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Sample records for abstract hydrogen atoms

  1. Concerted hydrogen-atom abstraction in photosynthetic water oxidation.

    PubMed

    Westphal, K L; Tommos, C; Cukier, R I; Babcock, G T

    2000-06-01

    Photosystem II evolves oxygen by using water in the unlikely role of a reductant. The absorption of sunlight by chlorophyll produces highly oxidizing equivalents that are filled with electrons stripped from water. This proton-coupled redox chemistry occurs at the oxygen-evolving complex, which contains a tetramanganese cluster, a redox-active tyrosine amino acid hydrogen-bonded to a histidine amino acid, a calcium ion and chloride. Hydrogen-atom abstraction by the tyrosyl radical from water bound to the manganese cluster is now widely held to occur in this process, at least for some of the steps in the catalytic cycle. We discuss kinetic and energetic constraints on the hydrogen-atom abstraction process. PMID:10837268

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

    PubMed

    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. PMID:27305520

  3. Transition state geometry in radical hydrogen atom abstraction

    NASA Astrophysics Data System (ADS)

    Denisov, Evgenii T.; Shestakov, Alexander F.; Denisova, Taisa G.

    2012-12-01

    The interatomic distances in the transition states of radical hydrogen atom abstraction reactions X•+HY → XH+Y• determined by quantum chemical calculations are systematized and generalized. It is shown that depending on the reaction centre structure, these reactions can be subdivided into classes with the same X...Y interatomic distance in each class. The transition state geometries found by the methods of intersecting parabolas and intersecting Morse curves are also presented. The X...H...Y fragments are almost linear, the hydrogen atom position being determined by the reaction enthalpy. The effects of triplet repulsion, electronegativities and radii of X and Y atoms, the presence of adjoining π-bonds, and steric effects on the X...Y interatomic distances are analyzed and characterized. The bibliography includes 62 references.

  4. THE DYNAMICS OF HYDROGEN ATOM ABSTRACTION FROM POLYATOMIC MOLECULES.

    SciTech Connect

    LIU,X.; SUITS,A.G.

    2002-11-21

    The hydrogen atom abstraction reaction is an important fundamental process that is extensively involved in atmospheric and combustion chemistry. The practical significance of this type of reaction with polyatomic hydrocarbons is manifest, which has led to many kinetics studies. The detailed understanding of these reactions requires corresponding dynamics studies. However, in comparison to the A + HX {radical} AH + X reactions, the study of the dynamics of A + HR {yields} AH + R reactions is much more difficult, both experimentally and theoretically (here and in the following, A stands for an atom, X stands for a halogen atom, and R stands for a polyatomic hydrocarbon radical). The complication stems from the structured R, in contrast to the structureless X. First of all, there are many internal degrees of freedom in R that can participate in the reaction. In addition, there are different carbon sites from which an H atom can be abstracted, and the dynamics are correspondingly different; there are also multiple identical carbon sites in HR and in the picture of a local reaction, there exist competitions between neighboring H atoms, and so on. Despite this complexity, there have been continuing efforts to obtain insight into the dynamics of these reactions. In this chapter, some examples are presented, including the reactions of ground state H, Cl, and O atoms, with particular focus on our recent work using imaging to obtain the differential cross sections for these reactions.

  5. Hydrogen bonding tunes the early stage of hydrogen-atom abstracting reaction.

    PubMed

    Yang, Yang; Liu, Lei; Chen, Junsheng; Han, Keli

    2014-09-01

    The spontaneous and collision-assisted hydrogen-atom abstracting reaction (HA) dynamics of triplet benzil are investigated through the combination of transient absorption spectroscopy with TD-DFT calculations. HA dynamics exhibit a remarkable dependence on the hydrogen donor properties. The effects of the triplet-state hydrogen bonding on the reaction dynamics are illustrated. In particular, it is experimentally observed that strengthened triplet-state hydrogen bonding could accelerate the HA, whereas weakened triplet-state hydrogen bonding would postpone the HA. The triplet-state hydrogen bonding has great influences on the early stage of the HA reaction, while the bond dissociation energy of the hydrogen donors determines the subsequent reaction pathways. Protic solvents could sustain longer lifetimes of the excited-state intermediate formed after HA than non-protic solvents by 10 μs. This investigation provides insights into the HA dynamics and guidance to improve the product efficiency of photochemical reactions. PMID:25036436

  6. Kinetic modeling of α-hydrogen abstractions from unsaturated and saturated oxygenate compounds by hydrogen atoms.

    PubMed

    Paraskevas, Paschalis D; Sabbe, Maarten K; Reyniers, Marie-Françoise; Papayannakos, Nikos G; Marin, Guy B

    2014-10-01

    Hydrogen-abstraction reactions play a significant role in thermal biomass conversion processes, as well as regular gasification, pyrolysis, or combustion. In this work, a group additivity model is constructed that allows prediction of reaction rates and Arrhenius parameters of hydrogen abstractions by hydrogen atoms from alcohols, ethers, esters, peroxides, ketones, aldehydes, acids, and diketones in a broad temperature range (300-2000 K). A training set of 60 reactions was developed with rate coefficients and Arrhenius parameters calculated by the CBS-QB3 method in the high-pressure limit with tunneling corrections using Eckart tunneling coefficients. From this set of reactions, 15 group additive values were derived for the forward and the reverse reaction, 4 referring to primary and 11 to secondary contributions. The accuracy of the model is validated upon an ab initio and an experimental validation set of 19 and 21 reaction rates, respectively, showing that reaction rates can be predicted with a mean factor of deviation of 2 for the ab initio and 3 for the experimental values. Hence, this work illustrates that the developed group additive model can be reliably applied for the accurate prediction of kinetics of α-hydrogen abstractions by hydrogen atoms from a broad range of oxygenates. PMID:25209711

  7. Correlation of Hydrogen-Atom Abstraction Reaction Efficiencies for Aryl Radicals with their Vertical Electron Affinities and the Vertical Ionization Energies of the Hydrogen Atom Donors

    PubMed Central

    Jing, Linhong; Nash, John J.

    2009-01-01

    The factors that control the reactivities of aryl radicals toward hydrogen-atom donors were studied by using a dual-cell Fourier-transform ion cyclotron resonance mass spectrometer (FT – ICR). Hydrogen-atom abstraction reaction efficiencies for two substrates, cyclohexane and isopropanol, were measured for twenty-three structurally different, positively-charged aryl radicals, which included dehydrobenzenes, dehydronaphthalenes, dehydropyridines, and dehydro(iso)quinolines. A logarithmic correlation was found between the hydrogen-atom abstraction reaction efficiencies and the (calculated) vertical electron affinities (EA) of the aryl radicals. Transition state energies calculated for three of the aryl radicals with isopropanol were found to correlate linearly with their (calculated) EAs. No correlation was found between the hydrogen-atom abstraction reaction efficiencies and the (calculated) enthalpy changes for the reactions. Measurement of the reaction efficiencies for the reactions of several different hydrogen-atom donors with a few selected aryl radicals revealed a logarithmic correlation between the hydrogen-atom abstraction reaction efficiencies and the vertical ionization energies (IE) of the hydrogen-atom donors, but not the lowest homolytic X – H (X = heavy atom) bond dissociation energies of the hydrogen-atom donors. Examination of the hydrogen-atom abstraction reactions of twenty-nine different aryl radicals and eighteen different hydrogen-atom donors showed that the reaction efficiency increases (logarithmically) as the difference between the IE of the hydrogen-atom donor and the EA of the aryl radical decreases. This dependence is likely to result from the increasing polarization, and concomitant stabilization, of the transition state as the energy difference between the neutral and ionic reactants decreases. Thus, the hydrogen-atom abstraction reaction efficiency for an aryl radical can be “tuned” by structural changes that influence either

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

    ERIC Educational Resources Information Center

    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…

  9. Hydrogen atom abstraction from aldehydes - OH + H2CO and O + H2CO

    NASA Technical Reports Server (NTRS)

    Dupuis, M.; Lester, W. A., Jr.

    1984-01-01

    The essential features of the potential energy surfaces governing hydrogen abstraction from formaldehyde by oxygen atom and hydroxyl radical have been characterized with ab inito multiconfiguration Hartree-Fock (MCHF) and configuration interaction (CI) wave functions. The results are consistent with a very small activation energy for the OH + H2CO reaction, and an activation energy of a few kcal/mol for the O + H2CO reaction. In the transition state structure of both systems, the attacking oxygen atom is nearly collinear with the attacked CH bond.

  10. The Influence of Hydrogen Bonding on Hydrogen-Atom Abstraction Reactions of Dehydropyridinium Cations in the Gas Phase

    PubMed Central

    Adeuya, Anthony; Nash, John J.; Kenttämaa, Hilkka I.

    2010-01-01

    The reactions of several substituted, positively-charged dehydropyridinium cations with cyclohexane, methanol and tetrahydrofuran have been examined in a Fourier-transform ion cyclotron resonance mass spectrometer. All of the charged monoradicals react with the neutral reagents exclusively via hydrogen atom abstraction. For cyclohexane, there is a good correlation between the reaction efficiencies and the calculated electron affinities at the radical sites; that is, the greater the electron affinity of the charged monoradical at the radical site, the faster the reaction. The reaction efficiencies with methanol and tetrahydrofuran, however, do not correlate with the calculated electron affinities. Density functional theory (DFT) calculations indicate that for these reagents a stabilizing hydrogen bonding interaction exists in the hydrogen atom abstraction transition states for some of the charged monoradicals but not for others. At both the MPW1K and G3MP2B3 levels of theory, there is a good correlation between the calculated activation enthalpies and the observed reaction efficiencies although the G3MP2B3 method provides a slightly better correlation than the MPW1K method. The extent of enhancement in the reaction efficiencies caused by the hydrogen bonding interactions parallels the calculated hydrogen bond lengths in the transition states. PMID:21080694

  11. Excited-state hydrogen atom abstraction initiates the photochemistry of β-2′-deoxycytidine

    PubMed Central

    Campos, Jesús; Šponer, Judit E.; Šponer, Jiřĺ

    2016-01-01

    Understanding the effects of ultraviolet radiation on nucleotides in solution is an important step towards a comprehensive description of the photochemistry of nucleic acids and their constituents. Apart from having implications for mutagenesis and DNA photoprotection mechanisms, the photochemistry of cytidines is a central element in UV-assisted syntheses of pyrimidine nucleotides under prebiotically plausible conditions. In this contribution, we present UV-irradiation experiments of β-2′-deoxycytidine in aqueous solution involving H–D exchange followed by NMR spectroscopic analysis of the photoproducts. We further elucidate the outcome of these experiments by means of high-level quantum chemical calculations. In particular, we show that prolonged UV-irradiation of cytidine may lead to H–C1′ hydrogen atom abstraction by the carbonyl oxygen atom of cytosine. This process may enable photoanomerisation and nucleobase loss, two previously unexplained photoreactions observed in pyrimidine nucleotides. PMID:27182431

  12. Ab initio kinetics studies of hydrogen atom abstraction from methyl propanoate.

    PubMed

    Tan, Ting; Yang, Xueliang; Ju, Yiguang; Carter, Emily A

    2016-02-14

    The kinetics of hydrogen abstraction by five radicals (H, CH3, O((3)P), OH, and HO2) from a biodiesel surrogate, methyl propanoate (MP), is theoretically investigated. We employ high-level ab initio quantum chemistry methods, coupled-cluster singles and doubles with perturbative triples correction (CCSD(T)) and multi-reference singles and doubles configuration interaction (MRSDCI) with the Davidson-Silver (DS) correction, and obtain chemically accurate reaction energetics. Overall, MRSDCI + DS predicts comparable energetics to CCSD(T) for MP + H/CH3/O/OH. The rate constants are computed using transition state theory (TST-Rice-Ramsperger-Kassel-Marcus theory) in conjunction with the separable-hindered-rotor approximation, variable reaction coordinate TST, and the multi-structure all-structure (MS-AS) approach. A simplified method, semi-multi-structure, is also employed for MP + OH/HO2, and the rate coefficients with this less expensive method are in good agreement with the results obtained with the MS-AS method. The fitted modified Arrhenius expressions are provided over a temperature range of 250 to 2000 K. The predicted rate coefficients for MP + OH agree remarkably well with experimental data over a wide temperature range. Branching ratio analysis of all the studied reactions shows that abstractions of the secondary H atoms within MP are expected to dominate the consumption of fuel at low temperatures, and the contributions of abstractions from the two methyl groups increase with temperature for all abstracting radicals. PMID:26796249

  13. Reaction of an Iron(IV) Nitrido Complex with Cyclohexadienes: Cycloaddition and Hydrogen-Atom Abstraction

    PubMed Central

    2015-01-01

    The iron(IV) nitrido complex PhB(MesIm)3Fe≡N reacts with 1,3-cyclohexadiene to yield the iron(II) pyrrolide complex PhB(MesIm)3Fe(η5-C4H4N) in high yield. The mechanism of product formation is proposed to involve sequential [4 + 1] cycloaddition and retro Diels–Alder reactions. Surprisingly, reaction with 1,4-cyclohexadiene yields the same iron-containing product, albeit in substantially lower yield. The proposed reaction mechanism, supported by electronic structure calculations, involves hydrogen-atom abstraction from 1,4-cyclohexadiene to provide the cyclohexadienyl radical. This radical is an intermediate in substrate isomerization to 1,3-cyclohexadiene, leading to formation of the pyrrolide product. PMID:25068927

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

    PubMed

    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. PMID:25581555

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

    PubMed Central

    2016-01-01

    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 pKa and E1/2 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 pKa of 18.8 ± 1.8 and a low E1/2 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. PMID:25581555

  16. Mechanistic studies of the radical SAM enzyme 4-demethylwyosine synthase reveals the site of hydrogen atom abstraction

    PubMed Central

    Young, Anthony P.; Bandarian, Vahe

    2015-01-01

    TYW1 catalyzes the formation of 4-demethylwyosine via the condensation of N-methylguanosine (m1G) with carbons 2 and 3 of pyruvate. In this study labeled transfer ribonucleic acid (tRNA) and pyruvate were utilized to determine the site of hydrogen atom abstraction and regiochemistry of the pyruvate addition. tRNA containing a 2H labeled m1G methyl group was used to identify the methyl group of m1G as the site of hydrogen atom abstraction by S-adenosyl-L-methionine. [2-13C1,3,3,3-2H3]-Pyruvate was used to demonstrate retention of all the pyruvate protons indicating that C2 of pyruvate forms the bridging carbon of the imidazoline ring and C3 the methyl. PMID:26052987

  17. Theoretical and kinetic study of the hydrogen atom abstraction reactions of unsaturated C6 methyl esters with hydroxyl radical

    NASA Astrophysics Data System (ADS)

    Wang, Quan-De; Ni, Zhong-Hai

    2016-04-01

    This work reports a systematic ab initio and chemical kinetic study of the rate constants for hydrogen atom abstraction reactions by hydroxyl radical (OH) on typical isomers of unsaturated C6 methyl esters at the CBS/QB3 level of theory. The high-pressure limit rate constants at different reaction sites for all the methyl esters in the temperature range from 500 to 2000 K are calculated via transition-state theory with the Wigner method for quantum tunneling effect and fitted to the modified three parameters Arrhenius expression using least-squares regression. Further, a branching ratio analysis for each reaction site has been performed.

  18. SkfB Abstracts a Hydrogen Atom from Cα on SkfA To Initiate Thioether Cross-Link Formation.

    PubMed

    Bruender, Nathan A; Bandarian, Vahe

    2016-08-01

    Sulfur to α-carbon thioether-containing peptides (sactipeptides) are ribosomally synthesized post-translationally modified peptides with bacteriocidal activities. The thioether cross-link, which is required for biological activity, is installed by a member of the radical S-adenosyl-l-methionine (SAM) superfamily in the peptide substrate. Herein, we show that the radical SAM enzyme, SkfB, utilizes the 5'-deoxyadenosyl radical generated from the reductive cleavage of SAM to abstract a hydrogen atom from the α-carbon of the amino acid at position 12 in the substrate, SkfA, to initiate the installation of a thioether cross-link. The insights from this work can be applied to all radical SAM sactipeptide maturases. PMID:27410522

  19. Theoretical study of the rate constants for the hydrogen atom abstraction reactions of esters with (•)OH radicals.

    PubMed

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

    2014-07-10

    A systematic investigation of the rate constants for hydrogen atom abstraction reactions by hydroxyl radicals on esters has been performed. The geometry optimizations and frequency calculations were obtained using the second-order Møller-Plesset method with the 6-311G(d,p) basis set. The same method was also used in order to determine the dihedral angle potential for each individual hindered rotor in each reactant and transition state. Intrinsic reaction coordinate calculations were used in order to connect each transition state to the corresponding local minimum. For the reactions of methyl ethanoate with an (•)OH radical, the relative electronic energies were calculated using the G3 and the CCSD(T)/cc-pVXZ (where X = D, T, and Q) methods, which were extrapolated to the complete basis set (CBS) limit. The electronic energies obtained using the G3 method were then benchmarked against the CBS results and were found to be within 1 kcal mol(-1) of one another. The high-pressure limit rate constants for every reaction channel were calculated by conventional transition-state theory, with an asymmetric Eckart tunneling correction, using the energies obtained with the G3 method. We report the individual, average, and total rate constants in the temperature range from 500 to 2200 K. Our calculated results are within a factor of 2 for methyl ethanoate and between 40% to 50% for methyl propanoate and methyl butanoate when compared to previously reported experimental data. PMID:24878337

  20. Kinetics and Mechanism of Hydrogen-Atom Abstraction from Rhodium Hydrides by Alkyl Radicals in Aqueous Solutions

    SciTech Connect

    Pestovsky, Oleg; Veysey, Stephen W.; Bakac, Andrej

    2011-03-22

    The kinetics of the reaction of benzyl radicals with [L{sup 1}(H{sub 2}O)RhH{l_brace}D{r_brace}]{sup 2+} (L{sup 1}=1,4,8,11-tetraazacyclotetradecane) were studied directly by laser-flash photolysis. The rate constants for the two isotopologues, k=(9.3 {+-} 0.6) x 10{sup 7} M{sup -1} s{sup -1} (H) and (6.2 {+-} 0.3) x 10{sup 7} M{sup -1} s{sup -1} (D), lead to a kinetic isotope effect k{sub H}/k{sub D}=1.5 {+-} 0.1. The same value was obtained from the relative yields of PhCH{sub 3} and PhCH{sub 2}D in a reaction of benzyl radicals with a mixture of rhodium hydride and deuteride. Similarly, the reaction of methyl radicals with {l_brace}[L{sup 1}(H{sub 2}O)RhH]{sup 2+} + [L{sup 1}(H{sub 2}O)RhD]{sup 2+}{r_brace} produced a mixture of CH{sub 4} and CH{sub 3}D that yielded k{sub H}/k{sub D}=1.42 {+-} 0.07. The observed small normal isotope effects in both reactions are consistent with reduced sensitivity to isotopic substitution in very fast hydrogen-atom abstraction reactions. These data disprove a literature report claiming much slower kinetics and an inverse kinetic isotope effect for the reaction of methyl radicals with hydrides of L{sup 1}Rh.

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

    PubMed

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

    2013-12-27

    This work details an ab initio and chemical kinetic study of the hydrogen atom abstraction reactions by the hydroperoxyl radical (HȮ2) on the following esters: methyl ethanoate, methyl propanoate, methyl butanoate, methyl pentanoate, methyl isobutyrate, ethyl ethanoate, propyl ethanoate, and isopropyl ethanoate. Geometry optimizations and frequency calculations of all of the species involved, as well as the hindrance potential descriptions for reactants and transition states, have been performed with the Møller-Plesset (MP2) method using the 6-311G(d,p) basis set. A validation of all of the connections between transition states and local minima was performed by intrinsic reaction coordinate calculations. Electronic energies for all of the species are reported at the CCSD(T)/cc-pVTZ level of theory in kcal mol(-1) with the zero-point energy corrections. The CCSD(T)/CBS (extrapolated from CCSD(T)/cc-pVXZ, in which X = D, T, Q) was used for the reactions of methyl ethanoate + HȮ2 radicals as a benchmark in the electronic energy calculations. High-pressure limit rate constants, in the temperature range 500-2000 K, have been calculated for all of the reaction channels using conventional transition state theory with asymmetric Eckart tunneling corrections. The 1-D hindered rotor approximation has been used for the low frequency torsional modes in both reactants and transition states. The calculated individual and total rate constants are reported for all of the reaction channels in each reaction system. A branching ratio analysis for each reaction site has also been investigated for all of the esters studied in this work. PMID:24175616

  2. Extension of structure-reactivity correlations for the hydrogen abstraction reaction by bromine atom and comparison to chlorine atom and hydroxyl radical

    SciTech Connect

    Poutsma, Marvin L.

    2015-12-14

    Recently we presented structure-reactivity correlations for the gas-phase ambient-temperature rate constants for hydrogen abstraction from sp3-hybridized carbon by chlorine atom and hydroxyl radical (Cl•/HO• + HCR3 → HCl/HOH + •CR3); the reaction enthalpy effect was represented by the independent variable ΔrH and the polar effect by the independent variables F and R, the Hammett constants for field/inductive and resonance effects. Both these reactions are predominantly exothermic and have early transition states. Here we present a parallel treatment for Br• whose reaction is significantly endothermic with a correspondingly late transition state. In spite of lower expectations because the available data base is less extensive and much more scattered and because long temperature extrapolations are often required, the resulting least-squares fit (log k298,Br = –0.147 ΔrH –4.32 ΣF –4.28 ΣR –12.38 with r2 = 0.92) was modestly successful and useful for initial predictions. The coefficient of ΔrH was ~4-fold greater, indicative of the change from an early to a late transition state; meanwhile the sizable coefficients of ΣF and ΣR indicate the persistence of the polar effect. Although the mean unsigned deviation of 0.79 log k298 units is rather large, it must be considered in the context of a total span of over 15 log units in the data set. Lastly, the major outliers are briefly discussed.

  3. Extension of Structure-Reactivity Correlations for the Hydrogen Abstraction Reaction by Bromine Atom and Comparison to Chlorine Atom and Hydroxyl Radical.

    PubMed

    Poutsma, Marvin L

    2016-01-21

    Recently we presented structure-reactivity correlations for the gas-phase ambient-temperature rate constants for hydrogen abstraction from sp(3)-hybridized carbon by chlorine atom and hydroxyl radical (Cl•/HO• + HCR3 → HCl/HOH + •CR3); the reaction enthalpy effect was represented by the independent variable ΔrH and the "polar effect" by the independent variables F and R, the Hammett constants for field/inductive and resonance effects. Both these reactions are predominantly exothermic and have early transition states. Here, we present a parallel treatment for Br• whose reaction is significantly endothermic with a correspondingly late transition state. Despite lower expectations because the available database is less extensive and much more scattered and because long temperature extrapolations are often required, the resulting least-squares fit (log k298,Br = -0.147 ΔrH - 4.32 ΣF - 4.28 ΣR - 12.38 with r(2) = 0.92) was modestly successful and useful for initial predictions. The coefficient of ΔrH was ∼4-fold greater, indicative of the change from an early to a late transition state; meanwhile the sizable coefficients of ΣF and ΣR indicate the persistence of the "polar effect". Although the mean unsigned deviation of 0.79 log k298 units is rather large, it must be considered in the context of a total span of over 15 log units in the data set. The major outliers are briefly discussed. PMID:26653077

  4. Extension of structure-reactivity correlations for the hydrogen abstraction reaction by bromine atom and comparison to chlorine atom and hydroxyl radical

    DOE PAGESBeta

    Poutsma, Marvin L.

