest in abstract algebra by introducing each new structure and topic via a real-world application. The down-to-earth presentation is accessible to a readership with no prior knowledge of abstract algebra. Students are led to algebraic concepts and questions in a natural way through their everyday experiences. Applications include: Identification numbers and modular arithmetic (linear) error-correcting codes, including cyclic codes ruler and compass constructions cryptography symmetry of patterns in the real plane Abstract Algebra: Structure and Application is suitable as a text for a first course on abstract algebra whose main purpose is to generate interest in the subject, or as a supplementary text for more advanced courses. The material paves the way to subsequent courses that further develop the theory of abstract algebra and will appeal to students of mathematics, mathematics education, computer science, and engineering interested in applications of algebraic concepts.

  17. ABSTRACTS

    Institute of Scientific and Technical Information of China (English)

    2011-01-01

    Wu Jie and Duan Yanchao. The current line drawing of Laterolog and its application. PI, 2011, 25(4) : 1 - 4 The current line plays an important role in the directly understanding the characteristics of Laterolog tool. A method of drawing current lines for the discrete potential data based on the Finite Element calculation is studied. It solves a series of key problems, including the selection of step length, the identification of direction, treatment of nmtation point and the control of stop. A drawing program is written by MATLAB software. Taking the current line drawing of the dual Laterolog logging as an example, we analyze the tool's investigation characteristics in the several formations such as homogeneous, low or high invasion, and invasion with shoulder. These results verify the effectiveness of the new method. The method can be applied to the other kinds of Laterolog tools to draw their current lines and analyze their investigation characteristics.

  18. ABSTRACTS

    Institute of Scientific and Technical Information of China (English)

    2011-01-01

    Through-bit-logging (TBL) technology is developed corporately by Shell and Reeves Oil Company. It can replace standard cable logging and logging while drilling technology. It has characteristics of saving cost and convenient operation.The principle is to transmit the logging tool into borehole through drill rod with a special bit. The acquired formation evaluation data are read on surface from the wire line tool or stored in the tool before pulling out the hole.The paper introduces the principle of work, advantages and development trend of TBL, and cases of its application in rough borehole in North Sea fields. Finally development of TBL technology is summarized. Keywords: TBL; logging while drilling wireline logging

  19. ABSTRACTS

    Institute of Scientific and Technical Information of China (English)

    2011-01-01

    Liu Diren, Xie Weibiao, Yin Qiuli and Zhou Liyan. Study on the Influence of induction logging response on tool eccentricity in horizontal well. Jiang Yiqing, Xu Lin, Wang Jianmin and Du Hui. Simulation of time spectrum by oxygen activation logging.Zhang Jiawei, Song Gongpu, Sai Fang, Xue Zhibo. Design of simulator based on NMR downhole tools.

  20. ABSTRACTS

    Institute of Scientific and Technical Information of China (English)

    2012-01-01

    Zhang Xionghui, You Chang, Tang Jie, Zhou Qizhi, Xu Feng, Li Ganghan and Ma Yan. Development of a series of logging tool long-time working under high temperature and high pressure condition. PI, 2012,26 (3) : 1-3

  1. ABSTRACTS

    Institute of Scientific and Technical Information of China (English)

    2011-01-01

    1.APPLICATION OF VSP TECHNOLOGY OF GREAT WALL DRILLING COMPANY IN OIL AND GAS EXPLORATION ABROAD/Du Xudong., Huang Daqin, Zhao Qihui.2011 (6)8-13 ( Interpretation Research Center of Great Wall Drilling Engineering Company ) Development and perfection of VSP technology have close relationship with the requirements of production. The paper presents 6 aspects of application about VSP technology in oil and gas exploration abroad: lproviding high-precision interpretation result----high-precision time-depth;

  2. ABSTRACTS

    Institute of Scientific and Technical Information of China (English)

    2012-01-01

    Overview of the development of the hybrid locomotive at home and abroad TIAN Rui, KANG Yi-nan (Dalian Locomotive Research Institute Co., Ltd., Dalian 116021, China ) Abstract: This paper analyzes the structure principle and classification feature of hybrid locomotive from the perspective of energy saving and emission reduction, discussing the key technology and summarizing its development and application at home and abroad. On this basis, the development prospect and problems to be solved of hybrid locomotive are analyzed. Key words: hybrid locomotive; principle; classification; application; prospect

  3. ABSTRACT

    African Journals Online (AJOL)

    identification of the poor and their characteristics; they should be given a chance to ... established to help eradicate the poverty, which include the People Empowerment ... Welfare Service Scheme has programmes like: Special Education ...