    2015-12-14

    Recently we presented structure-reactivity correlations for the gas-phase ambient-temperature rate constants for hydrogen abstraction from sp3-hybridized carbon by chlorine atom and hydroxyl radical (Cl•/HO• + HCR3 → HCl/HOH + •CR3); the reaction enthalpy effect was represented by the independent variable ΔrH and the polar effect by the independent variables F and R, the Hammett constants for field/inductive and resonance effects. Both these reactions are predominantly exothermic and have early transition states. Here we present a parallel treatment for Br• whose reaction is significantly endothermic with a correspondingly late transition state. In spite of lower expectations because the available data basemore » is less extensive and much more scattered and because long temperature extrapolations are often required, the resulting least-squares fit (log k298,Br = –0.147 ΔrH –4.32 ΣF –4.28 ΣR –12.38 with r2 = 0.92) was modestly successful and useful for initial predictions. The coefficient of ΔrH was ~4-fold greater, indicative of the change from an early to a late transition state; meanwhile the sizable coefficients of ΣF and ΣR indicate the persistence of the polar effect. Although the mean unsigned deviation of 0.79 log k298 units is rather large, it must be considered in the context of a total span of over 15 log units in the data set. Lastly, the major outliers are briefly discussed.« less

  5. Reduced-Dimensionality Semiclassical Transition State Theory: Application to Hydrogen Atom Abstraction and Exchange Reactions of Hydrocarbons.

    PubMed

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

    2015-12-17

    Quantum mechanical methods for calculating rate constants are often intractable for reactions involving many atoms. Semiclassical transition state theory (SCTST) offers computational advantages over these methods but nonetheless scales exponentially with the number of degrees of freedom (DOFs) of the system. Here we present a method with more favorable scaling, reduced-dimensionality SCTST (RD SCTST), that treats only a subset of DOFs of the system explicitly. We apply it to three H abstraction and exchange reactions for which two-dimensional potential energy surfaces (PESs) have previously been constructed and evaluated using RD quantum scattering calculations. We differentiated these PESs to calculate harmonic frequencies and anharmonic constants, which were then used to calculate cumulative reaction probabilities and rate constants by RD SCTST. This method yielded rate constants in good agreement with quantum scattering results. Notably, it performed well for a heavy-light-heavy reaction, even though it does not explicitly account for corner-cutting effects. Recent extensions to SCTST that improve its treatment of deep tunneling were also evaluated within the reduced-dimensionality framework. The success of RD SCTST in this study suggests its potential applicability to larger systems. PMID:26090556

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

    PubMed Central

    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

  7. Kinetics of the Hydrogen Atom Abstraction Reactions from 1-Butanol by Hydroxyl Radical: Theory Matches Experiment and More

    SciTech Connect

    Seal, Prasenjit; Oyedepo, Gbenga; Truhlar, Donald G.

    2013-01-17

    In the present work, we study the H atom abstraction reactions by hydroxyl radical at all five sites of 1-butanol. Multistructural variational transition state theory (MS-VTST) was employed to estimate the five thermal rate constants. MS-VTST utilizes a multifaceted dividing surface that accounts for the multiple conformational structures of the transition state, and we also include all the structures of the reactant molecule. The vibrational frequencies and minimum energy paths (MEPs) were computed using the M08-HX/MG3S electronic structure method. The required potential energy surfaces were obtained implicitly by direct dynamics employing interpolated variational transition state theory with mapping (IVTST-M) using a variational reaction path algorithm. The M08-HX/MG3S electronic model chemistry was then used to calculate multistructural torsional anharmonicity factors to complete the MS-VTST rate constant calculations. The results indicate that torsional anharmonicity is very important at higher temperatures, and neglecting it would lead to errors of 26 and 32 at 1000 and 1500 K, respectively. Our results for the sums of the site-specific rate constants agree very well with the experimental values of Hanson and co-workers at 896–1269 K and with the experimental results of Campbell et al. at 292 K, but slightly less well with the experiments of Wallington et al., Nelson et al., and Yujing and Mellouki at 253–372 K; nevertheless, the calculated rates are within a factor of 1.61 of all experimental values at all temperatures. Finally, this gives us confidence in the site-specific values, which are currently inaccessible to experiment.

  8. Extension of Structure-Reactivity Correlations for the Hydrogen Abstraction Reaction to Methyl Radical and Comparison to Chlorine Atom, Bromine Atom, and Hydroxyl Radical

    SciTech Connect

    Poutsma, Marvin L

    2016-01-01

    Recently we presented structure-reactivity correlations for the gas-phase rate constants for hydrogen abstraction from sp3-hybridized carbon by three electrophilic radicals (X + HCR3 XH + CR3; X = Cl , HO , and Br ); the reaction enthalpy effect was represented by the independent variable rH and the polar effect by the independent variables F and R, the Hammett-Taft constants for field/inductive and resonance effects. Here we present a parallel treatment for the less electronegative CH3 . In spite of a limited and scattered data base, the resulting least-squares fit [log k437(CH3 ) = 0.0251( rH) + 0.96( F) 0.56( R) 19.15] was modestly successful and useful for initial predictions. As expected, the polar effect appears to be minor and its directionality, i.e., the philicity of CH3 , may depend on the nature of the substituents.

  9. Photoelectrochemical cells based on hydrogen-atom abstraction and electron-transfer reactions in solution: systems based on benzophenone, 2-propanol, trialkylamines, and methyl viologen

    SciTech Connect

    Chandrasekaran, K.; Whitten, D.G.

    1981-12-02

    This paper reports the linking of well-studied solution photoprocesses such as hydrogen-atom abstraction by triplet benzophenone from 2-propanol and electron transfer from triethylamine to triplet benzophenone to proton reduction in aqueous acid via a two-compartment photoelectrochemical cell. In each case the intermediate reduction of N,N'-dimethyl-4,4'-bipyridinium (methyl viologen, MV/sup 2 +/) provides a means for circumventing undesirable radical reactions and generating a stable carrier in high overall efficiency. The net result is reasonably efficient generation of a photocurrent concurrent with the occurrence of an endothermic reaction providing products that can in principle be recycled. An interesting aspect of this work is the finding that the overall efficiency of these cells is enhanced by the photochemical self-sensitization of MV/sup +/ in the presence of 2-propanol or triethylamine and MV/sup 2 +/.

  10. Extension of Structure-Reactivity Correlations for the Hydrogen Abstraction Reaction to the Methyl Radical and Comparison to the Chlorine Atom, Bromine Atom, and Hydroxyl Radical.

    PubMed

    Poutsma, Marvin L

    2016-07-01

    Recently, we presented structure-reactivity correlations for the gas-phase rate constants for hydrogen abstraction from sp(3)-hybridized carbon by three electrophilic radicals (X(•) + HCR3 → XH + (•)CR3; X = Cl(•), HO(•), and Br(•)); the reaction enthalpy effect was represented by the independent variable ΔrH and the "polar effect" by the independent variables F and R, the Hammett-Taft constants for field/inductive and resonance effects. Here we present a parallel treatment for the less electronegative CH3(•). In spite of a limited and scattered database, the resulting least-squares fit [log k437(CH3(•)) = -0.0251(ΔrH) + 0.96(ΣF) - 0.56(ΣR) - 19.15] was modestly successful and useful for initial predictions. As expected, the polar effect appears to be minor and its directionality, i.e., the "philicity" of CH3(•), may depend on the nature of the substituents. PMID:27266850

  11. Extension of structure-reactivity correlations for the hydrogen abstraction reaction to methyl radical and comparison to chlorine atom, bromine atom, and hydroxyl radical

    DOE PAGESBeta

    Poutsma, Marvin L.

    2016-06-07

    In this study, we presented structure-reactivity correlations for the gas-phase rate constants for hydrogen abstraction from sp3-hybridized carbon by three electrophilic radicals (X• + HCR3 → XH + •CR3; X = Cl•, HO•, and Br); the reaction enthalpy effect was represented by the independent variable ΔrH and the polar effect by the independent variables F and R, the Hammett-Taft constants for field/inductive and resonance effects. Here we present a parallel treatment for the less electronegative CH3•. In spite of a limited and scattered data base, the resulting least-squares fit [log k437(CH3•) = 0.0251(ΔrH) + 0.96(ΣF) 0.56(ΣR) – 19.15] was modestlymore » successful and useful for initial predictions. As expected, the polar effect appears to be minor and its directionality, i.e., the philicity of CH3, may depend on the nature of the substituents.« less

  12. 2-Alkynyl-N-propargyl pyridinium salts: pyridinium-based heterocyclic skipped aza-enediynes that cleave DNA by deoxyribosyl hydrogen-atom abstraction and guanine oxidation.

    PubMed

    Tuesuwan, Bodin; Kerwin, Sean M

    2006-06-13

    Diradical-generating cyclizations such as the enediyne Bergman cyclization and the enyne allene Myers-Saito cyclization have been exploited by nature in the mechanism of DNA cleavage by a series of potent antitumor antibiotics. Alternative diradical-generating cyclizations have been proposed in the design of selective antitumor agents; however, little information is available concerning the utility of these alternative cyclizations in radical-based DNA cleavage chemistry. One such alternative diradical-generating cyclization, the aza-Myers-Saito cyclization of aza-enyne allenes that are derived from base-promoted isomerization of skipped aza-enediynes, has been recently reported. Here, we report the synthesis and DNA cleavage chemistry of a series of pyridinium skipped aza-enediynes (2-alkynyl-N-propargyl pyridinium salts). Efficient DNA cleavage requires the presence of the skipped aza-enediyne functionality, and optimal DNA cleavage occurs at basic pH. Within this series of compounds, the analogue bearing a p-methoxyphenyl group on the pyridinium 2-alkyne substituents was found to be the most effective DNA cleavage agent, displaying significant supercoiled DNA-nicking activity at concentrations as low as 1 microM. Detailed studies of this analogue show that DNA cleavage occurs through 4'-hydrogen-atom abstraction from the DNA backbone and oxidation of guanine bases. This is the first report of enediyne-like radical-based DNA cleavage by an agent designed to undergo an alternative diradical-generating cyclization. PMID:16752915

  13. Hydrogen energy. A bibliography with abstracts

    NASA Technical Reports Server (NTRS)

    1978-01-01

    Hydrogen Energy is a continuing bibliographic summary with abstracts of research and projections on the subject of hydrogen as a secondary fuel and as an energy carrier. This update to Hydrogen Energy cites additional references identified during the fourth quarter of 1978. It is the fourth in a 1978 quarterly series intended to provide current awareness to those interested in hydrogen energy. A series of cross indexes are included which track directly with those of the cumulative volume.

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

    PubMed

    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. PMID:27390885

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

    PubMed

    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. PMID:25230924

  16. 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}

    SciTech Connect

    Blank, D.A.; Hemmi, N.; Suits, A.G.; Lee, Y.T.

    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.

  17. Thin film atomic hydrogen detectors

    NASA Technical Reports Server (NTRS)

    Gruber, C. L.

    1977-01-01

    Thin film and bead thermistor atomic surface recombination hydrogen detectors were investigated both experimentally and theoretically. Devices were constructed on a thin Mylar film substrate. Using suitable Wheatstone bridge techniques sensitivities of 80 microvolts/2x10 to the 13th power atoms/sec are attainable with response time constants on the order of 5 seconds.

  18. Atomic hydrogen in planetary nebulae

    NASA Technical Reports Server (NTRS)

    Schneider, Stephen E.; Silverglate, Peter R.; Altschuler, Daniel R.; Giovanardi, Carlo

    1987-01-01

    The authors searched for neutral atomic hydrogen associated with 22 planetary nebulae and three evolved stars in the 21 cm line at the Arecibo Observatory. Objects whose radial velocities permitted discrimination from Galactic H I were chosen for observation. Hydrogen was detected in absorption from IC 4997. From the measurements new low limits are derived to the mass of atomic hydrogen associated with the undetected nebulae. Radio continuum observations were also made of several of the nebulae at 12.6 cm. The authors reexamine previous measurements of H I in planetary nebulae, and present the data on a consistent footing. The question of planetary nebula distances is considered at length. Finally, implications of the H I measurements for nebular evolution are discussed and it is suggested that atomic hydrogen seen in absorption was expelled from the progenitor star during the final 1000 yr prior to the onset of ionization.

  19. Precision Spectroscopy of Atomic Hydrogen

    NASA Astrophysics Data System (ADS)

    Beyer, A.; Parthey, Ch G.; Kolachevsky, N.; Alnis, J.; Khabarova, K.; Pohl, R.; Peters, E.; Yost, D. C.; Matveev, A.; Predehl, K.; Droste, S.; Wilken, T.; Holzwarth, R.; Hänsch, T. W.; Abgrall, M.; Rovera, D.; Salomon, Ch; Laurent, Ph; Udem, Th

    2013-12-01

    Precise determinations of transition frequencies of simple atomic systems are required for a number of fundamental applications such as tests of quantum electrodynamics (QED), the determination of fundamental constants and nuclear charge radii. The sharpest transition in atomic hydrogen occurs between the metastable 2S state and the 1S ground state. Its transition frequency has now been measured with almost 15 digits accuracy using an optical frequency comb and a cesium atomic clock as a reference [1]. A recent measurement of the 2S - 2P3/2 transition frequency in muonic hydrogen is in significant contradiction to the hydrogen data if QED calculations are assumed to be correct [2, 3]. We hope to contribute to this so-called "proton size puzzle" by providing additional experimental input from hydrogen spectroscopy.

  20. Symposium on atomic spectroscopy (SAS-83): abstracts and program

    SciTech Connect

    Not Available

    1983-09-01

    Abstracts of papers given at the symposium are presented. Session topics include: Rydbergs, optical radiators, and planetary atoms; highly ionized atoms; ultraviolet radiation; theory, ion traps, and laser cooling; beam foil; and astronomy. (GHT)

  1. Hydrogen Energy: A bibliography with abstracts

    NASA Technical Reports Server (NTRS)

    1976-01-01

    Bibliographic series cites documents relating to use of hydrogen as energy carrier. In addition to cumulative volume, annual supplement is available for 1974, and quarterly update program serves 1975 and current calendar year.

  2. An Atomic Hydrogen Mushroom

    NASA Astrophysics Data System (ADS)

    English, J.; Taylor, A. R.; Irwin, J. A.; Canadian Galactic Plane Survey Collaboration

    1998-12-01

    Neutral hydrogen ``worms'', which stream vertically from the mid-plane to high latitudes, may be conduits through which hot gas can escape into the halo. Using the Dominion Radio Astrophysical Observatory's (DRAO) Synthesis Telescope, as part of the Canadian Galactic Plane Survey, we have resolved an HI worm candidate. Although simulations have previously made general predictions, these data will constrain, for the first time, detailed numerical models of the dynamical processes generating disk-halo features. After the incorporation of the data from the 26-m DRAO's single-dish telescope, the mosaic data cube has full information on all spatial scales down to a resolution limit of 1 arcmin and a velocity resolution of 0.82 km s(-1) . Thus we delineate Rayleigh-Taylor instability-like structures and can distinguish a 5 km s(-1) line of sight velocity difference between the base and top of the worm. In general morphology, the worm is mushroom-shaped. Although it extends only a few hundred parsecs south of the midplane, the cap appears to be fragmenting. This may allow hot material from the stem's cavity, as well as UV photons, to escape to higher galactic latitudes. The preliminary estimate of the observed minimum HI mass is 1.3 x 10(5) Msolar. Our initial thin-shell model, which assumes supernovae explosions drive this outflow, gives a minimum total energy of about 100 x 10(51) ergs s(-1) .

  3. Energy storage possibilities of atomic hydrogen

    NASA Technical Reports Server (NTRS)

    Etters, R. D.; Dugan, J. V., Jr.; Palmer, R.

    1976-01-01

    The possibility of storing large amounts of energy in a free radical system such as atomic hydrogen is analyzed. Attention is focused on theoretical calculations of the ground state properties of spin-aligned atomic triplet hydrogen, deuterium, and tritium. The solid-liquid phase transition in atomic hydrogen is also examined.

  4. Hydrogen energy: A bibliography with abstracts. Cumulative volume, 1953 - 1973

    NASA Technical Reports Server (NTRS)

    Cox, K. E.

    1974-01-01

    A bibliography on hydrogen as an energy source is presented. Approximately 8,000 documents are abstracted covering the period 1953 through 1973. Topics covered include: production, utilization, transmission, distribution, storage, and safety.

  5. Hydrogen-Atom Transfer Reactions.

    PubMed

    Wang, Liang; Xiao, Jian

    2016-04-01

    The cascade [1,n]-hydrogen transfer/cyclization, recognized as the tert-amino effect one century ago, has received considerable interest in recent decades, and great achievements have been made. With the aid of this strategy, the inert C(sp(3))-H bonds can be directly functionalized into C-C, C-N, C-O bonds under catalysis of Lewis acids, Brønsted acids, as well as organocatalysts, and even merely under thermal conditions. Hydrogen can be transferred intramolecularly from hydrogen donor to acceptor in the form of hydride, or proton, followed by cyclization to furnish the cyclic products in processes featuring high atom economy. Methylene/methine adjacent to heteroatoms, e.g., nitrogen, oxygen, sulfur, can be exploited as hydride donor as well as methylene/methine without heteroatom assistance. Miscellaneous electrophilic subunits or intermediates, e.g., alkylidene malonate, carbophilic metal activated alkyne or allene, α,β-unsaturated aldehydes/ketone, saturated aldehydes/iminium, ketenimine/carbodiimide, metal carbenoid, electron-withdrawing groups activated allene/alkyne, in situ generated carbocation, can serve as hydride acceptors. This methodology has shown preeminent power to construct 5-, 6-, or 7-membered heterocyclic as well as carbon rings. In this chapter, various hydrogen donors and acceptors are adequately discussed. PMID:27573142

  6. Fluorine atom abstraction by Si(100). I. Experimental

    NASA Astrophysics Data System (ADS)

    Tate, M. R.; Gosalvez-Blanco, D.; Pullman, D. P.; Tsekouras, A. A.; Li, Y. L.; Yang, J. J.; Laughlin, K. B.; Eckman, S. C.; Bertino, M. F.; Ceyer, S. T.

    1999-08-01

    In the interaction of low energy F2 with Si(100) at 250 K, a dissociative chemisorption mechanism called atom abstraction is identified in which only one of the F atoms is adsorbed while the other F atom is scattered into the gas phase. The dynamics of atom abstraction are characterized via time-of-flight measurements of the scattered F atoms. The F atoms are translationally hyperthermal but only carry a small fraction (˜3%) of the tremendous exothermicity of the reaction. The angular distribution of F atoms is unusually broad for the product of an exothermic reaction. These results suggest an "attractive" interaction potential between F2 and the Si dangling bond with a transition state that is not constrained geometrically. These results are in disagreement with the results of theoretical investigations implying that the available potential energy surfaces are inadequate to describe the dynamics of this gas-surface interaction. In addition to single atom abstraction, two atom adsorption, a mechanism analogous to classic dissociative chemisorption in which both F atoms are adsorbed onto the surface, is also observed. The absolute probability of the three scattering channels (single atom abstraction, two atom adsorption, and unreactive scattering) for an incident F2 are determined as a function of F2 exposure. The fluorine coverage is determined by integrating the reaction probabilities over F2 exposure, and the reaction probabilities are recast as a function of fluorine coverage. Two atom adsorption is the dominant channel [P2=0.83±0.03(95%, N=9)] in the limit of zero coverage and decays monotonically to zero. Single atom abstraction is the minor channel (P1=0.13±0.03) at low coverage but increases to a maximum (P1=0.35±0.08) at about 0.5 monolayer (ML) coverage before decaying to zero. The reaction ceases at 0.94±0.11(95%, N=9) ML. Thermal desorption and helium diffraction confirm that the dangling bonds are the abstraction and adsorption sites. No Si lattice

  7. Progress towards trapping of atomic hydrogen isotopes

    NASA Astrophysics Data System (ADS)

    Chavez, Isaac; Libson, Adam; Mazur, Tom; Majors, Julia; Raizen, Mark

    2009-05-01

    Using a series of pulsed electromagnetic coils (atomic coilgun) we can stop supersonic beams of paramagnetic atoms and molecules. We will employ the coilgun method to stop and trap supersonic beams of hydrogen isotopes. The slowed atoms will be trapped in a quadrupole magnetic trap where single-photon atomic cooling will be applied. Further applications will be discussed.

  8. Quantum mechanical investigation on bimolecular hydrogen abstractions in butyl acrylate-based free radical polymerization processes.

    PubMed

    Mavroudakis, Evangelos; Cuccato, Danilo; Moscatelli, Davide

    2014-03-13

    The present computational study focuses on the investigation of bimolecular hydrogen abstractions that can occur during free radical polymerization (FRP) processes. In particular, several hydrogen abstractions from four monomers (butyl acrylate, BA; styrene, ST; butyl methacrylate, BMA; vinyl acetate, VA) and three different backbone chains (poly-BA, poly-BA-co-VA, and poly-BA-co-ST) have been studied. The aim is to provide an overview of the kinetics for all possible intermolecular hydrogen abstraction reactions from all chemical species present in a bulk FRP as well as to support the understanding of the influence of chemical environment on hydrogen abstractions. All simulations were performed using density functional theory (DFT) with quantum tunneling factors estimated using the Eckart model. This study provides proof that the presence of an electron donating group in the chemical environment of the abstracted hydrogen atoms can lead to lower activation energies and higher rate coefficients for abstraction whereas the presence of an electron withdrawing group leads to opposite effects. PMID:24555565

  9. Hydrogen abstraction by photoexcited benzophenone: consequences for DNA photosensitization.

    PubMed

    Marazzi, Marco; Wibowo, Meilani; Gattuso, Hugo; Dumont, Elise; Roca-Sanjuán, Daniel; Monari, Antonio

    2016-03-21

    We report a computational investigation of the hydrogen abstraction (H-abstraction) induced by triplet benzophenone ((3)BP) on thymine nucleobase and backbone sugar. The chemical process is studied using both high level multiconfigurational perturbation and density functional theory. Both methods show good agreement in predicting small kinetic barriers. Furthermore the behavior of benzophenone in DNA is simulated using molecular dynamics and hybrid quantum mechanics/molecular mechanics methods. The accessibility of benzophenone to the labile hydrogens within B-DNA is demonstrated, as well as the driving force for this reaction. We evidence a strong dependence of the H-abstraction with the non-covalent BP-DNA interaction mode, and a reaction that is less favorable when embedded in DNA than for the isolated system. PMID:26911193

  10. Direct dynamics simulations of the hydrogen abstraction reaction Cl + CF₃CF₂CH₂OH.

    PubMed

    Yu, Ang-Yang; Zhang, Hong-Xing

    2013-10-01

    The mechanism and kinetics of 2,2,3,3,3-pentafluoropropanol (CF₃CF₂CH₂OH) reaction with Chlorine atom (Cl) is investigated in this work. Two hydrogen abstraction channels of the title reaction are identified. The geometries of all the stationary points in the potential energy surface are obtained at the BHandHLYP/6-311G level, and the energies of the selected points along the minimum energy path (MEP) are improved by the CCSD(T) method. A dual-level direct dynamics method is employed to study the kinetic nature of the hydrogen-abstraction reaction channels. The calculated rate coefficients show that the hydrogen abstraction from the CH2 group is the primary channel. The calculated total rate coefficients are in best agreement with the experimental values. The four-parameter rate coefficients expression of the title reaction between the temperatures 200 K and 1000 K is provided. PMID:23942600

  11. Ionisation of atomic hydrogen by positron impact

    NASA Technical Reports Server (NTRS)

    Spicher, Gottfried; Olsson, Bjorn; Raith, Wilhelm; Sinapius, Guenther; Sperber, Wolfgang

    1990-01-01

    With the crossed beam apparatus the relative impact-ionization cross section of atomic hydrogen by positron impact was measured. A layout of the scattering region is given. The first measurements on the ionization of atomic hydrogen by positron impact are also given.

  12. NASA atomic hydrogen standards program - An update

    NASA Technical Reports Server (NTRS)

    Reinhardt, V. S.; Kaufmann, D. C.; Adams, W. A.; Deluca, J. J.; Soucy, J. L.

    1976-01-01

    Some of the design features of NASA hydrogen masers are discussed including the large hydrogen source bulb, the palladium purified, the state selector, the replaceable pumps, the small entrance stem, magnetic shields, the elongated storage bulb, the aluminum cavity, the electronics package, and the autotuner. Attention is also given to the reliability and operating life of these hydrogen atomic standards.

  13. Effects of hydrogen atom spin exchange collisions on atomic hydrogen maser oscillation frequency

    NASA Technical Reports Server (NTRS)

    Crampton, S. B.

    1979-01-01

    Frequency shifts due to collisions between hydrogen atoms in an atomic hydrogen maser frequency standard are studied. Investigations of frequency shifts proportional to the spin exchange frequency shift cross section and those proportional to the duration of exchange collisions are discussed. The feasibility of operating a hydrogen frequency standard at liquid helium temperatures is examined.

  14. Atomic hydrogen as a launch vehicle propellant

    NASA Technical Reports Server (NTRS)

    Palaszewski, Bryan A.

    1990-01-01

    An analysis of several atomic hydrogen launch vehicles was conducted. A discussion of the facilities and the technologies that would be needed for these vehicles is also presented. The Gross Liftoff Weights (GLOW) for two systems were estimated; their specific impulses (I sub sp) were 750 and 1500 lb (sub f)/s/lb(sub m). The atomic hydrogen launch vehicles were also compared to the currently planned Advanced Launch System design concepts. Very significant GLOW reductions of 52 to 58 percent are possible over the Advanced Launch System designs. Applying atomic hydrogen propellants to upper stages was also considered. Very high I(sub sp) (greater than 750 1b(sub f)/s/lb(sub m) is needed to enable a mass savings over advanced oxygen/hydrogen propulsion. Associated with the potential benefits of high I(sub sp) atomic hydrogen are several challenging problems. Very high magnetic fields are required to maintain the atomic hydrogen in a solid kilogauss (3 Tesla). Also the storage temperature of the propellant is 4 K. This very low temperature will require a large refrigeration facility for the launch vehicle. The design considerations for a very high recombination rate for the propellant are also discussed. A recombination rate of 210 cm/s is predicted for atomic hydrogen. This high recombination rate can produce very high acceleration for the launch vehicle. Unique insulation or segmentation to inhibit the propellant may be needed to reduce its recombination rate.

  15. The Hydrogen Abstraction from A Diamond(111) Surface in A Uniform Electric Field

    NASA Technical Reports Server (NTRS)

    Ricca, Alessandra; Bauschlicher, Charles W., Jr.; Kang, Jeung Ku.; Musgrave, Charles B.; Arnold, James O. (Technical Monitor)

    1998-01-01

    Bond breaking in a strong electric field is shown to arise from a crossing of the ionic and covalent asymptotes. The specific example of hydrogen abstraction from a diamond(111) surface is studied using a cluster model. The addition of nearby atoms in both the parallel and perpendicular direction to the electric field are found to have an effect. It is also shown that the barrier is not only related to the position of the ionic and covalent asymptotes.

  16. Enhanced Cooling of Hydrogen Atoms by Lithium Atoms

    SciTech Connect

    Cote, R.; Jamieson, M. J.; Yan, Z-C.; Geum, N.; Jeung, G.-H.; Dalgarno, A.

    2000-03-27

    We present calculated scattering lengths for collisions between various isotopic forms of lithium and hydrogen atoms interacting via singlet and triplet molecular states of LiH. We demonstrate that one bound triplet level is supported for each isotopomer {sup 7}LiH , {sup 6}LiH , {sup 7}LiD , and {sup 6}LiD . We obtain large calculated triplet scattering lengths that are stable against uncertainties in the potential. We present elastic and momentum transfer cross sections, and the corresponding rate coefficients, for hydrogen atoms colliding with {sup 7}Li atoms. We suggest that enhanced cooling of trapped atomic hydrogen by {sup 7}Li atoms is feasible. (c) 2000 The American Physical Society.

  17. Surface Production of Hydride Ions by Backscattering Hyperthermal Hydrogen Atoms

    NASA Astrophysics Data System (ADS)

    Lee, Brian Seungwhan

    . It shows that the H^ - ion current increases faster than linearly with power, and no saturation is observed with power up to 500 watts. Maximum H^- ion current is obtained at an H_2 gas flow rate of 8-9 sccm, which corresponds to 80-90 mTorr discharge pressure; this indicates that the surface collisions dominate the loss mechanism of the hyperthermal hydrogen atoms. (Abstract shortened by UMI.).

  18. The Hydrogen Atom: The Rutherford Model

    NASA Astrophysics Data System (ADS)

    Tilton, Homer Benjamin

    1996-06-01

    Early this century Ernest Rutherford established the nuclear model of the hydrogen atom, presently taught as representing the best visual model after modification by Niels Bohr and Arnold Sommerfeld. It replaced the so-called "plum pudding" model of J. J. Thomson which held sway previously. While the Rutherford model represented a large step forward in our understanding of the hydrogen atom, questions remained, and still do.

  19. Energy storage possibilities of atomic hydrogen

    NASA Technical Reports Server (NTRS)

    Etters, R. D.; Dugan, J. V., Jr.; Palmer, R.

    1976-01-01

    Several recent experiments designed to produce and store macroscopic quantities of atomic hydrogen are discussed. The bulk, ground state properties of atomic hydrogen, deuterium, and tritium systems are calculated assuming that all pair interactions occur via the atomic triplet potential. The conditions required to obtain this system, including inhibition of recombination through the energetically favorable singlet interaction, are discussed. The internal energy, pressure, and compressibility are calculated applying the Monte Carlo technique with a quantum mechanical variational wavefunction. The system studied consisted of 32 atoms in a box with periodic boundary conditions. Results show that atomic triplet hydrogen and deuterium remain gaseous at 0 K; i.e., the internal energy is positive at all molar volumes considered.

  20. Solid Hydrogen Formed for Atomic Propellants

    NASA Technical Reports Server (NTRS)

    Palaszewski, Bryan A.

    2000-01-01

    Several experiments on the formation of solid hydrogen particles in liquid helium were recently conducted at the NASA Glenn Research Center at Lewis Field. The solid hydrogen experiments are the first step toward seeing these particles and determining their shape and size. The particles will ultimately store atoms of boron, carbon, or hydrogen, forming an atomic propellant. Atomic propellants will allow rocket vehicles to carry payloads many times heavier than possible with existing rockets or allow them to be much smaller and lighter. Solid hydrogen particles are preferred for storing atoms. Hydrogen is generally an excellent fuel with a low molecular weight. Very low temperature hydrogen particles (T < 4 K) can prevent the atoms from recombining, making it possible for their lifetime to be controlled. Also, particles that are less than 1 mm in diameter are preferred because they can flow easily into a pipe when suspended in liquid helium. The particles and atoms must remain at this low temperature until the fuel is introduced into the engine combustion (or recombination) chamber. Experiments were, therefore, planned to look at the particles and observe their formation and any changes while in liquid helium.

  1. Atomic hydrogen as a launch vehicle propellant

    SciTech Connect

    Palaszewski, B.A.

    1990-01-01

    An analysis of several atomic hydrogen launch vehicles was conducted. A discussion of the facilities and the technologies that would be needed for these vehicles is also presented. The Gross Liftoff Weights (GLOW) for two systems were estimated; their specific impulses (I{sub sp}) were 750 and 1500 lb{sub f}/s/lb{sub m}. The atomic hydrogen launch vehicles were also compared to the currently planned Advanced Launch System design concepts. Very significant GLOW reductions of 52 to 58 percent are possible over the Advanced Launch System designs. Applying atomic hydrogen propellants to upper stages was also considered. Very high I{sub sp} (greater than 750 lb{sub f}/s/lb{sub m}) is needed to enable a mass savings over advanced oxygen/hydrogen propulsion. Associated with the potential benefits of high I(sub sp) atomic hydrogen are several challenging problems. Very high magnetic fields are required to maintain the atomic hydrogen in a solid hydrogen matrix. The magnetic field strength was estimated to be 30 kilogauss (3 Tesla). Also the storage temperature of the propellant is 4 K. This very low temperature will require a large refrigeration facility for the launch vehicle. The design considerations for a very high recombination rate for the propellant are also discussed. A recombination rate of 210 cm/s is predicted for atomic hydrogen. This high recombination rate can produce very high acceleration for the launch vehicle. Unique insulation or segmentation to inhibit the propellant may be needed to reduce its recombination rate.

  2. Atomic hydrogen as a launch vehicle propellant

    NASA Technical Reports Server (NTRS)

    Palaszewski, Bryan A.

    1990-01-01

    An analysis of several atomic hydrogen launch vehicles was conducted. A discussion of the facilities and the technologies that would be needed for these vehicles is also presented. The Gross Liftoff Weights (GLOW) for two systems were estimated; their specific impulses (I sub sp) were 750 and 1500 lb(sub f)/s/lb(sub m). The atomic hydrogen launch vehicles were also compared to the currently planned Advanced Launch System design concepts. Very significant GLOW reductions of 52 to 58 percent are possible over the Advanced Launch System designs. Applying atomic hydrogen propellants to upper stages was also considered. Very high I(sub sp) (greater than 750 lb(sub f)/s/lb(sub m)) is needed to enable a mass savings over advanced oxygen/hydrogen propulsion. Associated with the potential benefits of high I(sub sp) atomic hydrogen are several challenging problems. Very high magnetic fields are required to maintain the atomic hydrogen in a solid hydrogen matrix. The magnetic field strength was estimated to be 30 kilogauss (3 Tesla). Also the storage temperature of the propellant is 4 K. This very low temperature will require a large refrigeration facility for the launch vehicle. The design considerations for a very high recombination rate for the propellant are also discussed. A recombination rate of 210 cm/s is predicted for atomic hydrogen. This high recombination rate can produce very high acceleration for the launch vehicle. Unique insulation or segmentation to inhibit the propellant may be needed to reduce its recombination rate.

  3. Reversible H Atom Abstraction Catalyzed by the Radical S-Adenosylmethionine Enzyme HydG

    PubMed Central

    2015-01-01

    The organometallic H-cluster at the active site of [FeFe]-hydrogenases is synthesized by three accessory proteins, two of which are radical S-adenosylmethionine enzymes (HydE, HydG) and one of which is a GTPase (HydF). In this work we probed the specific role of H atom abstraction in HydG-catalyzed carbon monoxide and cyanide production from tyrosine. The isotope distributions of 5′-deoxyadenosine and p-cresol were evaluated using deuterium-labeled tyrosine substrates in H2O and D2O. The observation of multiply deuterated 5′-deoxyadenosine and deuterated S-adenosylmethionine when the reaction is carried out in D2O provides evidence for a 5′-deoxyadenosyl radical-mediated abstraction of a hydrogen atom from a solvent-exchangeable position as a reversible event. PMID:25099480

  4. Applications of light-induced electron-transfer and hydrogen-abstraction processes: photoelectrochemical production of hydrogen from reducing radicals

    SciTech Connect

    Chandrasekaran, K.; Whitten, D.G.

    1980-07-16

    A study of several photoprocesses which generate reducing radicals in similar photoelectrochemical cells was reported. Coupling of a light-induced reaction to produce a photocurrent concurrent with hydrogen generation in a second compartment can occur for a number of electron transfers and hydrogen abstractions in what appears to be a fairly general process. Irradiation of the RuL/sub 3//sup +2//Et/sub 3/N: photoanode compartment leads to production of a photocurrent together with generation of hydrogen at the cathode. A rather different type of reaction that also results in formation of two reducing radicals as primary photoproducts if the photoreduction of ketones and H-heteroaromatics by alcohols and other hydrogen atom donors. Irradiation of benzophenone/2-propanol/MV/sup +2/ solutions in the photoanode compartment (intensity 1.4 x 10/sup -8/ einstein/s) leads to a buildup of moderate levels of MV/sup +/ and to a steady photocurrent of 320 ..mu..A. The MV/sup +/ is oxidized at the anode of the photolyzed compartment with concomitant reduction of H/sup +/ in the cathode compartment. There was no decrease in benzophenone concentration over moderate periods of irradiation, and a steady production of hydrogen in the cathode compartment was observed. The photocurrent produced was linear with the square of absorbed light intensity. The quantum efficiency at the above-indicated intensity is 22%; quantitative analysis of the hydrogen produced gives good agreement with this value. 1 figure, 1 table. (DP)

  5. Vibrationally Driven Hydrogen Abstraction Reaction by Bromine Radical in Solution

    NASA Astrophysics Data System (ADS)

    Shin, Jae Yoon; Shalowski, Michael A.; Crim, F. Fleming

    2013-06-01

    Previously, we have shown that preparing reactants in specific vibrational states can affect the product state distribution and branching ratios in gas phase reactions. In the solution phase, however, no vibrational mediation study has been reported to date. In this work, we present our first attempt of vibrationally mediated bimolecular reaction in solution. Hydrogen abstraction from a solvent by a bromine radical can be a good candidate to test the effect of vibrational excitation on reaction dynamics because this reaction is highly endothermic and thus we can suppress any thermally initiated reaction in our experiment. Br radical quickly forms CT (charge transfer) complex with solvent molecule once it is generated from photolysis of a bromine source. The CT complex strongly absorbs visible light, which allows us to use electronic transient absorption for tracking Br radical population. For this experiment, we photolyze bromoform solution in dimethyl sulfoxide (DMSO) solvent with 267 nm to generate Br radical and excite the C-H stretch overtone of DMSO with 1700 nm a few hundred femtoseconds after the photolysis. Then, we monitor the population of Br-DMSO complex with 400 nm as a function of delay time between two pump beams and probe beam. As a preliminary result, we observed the enhancement of loss of Br-DMSO complex population due to the vibrational excitation. We think that increased loss of Br-DMSO complex is attributed to more loss of Br radical that abstracts hydrogen from DMSO and it is the vibrational excitation that promotes the reaction. To make a clear conclusion, we will next utilize infrared probing to directly detect HBr product formation.

  6. Experimental and theoretical studies of the reactions of chlorine atoms with 1,2-dichloroethane and 1,2-dichloroethane-d4 in the gas phase. The kinetics of hydrogen atom abstraction from the -CH2Cl group in chloroethane and 1,2-dichloroethane

    NASA Astrophysics Data System (ADS)

    Sarzyński, Dariusz S.; Fojcik, Łukasz; Gola, Agnieszka A.; Berkowski, Ryszard; Jodkowski, Jerzy T.; Latajka, Zdzisław

    2014-03-01

    The rate constant for H-abstraction (kH) from CH2ClCH2Cl and D-abstraction (kD) from CD2ClCD2Cl by chlorine atoms is described by the expressions: kH = (1.99 ± 0.12) × 10-11 exp(-777 ± 23/T) cm3 molecule-1 s-1 and kD = (1.73 ± 0.12) × 10-11 exp(-1148 ± 16/T) cm3 molecule-1 s-1. The experiment revealed significant differences in the values of the rate constants for the abstraction of H-atom from the -CH2Cl group in chloroethane and 1,2-dichloroethane. The explanation of these differences was the subject of theoretical studies. The calculated potential energy barriers for the abstraction reaction confirmed the experimental results.

  7. Ionization of polarized hydrogen atoms

    SciTech Connect

    Alessi, J.G.

    1983-01-01

    Methods are discussed for the production of polarized H/sup -/ ions from polarized atoms produced in ground state atomic beam sources. Present day sources use ionizers of two basic types - electron ionizers for H/sup +/ Vector production followed by double charge exchange in a vapor, or direct H/sup -/ Vector production by charge exchange of H/sup 0/ with Cs/sup 0/. Both methods have ionization efficiencies of less than 0.5%. Ionization efficiencies in excess of 10% may be obtained in the future by the use of a plasma ionizer plus charge exchange in Cs or Sr vapor, or ionization by resonant charge exchange with a self-extracted D/sup -/ beam from a ring magnetron or HCD source. 36 references, 4 figures.

  8. Moller Polarimetry with Atomic Hydrogen Targets

    SciTech Connect

    Eugene Chudakov; Vladimir Luppov

    2003-10-19

    A novel proposal of using polarized atomic hydrogen gas, stored in an ultra-cold magnetic trap, as the target for electron beam polarimetry based on Moller scattering is discussed. Such a target of practically 100% polarized electrons could provide a superb systematic accuracy of about 0.5% for beam polarization measurements. The feasibility studies for the CEBAF electron beam have been performed.

  9. Compact microwave cavity for hydrogen atomic clock

    NASA Technical Reports Server (NTRS)

    Zhang, Dejun; Zhang, Yan; Fu, Yigen; Zhang, Yanjun

    1992-01-01

    A summary is presented that introduces the compact microwave cavity used in the hydrogen atomic clock. Special emphasis is placed on derivation of theoretical calculating equations of main parameters of the microwave cavity. A brief description is given of several methods for discriminating the oscillating modes. Experimental data and respective calculated values are also presented.

  10. Hydrogen abstraction from deoxyribose by a neighboring 3'-uracil peroxyl radical.

    PubMed

    Schyman, Patric; Eriksson, Leif A; Laaksonen, Aatto

    2009-05-01

    Theoretical examination of the reactivity of the uracil-5-peroxyl radical when abstracting a hydrogen atom from a neighboring 5'-deoxyribose in 5'-ApU-5-peroxyl-3' has been performed using density functional theory with the MPWB1K functional. Halogenated uracils are often used as radiosensitizers in DNA since the reactive uracil-5-yl radical is formed upon radiation and is known to create strand break and alkali-labile sites. Under aerobic conditions, such as in the cell, it has been proposed that the uracil-5-peroxyl radical is formed and would be the damaging agent. Our results show low reactivity for the uracil-5-peroxyl radical, determined by calculating the activation and reaction energies for the plausible hydrogen abstraction sites C1', C2', and C3' of the neighboring 5'-deoxyribose. These findings support the hypothesis that hydrogen abstraction primarily occurs by the uracil-5-yl radical, also under aerobic conditions, prior to formation of the peroxyl radical. PMID:19402732

  11. Atomic hydrogen cleaning of semiconductor photocathodes

    SciTech Connect

    Sinclair, C.K.; Poelker, B.M.; Price, J.S.

    1997-06-01

    Negative Electron Affinity (NEA) semiconductor photocathodes are widely used for the production of polarized electron beams, and are also useful for the production of high brightness electron beams which can be modulated at very high frequencies. Preparation of an atomically clean semiconductor surface is an essential step in the fabrication of a NEA photocathode. This cleaning step is difficult for certain semiconductors, such as the very thin materials which produce the highest beam polarization, and those which have tightly bound oxides and carbides. Using a small RF dissociation atomic hydrogen source, the authors have reproducibly cleaned GaAs wafers which have been only degreased prior to installation in vacuum. They have consistently prepared very high quantum efficiency photocathodes following atomic hydrogen cleaning. Details of their apparatus and most recent results are presented.

  12. Atomic line emission analyzer for hydrogen isotopes

    DOEpatents

    Kronberg, J.W.

    1993-03-30

    Apparatus for isotopic analysis of hydrogen comprises a low pressure chamber into which a sample of hydrogen is introduced and then exposed to an electrical discharge to excite the electrons of the hydrogen atoms to higher energy states and thereby cause the emission of light on the return to lower energy states, a Fresnel prism made at least in part of a material anomalously dispersive to the wavelengths of interest for dispersing the emitted light, and a photodiode array for receiving the dispersed light. The light emitted by the sample is filtered to pass only the desired wavelengths, such as one of the lines of the Balmer series for hydrogen, the wavelengths of which differ slightly from one isotope to another. The output of the photodiode array is processed to determine the relative amounts of each isotope present in the sample. Additionally, the sample itself may be recovered using a metal hydride.

  13. Atomic line emission analyzer for hydrogen isotopes

    DOEpatents

    Kronberg, J.W.

    1991-05-08

    Apparatus for isotopic analysis of hydrogen comprises a low pressure chamber into which a sample of hydrogen is introduced and then exposed to an electrical discharge to excite the electrons of the hydrogen atoms to higher energy states and thereby cause the emission of light on the return to lower energy states, a Fresnel prism made at least in part of a material anomalously dispersive to the wavelengths of interest for dispersing the emitted light, and a photodiode array for receiving the dispersed light. The light emitted by the sample is filtered to pass only the desired wavelengths, such as one of the lines of the Balmer series for hydrogen, the wavelengths of which differ slightly from one isotope to another. The output of the photodiode array is processed to determine the relative amounts of each isotope present in the sample. Additionally, the sample itself may be recovered using, a metal hydride.

  14. Atomic line emission analyzer for hydrogen isotopes

    DOEpatents

    Kronberg, James W.

    1993-01-01

    Apparatus for isotopic analysis of hydrogen comprises a low pressure chamber into which a sample of hydrogen is introduced and then exposed to an electrical discharge to excite the electrons of the hydrogen atoms to higher energy states and thereby cause the emission of light on the return to lower energy states, a Fresnel prism made at least in part of a material anomalously dispersive to the wavelengths of interest for dispersing the emitted light, and a photodiode array for receiving the dispersed light. The light emitted by the sample is filtered to pass only the desired wavelengths, such as one of the lines of the Balmer series for hydrogen, the wavelengths of which differ slightly from one isotope to another. The output of the photodiode array is processed to determine the relative amounts of each isotope present in the sample. Additionally, the sample itself may be recovered using a metal hydride.

  15. Beam transport of low temperature atomic hydrogen

    NASA Astrophysics Data System (ADS)

    Kaufman, W. A.

    1993-12-01

    Analytic calculations and particle tracking simulations are presented for a polarized atomic hydrogen beam produced by extraction from an ultra-cold (T=300 mK) helium film coated cell in a large solenoidal magnetic field (12 T). Initial focusing of states 1 and 2 by the solenoidal field and subsequent focusing by a sextupole are examined within the constraints imposed by the requirements of the polarized jet for the experiments NEPTUN and NEPTUN-A at UNK.

  16. Solid Hydrogen Experiments for Atomic Propellants

    NASA Technical Reports Server (NTRS)

    Palaszewski, Bryan

    2001-01-01

    This paper illustrates experiments that were conducted on the formation of solid hydrogen particles in liquid helium. Solid particles of hydrogen were frozen in liquid helium, and observed with a video camera. The solid hydrogen particle sizes, their molecular structure transitions, and their agglomeration times were estimated. article sizes of 1.8 to 4.6 mm (0.07 to 0. 18 in.) were measured. The particle agglomeration times were 0.5 to 11 min, depending on the loading of particles in the dewar. These experiments are the first step toward visually characterizing these particles, and allow designers to understand what issues must be addressed in atomic propellant feed system designs for future aerospace vehicles.

  17. Solid Hydrogen Particles Analyzed for Atomic Fuels

    NASA Technical Reports Server (NTRS)

    Palaszewski, Bryan A.

    2001-01-01

    Solid hydrogen particles have been selected as a means of storing atomic propellants in future launch vehicles (refs. 1 to 2). In preparation for this, hydrogen particle formation in liquid helium was tested experimentally. These experiments were conducted to visually characterize the particles and to observe their formation and molecular transformations (aging) while in liquid helium. The particle sizes, molecular transformations, and agglomeration times were estimated from video image analyses. The experiments were conducted at the NASA Glenn Research Center in the Supplemental Multilayer Insulation Research Facility (SMIRF, ref. 3). The facility has a vacuum tank, into which the experimental setup was placed. The vacuum tank prevented heat leaks and subsequent boiloff of the liquid helium, and the supporting systems maintained the temperature and pressure of the liquid helium bath where the solid particles were created. As the operation of the apparatus was developed, the hydrogen particles were easily visualized. The figures (ref. 1) show images from the experimental runs. The first image shows the initial particle freezing, and the second image shows the particles after the small particles have agglomerated. The particles finally all clump, but stick together loosely. The solid particles tended to agglomerate within a maximum of 11 min, and the agglomerate was very weak. Because the hydrogen particles are buoyant in the helium, the agglomerate tends to compact itself into a flat pancake on the surface of the helium. This pancake agglomerate is easily broken apart by reducing the pressure above the liquid. The weak agglomerate implies that the particles can be used as a gelling agent for the liquid helium, as well as a storage medium for atomic boron, carbon, or hydrogen. The smallest particle sizes that resulted from the initial freezing experiments were about 1.8 mm. About 50 percent of the particles formed were between 1.8 to 4.6 mm in diameter. These very

  18. A Newtonian Model of the Hydrogen Atom

    NASA Astrophysics Data System (ADS)

    Espinosa, James; Woodyard, James

    2010-03-01

    Classical physics was deemed useless in atomic physics in the early 1900's by the vast majority of the physics community. There were multiple problems that were believed to be insoluble, such as blackbody radiation and the photoelectric and Compton effects. Another outstanding problem had been the explanation of atomic spectra. By the 1920's, a very powerful theory called quantum mechanics was created which explained all atomic experiments. Nevertheless, a few physicists, most notably Albert Einstein, rejected this theory on the grounds that it did not give a complete description of the microscopic world. Another more radical view held by Walter Ritz is that Newtonian physics is applicable to all of atomic physics. Over the last couple of years, we have presented classical explanations of many of the ``insoluble'' problems given by textbooks. We will present a model of the hydrogen atom that stays within the framework of Newton. Using only the assumption that the stable building blocks of matter are the electron, positron, and neutrino, we will deduce the following results from our model: orbital stability, line spectra, and scattering cross sections for electrons and protons. We will also qualitatively demonstrate how to explain the lifetime of excited states.