  4. ABSTRACTS

    Institute of Scientific and Technical Information of China (English)

    2012-01-01

    A Representative work that Vainly Attempts to Westernize China On Yang Ji.sheng's Paper "My View of Chinese Pattern" XU Chong-wenAbstract: Mr. Yang Ji-sheng calls economic connotation of Chinese pattern "market economy of power" with all sorts of drawbacks, it is to take the problems that Chinese model deliberately struggles with and even the objects must be resolutely eliminated as the parts of Chinese pattern, thus they are absolute nonsense; he boils down political connotation of Chinese pattern to "authority politics" of "thoroughly denying modem democratic system",

  5. Abstracts

    National Research Council Canada - National Science Library

    2016-01-01

    ... , Abduljaleel Al Alwan 1,2 , Abeer Ibrahim 4 , Hadi Kuriry 3 , Ali Albenmousa 6 1 Department of Hepatobiliary Sciences, Division of Hepatology, King Abdulaziz Medical City, National Guard Health Affairs, 2...

  6. Abstract

    Institute of Scientific and Technical Information of China (English)

    2011-01-01

    Representation or Construction? An Interpretation of Quantum Field Theory Abstract: In this essay, I argue that the basic entities in the causality organized hierarchy of entities that quantum field theory describes are not particles but fields. Then I

  7. ABSTRACTS

    Institute of Scientific and Technical Information of China (English)

    2012-01-01

    On the Logic of Heart and the Intuitive Approach: An Outline of Modern Idealism Linked Chinese and Western Philosophical Ideas,A Reflection and Analogical Interpretation of Active Justice,Channel of the Effectiveness of Public Policy in the Perspective of Social Equality: A Theoretical Analysis of the Efficacy of Public Policy

  8. ABSTRACTS

    Institute of Scientific and Technical Information of China (English)

    2012-01-01

    Chinese foreign trade enterprises enter the crucial period of transformation and upgrade The global economy is likely into a long-term downturn and recovery is difficult. For a long time, the foreign trade development environment is difficult to be improved obviously. Many negative factors are overlaid and will bring the foreign trade greater challenge. Impacted by the dual factors of intemational market fluctuation, domestic economic environment tightening,

  9. Abstract

    African Journals Online (AJOL)

    dell

    per week; processed in a team work, and finalized by a local work shop accommodating the ... biological, health sciences, social sciences ... the new education and training policy of Ethiopia ...... schools were budget, staff shortage, classrooms ...

  10. ABSTRACTS

    Institute of Scientific and Technical Information of China (English)

    2012-01-01

    Effect of Coolant Temperature on Fuel Consumption and Emissions in YC6A220C Diesel Engine;Optimizing NOx emission performance for 16V280ZC diesel engine;CA3-13 coupler of DFsBI diesel locomotive exported to Iran;Mixed traction technology with LOCOTROL system;

  11. ABSTRACTS

    Institute of Scientific and Technical Information of China (English)

    2011-01-01

    Design of the LabVIEW-based test stand for diesel engine hydraulic governor ZHANG Wei-dong1, LIU Li-hua2, ZONG Ya-ping1 ( 1. Air Force Radar Academy, Wuhan 430019, China; 2. Second Artillery Command College, Wuhan 430019, China)Abstract: the test stand The structure for diesel engine and working principle of hydraulic governor were introduced. The user interface, speed governing curves display and data analysis were realized by IabVIEW to conduct calibration and draulic governor diagnosis for diesel engine hy-

  12. ABSTRACTS

    Institute of Scientific and Technical Information of China (English)