  19. Fourteen Years of Atomic Hydrogen from SABER

    NASA Astrophysics Data System (ADS)

    Hunt, L. A.; Mlynczak, M. G.

    2015-12-01

    We present results for atomic hydrogen in the mesopause region (80-100 km) derived from measurements made by the Sounding of the Atmosphere using Broadband Emission Radiometry (SABER) instrument on the TIMED satellite. SABER has been measuring the vertical distribution of infrared radiation emitted by various atmospheric gases for nearly 14 years, providing important information about chemical species, including atomic oxygen, atomic hydrogen, ozone and hydroxyl; temperature; and the radiation budget in the upper atmosphere. The methodology for the derivation of daytime and nighttime concentrations and volume mixing ratios will be presented. Zonal mean and global average daytime and nighttime concentrations of H, which demonstrate excellent agreement between 87 and 95 km, have been calculated and the results are compared with observations from the Solar Mesosphere Explorer (SME) satellite made nearly 30 years ago. Variability over the course of the SABER mission will be shown, including the apparent inverse dependence on the solar cycle, which stems from the temperature dependence of various reaction rate coefficients for H photochemistry. Results for H near solar max will be compared for Solar Cycles 23 and 24.

  20. Uranyl photochemistry with alkenes: Distinguishing between H-atom abstraction and electron transfer

    SciTech Connect

    McCleskey, T.M.; Burns, C.J.; Tumas, W.

    1999-12-13

    Recent studies with the uranyl ion (UO{sub 2{sup 2+}}) have shown that it has the potential to photocatalytically oxidize organic substrates in the presence of air. The excited-state UO{sub 2}{sup 2+}* is a potent oxidant (E{degree} = 2.6 V), and is quenched by a variety of organic substrates. The resulting U(V) species can then be oxidized back to UO{sub 2}{sup 2+} in the presence of oxygen. Previous studies with alcohols have shown, through kinetic isotope effects, that the quenching of the uranyl excited state occurs by hydrogen atom abstraction to give UO{sub 2}H{sup +} and an organic radical. The mechanism of quenching with alkenes has not been definitely determined. Proposals for quenching mechanisms with alkenes have included exciplex formation, H-atom abstraction, and electron transfer. The authors report here on a series of quenching studies between uranyl and a variety of alkene substrates that unequivocally demonstrate quenching of the uranyl excited state with alkenes occurs by electron transfer.

  1. Positron impact ionization of atomic hydrogen

    SciTech Connect

    Acacia, P.; Campeanu, R.I.; Horbatsch, M.

    1993-05-01

    We will present integrated cross sections for ionization of atomic hydrogen by positrons. These have been calculated in a distorted-wave approximation using energy-dependent effective charges in the final channel as well as static and polarization potentials in the initial channel. We present two models for calculating the energy-dependent effective charges both of which produce results in good agreement with the recent experimental measurements of Spicher et al. This is in contrast to previous distorted-wave calculations which used fixed effective charges as well as classical trajectory calculations. Both of these latter methods produced results which were substantially below ours and the experimental data.

  2. Parity nonconservation in the hydrogen atom

    SciTech Connect

    Chupp, T.E.

    1983-01-01

    The development of experiments to detect parity nonconserving (PNC) mixing of the 2s/sub a/2/ and 2p/sub 1/2/ levels of the hydrogen atom in a 570 Gauss magnetic field is described. The technique involves observation of an asymmetry in the rate of microwave induced transitions at 1608 MHz due to the interference of two amplitudes, one produced by applied microwave and static electric fields and the other produced by an applied microwave field and the 2s/sub 1/2/-2p/sub 1/2/ mixing inducd by a PNC Hamiltonian.

  3. ATOMIC HYDROGEN IN A GALACTIC CENTER OUTFLOW

    SciTech Connect

    McClure-Griffiths, N. M.; Green, J. A.; Hill, A. S.; Lockman, F. J.; Dickey, J. M.; Gaensler, B. M.; Green, A. J.

    2013-06-10

    We describe a population of small, high-velocity, atomic hydrogen clouds, loops, and filaments found above and below the disk near the Galactic center. The objects have a mean radius of 15 pc, velocity widths of {approx}14 km s{sup -1}, and are observed at |z| heights up to 700 pc. The velocity distribution of the clouds shows no signature of Galactic rotation. We propose a scenario where the clouds are associated with an outflow from a central star-forming region at the Galactic center. We discuss the clouds as entrained material traveling at {approx}200 km s{sup -1} in a Galactic wind.

  4. Isotope effects of hydrogen and atom tunnelling

    NASA Astrophysics Data System (ADS)

    Buchachenko, A. L.; Pliss, E. M.

    2016-06-01

    The abnormally high mass-dependent isotope effects in liquid-phase hydrogen (deuterium) atom transfer reactions, which are customarily regarded as quantum effects, are actually the products of two classical effects, namely, kinetic and thermodynamic ones. The former is determined by the rate constants for atom transfer and the latter is caused by nonbonded (or noncovalent) isotope effects in the solvation of protiated and deuterated reacting molecules. This product can mimic the large isotope effects that are usually attributed to tunnelling. In enzymatic reactions, tunnelling is of particular interest; its existence characterizes an enzyme as a rigid molecular machine in which the residence time of reactants on the reaction coordinate exceeds the waiting time for the tunnelling event. The magnitude of isotope effect becomes a characteristic parameter of the internal dynamics of the enzyme catalytic site. The bibliography includes 61 references.

  5. Functionalization of Carbon Nanotubes using Atomic Hydrogen

    NASA Technical Reports Server (NTRS)

    Khare, Bishun N.; Cassell, Alan M.; Nguyen, Cattien V.; Meyyappan, M.; Han, Jie; Arnold, Jim (Technical Monitor)

    2001-01-01

    We have investigated the irradiation of multi walled and single walled carbon nanotubes (SWNTs) with atomic hydrogen. After irradiating the SWNT sample, a band at 2940/cm (3.4 microns) that is characteristic of the C-H stretching mode is observed using Fourier transform infrared (FTIR) spectroscopy. Additional confirmation of SWNT functionalization is tested by irradiating with atomic deuterium. A weak band in the region 1940/cm (5.2 micron) to 2450/cm (4.1 micron) corresponding to C-D stretching mode is also observed in the FTIR spectrum. This technique provides a clean gas phase process for the functionalization of SWNTs, which could lead to further chemical manipulation and/or the tuning of the electronic properties of SWNTs for nanodevice applications.

  6. Ab initio studies on hydrogen-transfer tunneling for Cl + HCl abstraction hydrogen reaction

    SciTech Connect

    Yuxiang Bu; Zhaohua Cao; Xinyu Song

    1996-01-05

    This article presents a treatment scheme of the tunneling of hydrogen between two molecular centers (Cl...Cl). The purpose is to calculate the tunneling probabilities of hydrogen atom transfer from the initial (the proceeding complex) to the final-state energy minima (the succeeding complex) in two anharmonic vibrational states (0 {r_arrow} 0 and 1 {r_arrow} 1) in terms of the time-dependent perturbation theory expression and to see whether spectroscopic signatures of tunneling persist in the form of splittings of the vibrational modes. The analysis uses the realistic potential energy function calculated at the HF/6-31 + G** self-consistent-field basis-set level for the interaction between transferred hydrogen and its molecular skeleton (Cl ... H ... Cl). This potential energy surface is calibrated by comparing its properties with those from s POLO and the LEPS potential-energy surfaces. The anharmonic vibrational state is characterized by the corrected vibrational energy levels and a set of linear combination coefficients obtained via perturbation theory. The tunneling probabilities for two transitions (0 {r_arrow} 0 and 1 {r_arrow} 1) were calculated and compared with those from Gamow`s equation. Applicability of the time-dependent perturbation theory expression and Gamow`s equation to the [Cl-H ... Cl] system is discussed. The vibrational splitting energies are obtained, and a spectroscopic signature caused by tunneling is expected and should be observable. 28 refs., 1 fig., 4 tabs.

  7. Atomic hydrogen propellants: Historical perspectives and future possibilities

    NASA Technical Reports Server (NTRS)

    Palaszewski, Bryan

    1993-01-01

    Atomic hydrogen, a very high density free-radical propellant, is anticipated to generate a specific impulse of 600-1500 lb-f sec/lb-mass performance; this may facilitate the development of unique launch vehicles. A development status evaluation is presently given for atomic hydrogen investigations. It is noted that breakthroughs are required in the production, storage, and transfer of atomic hydrogen, before this fuel can become a viable rocket propellant.

  8. In-Vacuum Dissociator for Atomic-Hydrogen Masers

    NASA Technical Reports Server (NTRS)

    Vessot, R. F.

    1987-01-01

    Thermal control and vacuum sealing achieved while contamination avoided. Simple, relatively inexpensive molecular-hydrogen dissociator for atomic-hydrogen masers used on Earth or in vacuum of space. No air cooling required, and absence of elastomeric O-ring seals prevents contamination. In-vacuum dissociator for atomic hydrogen masers, hydrogen gas in glass dissociator dissociated by radio-frequency signal transmitted from surrounding 3-turn coil. Heat in glass conducted away by contacting metal surfaces.

  9. Theoretical study of the kinetics of chlorine atom abstraction from chloromethanes by atomic chlorine.

    PubMed

    Brudnik, Katarzyna; Twarda, Maria; Sarzyński, Dariusz; Jodkowski, Jerzy T

    2013-10-01

    Ab initio calculations at the G3 level were used in a theoretical description of the kinetics and mechanism of the chlorine abstraction reactions from mono-, di-, tri- and tetra-chloromethane by chlorine atoms. The calculated profiles of the potential energy surface of the reaction systems show that the mechanism of the studied reactions is complex and the Cl-abstraction proceeds via the formation of intermediate complexes. The multi-step reaction mechanism consists of two elementary steps in the case of CCl4 + Cl, and three for the other reactions. Rate constants were calculated using the theoretical method based on the RRKM theory and the simplified version of the statistical adiabatic channel model. The temperature dependencies of the calculated rate constants can be expressed, in temperature range of 200-3,000 K as [Formula: see text]. The rate constants for the reverse reactions CH3/CH2Cl/CHCl2/CCl3 + Cl2 were calculated via the equilibrium constants derived theoretically. The kinetic equations [Formula: see text] allow a very good description of the reaction kinetics. The derived expressions are a substantial supplement to the kinetic data necessary to describe and model the complex gas-phase reactions of importance in combustion and atmospheric chemistry. PMID:23455925

  10. Hydrogen atom scrambling in ion-molecule reactions of methane and ethylene.

    NASA Technical Reports Server (NTRS)

    Huntress, W. T., Jr.

    1972-01-01

    The extent of hydrogen atom exchange in the reaction, CH3(+) + CH4 yields C2H5(+) + H2, is determined by examining the product distribution for the reactions CH3(+) + CD4 and CD3(+) + CH4 as a function of relative kinetic energy from thermal energies to 10 eV. It is found that the reaction of CH4(+) with the parent neutral proceeds both via proton transfer and hydrogen abstraction accompanied by approximately 10% hydrogen atom exchange during the reaction.

  11. Atomic hydrogen cleaning of Ru-capped EUV multilayer mirror

    NASA Astrophysics Data System (ADS)

    Motai, Kumi; Oizumi, Hiroaki; Miyagaki, Shinji; Nishiyama, I.; Izumi, Akira; Ueno, Tomoya; Miyazaki, Yasuo; Namiki, Akira

    2007-03-01

    Atomic hydrogen cleaning has been developed to reduce the amount of surface oxide on Ru-capped Mo/Si multilayer mirrors for EUVL. Atomic hydrogen generated by a heated W wire catalyzer was supplied to a Ru cap layer that had been lightly oxidized by ECR O2 plasma or EUV irradiation. The effectiveness of atomic hydrogen in deoxidizing it was examined by ex situ AES, XPS, and EUV absolute reflectivity measurements; and it was found that the amount of surface oxide was reduced to the initial level and that the EUV reflectivity of a multilayer degraded by oxidation recovered. In addition, the transport of atomic hydrogen thorough a winding quartz tube was demonstrated to be a promising technique. The actual density of hydrogen radicals was directly measured under various conditions so that the conditions for generating atomic hydrogen could be optimized and the required treatment time shortened.

  12. Role of Double Hydrogen Atom Transfer Reactions in Atmospheric Chemistry.

    PubMed

    Kumar, Manoj; Sinha, Amitabha; Francisco, Joseph S

    2016-05-17

    Hydrogen atom transfer (HAT) reactions are ubiquitous and play a crucial role in chemistries occurring in the atmosphere, biology, and industry. In the atmosphere, the most common and traditional HAT reaction is that associated with the OH radical abstracting a hydrogen atom from the plethora of organic molecules in the troposphere via R-H + OH → R + H2O. This reaction motif involves a single hydrogen transfer. More recently, in the literature, there is an emerging framework for a new class of HAT reactions that involves double hydrogen transfers. These reactions are broadly classified into four categories: (i) addition, (ii) elimination, (iii) substitution, and (iv) rearrangement. Hydration and dehydration are classic examples of addition and elimination reactions, respectively whereas tautomerization or isomerization belongs to a class of rearrangement reactions. Atmospheric acids and water typically mediate these reactions. Organic and inorganic acids are present in appreciable levels in the atmosphere and are capable of facilitating two-point hydrogen bonding interactions with oxygenates possessing an hydroxyl and/or carbonyl-type functionality. As a result, acids influence the reactivity of oxygenates and, thus, the energetics and kinetics of their HAT-based chemistries. The steric and electronic effects of acids play an important role in determining the efficacy of acid catalysis. Acids that reduce the steric strain of 1:1 substrate···acid complex are generally better catalysts. Among a family of monocarboxylic acids, the electronic effects become important; barrier to the catalyzed reaction correlates strongly with the pKa of the acid. Under acid catalysis, the hydration of carbonyl compounds leads to the barrierless formation of diols, which can serve as seed particles for atmospheric aerosol growth. The hydration of sulfur trioxide, which is the principle mechanism for atmospheric sulfuric acid formation, also becomes barrierless under acid catalysis

  13. Hydrogen atom in intense magnetic field.

    NASA Technical Reports Server (NTRS)

    Canuto, V.; Kelly, D. C.

    1972-01-01

    The structure of a hydrogen atom situated in an intense magnetic field is investigaged. Three approaches are employed. An elementary Bohr picture establishes a crucial magnetic field strength, H sub a approximately equal to 5 x 10 to the 9th G. Fields in excess of H sub a are intense in that they are able to modify the characteristic atomic scales of length and binding energy. A second approach solves the Schrodinger equation by a combination of variational methods and perturbation theory. It yields analytic expressions for the wave functions and energy eigenvalues. A third approach determines the energy eigenvalues by reducing the Schrodinger equation to a one-dimensional wave equation, which is then solved numerically. Energy eigenvalues are tabulated for field strengths of 2 x 10 to the 10th G and 2 x 10 to the 12th G. It is found that at 2 x 10 to the 12th G the lowest energy eigenvalue is changed from -13.6 to about -180 eV in agreement with previous variational computations.

  14. Hydrogen atom reactions in coal liquefaction. [Demethylation of methylnaphthalene by hydrogen

    SciTech Connect

    Bockrath, B.C.; Schroeder, K.T.; Keldsen, G.L.

    1985-06-01

    Hydrogen atom reactions were investigated in the demethylation of methylnaphthalenes at 450/sup 0/C. Demethylation by the hydrogen atom at the 1-position was about 4 times faster than at the 2-position. The methylnaphthalenes were somewhat more reactive toward hydrocracking than was bibenzyl. The extent of hydrocracking was a function of hydrogen pressure and initiator concentration. 3 refs., 2 figs., 1 tab.

  15. Hot hydrogen atom reactions moderated by H2 and He

    NASA Technical Reports Server (NTRS)

    Aronowitz, S.; Scattergood, T.; Flores, J.; Chang, S.

    1986-01-01

    Photolysis experiments were performed on the H2-CD4-NH3 and He-CD4-NH3 systems. The photolysis (1849 A) involved only NH3. Mixtures of H2:CD4:NH3 included all combinations of the ratios (200,400,800):(10,20,40):4. Two He:CD4:NH3 mixtures were examined where the ratios equalled the combinations 100:(10,20):4. Abstraction of a D from CD4 by the photolytically produced hot hydrogen from ammonia was monitored by mass spectrometric determination of HD. Both experiment and semiempirical hot-atom theory show that H2 is a very poor thermalizer of hot hydrogens with excess kinetic energy of about 2 eV. Applications of the hard-sphere collision model to the H2-CD4-NH3 system resulted in predicted ratios of net HD production to NH3 decomposition that were two orders of magnitude smaller than the experimental ratios. On the other hand, helium is found to be a very efficient thermalizer; here, the classical model yields reasonable agreement with experiments. Application of a semiempirical hot-atom program gave quantitative agreement with experiment for either system.

  16. Atomic-scale control of graphene magnetism by using hydrogen atoms

    NASA Astrophysics Data System (ADS)

    González-Herrero, Héctor; Gómez-Rodríguez, José M.; Mallet, Pierre; Moaied, Mohamed; Palacios, Juan José; Salgado, Carlos; Ugeda, Miguel M.; Veuillen, Jean-Yves; Yndurain, Félix; Brihuega, Iván

    2016-04-01

    Isolated hydrogen atoms absorbed on graphene are predicted to induce magnetic moments. Here we demonstrate that the adsorption of a single hydrogen atom on graphene induces a magnetic moment characterized by a ~20–millielectron volt spin-split state at the Fermi energy. Our scanning tunneling microscopy (STM) experiments, complemented by first-principles calculations, show that such a spin-polarized state is essentially localized on the carbon sublattice opposite to the one where the hydrogen atom is chemisorbed. This atomically modulated spin texture, which extends several nanometers away from the hydrogen atom, drives the direct coupling between the magnetic moments at unusually long distances. By using the STM tip to manipulate hydrogen atoms with atomic precision, it is possible to tailor the magnetism of selected graphene regions.

  17. Atomic-scale control of graphene magnetism by using hydrogen atoms.

    PubMed

    González-Herrero, Héctor; Gómez-Rodríguez, José M; Mallet, Pierre; Moaied, Mohamed; Palacios, Juan José; Salgado, Carlos; Ugeda, Miguel M; Veuillen, Jean-Yves; Yndurain, Félix; Brihuega, Iván

    2016-04-22

    Isolated hydrogen atoms absorbed on graphene are predicted to induce magnetic moments. Here we demonstrate that the adsorption of a single hydrogen atom on graphene induces a magnetic moment characterized by a ~20-millielectron volt spin-split state at the Fermi energy. Our scanning tunneling microscopy (STM) experiments, complemented by first-principles calculations, show that such a spin-polarized state is essentially localized on the carbon sublattice opposite to the one where the hydrogen atom is chemisorbed. This atomically modulated spin texture, which extends several nanometers away from the hydrogen atom, drives the direct coupling between the magnetic moments at unusually long distances. By using the STM tip to manipulate hydrogen atoms with atomic precision, it is possible to tailor the magnetism of selected graphene regions. PMID:27102478

  18. Quantum Sticking of Atomic Hydrogen to Graphene

    NASA Astrophysics Data System (ADS)

    Zhang, Yanting; Doherty, Adam; Geragotelis, Andrew; Clougherty, Dennis

    2013-03-01

    We consider the low-energy behavior of the sticking probability of atomic hydrogen to suspended graphene. For energy transfer through the flexural modes of graphene, we find that the inelastic coupling falls in the subOhmic regime. Thus the effects of low-frequency fluctuations of the graphene sheet are crucially important for quantum sticking. We analytically solve for the low-energy asymptotic behavior of the sticking coefficient using a variational mean-field method [D.P. Clougherty and Y. Zhang, Phys. Rev. Lett. 109, 120401 (2012)]. We find that as a result of strong coupling to the low-frequency flexural modes of graphene, a new scaling law results. For suspended graphene at finite temperature, we find that at a critical incident energy, the sticking probability drops discontinuously; below this critical energy, the sticking probability is suppressed by the orthogonality catastrophe. We compare our nonperturbative variational results to those obtained by using Fermi's golden rule. We gratefully acknowledge support by the National Science Foundation under DMR-1062966.

  19. The one-dimensional hydrogen atom revisited

    NASA Astrophysics Data System (ADS)

    Palma, G.; Raff, U.

    2006-09-01

    The one-dimensional Schrodinger hydrogen atom is an interesting mathematical and physical problem for the study of bound states, eigenfunctions, and quantum-degeneracy issues. This one-dimensional physical system has given rise to some intriguing controversy for more than four decades. Presently, still no definite consensus seems to have been reached. We reanalyzed this apparently controversial problem, approaching it from a Fourier-transform representation method combined with some fundamental (basic) ideas found in self-adjoint extensions of symmetric operators. In disagreement with some previous claims, we found that the complete Balmer energy spectrum is obtained together with an odd-parity set of eigenfunctions. Closed-form solutions in both coordinate and momentum spaces were obtained. No twofold degeneracy was observed as predicted by the degeneracy theorem in one dimension, though it does not necessarily have to hold for potentials with singularities. No ground state with infinite energy exists since the corresponding eigenfunction does not satisfy the Schrodinger equation at the origin.

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

    SciTech Connect

    Liu, Fengbin Cui, Yan; Qu, Min; Di, Jiejian

    2015-04-15

    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-3H{sub bc}-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.

  1. Rate constant calculations of H-atom abstraction reactions from ethers by HȮ2 radicals.

    PubMed

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

    2014-02-27

    In this work, we detail hydrogen atom abstraction reactions from six ethers by the hydroperoxyl radical, including dimethyl ether, ethyl methyl ether, propyl methyl ether, isopropyl methyl ether, butyl methyl ether, and isobutyl methyl ether, in order to test the effect of the functional group on the rate constant calculations. The Møller-Plesset (MP2) method with the 6-311G(d,p) basis set has been employed in the geometry optimizations and frequency calculations of all of the species involved in the above reaction systems. The connections between each transition state and the corresponding local minima have been determined by intrinsic reaction coordinate calculations. Energies are reported at the CCSD(T)/cc-pVTZ level of theory and include the zero-point energy corrections. As a benchmark in the electronic energy calculations, the CCSD(T)/CBS extrapolation was used for the reactions of dimethyl ether + HȮ2 radicals. A systematic calculation of the high-pressure limit rate constants has been performed using conventional transition-state theory, including asymmetric Eckart tunneling corrections, in the temperature range of 500-2000 K. The one dimensional hindrance potentials obtained at MP2/6-311G(d,p) for the reactants and transition states have been used to describe the low frequency torsional modes. Herein, we report the calculated individual, average, and total rate constants. A branching ratio analysis for every reaction site has also been performed. PMID:24483837

  2. Surface production of H(-) ions by hyperthermal hydrogen atoms

    NASA Astrophysics Data System (ADS)

    Lee, Brian S.; Seidl, M.

    1992-12-01

    Hyperthermal atomic hydrogen of energy in the range of 1-10 eV has been produced by electron impact dissociation in a CW 2.45 GHz microwave electron cyclotron resonance discharge using a Lisitano-Coil (Lisitano, 1970). The flux and the energy of the hydrogen atoms have been measured by negative surface ionization of the atoms backscattered from pure and cesiated metal surfaces. A hyperthermal atomic hydrogen flux density equivalent to more than 0.5 A/sq cm and a temperature of about 5 eV has been produced for 420 W discharge power under CW condition. These hydrogen atoms can be directed onto an external converter located outside the discharge. This opens up new possibilities for H(-) ion source design.

  3. Surface characterization of silica glass substrates treated by atomic hydrogen

    SciTech Connect

    Inoue, Hiroyuki; Masuno, Atsunobu; Ishibashi, Keiji; Tawarayama, Hiromasa; Zhang, Yingjiu; Utsuno, Futoshi; Koya, Kazuo; Fujinoki, Akira; Kawazoe, Hiroshi

    2013-12-15

    Silica glass substrates with very flat surfaces were exposed to atomic hydrogen at different temperatures and durations. An atomic force microscope was used to measure root-mean-square (RMS) roughness and two-dimensional power spectral density (PSD). In the treatment with atomic hydrogen up to 900 °C, there was no significant change in the surface. By the treatment at 1000 °C, the changes in the RMS roughness and the PSD curves were observed. It was suggested that these changes were caused by etching due to reactions of atomic hydrogen with surface silica. By analysis based on the k-correlation model, it was found that the spatial frequency of the asperities became higher with an increase of the treatment time. Furthermore, the data showed that atomic hydrogen can flatten silica glass surfaces by controlling heat-treatment conditions. - Highlights: • Silica glass surface was treated by atomic hydrogen at various temperatures. • Surface roughness was measured by an atomic force microscope. • Roughness data were analyzed by two-dimensional power spectral density. • Atomic hydrogen can flatten silica glass surfaces.

  4. Hydrogen atom as a four-dimensional oscillator

    SciTech Connect

    Chen, A.C.

    1980-08-01

    A coordinate transformation which exhibits the rotational invariance of the hydrogen atom in four-dimensional Hilbert space is introduced. The coordinates are shown to be directly related to the spherical polar and parabolic coordinates in position space. With the use of the transformation, the Schroedinger equation for the hydrogen atom left-multiplied by 4r is transformed into one for a four-dimensional harmonic oscillator. Solutions are obtained and related to the hydrogenic wave functions. Group-theoretical implications of the transformation and its application to the hydrogen Stark problem are briefly discussed.

  5. Parity nonconservation in the hydrogen atom

    SciTech Connect

    Chupp, T.E.

    1983-01-01

    The development of experiments to detect parity nonconserving (PNC) mixing of the 2s/sub 1///sub 2/ and 2p/sub 1///sub 2/ levels of the hydrogen atom in a 570 Gauss magnetic field is described. The technique involves observation of an asymmetry in the rate of microwave induced transitions at 1608 MHz due to the interference of two amplitudes, one produced by applied microwave and static electric fields and the other produced by an applied microwave field and the 2s/sub 1///sub 2/ - 2p/sub 1///sub 2/ mixing induced by a PNC Hamiltonian. These investigations, underway since 1977, have led to an experiment in which the two amplitudes are produced in two independently phased microwave cavities. The apparatus has the great advantage that all applied fields are cylindrically symmetric, thus false PNC effects can be generated only by departures from cylindrical symmetry which enter as the product of two small misalignment angles. The apparatus also has great diagnostic power since the sectioned microwave cavities can be used to produce static electric fields over short, well localized regions of space. This permits alignment of the apparatus and provides a sensitive probe of cylindrical symmetry. A phase regulation loop greatly reduces phase noise due to instabilities of the magnetic field, microwave generators, and resonant cavities. A preliminary measurement following alignment of the apparatus sets an upper limit of 575 on the parameter C/sub 2/p, which gives the strength of the PNC-induced mixing of the ..beta../sub 0/ (2s/sub 1///sub 2/) and e/sub 0/ (2p/sub 1///sub 2/) states. The prediction of the standard model, including radiative corrections, is C/sub 2/p = 0.08 +/- 0.037.

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

    NASA Astrophysics Data System (ADS)

    Chuang, K.-J.; Fedoseev, G.; 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 addition reactions, but is also subject to H-atom-induced abstraction reactions, yielding CO again. In a similar way, H2CO is also formed in abstraction reactions involving CH3OH. The dominant methanol H-atom abstraction product is expected to be CH2OH, while H-atom additions to H2CO should at least partially proceed through CH3O intermediate radicals. The occurrence of H-atom abstraction reactions in ice mantles leads to more reactive intermediates (HCO, CH3O and CH2OH) than previously thought, when assuming sequential H-atom addition reactions only. This enhances the probability to form COMs through radical-radical recombination without the need of UV photolysis or cosmic rays as external triggers.

  7. Muon transfer from hot muonic hydrogen atoms to neon

    SciTech Connect

    Jacot-Guillarmod, R. . Inst. de Physique); Bailey, J.M. ); Beer, G.A.; Knowles, P.E.; Mason, G.R.; Olin, A. ); Beveridge, J.L.; Marshall, G.M.; Brewer, J.H.; Forster, B.M. ); Huber, T.M. ); Kammel, P.; Zmeskal, J.

    1992-01-01

    A negative muon beam has been directed on adjacent solid layers of hydrogen and neon. Three targets differing by their deuterium concentration were investigated. Muonic hydrogen atoms can drift to the neon layer where the muon is immediately transferred. The time structure of the muonic neon X-rays follows the exponential law with a disappearance rate corresponding to the one of [mu][sup [minus]p] atoms in each target. The rates [lambda][sub pp[mu

  8. Atomic hydrogen and nitrogen distributions from atmosphere explorer measurements

    NASA Technical Reports Server (NTRS)

    Breig, Edward L.

    1992-01-01

    We were selective as to our approach to research activities, and devoted primary attention to two investigations concerning the global behavior of atomic hydrogen in the Earth's upper atmosphere. We derive the thermospheric concentration of H by applying the condition of charge-exchange equilibrium between hydrogen and oxygen atoms and ions to in-situ measurements of F-region composition and temperature from the series of Atmosphere Explorer (AE) aeronomy satellites. Progress and accomplishments on these chosen research projects are summarized.

  9. MOBILE SOURCE NOX MONITOR, HYDROGEN-ATOM DIRECT CHEMILUMINESCENCE METHOD

    EPA Science Inventory

    An analyzer was developed for measuring motor vehicle NOx (NO and NO2) emissions based on the chemiluminescence reaction of NO and NO2 with hydrogen atoms. This eliminated the need for an NO2 to NO converter as required with ozone chemiluminescence for NOx analysis. The hydrogen-...

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

    PubMed

    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. PMID:27253670

  11. Topics in atomic hydrogen standard research and applications

    NASA Technical Reports Server (NTRS)

    Peters, H. E.

    1971-01-01

    Hydrogen maser based frequency and time standards have been in continuous use at NASA tracking stations since February 1970, while laboratory work at Goddard has continued in the further development and improvement of hydrogen masers. Concurrently, experimental work has been in progress with a new frequency standard based upon the hydrogen atom using the molecular beam magnetic resonance method. Much of the hydrogen maser technology is directly applicable to the new hydrogen beam standard, and calculations based upon realistic data indicate that the accuracy potential of the hydrogen atomic beam exceeds that of either the cesium beam tube or the hydrogen maser, possibly by several orders of magnitude. In addition, with successful development, the hydrogen beam standard will have several other performance advantages over other devices, particularly exceptional stability and long continuous operating life. Experimental work with a new laboratory hydrogen beam device has recently resulted in the first resonance transition curves, measurements of relative state populations, beam intensities, etc. The most important aspects of both the hydrogen maser and the hydrogen beam work are covered.

  12. Absolute frequency of an atomic hydrogen maser clock

    NASA Technical Reports Server (NTRS)

    Peters, H. E.; Hall, R. G.; Percival, D. B.

    1972-01-01

    An accurate determination was made of the unperturbed atomic hydrogen ground state hyperfine transition frequency (F=1,m=0 - F=0,m=0) in reference to present world wide realizations of internationally defined time interval. In relation to the international atomic time system, the composite value is 1,420,405,751.7755 plus or minus 0.0031 HZ.

  13. Hydrogenation and Transfer Hydrogenation Promoted by Tethered Ru-S Complexes: From Cooperative Dihydrogen Activation to Hydride Abstraction/Proton Release from Dihydrogen Surrogates.

    PubMed

    Lefranc, Alice; Qu, Zheng-Wang; Grimme, Stefan; Oestreich, Martin

    2016-07-11

    Hydrogenation and transfer hydrogenation of imines with cyclohexa-1,4-dienes, as well as with a representative Hantzsch ester dihydrogen surrogate, are reported. Both processes are catalyzed by tethered Ru-S complexes but differ in the activation mode of the dihydrogen source: cooperative activation of the H-H bond at the Ru-S bond leads to the corresponding Ru-H complex and protonation of the sulfur atom, whereas the same cationic Ru-S catalyst abstracts a hydride from a donor-substituted cyclohexa-1,4-diene to form the neutral Ru-H complex and a low-energy Wheland intermediate. A sequence of proton and hydride transfers on the imine substrate then yields an amine. The reaction pathways are analyzed computationally, and the established mechanistic pictures are in agreement with the experimental observations. PMID:27311877

  14. Concerted hydrogen atom exchange between three HF molecules

    NASA Technical Reports Server (NTRS)

    Komornicki, Andrew; Dixon, David A.; Taylor, Peter R.

    1992-01-01

    The termolecular reaction involving concerted hydrogen-atom exchange between three HF molecules was investigated with particular attention given to the effects of correlation at the various stationary points along the reaction. Using large segmented Gaussian basis sets to locate the (HF)3 stationary points at the SCF level, the geometries of the stable hydrogen-bonded trimer, which is of C(3h) symmetry, were located, together with the transition state for hydrogen exchange, which is of D(3h) symmetry. Then, using a large atomic natural orbital basis and correlating all valence electrons, the energetics of the exchange reaction were evaluated at the correlated level.

  15. Modeling atomic hydrogen diffusion in GaAs

    NASA Astrophysics Data System (ADS)

    Kagadei, Valerii A.; Nefyodtsev, E.

    2004-05-01

    The hydrogen diffusion model in GaAs in conditions of an intense flow of penetrating atoms has been developed. It is shown that the formation undersurface diffusion barrier layer from immobile interstitial molecules of hydrogen reduce probability of atoms penetration into crystal and rate of their diffusion in GaAs, and influence on the process of shallow- and/or deep-centers passivation. It is exhibited that the influence of diffusion barrier should be taken into account at optimum mode selection of GaAs structure hydrogenation.

  16. Influence of probe contamination on recombination of atomic hydrogen

    NASA Technical Reports Server (NTRS)

    Collins, L. W.; Downs, W. R.

    1975-01-01

    Atomic hydrogen concentration profiles were measured through a screen-stabilized one-dimensional propane/oxygen front using a specially modified electron spin resonance (ESR) spectrometer. The ESR line occurring at 3075.5 G at 9261.2 MHz was monitored in the presence and absence of various halogenated hydrocarbons. A significant cumulative decrease in peak intensity occurred with addition of any halogenated compound. Further results suggest that the effect is due to inhibitor action on the transport tube walls followed by changes in atomic hydrogen interaction with the walls, and that hydrogen decay is nonlinear in the halogenated tube.

  17. Theoretical study of the hydrogen abstraction of substituted phenols by nitrogen dioxide as a source of HONO.

    PubMed

    Shenghur, Abraham; Weber, Kevin H; Nguyen, Nhan D; Sontising, Watit; Tao, Fu-Ming

    2014-11-20

    The mild yet promiscuous reactions of nitrogen dioxide (NO2) and phenolic derivatives to produce nitrous acid (HONO) have been explored with density functional theory calculations. The reaction is found to occur via four distinct pathways with both proton coupled electron transfer (PCET) and hydrogen atom transfer (HAT) mechanisms available. While the parent reaction with phenol may not be significant in the gas phase, electron donating groups in the ortho and para positions facilitate the reduction of nitrogen dioxide by electronically stabilizing the product phenoxy radical. Hydrogen bonding groups in the ortho position may additionally stabilize the nascent resonantly stabilized radical product, thus enhancing the reaction. Catechol (ortho-hydroxy phenol) has a predicted overall free energy change ΔG(0) = -0.8 kcal mol(-1) and electronic activation energy Ea = 7.0 kcal mol(-1). Free amines at the ortho and para positions have ΔG(0) = -3.8 and -1.5 kcal mol(-1); Ea = 2.3 and 2.1 kcal mol(-1), respectively. The results indicate that the hydrogen abstraction reactions of these substituted phenols by NO2 are fast and spontaneous. Hammett constants produce a linear correlation with bond dissociation energy (BDE) demonstrating that the BDE is the main parameter controlling the dark abstraction reaction. The implications for atmospheric chemistry and ground-level nitrous acid production are discussed. PMID:25325182

  18. Theoretical investigations of reactions of some radicals with HO sub 2. 1. Hydrogen abstractions by direct mechanisms

    SciTech Connect

    Toohey, D.W.; Anderson, J.G. )

    1989-02-09

    Ab initio quantum mechanical methods are used to calculate saddle-point geometries and energies for hydrogen abstractions from HO{sub 2} by N, ClO, O, Cl, H, OH, and F assuming direct attack at the hydrogen atom. Results are consistent with bond energy-bond order principles and indicate that activation energies for these reactions should decrease with increasing exothermicity of reaction. In addition, the large rate constant for OH + HO{sub 2} {yields} H{sub 2}O + O{sub 2} is interpreted to be due to long-range dipole-dipole attraction, leading ultimately to formation of a hydrogen bond and to stabilization of an early transition state. Results for the ClO + HO{sub 2} {yields} HOCl + O{sub 2} reaction suggest a dual mechanism dominated by direct abstraction at high temperatures and by elimination from a stable intermediate at lower temperatures, perhaps the only reaction in this series which does so. These results are in good agreement with current experimental rate data.

  19. Precision Spectroscopy of Atomic Hydrogen and the Proton Size Puzzle

    NASA Astrophysics Data System (ADS)

    Udem, Thomas

    2016-05-01

    Precise determination of transition frequencies of simple atomic systems are required for a number of fundamental applications such as tests of quantum electrodynamics (QED), the determination of fundamental constants and nuclear charge radii. The sharpest transition in atomic hydrogen occurs between the metastable 2S state and the 1S ground state. Its transition frequency has now been measured with almost 15 digits accuracy using an optical frequency comb and a cesium atomic clock as a reference. A recent measurement of the Lamb shift in muonic hydrogen is in significant contradiction to the hydrogen data if QED calculations are assumed to be correct. We hope to contribute to the resolution of this so called `proton size puzzle' by providing additional experimental input from the hydrogen side.

  20. The sticking of atomic hydrogen on amorphous water ice

    SciTech Connect

    Veeraghattam, Vijay K.; Manrodt, Katie; Lewis, Steven P.; Stancil, P. C. E-mail: lewis@physast.uga.edu

    2014-07-20

    Using classical molecular dynamics, we have simulated the sticking and scattering process of a hydrogen atom on an amorphous ice film to predict the sticking probability of hydrogen on ice surfaces. A wide range of initial kinetic energies of the incident hydrogen atom (10 K-600 K) and two different ice temperatures (10 K and 70 K) were used to investigate this fundamental process in interstellar chemistry. We report here the sticking probability of atomic hydrogen as a function of incident kinetic energy, gas temperature, and substrate temperature, which can be used in astrophysical models. The current results are compared to previous theoretical and experimental studies that have reported a wide range in the sticking coefficient.

  1. Hydrogen abstraction from methane on an MgO(OO1) surface

    SciTech Connect

    Boerve, K.J.; Pettersson, L.G.M. )

    1991-09-19

    Hydrogen abstraction from methane over the pure and doped MgO(001) crystal surface has been studied at the SCF, CASSCF, and multireference CI levels by use of a cluster model combined with the surface Madelung potential. Li and As as dopants stabilize a reactive O{sup {minus}} state at the surface and give abstraction reactions with low barrier (4-6 kcal/mol). Second-layer Mg and Mg{sup +} vacancies also result in a low barrier, but somewhat endothermic reactions. Be and Mg stabilize O{sup 2{minus}}, which is very unreactive toward hydrogen abstraction. This is in agreement with experimental evidence indicating O{sup {minus}} as the reactive site. Large near-degeneracy effects (20 kcal/mol) make at least a multiconfiguration SCF treatment necessary to compute the barrier heights.

  2. Atomic Diffusion in Solid Molecular Hydrogen

    PubMed Central

    Belonoshko, Anatoly B.; Ramzan, Muhammad; Mao, Ho-kwang; Ahuja, Rajeev

    2013-01-01

    We performed ab initio molecular dynamics simulations of the C2c and Cmca-12 phases of hydrogen at pressures from 210 to 350 GPa. These phases were predicted to be stable at 0 K and pressures above 200 GPa. However, systematic studies of temperature impact on properties of these phases have not been performed so far. Filling this gap, we observed that on temperature increase diffusion sets in the Cmca-12 phase, being absent in C2c. We explored the mechanism of diffusion and computed melting curve of hydrogen at extreme pressures. The results suggest that the recent experiments claiming conductive hydrogen at the pressure around 260 GPa and ambient temperature might be explained by the diffusion. The diffusion might also be the reason for the difference in Raman spectra obtained in recent experiments. PMID:23902995

  3. Atomic Structures of Molecules Based on Additivity of Atomic and/or Ionic Radii (abstract)

    NASA Astrophysics Data System (ADS)

    Heyrovska, Raji; Narayan, Sara

    2009-04-01

    We have shown in recent years that interatomic and interionic distances are sums of the radii of the adjacent atoms or ions. Many examples are provided and it is shown how the experimental bond lengths agree with the radii sums. The examples include inorganic compounds such as alkali halides, metal hydrides, and graphene; organic compounds such as aliphatic and aromatic compounds; and biochemical compounds such as nucleic acids, amino acids, caffeine-related compounds, and vitamins.

  4. Substituent effects on the reaction rates of hydrogen abstraction in the pyrolysis of phenethyl phenyl ethers

    SciTech Connect

    Beste, Ariana; Buchanan III, A C

    2010-01-01

    We report reaction profiles and forward rate constants for hydrogen abstraction reactions occurring in the pyrolysis of methoxy-substituted derivatives of phenethyl phenyl ether (PhCH{sub 2}CH{sub 2}OPh, PPE), where the substituents are located on the aryl ether ring (PhCH{sub 2}CH{sub 2}OPh-X). We use density functional theory in combination with transition-state theory, and anharmonic corrections are included within the independent mode approximation. PPE is the simplest model of the abundant {beta}-O-4 linkage in lignin. The mechanism of PPE pyrolysis and overall product selectivities have been studied experimentally by one of us, which was followed by computational analysis of key individual hydrogen-transfer reaction steps. In the previous work, we have been able to use a simplified kinetic model based on quasi-steady-state conditions to reproduce experimental {alpha}/{beta} selectivities for PPE and PPEs with substituents on the phenethyl ring (X-PhCH{sub 2}CH{sub 2}OPh). This model is not applicable to PPE derivatives where methoxy substituents are located on the phenyl ring adjacent to the ether oxygen because of the strongly endothermic character of the hydrogen abstraction by substituted phenoxy radicals as well as the decreased kinetic chain lengths resulting from enhanced rates of the initial C?O homolysis step. Substituents decelerate the hydrogen abstraction by the phenoxy radical, while the influence on the benzyl abstraction is less homogeneous. The calculations provide insight into the contributions of steric and polar effects in these important hydrogen-transfer steps. We emphasize the importance of an exhaustive conformational space search to calculate rate constants and product selectivities. The computed rate constants will be used in future work to numerically simulate the pyrolysis mechanism, pending the calculation of the rate constants of all participating reactions.

  5. Cold atomic hydrogen in the inner galaxy

    NASA Technical Reports Server (NTRS)

    Dickey, J. M.; Garwood, R. W.

    1986-01-01

    The VLA is used to measure 21 cm absorption in directions with the absolute value of b less than 1 deg., the absolute value of 1 less than 25 deg. to probe the cool atomic gas in the inner galaxy. Abundant H I absorption is detected; typical lines are deep and narrow, sometimes blending in velocity with adjacent features. Unlike 21 cm emission not all allowed velocities are covered: large portions of the l-v diagram are optically thin. Although not similar to H I emission, the absorption shows a striking correspondence with CO emission in the inner galaxy: essentially every strong feature detected in one survey is seen in the other. The provisional conclusion is that in the inner galaxy most cool atomic gas is associated with molecular cloud complexes. There are few or no cold atomic clouds devoid of molecules in the inner galaxy, although these are common in the outer galaxy.

  6. Ab initio reaction kinetics of hydrogen abstraction from methyl formate by hydrogen, methyl, oxygen, hydroxyl, and hydroperoxy radicals.

    PubMed

    Tan, Ting; Pavone, Michele; Krisiloff, David B; Carter, Emily A

    2012-08-23

    Combustion of renewable biofuels, including energy-dense biodiesel, is expected to contribute significantly toward meeting future energy demands in the transportation sector. Elucidating detailed reaction mechanisms will be crucial to understanding biodiesel combustion, and hydrogen abstraction reactions are expected to dominate biodiesel combustion during ignition. In this work, we investigate hydrogen abstraction by the radicals H·, CH(3)·, O·, HO(2)·, and OH· from methyl formate, the simplest surrogate for complex biodiesels. We evaluate the H abstraction barrier heights and reaction enthalpies, using multireference correlated wave function methods including size-extensivity corrections and extrapolation to the complete basis set limit. The barrier heights predicted for abstraction by H·, CH(3)·, and O· are in excellent agreement with derived experimental values, with errors ≤1 kcal/mol. We also predict the reaction energetics for forming reactant complexes, transition states, and product complexes for reactions involving HO(2)· and OH·. High-pressure-limit rate constants are computed using transition state theory within the separable-hindered-rotor approximation for torsions and the harmonic oscillator approximation for other vibrational modes. The predicted rate constants differ significantly from those appearing in the latest combustion kinetics models of these reactions. PMID:22830521

  7. Ab Initio Kinetics of Hydrogen Abstraction from Methyl Acetate by Hydrogen, Methyl, Oxygen, Hydroxyl, and Hydroperoxy Radicals.

    PubMed

    Tan, Ting; Yang, Xueliang; Krauter, Caroline M; Ju, Yiguang; Carter, Emily A

    2015-06-18

    The kinetics of hydrogen abstraction by five radicals (H, O((3)P), OH, CH3, and HO2) from methyl acetate (MA) is investigated theoretically in order to gain further understanding of certain aspects of the combustion chemistry of biodiesels, such as the effect of the ester moiety. We employ ab initio quantum chemistry methods, coupled cluster singles and doubles with perturbative triples correction (CCSD(T)) and multireference averaged coupled pair functional theory (MRACPF2), to predict chemically accurate reaction energetics. Overall, MRACPF2 predicts slightly higher barrier heights than CCSD(T) for MA + H/CH3/O/OH, but slightly lower barrier heights for hydrogen abstraction by HO2. Based on the obtained reaction energies, we also report high-pressure-limit rate constants using transition state theory (TST) in conjunction with the separable-hindered-rotor approximation, the variable reaction coordinate TST, and the multi-structure all-structure approach. The fitted modified Arrhenius expressions are provided over a temperature range of 250 to 2000 K. The predictions are in good agreement with available experimental results. Abstractions from both of the methyl groups in MA are expected to contribute to consumption of the fuel as they exhibit similar rate coefficients. The reactions involving the OH radical are predicted to have the highest rates among the five abstracting radicals, while those initiated by HO2 are expected to be the lowest. PMID:25974050

  8. Atomic hydrogen on Mars - Measurements at solar minimum

    NASA Technical Reports Server (NTRS)

    Levine, J. S.; Mcdougal, D. S.; Anderson, D. E., Jr.; Barker, E. S.