    2012-01-01

    Application of UIC standards to Chinese railway traction diesel engine industry WANG Xian (Dalian Locomotive Research Institute Co., Ltd., Dalian 116021, China) Abstract: The development, main contents and the practical application of the standards for type test for Chinese railway traction diesel engine were discussed. Key words: UIC standards; locomotive diesel en- gine; type test

  13. ABSTRACTS

    Institute of Scientific and Technical Information of China (English)

    2011-01-01

    Solving the vibration problem of diesel engine and its peripheral equipments with MK II PAK analysis system,Quality situation and analysis of copper radiator for diesel locomotive,Development of cooling system for GMC-96 rail grinding car

  14. ABSTRACTS

    Institute of Scientific and Technical Information of China (English)

    2011-01-01

    Development status of domestic and foreign hydraulic transmissions;Effect of advance angle of fuel supply on exhaust emissions for a diesel engine with EGR technology;Effect on noise of diesel engine under different atmospheric preessure and biodiesel blends;Application of digital governing system to V280/285 series marine diesel engine;

  15. Abstracts

    Institute of Scientific and Technical Information of China (English)

    2012-01-01

    Post-Western International System and the Rise of the East;Hegemonlc Dependence and the Logic in the Declining Asceudance of Leading Powers;Constructive Leadership and China's Diplomatic Transformation;The Bargaining Model of International Mediation Onset:A Quantitative Test;The Imnact of Gender Differences on National Military Expenditure

  16. Abstract

    Institute of Scientific and Technical Information of China (English)

    2012-01-01

    The Establishment and Distribution of the Police Stations in the Public Concessions in Modern Shanghai -Also on the Substitution Index of the Expansion of City Space WU Heng By analyzing relevant materials, this paper finds that the total number of police stations and the population is closely related to each other and regards it as the substitution index of city expansion. The author thinks that the urbanization of the public concessions can be divided into three phases, while this process is not in synchronization with the expansion of the land expansion of public concessions.

  17. ABSTRACTS

    Institute of Scientific and Technical Information of China (English)

    2012-01-01

    South Korea's strategy and the economic and trade relations with China South Korea in a relatively short period of time has obtained the economic fast boom, creating "the Han River Miracle" remarkably. Due to the typical export-oriented economy, the South Korea is very sensitive to the international situation.

  18. Abstracts

    Institute of Scientific and Technical Information of China (English)

    2011-01-01

    Changing the Means of Structural Adjustment for Transformation of Development Pattern SONG Ze Abstract: History of China's reform and opening up has proven that government-led industrial structural adjustment is unsuccessful. Facing the new situation and economic development tasks, new ideas of industrial restructuring should be clearly put forward that the government will create conditions to adjust the structure by the market. During the Twelve-Five Years, the most priority should be how to reform the way how to change the structural adjustment. If the "structural adjustment" approach, especially in the manufacturing sector can not be changed, many goals on economic transition are likely to fall again. Under the circumstance it is necessary to accelerate the development of a unified, open and orderly modern market system, and effectively implement the market-pushed industrial restructuring approach, and strengthen the intermediary function of finance and inner trade and create good policy environment conducive to promoting the services sector in the process of structural adjustment and industrial upgrading. Key Words:industrial structure; adjustment approach

  19. ABSTRACT

    Institute of Scientific and Technical Information of China (English)

    2012-01-01

    Probe into The Production of Songhua Inkstone in Kangxi period and His Bestowing Them upon His Subjects;A Study of Kiln-Firing Production for Construction of Beijing in The Ming Dynasty: Focus on The Changes of Kiln Sites, Product Structure and Manufacture System of Supplies;More on The Design of The Large Timbers in The Structure of Daxiong Dian(Hall) of Fengguo Temple of Yi County with The Enlightenment from The Latest Research Available;

  20. ABSTRACTS

    Institute of Scientific and Technical Information of China (English)

    2011-01-01

    Energy transformation is the only way of the transformation of the world economy Describing and explaining from different view of the world from the angle of political, economic, cultural and environmental development, the presentation of the transformation, change, adjustment, conversion and a series of concept reflects that the current world situation is undergoing profound changes, multi-polarization and globalization. The global problems such as financial crisis, recession, climate change, energy transformation and the environment change,