    1978-01-01

    The Copernicus Orbiting Astronomical Observatory was used to obtain measurements of Mars Lyman-alpha (1215.671-angstrom) emission at the solar minimum, which has resulted in the first information on atomic hydrogen concentrations in the upper atmosphere of Mars at the solar minimum. The Copernicus measurements, coupled with the Viking in situ measurements of the temperature (170 plus or minus 30 K) of the upper atmosphere of Mars, indicate that the atomic hydrogen number density at the exobase of Mars (250 kilometers) is about 60 times greater than that deduced from Mariner 6 and 7 Lyman-alpha measurements obtained during a period of high solar activity. The Copernicus results are consistent with Hunten's hypothesis of the diffusion-limited escape of atomic hydrogen from Mars.

  9. Atomic Hydrogen in the Circumstellar Envelope of IRC+10216

    NASA Astrophysics Data System (ADS)

    Matthews, L. D.; Gérard, E.; Le Bertre, T.

    2015-08-01

    Using the Robert C. Byrd Green Bank Telescope (GBT), we have performed the most sensitive search to date for neutral atomic hydrogen (HI) associated with the circumstellar envelope (CSE) of the carbon star IRC+10216. We report the discovery of a low surface brightness HI shell of diameter ˜1280'' (˜0.8 pc) surrounding the star. The shell's kinematics are consistent with matter that has been decelerated through interaction with the interstellar medium (ISM). The angular extent of the shell is comparable to the far ultraviolet (FUV)-emitting astrosphere previously detected with GALEX. The total mass of atomic hydrogen associated with IRC+10216 is < 1% of the expected total mass of the CSE. We briefly discuss implications for the possible origins of the circumstellar atomic hydrogen.

  10. Thermochemical nonequilibrium in atomic hydrogen at elevated temperatures

    NASA Technical Reports Server (NTRS)

    Scott, R. K.

    1972-01-01

    A numerical study of the nonequilibrium flow of atomic hydrogen in a cascade arc was performed to obtain insight into the physics of the hydrogen cascade arc. A rigorous mathematical model of the flow problem was formulated, incorporating the important nonequilibrium transport phenomena and atomic processes which occur in atomic hydrogen. Realistic boundary conditions, including consideration of the wall electrostatic sheath phenomenon, were included in the model. The governing equations of the asymptotic region of the cascade arc were obtained by writing conservation of mass and energy equations for the electron subgas, an energy conservation equation for heavy particles and an equation of state. Finite-difference operators for variable grid spacing were applied to the governing equations and the resulting system of strongly coupled, stiff equations were solved numerically by the Newton-Raphson method.

  11. Molecular hydrogen formation by excited atom radiative association

    NASA Technical Reports Server (NTRS)

    Latter, William B.; Black, John H.

    1991-01-01

    The results from a semiclassical calculation of the thermal rate coefficient for the radiative association process H(n = 2) + H(n = 1) - H2 + hv are presented (n is the principal quantum number of the separated hydrogen atoms). The relative importance of this reaction in various environments is briefly discussed. Models of the early universe around the epoch of recombination and protostellar winds have been calculated which include the excited atom process. Not surprisingly, it is shown that the excited atom process will not be important in the general interstellar medium, except possibly in environments where the amount of Ly-alpha photon trapping is large. Examples may be the material surrounding quasars, active galactic nuclei, and bright H II regions. The most likely application of this process might be within rapidly evolving systems where a large transient n = 2 population of neutral hydrogen could result in a burst of molecular hydrogen formation.

  12. Multiple scattering and charged-particle - hydrogen-atom collisions

    NASA Technical Reports Server (NTRS)

    Franco, V.; Thomas, B. K.

    1979-01-01

    Glauber-approximation scattering amplitudes for charged-particle - hydrogen-atom elastic and inelastic collisions are derived directly in terms of the known particle-electron and particle-proton Coulomb scattering amplitudes and the known hydrogen-atom form factors. It is shown that the particle-hydrogen amplitude contains no single-scattering term. The double-scattering term is obtained as a two-dimensional integral in momentum space. It is demonstrated how the result can be used as the starting point for an alternative and relatively simple derivation, in closed form, of the Glauber particle-hydrogen scattering amplitude for transitions from the ground state to an arbitrary (nlm) state.

  13. Proton form factor effects in hydrogenic atoms

    SciTech Connect

    Daza, F. Garcia; Kelkar, N. G.; Nowakowski, M.

    2011-10-21

    The proton structure corrections to the hyperfine splittings in electronic and muonic hydrogen are evaluated using the Breit potential with electromagnetic form factors. In contrast to other methods, the Breit equation with q{sup 2} dependent form factors is just an extension of the standard Breit equation which gives the hyperfine splitting Hamiltonian. Precise QED corrections are comparable to the structure corrections which therefore need to be evaluated ab initio.

  14. Atomic hydrogen distribution. [in Titan atmospheric model

    NASA Technical Reports Server (NTRS)

    Tabarie, N.

    1974-01-01

    Several possible H2 vertical distributions in Titan's atmosphere are considered with the constraint of 5 km-A a total quantity. Approximative calculations show that hydrogen distribution is quite sensitive to two other parameters of Titan's atmosphere: the temperature and the presence of other constituents. The escape fluxes of H and H2 are also estimated as well as the consequent distributions trapped in the Saturnian system.

  15. Effect of hydration on the hydrogen abstraction reaction by HO in DMS and its oxidation products.

    PubMed

    Jørgensen, Solvejg; Kjaergaard, Henrik G

    2010-04-15

    The gas-phase hydrogen abstraction reaction between the HO radical and sulfur containing species in the absence and presence of a single water molecule is investigated theoretically. The sulfur containing species dimethyl sulfide, dimethyl sulfoxide, and dimethyl sulfone are considered. The calculations are carried out with a mixture of density function theory and second order Møller-Plesset perturbation theory. We find that the energy of the hydrated transition state structures for the hydrogen abstraction reactions is lowered compared to that of the nonhydrated ones. Furthermore, the energy difference between the reaction complex and the transition state is reduced when one water molecule is added. The atmospheric abundance of the different hydrated complexes is estimated in order to assess the relative importance of the possible reaction mechanisms. PMID:20088555

  16. Ab initio study of the kinetics of hydrogen abstraction reactions on toluene and tetralin

    SciTech Connect

    Beste, Ariana; Britt, Phillip F; Buchanan III, A C; Harrison, Robert J; Hathorn, Bryan C

    2008-01-01

    Hydrogen abstraction reactions play a key role in many thermal and catalytic processes involved in the production of fuels and chemicals. In this paper, the reaction barriers and rate constants for the hydrogen abstraction reactions on toluene and tetralin by the benzyl radical are calculated by ab initio methods. These reactions are representatives of similar reactions occurring in the thermolysis of lignin model compounds containing the phenethyl phenyl ether (PPE) structural moiety. Thermolysis of PPE occurs by a free radical chain mechanism in which the product selectivity arises from competitive hydrogen abstraction at the benzylic and nonbenzylic methylen sites by chain carrying benzyl and phenoxyl radicals. The title reactions serve to calibrate the theoretical methods to be used in the study of PPE through comparison of the rate constants and the reaction enthalpies with reliable experimental values. In this study, we used two different hybrid density functionals (BHandHLYP, B3LYP) and second-order perturbation theory to obtain equilibrium and transition state geometries. Multiple transition states were found for both reactions. BHandHLYP underestimates and second-order perturbation theory overestimates the reaction barriers; B3LYP energy barriers agree well with experiment. Absolute and relative rate constants were calculated using transition state theory. We found that the relative rate constant using the B3LYP functional agrees within a factor of 2.0 with experiment at the experimental temperature of 333 K, indicating that the B3LYP functional will be successful in predicting relative rate constants for hydrogen abstraction reactions participating in the pyrolysis of PPE.

  17. Michigan ultra-cold polarized atomic hydrogen jet target

    NASA Astrophysics Data System (ADS)

    Blinov, B. B.; Gladycheva, S. E.; Kageya, T.; Kantsyrev, D. Yu.; Krisch, A. D.; Luppov, V. G.; Morozov, V. S.; Murray, J. R.; Raymond, R. S.; Borisov, N. S.; Fimushkin, V. V.; Grishin, V. N.; Mysnik, A. I.; Kleppner, D.

    2001-06-01

    To study spin effects in high energy collisions, we are developing an ultra-cold high-density jet target of proton-spin-polarized hydrogen atoms. The target uses a 12 Tesla magnetic field and a 0.3 K separation cell coated with superfluid helium-4 to produce a slow monochromatic electron-spin-polarized atomic hydrogen beam, which is then focused by a superconducting sextupole into the interaction region. In recent tests, we studied a polarized beam of hydrogen atoms focused by the superconducting sextupole into a compression tube detector, which measured the polarized atoms' intensity. The Jet produced, at the detector, a spin-polarized atomic hydrogen beam with a measured intensity of about 2.8.1015 H s-1 and a FWHM area of less than 0.13 cm2. This intensity corresponds to a free jet density of about 1.1012 H cm-3 with a proton polarization of about 50%. When the transition RF unit is installed, we expect a proton polarization higher than 90%. .

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

    SciTech Connect

    Nakano, H. Goto, M.; Tsumori, K.; Kisaki, M.; Ikeda, K.; Nagaoka, K.; Osakabe, M.; Takeiri, Y.; Kaneko, O.; Nishiyama, S.; Sasaki, K.

    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.

  19. Photoionization of atoms and molecules. [of hydrogen, helium, and xenon

    NASA Technical Reports Server (NTRS)

    Samson, J. A. R.

    1976-01-01

    A literature review on the present state of knowledge in photoionization is presented. Various experimental techniques that have been developed to study photoionization, such as fluorescence and photoelectron spectroscopy, mass spectroscopy, are examined. Various atoms and molecules were chosen to illustrate these techniques, specifically helium and xenon atoms and hydrogen molecules. Specialized photoionization such as in positive and negative ions, excited states, and free radicals is also treated. Absorption cross sections and ionization potentials are also discussed.

  20. Hydrogen Abstraction from Methane by Bromine and Chlorine Radicals: a Dynamics Comparison

    NASA Astrophysics Data System (ADS)

    Berke, Rew E.; Volpa, Ethan H.; Crim, F. Fleming

    2013-06-01

    The abstraction of H or D from methane and its isotopologues by H, F, or Cl radicals has long been the poster child for gas phase bimolecular reaction dynamics experiments. Recently, our group has successfully carried out a reaction dynamics study of the hydrogen abstraction from CH_4 by Br radicals to produce CH_3 and HBr. To our knowledge, this is the first successful attempt at adding bromine to the repertoire of H abstraction collision partners in a molecular beam study. As a point of comparison for our Br experiments, we have also revisited the well understood H-abstraction from CH_4 by Cl. In the Br system, we see dramatic vibrational mode selectivity similar to that observed in previous studies done on the Cl analog system. However, due to the large barrier height of the H-abstraction by Br ( 4500 cm^{-1}) compared to that of abstraction by Cl ( 1200 cm^{-1}), the manifestations of the mode selectivity are markedly different in the two systems.

  1. Research Toward Laser Spectroscopy of Trapped Atomic Hydrogen

    NASA Astrophysics Data System (ADS)

    Sandberg, Jon Carl

    An apparatus has been designed and constructed to perform laser spectroscopy on magnetically trapped atomic hydrogen. Earlier experiments demonstrated the feasibility of magnetic trapping and evaporative cooling of atomic hydrogen. The current apparatus has been designed to explore two areas of research: high resolution laser spectroscopy of hydrogen, and the possible production and detection of Bose condensation. The 1S{-}2S two-photon transition was chosen for study because of its extremely narrow natural linewidth. The techniques developed here should ultimately permit laser spectroscopy with a resolution approaching 1 part in 10^{15 } and should be well suited to the detection of Bose condensation. The apparatus consists of two subsystems: a cryogenic apparatus for magnetically trapping hydrogen, and a laser source for producing the ultraviolet light necessary to excite the 1S{-}2S transition. The two subsystems have independently demonstrated exceptional performance. The magnetic trap has produced gas densities approaching 10^{14} cm ^{-3} at temperatures as low as 100 muK, the closest approach to Bose condensation achieved to date with atomic hydrogen. The continuous wave laser source has produced 20 mW of 243 nm light with an estimated spectral linewidth of 2 kHz. The optimum experimental conditions for excitation and detection of the 1S{-}2S transition in trapped hydrogen have been identified. Initial trials with the apparatus revealed an unexpected operational problem, however several strategies have been proposed that should allow observation of the transition. The expected features of the 1S{-}2S transition lineshape with magnetically trapped hydrogen have been calculated. The possibilities for future research with laser spectroscopy of magnetically trapped hydrogen are described, and a promising strategy for the detection of Bose condensation is proposed. (Copies available exclusively from MIT Libraries, Rm. 14-0551 Cambridge, MA 02139-4307. Ph. 617

  2. Triggered energy releases in solid hydrogen hosts containing unpaired atoms

    SciTech Connect

    Collins, G.W.; Fearon, E.M.; Maienschein, J.L.; Mapoles, E.R.; Tsugawa, R.T.; Souers, P.C. ); Gaines, J.R. )

    1990-07-23

    We have observed both triggered and spontaneous energy releases in tritiated solid hydrogens at temperatures above 1.2 K in several different experiments. These energy releases, which can be triggered by a temperature increase, were observed by monitoring the temperature excursion ( heat spike'') versus time, the atom spin density, and nuclear-magnetic-resonance signal heights. The heat spikes correlate with a disappearance of free-atom spin density so that fast atomic recombination is the probable cause. The spontaneous heat spikes may be suppressed by improved heat extraction.

  3. Modelling spectral properties of non-equilibrium atomic hydrogen plasma

    NASA Astrophysics Data System (ADS)

    D'Ammando, G.; Pietanza, L. D.; Colonna, G.; Longo, S.; Capitelli, M.

    2010-02-01

    A model to predict the emissivity and absorption coefficient of atomic hydrogen plasma is presented in detail. Non-equilibrium plasma is studied through coupling of the model with a collisional-radiative code for the excited states population as well as with the Boltzmann equation for the electron energy distribution function.

  4. The Confined Hydrogen Atom with a Moving Nucleus

    ERIC Educational Resources Information Center

    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…

  5. Variational Perturbation Treatment of the Confined Hydrogen Atom

    ERIC Educational Resources Information Center

    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…

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

    ERIC Educational Resources Information Center

    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…

  7. Probability of Locating the Electron in a Hydrogen Atom

    NASA Astrophysics Data System (ADS)

    Mak, Thomas C. W.; Li, Wai-Kee

    2000-04-01

    A variety of numerical problems, along with their solutions, regarding the probability of locating the electron in a hydrogen atom are given. These problems range from simple substitution exercises to graduate-level take-home questions. Comments on the physical meaning of some of the results are also provided. These problems may be easily modified by teachers to suit their purposes.

  8. Microwave plasma generation of hydrogen atoms for rocket propulsion

    NASA Technical Reports Server (NTRS)

    Chapman, R.; Filpus, J.; Morin, T.; Snellenberger, R.; Asmussen, J.; Hawley, M.; Kerber, R.

    1981-01-01

    A flow microwave plasma reaction system is used to study the conversion of hydrogen to hydrogen atoms as a function of pressure, power density, cavity tuning, cavity mode, and time in the plasma zone. Hydrogen atom concentration is measured down-stream from the plasma by NOCl titration. Extensive modeling of the plasma and recombination zones is performed with the plasma zone treated as a backmix reaction system and the recombination zone treated as a plug flow. The thermodynamics and kinetics of the recombination process are examined in detail to provide an understanding of the conversion of recombination energy to gas kinetic energy. It is found that cavity tuning, discharge stability, and optimum power coupling are critically dependent on the system pressure, but nearly independent of the flow rate.

  9. Production of Excited Atomic Hydrogen from Methane

    NASA Astrophysics Data System (ADS)

    Machacek, J. R.; Andrianarijaona, V. M.; Furst, J. E.; Gay, T. J.; Kilcoyne, A. L. D.; Landers, A. L.; McLaughlin, K. W.

    2009-05-01

    We have measured the production of Lyα and Hα fluorescence from atomic H for the photodissociation of CH4 by linearly-polarized photons with energies between 20 and 65 eV. Comparison between our Lyα relative cross section and that previously reported [1] show different peak height ratios. This also occurs in the Hα cross section when compared to previous data [2]. We do not observe as significant a drop in either cross section above 35 eV. Our measurements were taken with pressures two orders of magnitude lower than those used in ref. [1]. We present comparisons between data sets and a discussion of possible systematic effects. [1] H. Fukuzawa et al., J. Phys. B. 38, 565 (2005). [2] M. Kato et al., J. Phys. B. 35, 4383 (2002). Support provided by the NSF (Grant PHY-0653379), DOE (LBNL/ALS) and ANSTO (Access to Major Research Facilities Programme).

  10. Depopulation of Single-Phthalocyanine Molecular Orbitals upon Pyrrolic-Hydrogen Abstraction on Graphene.

    PubMed

    Néel, Nicolas; Lattelais, Marie; Bocquet, Marie-Laure; Kröger, Jörg

    2016-02-23

    Single-molecule chemistry with a scanning tunneling microscope has preponderantly been performed on metal surfaces. The molecule-metal hybridization, however, is often detrimental to genuine molecular properties and obscures their changes upon chemical reactions. We used graphene on Ir(111) to reduce the coupling between Ir(111) and adsorbed phthalocyanine molecules. By local electron injection from the tip of a scanning tunneling microscope the two pyrrolic H atoms were removed from single phthalocyanines. The detachment of the H atom pair induced a strong modification of the molecular electronic structure, albeit with no change in the adsorption geometry. Spectra and maps of the differential conductance combined with density functional calculations unveiled the entire depopulation of the highest occupied molecular orbital upon H abstraction. Occupied π states of intact molecules are proposed to be emptied via intramolecular electron transfer to dangling σ states of H-free N atoms. PMID:26812093

  11. Atomic hydrogen maser active oscillator cavity and bulb design optimization

    NASA Technical Reports Server (NTRS)

    Peters, H. E.; Washburn, P. J.

    1984-01-01

    The performance characteristics and reliability of the active oscillator atomic hydrogen maser depend upon oscillation parameters which characterize the interaction region of the maser, the resonant cavity and atom storage bulb assembly. With particular attention to use of the cavity frequency switching servo (1) to reduce cavity pulling, it is important to maintain high oscillation level, high atomic beam flux utilization efficiency, small spin exchange parameter and high cavity quality factor. It is also desirable to have a small and rigid cavity and bulb structure and to minimize the cavity temperature sensitivity. Curves for a novel hydrogen maser cavity configuration which is partially loaded with a quartz dielectric cylinder and show the relationships between cavity length, cavity diameter, bulb size, dielectric thickness, cavity quality factor, filling factor and cavity frequency temperature coefficient are presented. The results are discussed in terms of improvement in maser performance resulting from particular design choices.

  12. Atomic cobalt on nitrogen-doped graphene for hydrogen generation

    NASA Astrophysics Data System (ADS)

    Fei, Huilong; Dong, Juncai; Arellano-Jiménez, M. Josefina; Ye, Gonglan; Dong Kim, Nam; Samuel, Errol L. G.; Peng, Zhiwei; Zhu, Zhuan; Qin, Fan; Bao, Jiming; Yacaman, Miguel Jose; Ajayan, Pulickel M.; Chen, Dongliang; Tour, James M.

    2015-10-01

    Reduction of water to hydrogen through electrocatalysis holds great promise for clean energy, but its large-scale application relies on the development of inexpensive and efficient catalysts to replace precious platinum catalysts. Here we report an electrocatalyst for hydrogen generation based on very small amounts of cobalt dispersed as individual atoms on nitrogen-doped graphene. This catalyst is robust and highly active in aqueous media with very low overpotentials (30 mV). A variety of analytical techniques and electrochemical measurements suggest that the catalytically active sites are associated with the metal centres coordinated to nitrogen. This unusual atomic constitution of supported metals is suggestive of a new approach to preparing extremely efficient single-atom catalysts.

  13. Induced absorption and annihilation in hadronic hydrogen atoms

    NASA Astrophysics Data System (ADS)

    Pomerantsev, Vladimir N.; Popov, Vladimir P.

    The induced absorption or annihilation in the collisions of the hydrogen hadronic atoms in the excited states with ordinary hydrogen have been described in a unified manner with the elastic scattering, Stark transitions, and Coulomb de-excitation in the framework of a close-coupling approach including both the open and closed channels corresponding to both the stationary and non-stationary states of hadronic atom. The general features of the induced absorption cross sections have been studied in a wide range of the complex energy-shift values. The total and differential cross sections of all processes have been calculated for π - p, K - p, and bar p p atoms with the principal quantum numbers n = 2 - 8 and kinetic energy from 0.001 eV up to 100 eV.

  14. Induced absorption and annihilation in hadronic hydrogen atoms

    NASA Astrophysics Data System (ADS)

    Pomerantsev, Vladimir N.; Popov, Vladimir P.

    2012-05-01

    The induced absorption or annihilation in the collisions of the hydrogen hadronic atoms in the excited states with ordinary hydrogen have been described in a unified manner with the elastic scattering, Stark transitions, and Coulomb de-excitation in the framework of a close-coupling approach including both the open and closed channels corresponding to both the stationary and non-stationary states of hadronic atom. The general features of the induced absorption cross sections have been studied in a wide range of the complex energy-shift values. The total and differential cross sections of all processes have been calculated for π - p, K - p, and bar p p atoms with the principal quantum numbers n = 2 - 8 and kinetic energy from 0.001 eV up to 100 eV.

  15. Atomic cobalt on nitrogen-doped graphene for hydrogen generation

    PubMed Central

    Fei, Huilong; Dong, Juncai; Arellano-Jiménez, M. Josefina; Ye, Gonglan; Dong Kim, Nam; Samuel, Errol L.G.; Peng, Zhiwei; Zhu, Zhuan; Qin, Fan; Bao, Jiming; Yacaman, Miguel Jose; Ajayan, Pulickel M.; Chen, Dongliang; Tour, James M.

    2015-01-01

    Reduction of water to hydrogen through electrocatalysis holds great promise for clean energy, but its large-scale application relies on the development of inexpensive and efficient catalysts to replace precious platinum catalysts. Here we report an electrocatalyst for hydrogen generation based on very small amounts of cobalt dispersed as individual atoms on nitrogen-doped graphene. This catalyst is robust and highly active in aqueous media with very low overpotentials (30 mV). A variety of analytical techniques and electrochemical measurements suggest that the catalytically active sites are associated with the metal centres coordinated to nitrogen. This unusual atomic constitution of supported metals is suggestive of a new approach to preparing extremely efficient single-atom catalysts. PMID:26487368

  16. Atomic cobalt on nitrogen-doped graphene for hydrogen generation.

    PubMed

    Fei, Huilong; Dong, Juncai; Arellano-Jiménez, M Josefina; Ye, Gonglan; Dong Kim, Nam; Samuel, Errol L G; Peng, Zhiwei; Zhu, Zhuan; Qin, Fan; Bao, Jiming; Yacaman, Miguel Jose; Ajayan, Pulickel M; Chen, Dongliang; Tour, James M

    2015-01-01

    Reduction of water to hydrogen through electrocatalysis holds great promise for clean energy, but its large-scale application relies on the development of inexpensive and efficient catalysts to replace precious platinum catalysts. Here we report an electrocatalyst for hydrogen generation based on very small amounts of cobalt dispersed as individual atoms on nitrogen-doped graphene. This catalyst is robust and highly active in aqueous media with very low overpotentials (30 mV). A variety of analytical techniques and electrochemical measurements suggest that the catalytically active sites are associated with the metal centres coordinated to nitrogen. This unusual atomic constitution of supported metals is suggestive of a new approach to preparing extremely efficient single-atom catalysts. PMID:26487368

  17. Reactivity and Catalytic Activity of Hydrogen Atom Chemisorbed Silver Clusters.

    PubMed

    Manzoor, Dar; Pal, Sourav

    2015-06-18

    Metal clusters of silver have attracted recent interest of researchers as a result of their potential in different catalytic applications and low cost. However, due to the completely filled d orbital and very high first ionization potential of the silver atom, the silver-based catalysts interact very weakly with the reacting molecules. In the current work, density functional theory calculations were carried out to investigate the effect of hydrogen atom chemisorption on the reactivity and catalytic properties of inert silver clusters. Our results affirm that the hydrogen atom chemisorption leads to enhancement in the binding energy of the adsorbed O2 molecule on the inert silver clusters. The increase in the binding energy is also characterized by the decrease in the Ag-O and increase in the O-O bond lengths in the case of the AgnH silver clusters. Pertinent to the increase in the O-O bond length, a significant red shift in the O-O stretching frequency is also noted in the case of the AgnH silver clusters. Moreover, the hydrogen atom chemisorbed silver clusters show low reaction barriers and high heat of formation of the final products for the environmentally important CO oxidation reaction as compared to the parent catalytically inactive clusters. The obtained results were compared with those of the corresponding gold and hydrogen atom chemisorbed gold clusters obtained at the same level of theory. It is expected the current computational study will provide key insights for future advances in the design of efficient nanosilver-based catalysts through the adsorption of a small atom or a ligand. PMID:25988294

  18. Kinetics of hydrogen abstraction reactions of butene isomers by OH radical

    SciTech Connect

    Sun, Hongyan; Law, Chung K.

    2010-11-26

    The rate coefficients of H-abstraction reactions of butene isomers by the OH radical were determined by both canonical variational transition-state theory and transition-state theory, with potential energy surfaces calculated at the CCSD(T)/6-311++G(d,p)//BH&HLYP/6-311G(d,p) level and CCSD(T)/6-311++G(d,p)//BH&HLYP/cc-pVTZ level and quantum mechanical tunneling effect corrected by either the small-curvature tunneling method or the Eckart method. While 1-butene contains allylic, vinylic, and alkyl hydrogens that can be abstracted to form different butene radicals, results reveal that s-allylic H-abstraction channels have low and broad energy barriers, and they are the most dominant channels which can occur via direct and indirect H-abstraction channels. For the indirect H-abstraction s-allylic channel, the reaction can proceed via forming two van der Waals prereactive complexes with energies that are 2.7-2.8 kcal mol-1 lower than that of the entrance channel at 0 K. Assuming that neither mixing nor crossover occurs between different reaction pathways, the overall rate coefficient was calculated by summing the rate coefficients of the s-allyic, methyl, and vinyl H-abstraction paths and found to agree well with the experimentally measured OH disappearance rate. Furthermore, the rate coefficients of p-allylic H abstraction of cis-2-butene, trans-2-butene, and isobutene by the OH radical were also determined at 300-1500 K, with results analyzed and compared with available experimental data.

  19. Atomic-scale studies of hydrogenated semiconductor surfaces

    NASA Astrophysics Data System (ADS)

    Mayne, A. J.; Riedel, D.; Comtet, G.; Dujardin, G.

    The adsorption of hydrogen on semiconductors strongly modifies the electronic and chemical properties of the surfaces, whether on the surface or in the sub-surface region. This has been the starting point, in recent years, of many new areas of research and technology. This paper will discuss the properties, at the atomic scale, of hydrogenated semiconductor surfaces studied with scanning tunnelling microscopy (STM) and synchrotron radiation. Four semiconductor surfaces will be described - germanium(1 1 1), silicon(1 0 0), silicon carbide(1 0 0) and diamond(1 0 0). Each surface has its particularities in terms of the physical and electronic structure and in regard to the adsorption of hydrogen. The manipulation of hydrogen on these surfaces by electronic excitation using electrons from the STM tip will be discussed in detail highlighting the excitation mechanisms. The reactivity of these surfaces towards various molecules and semiconductor nanocrystals will be illustrated.

  20. Electron-impact ionization of atomic hydrogen

    SciTech Connect

    Baertschy, Mark D.

    2000-02-14

    Since the invention of quantum mechanics, even the simplest example of collisional breakup in a system of charged particles, e{sup {minus}} + H {r_arrow} H{sup +} + e{sup {minus}} + e{sup {minus}}, has stood as one of the last unsolved fundamental problems in atomic physics. A complete solution requires calculating the energies and directions for a final state in which three charged particles are moving apart. Advances in the formal description of three-body breakup have yet to lead to a viable computational method. Traditional approaches, based on two-body formalisms, have been unable to produce differential cross sections for the three-body final state. Now, by using a mathematical transformation of the Schrodinger equation that makes the final state tractable, a complete solution has finally been achieved, Under this transformation, the scattering wave function can be calculated without imposing explicit scattering boundary conditions. This approach has produced the first triple differential cross sections that agree on an absolute scale with experiment as well as the first ab initio calculations of the single differential cross section.

  1. 2,5-dichlorothiophenol on Cu(111): Initial adsorption site and scanning tunnel microscope-based abstraction of hydrogen at high intramolecular selectivity

    NASA Astrophysics Data System (ADS)

    Rao, Bommisetty V.; Kwon, Ki-Young; Liu, Anwei; Bartels, Ludwig

    2003-11-01

    We investigated the adsorption of 2,5-di-chloro-thio-phenol (DCTP) on Cu(111) at 15 K and the formation of the thiolate upon electronic and thermal excitation. Initially, the sulfur atom of DCTP adsorbs at an on-top site and the molecule is able to rotate through six almost identical surface orientations. Attachment or removal of electrons from anywhere within the molecule at several hundred mV bias leads to the abstraction of the hydrogen atom from the thiol group in a nonthermal one-electron process with perfect selectivity. The resultant thiolate is locked into position on the surface.

  2. Hydrogen abstraction reactions of the [FeO]2+ moiety: The role of the electronic state

    NASA Astrophysics Data System (ADS)

    Malykhin, Sergei

    2015-02-01

    Hydrogen abstraction reactions of the ferryl [FeO]2+ moiety are investigated theoretically using a simple molecular model (OH)2FeO by DFT methods. Obtained thermochemical and structural data are compared with high-level electron-correlated methods: CCSD(T), BD and MCQDPT2. Two bonding patterns are observed: triple oxo-iron bond Fe+≡O+ and single Fesbnd Orad bond with radical oxygen. Predicted thermochemistry and reactivity with H2 and CH4 molecules for the later one fits well with available experimental data on the N2O + FeZSM5 catalytic system.

  3. How is a metabolic intermediate formed in the mechanism-based inactivation of cytochrome P450 by using 1,1-dimethylhydrazine: hydrogen abstraction or nitrogen oxidation?

    PubMed

    Hirao, Hajime; Chuanprasit, Pratanphorn; Cheong, Ying Yi; Wang, Xiaoqing

    2013-06-01

    A precise understanding of the mechanism-based inactivation of cytochrome P450 enzymes (P450s) at the quantum mechanical level should allow more reliable predictions of drug-drug interactions than those currently available. Hydrazines are among the molecules that act as mechanism-based inactivators to terminate the function of P450s, which are essential heme enzymes responsible for drug metabolism in the human body. Despite its importance, the mechanism explaining how a metabolic intermediate (MI) is formed from hydrazine is not fully understood. We used density functional theory (DFT) calculations to compare four possible mechanisms underlying the reaction between 1,1-dimethylhydrazine (or unsymmetrical dimethylhydrazine, UDMH) and the reactive compound I (Cpd I) intermediate of P450. Our DFT calculations provided a clear view on how an aminonitrene-type MI is formed from UDMH. In the most favorable pathway, hydrogen is spontaneously abstracted from the N2 atom of UDMH by Cpd I, followed by a second hydrogen abstraction from the N2 atom by Cpd II. Nitrogen oxidation of nitrogen atoms and hydrogen abstraction from the C-H bond of the methyl group were found to be less favorable than the hydrogen abstraction from the N-H bond. We also found that the reaction of protonated UDMH with Cpd I is rather sluggish. The aminonitrene-type MI binds to the ferric heme more strongly than a water molecule. This is consistent with the notion that the catalytic cycle of P450 is impeded when such an MI is produced through the P450-catalyzed reaction. PMID:23592585

  4. Rotational excitation of hydrogen molecules by collisions with hydrogen atoms. [interstellar gas energetics

    NASA Technical Reports Server (NTRS)

    Green, S.; Truhlar, D. G.

    1979-01-01

    Rate constants for rotational excitation of hydrogen molecules by collisions with hydrogen atoms have been obtained from quantum-mechanical calculations for kinetic temperatures between 100 and 5000 K. These calculations involve the rigid-rotator approximation, but other possible sources of error should be small. The calculations indicate that the early values of Nishimura are larger than accurate rigid-rotator values by about a factor of 20 or more.

  5. Sudden perturbation of hydrogen atoms by intense ultrashort laser pulses

    SciTech Connect

    Lugovskoy, A. V.; Bray, I.

    2005-12-15

    We study theoretically how hydrogen atoms respond to intense ultrashort laser pulses of duration {tau} shorter than the inverse of the initial-state energy {epsilon}{sub i}{sup -1}. An analytical expression for the evolution operator S is derived up to the first order of the sudden perturbation approximation. This approximation treats the laser-atom interaction beyond the dipole approximation and yields S as a series in the small parameter {epsilon}{sub i}{tau}. It is shown that the effect of realistic laser pulses on atoms begins at the first order of {epsilon}{sub i}{tau}. Transitions between atomic (nlm) states of different m become possible due to the action of the pulse's magnetic field. Transitions between states of same m and arbitrary l become possible if the static Coulomb potential is taken into account during the pulse.

  6. Ab initio study for the hydrogen abstraction reactions on toluene and tetralin.

    SciTech Connect

    Beste, Ariana; Harrison, Robert J; Britt, Phillip F; Buchanan III, A C

    2006-01-01

    Hydrogen abstraction reactions play a key role in many thermal and catalytic processes involved in the production of fuels and chemicals. In this paper, the hydrogen abstraction reactions on toluene and tetralin by the benzyl radical are investigated by ab initio methods. These reactions are representatives of similar reactions occurring in the thermolysis of lignin model compounds containing the phenethyl phenyl ether (PPE) structural moiety. The title reactions serve to calibrate the theoretical methods to be used in the study of PPE pyrolysis through comparison of the reaction barriers with reliable experimental values. We used two different hybrid density functionals (BHandHLYP, B3LYP) and second-order perturbation theory to obtain equilibrium and transition state geometries. We recomputed selected energy barriers at the B3LYP geometries with the coupled cluster singles and doubles (CCSD) method. Multiple transition states were found for both reactions. BHandHLYP underestimates and second-order perturbation theory overestimates the reaction barriers; B3LYP energy barriers agree well with experiment and the corresponding CCSD energy barriers. The flat potential energy surface around the saddle points causes numerical inaccuracies. We observe the break down of the harmonic approximation in the calculation of low frequencies.

  7. Unparticle contribution to the hydrogen atom ground state energy

    NASA Astrophysics Data System (ADS)

    Wondrak, Michael F.; Nicolini, Piero; Bleicher, Marcus

    2016-08-01

    In the present work we study the effect of unparticle modified static potentials on the energy levels of the hydrogen atom. By using Rayleigh-Schrödinger perturbation theory, we obtain the energy shift of the ground state and compare it with experimental data. Bounds on the unparticle energy scale ΛU as a function of the scaling dimension dU and the coupling constant λ are derived. We show that there exists a parameter region where bounds on ΛU are stringent, signaling that unparticles could be tested in atomic physics experiments.

  8. Laser stripping of hydrogen atoms by direct ionization

    DOE PAGESBeta

    Brunetti, E.; Becker, W.; Bryant, H. C.; Jaroszynski, D. A.; Chou, W.

    2015-05-08

    Direct ionization of hydrogen atoms by laser irradiation is investigated as a potential new scheme to generate proton beams without stripping foils. The time-dependent Schrödinger equation describing the atom-radiation interaction is numerically solved obtaining accurate ionization cross-sections for a broad range of laser wavelengths, durations and energies. Parameters are identified where the Doppler frequency up-shift of radiation colliding with relativistic particles can lead to efficient ionization over large volumes and broad bandwidths using currently available lasers.

  9. Solid Hydrogen Experiments for Atomic Propellants: Image Analyses

    NASA Technical Reports Server (NTRS)

    Palaszewski, Bryan

    2002-01-01

    This paper presents the results of detailed analyses of the images from experiments that were conducted on the formation of solid hydrogen particles in liquid helium. Solid particles of hydrogen were frozen in liquid helium, and observed with a video camera. The solid hydrogen particle sizes, their agglomerates, and the total mass of hydrogen particles were estimated. Particle sizes of 1.9 to 8 mm (0.075 to 0.315 in.) were measured. The particle agglomerate sizes and areas were measured, and the total mass of solid hydrogen was computed. A total mass of from 0.22 to 7.9 grams of hydrogen was frozen. Compaction and expansion of the agglomerate implied that the particles remain independent particles, and can be separated and controlled. These experiment image analyses are one of the first steps toward visually characterizing these particles, and allow designers to understand what issues must be addressed in atomic propellant feed system designs for future aerospace vehicles.

  10. Hydrogenated fullerenes dimer, peanut and capsule: An atomic comparison

    NASA Astrophysics Data System (ADS)

    EL-Barbary, A. A.

    2016-04-01

    Hydrogenated fullerenes are detected in the Universe in space but their identification is still unsolved task. Therefore, this paper provides useful information about hydrogenated fullerenes (dimer, peanut and capsule) using DFT method at the B3LYP/6-31G(d) level of theory. The stability, geometric structures, hydrogen adsorption energies and NMR chemical shifts are calculated. The results show that the energy of most stable isomer of C118 dimer is lower than the energies sum of C60 and C58 cages by 1.77 eV and the energy per carbon atom of C144 capsule is more stable than C60 cage by 126.98 meV. Also, endohedral Ti-doped C118 dimer and C128 peanut are found to be most stable structures than exohedral Ti-doped C118 dimer and C128 peanut by 2.19 eV/Ti and 3.52 eV/Ti, respectively. The hydrogenation process is found to be enhanced (especially at the caps) for endohedral Ti-doped C118 dimer and C128 peanut through electronic surface modifications. The most active hydrogenation sites are selected and it is found that the most stable hydrogenation sites are Houts1 and Houts3 for fullerenes and endohedral Ti-doped fullerenes, respectively.

  11. The Absolute Rates of the Solution Phase Addition of Atomic Hydrogen to a Vinyl Ether and a Vinyl Ester. The Effect of Oxygen Substitution on Hydrogen Atom Reactivity with Olefins

    SciTech Connect

    Tanner, D. D.; Kandanarachchi, P.; Das, N. C.; Franz, James A.

    2003-04-08

    The reactions of vinyl butyl ether and vinyl butyrate with atomic hydrogen and deuterium lead to addition of atomic hydrogen to the terminal position of the olefins. This observation is consistent with the reactions carried out earlier with other olefins. Both the absolute rates of addition to vinylbutyl ether and vinyl butyrate in acetone and hexane were carried out at several temperatures. The relative rates are consistent with only modest stabilization of the transition state of the radical adduct by the ??-o substituent compared with hydrogen atom addition to 1-octene. The relative rates measured in acetone and hexane indicate no significant differential solvation of ground state relative to the transition structures of the hydrogen atom addition. The kinetics reveal that the early transition states of hydrogen atom addition exhibit little selectivity (vinyl ether versus simple olefin) in either abstraction of hydrogen ??- to the oxygen or by terminal addition to the olefinic ether, reflecting the modest influence of the increased enthalpy of reaction associated with resonance stabilization by the oxygen substituent at the developing radical site.

  12. Semirelativistic model for ionization of atomic hydrogen by electron impact

    SciTech Connect

    Attaourti, Y.; Taj, S.; Manaut, B.

    2005-06-15

    We present a semirelativistic model for the description of the ionization process of atomic hydrogen by electron impact in the first Born approximation by using the Darwin wave function to describe the bound state of atomic hydrogen and the Sommerfeld-Maue wave function to describe the ejected electron. This model, accurate to first order in Z/c in the relativistic correction, shows that, even at low kinetic energies of the incident electron, spin effects are small but not negligible. These effects become noticeable with increasing incident electron energies. All analytical calculations are exact and our semirelativistic results are compared with the results obtained in the nonrelativistic Coulomb Born approximation both for the coplanar asymmetric and the binary coplanar geometries.

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

    NASA Astrophysics Data System (ADS)

    Gaucher, Lionel Francis

    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.

  14. Infrared atomic hydrogen line formation in luminous stars

    NASA Technical Reports Server (NTRS)

    Krolik, J. H.; Smith, H. A.

    1981-01-01

    Infrared atomic hydrogen lines observed in luminous stars, generally attributed to compact circumstellar H II regions, can also be formed in the winds likely to emanate from these stars. Implications are discussed for the class of obscured infrared point sources showing these lines, and an illustrative model is derived for the BN object in Orion. Such stellar winds should also produce weak, but detectable, radio emission.

  15. Amide-Substituted Titanocenes in Hydrogen-Atom Transfer Catalysis.

    PubMed

    Zhang, Yong-Qiang; Jakoby, Verena; Stainer, Katharina; Schmer, Alexander; Klare, Sven; Bauer, Mirko; Grimme, Stefan; Cuerva, Juan Manuel; Gansäuer, Andreas

    2016-01-22

    Two new catalytic systems for hydrogen-atom transfer (HAT) catalysis involving the N-H bonds of titanocene(III) complexes with pendant amide ligands are reported. In a monometallic system, a bifunctional catalyst for radical generation and reduction through HAT catalysis depending on the coordination of the amide ligand is employed. The pendant amide ligand is used to activate Crabtree's catalyst to yield an efficient bimetallic system for radical generation and HAT catalysis. PMID:26636435

  16. Two-photon transitions to excited states in atomic hydrogen

    SciTech Connect

    Quattropani, A.; Bassani, F.; Carillo, S.

    1982-06-01

    Resonant two-photon transition rates from the ground state of atomic hydrogen to ns excited states have been computed as a function of photon frequencies in the length and velocity gauges in order to test the accuracy of the calculation and to discuss the rate of convergence over the intermediate states. The dramatic structure of the transition rates produced by intermediate-state resonances is exhibited. A two-photon transparency is found in correspondence to each resonance.

  17. Thermochemical and kinetics studies of the CH3SH+S (3P) hydrogen abstraction and insertion reactions.

    PubMed

    Cardoso, Daniely V V; Cunha, Leonardo A; Spada, Rene F K; Ferrão, Luiz F A; Roberto-Neto, Orlando; Machado, Francisco B C

    2014-09-01

    Sulfur-containing molecules have a significant impact on atmosphere and biosphere. In this work we studied, from the point of view of electronic structure and chemical kinetics methods, the elementary reactions between a methanethiol molecule and a sulfur atom leading to hydrogen abstraction C-S bond cleavage (CH(3)SH+S; R1:→ CH(3)S+SH; R2: → CH(2)SH+SH; R3:→ CH(3)+HS(2)). The geometrical structures of the reactants, products, and saddle points for the three reaction paths were optimized using the BB1K method with the aug-cc-pV(T+d)Z basis set. The thermochemical properties were improved using single point coupled-cluster (CCSD(T)) calculations on the BB1K geometries followed by extrapolation to the complete basis set (CBS) limit. This methodology was previously applied and has given accurate values of thermochemical and kinetics properties when compared to benchmark calculations and experimental data. For each reaction, the thermal rate constants were calculated using the improved canonical variational theory (ICVT) including the zero-curvature (ICVT/ZCT) and small-curvature (ICVT/SCT) tunneling corrections. For comparison, the overall ICVT/SCT reaction rate constant at 300 K obtained with single-point CCSD(T)/CBS calculations for the CH(3)SH+S reaction is approximately 1400 times lower than the isovalent CH(3)SH+O reaction, obtained with CVT/SCT. The reaction path involving the hydrogen abstraction from the thiol group is the most important reactive path in all temperatures. PMID:25204585

  18. Effects of wall coatings and temperature on hydrogen atom surface recombination

    NASA Technical Reports Server (NTRS)

    Wong, E. L.; Baker, C. E.

    1973-01-01

    The efficiency of various surface coatings and materials toward inhibiting hydrogen atom surface recombination was investigated over a temperature range of 77 to 298 K. A flow discharge, mass spectrometer technique was used to make the experimental measurements. Hydrogen atoms were monitored directly, and these measurements were expressed as ratios of mass spectrometer peak heights for atomic and molecular hydrogen. Several of the surface coatings studied were efficient at reducing hydrogen atom surface recombination at room temperature. However, as the temperature was lowered, this efficiency was drastically reduced. Calibration of the mass spectrometer for atomic and molecular hydrogen indicated that mass spectrometer discrimination against hydrogen atoms was severe. Mass spectrometer sensitivity for hydrogen atoms was only about one-sixth of that for molecular hydrogen.

  19. Ground-State Structures of Atomic Metallic Hydrogen

    NASA Astrophysics Data System (ADS)

    McMahon, Jeffrey M.; Ceperley, David M.

    2011-04-01

    Ab initio random structure searching using density functional theory is used to determine the ground-state structures of atomic metallic hydrogen from 500 GPa to 5 TPa. Including proton zero-point motion within the harmonic approximation, we estimate that molecular hydrogen dissociates into a monatomic body-centered tetragonal structure near 500 GPa (rs=1.23) that remains stable to 1 TPa (rs=1.11). At higher pressures, hydrogen stabilizes in an …ABCABC… planar structure that is similar to the ground state of lithium, but with a different stacking sequence. With increasing pressure, this structure compresses to the face-centered cubic lattice near 3.5 TPa (rs=0.92).

  20. The hydrogen atom in plasmas with an external electric field

    SciTech Connect

    Bahar, M. K.; Soylu, A.

    2014-09-15

    We numerically solve the Schrödinger equation, using a more general exponential cosine screened Coulomb (MGECSC) potential with an electric field, in order to investigate the screening and weak external electric field effects on the hydrogen atom in plasmas. The MGECSC potential is examined for four different cases, corresponding to different screening parameters of the potential and the external electric field. The influences of the different screening parameters and the weak external electric field on the energy eigenvalues are determined by solving the corresponding equations using the asymptotic iteration method (AIM). It is found that the corresponding energy values shift when a weak external electric field is applied to the hydrogen atom in a plasma. This study shows that a more general exponential cosine screened Coulomb potential allows the influence of an applied, weak, external electric field on the hydrogen atom to be investigated in detail, for both Debye and quantum plasmas simultaneously. This suggests that such a potential would be useful in modeling similar effects in other applications of plasma physics, and that AIM is an appropriate method for solving the Schrödinger equation, the solution of which becomes more complex due to the use of the MGECSC potential with an applied external electric field.

  1. The atomic hydrogen cloud in the saturnian system

    NASA Astrophysics Data System (ADS)

    Tseng, W.-L.; Johnson, R. E.; Ip, W.-H.

    2013-09-01

    The importance of Titan's H torus shaped by solar radiation pressure and of hydrogen atoms flowing out of Saturn's atmosphere in forming the broad hydrogen cloud in Saturn's magnetosphere is still debated. Since the Saturnian system also contains a water product torus which originates from the Enceladus plumes, the icy ring particles, and the inner icy satellites, as well as Titan's H2 torus, we have carried out a global investigation of the atomic hydrogen cloud taking into account all sources. We show that the velocity and angle distributions of the hot H ejected from Saturn's atmosphere following electron-impact dissociation of H2 are modified by collisions with the ambient atmospheric H2 and H. This in turn affects the morphology of the escaping hydrogen from Saturn, as does the morphology of the ionospheric electron distribution. Although an exact agreement with the Cassini observations is not obtained, our simulations show that H directly escaping from Titan is the dominant contributor in the outer magnetosphere. Of the total number of H observed by Cassini from 1 to 5RS, ∼5.7×1034, our simulations suggest ∼20% is from dissociation in the Enceladus torus, ∼5-10% is from dissociation of H2 in the atmosphere of the main rings, and ∼50% is from Titan's H torus, implying that ∼20% comes from Saturn atmosphere.

  2. Zero-Temperature Structures of Atomic Metallic Hydrogen

    NASA Astrophysics Data System (ADS)

    McMahon, Jeffrey; Ceperley, David

    2011-03-01

    Since the first prediction of an atomic metallic phase of hydrogen by Wigner and Huntington over 75 years ago, there have been many theoretical efforts aimed at determining the crystal structures of the zero-temperature phases. We present results from ab initio random structure searching with density functional theory performed to determine the ground state structures from 500 GPa to 5 TPa. We estimate that molecular hydrogen dissociates into a monatomic body-centered tetragonal structure near 500 GPa (rs = 1.225), which then remains stable to 2.5 TPa (rs = 0.969). At higher pressures, hydrogen stabilizes in an . . . ABCABC . . . planar structure that is remarkably similar to the ground state of lithium, which compresses to the face-centered cubic lattice beyond 5 TPa (rs < 0.86). Our results provide a complete ab initio description of the atomic metallic crystal structures of hydrogen, resolving one of the most fundamental and long outstanding issues concerning the structures of the elements.

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

    NASA Technical Reports Server (NTRS)

    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.

  4. Detecting extra dimensions by Hydrogen-like atoms

    NASA Astrophysics Data System (ADS)

    Wan-Ping, Zhou; Peng, Zhou; Hao-Xue, Qiao

    2015-01-01

    We reconsider the idea in spectroscopy of detecting extra dimensions by regarding the nucleus as a homogeneous sphere. In our results, it turns out that the gravitational potential inside the nucleus is much stronger than the potential induced by a particle in the same regime in ref. [16], and thus a more significant correction of the ground state energy of hydrogen-like atoms is obtained, which can be used to determine the existence of ADD's extra dimensions. In order to get a larger order of magnitude for the correction, it is better to apply our theory to high-Z atoms or muonic atoms, where the volume of the nucleus can't be ignored and the relativistic effect is important. Our work is based on the Dirac equation in aweak gravity field, and the result is more precise.

  5. Concerted hydrogen atom exchange between three HF molecules

    NASA Technical Reports Server (NTRS)

    Komornicki, Andrew; Dixon, David A.; Taylor, Peter R.

    1992-01-01

    We have investigated the termolecular reaction involving concerted hydrogen exchange between three HF molecules, with particular emphasis on the effects of correlation at the various stationary points along the reaction. Using an extended basis, we have located the geometries of the stable hydrogen-bonded trimer, which is of C(sub 3h) symmetry, and the transition state for hydrogen exchange, which is of D(sub 3h) symmetry. The energies of the exchange reation were then evaluated at the correlated level, using a large atomic natural orbital basis and correlating all valence electrons. Several correlation treatments were used, namely, configration interaction with single and double excitations, coupled-pair functional, and coupled-cluster methods. We are thus able to measure the effect of accounting for size-extensivity. Zero-point corrections to the correlated level energetics were determined using analytic second derivative techniques at the SCF level. Our best calculations, which include the effects of connected triple excitations in the coupled-cluster procedure, indicate that the trimer is bound by 9 +/- 1 kcal/mol relative to three separate monomers, in excellent agreement with previous estimates. The barrier to concerted hydrogen exchange is 15 kcal/mol above the trimer, or only 4.7 kcal/mol above three separated monomers. Thus the barrier to hydrogen exchange between HF molecules via this termolecular process is very low.

  6. Hydrogen Atom Reactivity toward Aqueous tert-Butyl Alcohol

    SciTech Connect

    Lymar S. V.; Schwarz, H.A.

    2012-02-09

    Through a combination of pulse radiolysis, purification, and analysis techniques, the rate constant for the H + (CH{sub 3}){sub 3}COH {yields} H{sub 2} + {sm_bullet}CH{sub 2}C(CH{sub 3}){sub 2}OH reaction in aqueous solution is definitively determined to be (1.0 {+-} 0.15) x 10{sup 5} M{sup -1} s{sup -1}, which is about half of the tabulated number and 10 times lower than the more recently suggested revision. Our value fits on the Polanyi-type, rate-enthalpy linear correlation ln(k/n) = (0.80 {+-} 0.05){Delta}H + (3.2 {+-} 0.8) that is found for the analogous reactions of other aqueous aliphatic alcohols with n equivalent abstractable H atoms. The existence of such a correlation and its large slope are interpreted as an indication of the mechanistic similarity of the H atom abstraction from {alpha}- and {beta}-carbon atoms in alcohols occurring through the late, product-like transition state. tert-Butyl alcohol is commonly contaminated by much more reactive secondary and primary alcohols (2-propanol, 2-butanol, ethanol, and methanol), whose content can be sufficient for nearly quantitative scavenging of the H atoms, skewing the H atom reactivity pattern, and explaining the disparity of the literature data on the H + (CH{sub 3}){sub 3}COH rate constant. The ubiquitous use of tert-butyl alcohol in pulse radiolysis for investigating H atom reactivity and the results of this work suggest that many other previously reported rate constants for the H atom, particularly the smaller ones, may be in jeopardy.

  7. Hydrogen atom density in narrow-gap microwave hydrogen plasma determined by calorimetry

    NASA Astrophysics Data System (ADS)

    Yamada, Takahiro; Ohmi, Hiromasa; Kakiuchi, Hiroaki; Yasutake, Kiyoshi

    2016-02-01

    The density of hydrogen (H) atoms in the narrow-gap microwave hydrogen plasma generated under high-pressure conditions is expected to be very high because of the high input power density of the order of 104 W/cm3. For measuring the H atom density in such a high-pressure and high-density plasma, power-balance calorimetry is suited since a sufficient signal to noise ratio is expected. In this study, H atom density in the narrow-gap microwave hydrogen plasma has been determined by the power-balance calorimetry. The effective input power to the plasma is balanced with the sum of the powers related to the out-going energy per unit time from the plasma region via heat conduction, outflow of high-energy particles, and radiation. These powers can be estimated by simple temperature measurements using thermocouples and optical emission spectroscopy. From the power-balance data, the dissociation fraction of H2 molecules is determined, and the obtained maximum H atom density is (1.3 ± 0.2) × 1018 cm-3. It is found that the H atom density increases monotonically with increasing the energy invested per one H2 molecule within a constant plasma volume.

  8. Ultrafast effective multilevel atom method for primordial hydrogen recombination

    SciTech Connect

    Ali-Haiemoud, Yacine; Hirata, Christopher M.

    2010-09-15

    Cosmological hydrogen recombination has recently been the subject of renewed attention because of its importance for predicting the power spectrum of cosmic microwave background anisotropies. It has become clear that it is necessary to account for a large number n > or approx. 100 of energy shells of the hydrogen atom, separately following the angular momentum substates in order to obtain sufficiently accurate recombination histories. However, the multilevel atom codes that follow the populations of all these levels are computationally expensive, limiting recent analyses to only a few points in parameter space. In this paper, we present a new method for solving the multilevel atom recombination problem, which splits the problem into a computationally expensive atomic physics component that is independent of the cosmology and an ultrafast cosmological evolution component. The atomic physics component follows the network of bound-bound and bound-free transitions among excited states and computes the resulting effective transition rates for the small set of 'interface' states radiatively connected to the ground state. The cosmological evolution component only follows the populations of the interface states. By pretabulating the effective rates, we can reduce the recurring cost of multilevel atom calculations by more than 5 orders of magnitude. The resulting code is fast enough for inclusion in Markov chain Monte Carlo parameter estimation algorithms. It does not yet include the radiative transfer or high-n two-photon processes considered in some recent papers. Further work on analytic treatments for these effects will be required in order to produce a recombination code usable for Planck data analysis.

  9. Ultrafast effective multilevel atom method for primordial hydrogen recombination

    NASA Astrophysics Data System (ADS)

    Ali-Haïmoud, Yacine; Hirata, Christopher M.

    2010-09-01

    Cosmological hydrogen recombination has recently been the subject of renewed attention because of its importance for predicting the power spectrum of cosmic microwave background anisotropies. It has become clear that it is necessary to account for a large number n≳100 of energy shells of the hydrogen atom, separately following the angular momentum substates in order to obtain sufficiently accurate recombination histories. However, the multilevel atom codes that follow the populations of all these levels are computationally expensive, limiting recent analyses to only a few points in parameter space. In this paper, we present a new method for solving the multilevel atom recombination problem, which splits the problem into a computationally expensive atomic physics component that is independent of the cosmology and an ultrafast cosmological evolution component. The atomic physics component follows the network of bound-bound and bound-free transitions among excited states and computes the resulting effective transition rates for the small set of “interface” states radiatively connected to the ground state. The cosmological evolution component only follows the populations of the interface states. By pretabulating the effective rates, we can reduce the recurring cost of multilevel atom calculations by more than 5 orders of magnitude. The resulting code is fast enough for inclusion in Markov chain Monte Carlo parameter estimation algorithms. It does not yet include the radiative transfer or high-n two-photon processes considered in some recent papers. Further work on analytic treatments for these effects will be required in order to produce a recombination code usable for Planck data analysis.

  10. The Simplicity of Perfect Atoms: Degeneracies in Supersymmetric Hydrogen

    SciTech Connect

    Rube, Tomas; Wacker, Jay G.; /SLAC /Stanford U., ITP

    2011-08-19

    Supersymmetric QED hydrogen-like bound states are remarkably similar to non-supersymmetric hydrogen, including an accidental degeneracy of the fine structure and which is broken by the Lamb shift. This article classifies the states, calculates the leading order spectrum, and illustrates the results in several limits. The relation to other non-relativistic bound states is explored. Supersymmetric bound states provide a laboratory for studying dynamics in supersymmetric theories. Bound states like hydrogen provide a framework for understanding the qualitative dynamics of QCD mesons, a supersymmetric version of QED can provide a qualitative picture for the symmetries and states of superQCD mesons. Furthermore, recent interest in dark matter as a composite state, leads to asking how supersymmetry acts upon these composite states [4-7]. This article calculates the leading order corrections to a hydrogen-like atoms in an exactly supersymmetric version of QED. Much of the degeneracy is broken by the fine structure and a seminal calculation was performed in [1] for positronium, see [2] for an N = 2 version of positronium. Supersymmetric hydrogen is a similar except for the absence of annihilation diagrams, see [3] for an independent calculation. In the heavy proton mass limit, the supersymmetric interactions of the theory become irrelevant operators, suppressed by powers of the proton mass like the magnetic moment operator in QED and the fine structure is identical to the non-supersymmetric theory. This article finds that fine structure spectrum of supersymmetric spectrum of hydrogen has an accidental degeneracy which is exactly analogous to the accidental degeneracy of the l = 0 and l = 1 levels of the n = 2; j = 1/2 state of hydrogen. The supersymmetric version of the Lamb shift lifts the residual degeneracy and this article computes the logarithmically enhanced breaking.

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

    NASA Astrophysics Data System (ADS)

    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.

  12. US-Japan workshop on atomic collisions in solids: Abstracts of lectures

    SciTech Connect

    Not Available

    1990-03-01

    This report contains abstracts on the following topics: techniques of scanning probe microscopy; new types of radiation; a search for wake-riding electrons using slow antiproton beams; antiproton wake: theory; bending of swift ion beams by graphite foils; angular momentum distribution of autoionizing rydberg states: produced by 64 MeV S ions in collisions with C foils; multiphonon energy exchange in atom-surface collisions; plans for positron experiments; resonant coherent excitation: experiment; line shapes in resonant coherent excitation: theory; MUSE experiments and Monte Carlo simulation; inelastic interactions of electrons and positrons with solids; density fluctuation detection; cluster-impact fusion; a model for cluster-impact fusion; thoughts on cold fusion; and plasmon decay.

  13. Some properties of Stark states of hydrogenic atoms and ions

    NASA Astrophysics Data System (ADS)

    Hey, J. D.

    2007-10-01

    The motivation for this work is the problem of providing accurate values of the atomic transition matrix elements for the Stark components of Rydberg Rydberg transitions in atomic hydrogen and hydrogenic ions, for use in spectral line broadening calculations applicable to cool, low-density plasmas, such as those found in H II regions. Since conventional methods of calculating these transition matrix elements cannot be used for the high principal quantum numbers now easily attained in radio astronomical spectra, we attempt to show that the recurrence relation (ladder operator) method recently employed by Watson (2006 J. Phys. B: At. Mol. Opt. Phys. 39 1889 97) and Hey (2006 J. Phys. B: At. Mol. Opt. Phys. 39 2641 64) can be taken over into the parabolic coordinate system used to describe the Stark states of the atomic (ionic) radiators. The present method is therefore suggested as potentially useful for extending the work of Griem (1967 Astrophys. J. 148 547 58, 2005 Astrophys. J. 620 L133 4), Watson (2006), Stambulchik et al (2007 Phys. Rev. E 75 016401(9 pp) on Stark broadening in transitions between states of high principal quantum number, to physical conditions where the binary, impact approximation is no longer strictly applicable to both electron and ion perturbers. Another possible field of application is the study of Stark mixing transitions in 'ultracold' Rydberg atoms perturbed by long-range interactions with slow atoms and ions. Preparatory to the derivation of recurrence relations for states of different principal quantum number, a number of properties and recurrence relations are also found for states of identical principal quantum number, including the analogue in parabolic coordinates to the relations of Pasternack (1937 Proc. Natl Acad. Sci. USA 23 91 4, 250) in spherical polar coordinates.

  14. Relativistic effects on information measures for hydrogen-like atoms

    NASA Astrophysics Data System (ADS)

    Katriel, Jacob; Sen, K. D.

    2010-01-01

    Position and momentum information measures are evaluated for the ground state of the relativistic hydrogen-like atoms. Consequences of the fact that the radial momentum operator is not self-adjoint are explicitly studied, exhibiting fundamental shortcomings of the conventional uncertainty measures in terms of the radial position and momentum variances. The Shannon and Rényi entropies, the Fisher information measure, as well as several related information measures, are considered as viable alternatives. Detailed results on the onset of relativistic effects for low nuclear charges, and on the extreme relativistic limit, are presented. The relativistic position density decays exponentially at large r, but is singular at the origin. Correspondingly, the momentum density decays as an inverse power of p. Both features yield divergent Rényi entropies away from a finite vicinity of the Shannon entropy. While the position space information measures can be evaluated analytically for both the nonrelativistic and the relativistic hydrogen atom, this is not the case for the relativistic momentum space. Some of the results allow interesting insight into the significance of recently evaluated Dirac-Fock vs. Hartree-Fock complexity measures for many-electron neutral atoms.

  15. Thermal hydrogen-atom transfer from methane: A mechanistic exercise

    NASA Astrophysics Data System (ADS)

    Schwarz, Helmut

    2015-06-01

    Hydrogen-atom transfer (HAT) constitutes a key process in a broad range of chemical transformations as it covers heterogeneous, homogeneous, and enzymatic reactions. While open-shell metal oxo species [MO]rad are no longer regarded as being involved in the heterogeneously catalyzed oxidative coupling of methane (2CH4 + → C2H6 + H2O), these reagents are rather versatile in bringing about (gas-phase) hydrogen-atom transfer, even from methane at ambient conditions. In this mini-review, various mechanistic scenarios will be presented, and it will be demonstrated how these are affected by the composition of the metal-oxide cluster ions. Examples will be discussed, how 'doping' the clusters permits the control of the charge and spin situation at the active site and, thus, the course of the reaction. Also, the interplay between supposedly inert support material and the active site - the so-called 'aristocratic atoms' - of the gas-phase catalyst will be addressed. Finally, gas-phase HAT from methane will be analyzed in the broader context of thermal activation of inert Csbnd H bonds by metal-oxo species.

  16. Site Change of Hydrogen in Niobium on Alloying with Oversized Ta Atoms

    NASA Astrophysics Data System (ADS)

    Yagi, Eiichi; Yoshii, Motoyasu; Okada, Yoshinori; Matsuba, Hiroshi; Miyahara, Kazuya; Koike, Shigetoshi; Sugawara, Takamasa; Shishido, Toetsu; Ogiwara, Kiyoshi

    2009-06-01

    In order to clarify a difference in hydrogen interaction with oversized solute atoms and with undersized solute atoms in bcc metals in the low solute concentration region, the site occupancy of hydrogen in Nb alloyed with 5 at. % of oversized Ta atoms has been studied at room temperature for hydrogen concentrations of 0.018 and 0.025 at the hydrogen-to-metal-atom ratio (CH=[H]/[M]) by the channelling method utilizing a nuclear reaction 1H(11B,α)αα with a 11B beam of an energy of 2.03 MeV. Clearly different from the result on hydrogen in Nb alloyed with undersized Mo atoms, in both specimens H atoms are distributed over tetrahedral (T) sites and the displaced-T sites (d-T sites) which are displaced from T sites by about 0.25 Å towards their nearest neighbour octahedral (O) sites. The T site is more favourable for hydrogen occupancy, but the number of available T sites is limited, and excess H atoms occupy the d-T sites. Therefore, in contrast to a strong attractive interaction between hydrogen and undersized Mo atoms (trapping), there exists no such a strong attractive interaction between hydrogen and oversized Ta atoms. It is considered that the trapping of hydrogen by undersized solute atoms is effective to the large enhancement of the terminal solubility of hydrogen (TSH) on alloying with undersized solute atoms, at least, in the low solute concentration region.

  17. Electrochemical desorption of hydrogen atoms adsorbed on liquid gallium

    SciTech Connect

    Krivenko, A.G.; Vekin, A.B.; Benderskii, V.A.

    1987-12-01

    Laser-pulse electron photoemission was used to measure absolute values of the rate constants, W/sub 3/, of electrochemical desorption (ECD) of hydrogen atoms from liquid gallium. The W/sub 3/ were shown to be a linear function of hydrogen concentration, in accord with the fact that both hydrogen ions and water molecules are involved in desorption. The components of W/sub 3/ arising from the two reaction channels are exponential functions of electrode potential, and in their order of magnitude (approx. 10/sup 8/ liter/mole x sec and approx. 10/sup 6/ sec/sup -1/) are close to the corresponding constants for mercury and bismuth. In the desorption involving hydrogen ions, the H/D isotope effect decreases from 5 to 3 as the overpotential is raised from 0.75 to 1.15 V. It was suggested that isotope effects which are higher than those found for Hg and Bi electrodes arise from longer proton tunneling distance.

  18. Some design constraints required for the assembly of software components: The incorporation of atomic abstract types into generically structured abstract types

    NASA Technical Reports Server (NTRS)

    Johnson, Charles S.

    1986-01-01

    It is nearly axiomatic, that to take the greatest advantage of the useful features available in a development system, and to avoid the negative interactions of those features, requires the exercise of a design methodology which constrains their use. A major design support feature of the Ada language is abstraction: for data, functions processes, resources, and system elements in general. Atomic abstract types can be created in packages defining those private types and all of the overloaded operators, functions, and hidden data required for their use in an application. Generically structured abstract types can be created in generic packages defining those structured private types, as buildups from the user-defined data types which are input as parameters. A study is made of the design constraints required for software incorporating either atomic or generically structured abstract types, if the integration of software components based on them is to be subsequently performed. The impact of these techniques on the reusability of software and the creation of project-specific software support environments is also discussed.

  19. Electron-impact-ionization cross section for the hydrogen atom

    NASA Astrophysics Data System (ADS)

    Hu, W.; Fang, D.; Wang, Y.; Yang, F.

    1994-02-01

    A distorted-wave Born exchange approximation was used to calculate the cross section for electron-impact ionization of the hydrogen atoms. Both the integral and energy-differential cross section were calculated. The results were compared with the latest experimental data and other theoretical calculations. Comparison shows that the calculations agree with differential cross-section measurements in general. For integral cross sections the calculation shows a better agreement with an earlier measurement [M.B. Shah, D. S. Elliott, and H. B. Gilbody, J. Phys. B 20, 3501 (1987)] in which the cross sections are normalized to the first Born approximation.

  20. Reflection of hydrogen atoms from the surface of superfluid helium

    SciTech Connect

    Tiesinga, E.; Stoof, H.T.C.; Verhaar, B.J. )

    1990-05-01

    We propose a new method for studying the reflection of a hydrogen atom from a superfluid-helium film. Starting from the narrow width of the reflected angular distribution recently found experimentally, we tentatively extrapolate to the extreme limit of low ripplon wave numbers in which the adiabatic or degenerate-internal-states approximation becomes valid. We obtain simple closed expressions for single- and multiple-ripplon processes, which do not require the integration of a Schroedinger equation for their evaluation and do not depend on the specific form of the potential.

  1. Novel Atomic Rearrangement in the Pb Monolayer on Si(111) surfaces Induced by Atomic Hydrogen Adsorption.

    NASA Astrophysics Data System (ADS)

    Fang, Chung-Kai; Hwang, Ing-Shouh; Chang, Shih-Hsin; Chen, Lih-Juann; Tsong, Tien-Tzou

    2006-03-01

    Using a scanning tunneling microscopy, we have observed interesting hydrogen-adsorption induced atomic rearrangements on Pb/Si(111) system at room temperature. A hexagonal ring-like pattern with decaying intensity is formed around the hydrogen-induced point defect. Moreover, interference-like patterns can be seen in the region among the H-induced point defects. The detailed pattern depends on the relative position of defects. With certain relative positions, a new superstructure of hexagonal cells can be seen. The phase boundaries are found to either enhance or suppress the formation of the hexagonal ring-like pattern. We believe that the intricate interplay between atomic displacement and electronic structure causes the formation of the patterns. [Ref] : I. S. Hwang, S. H. Chang, C. K. Fang, L. J. Chen, and T. T. Tsong, Phys. Rev. Lett. 94, 045505 (2005)

  2. Atomic hydrogen cleaning of GaAS Photocathodes

    SciTech Connect

    M. Poelker; J. Price; C. Sinclair

    1997-01-01

    It is well known that surface contaminants on semiconductors can be removed when samples are exposed to atomic hydrogen. Atomic H reacts with oxides and carbides on the surface, forming compounds that are liberated and subsequently pumped away. Experiments at Jefferson lab with bulk GaAs in a low-voltage ultra-high vacuum H cleaning chamber have resulted in the production of photocathodes with high photoelectron yield (i.e., quantum efficiency) and long lifetime. A small, portable H cleaning apparatus also has been constructed to successfully clean GaAs samples that are later removed from the vacuum apparatus, transported through air and installed in a high-voltage laser-driven spin-polarized electron source. These results indicate that this method is a versatile and robust alternative to conventional wet chemical etching procedures usually employed to clean bulk GaAs.

  3. Diffusion of atoms and molecules in the solid hydrogens

    SciTech Connect

    Gaines, J.R.; Fedders, P.A.; Collins, G.W.; Sater, J.D.; Souers, P.C.

    1995-09-01

    The ``motional averaging`` of the NMR spectra has been used to determine the diffusion coefficient of molecules in HD, D-T, and T{sub 2} solids. The molecular hop frequency and diffusion coefficient are calculated from the measured spin-spin relaxation time and the rigid lattice second moment. Samples prepared by depositing streams of H{sub 2} or D{sub 2} gas, containing atoms produced by microwave discharge, onto cold substrates, held at 2 K or below are designated ``amorphous`` while those prepared by slow cooling from the liquid state are designated ``crystalline.`` We find that the diffusion in crystalline solids ({ital c}-H{sub 2}, etc.) is controlled by the number of vacancies in the lattice and have obtained values of the vacancy formation energy, {ital E}{sub {ital V}}, the barrier height energy, {ital E}{sub {ital b}}, and the energy of the first tunneling level in the hydrogen potential, {ital E}{sub {ital t}}, for all the isotopes. The vacancy hopping rate, at the triple point, is approximately the same for all the isotopes. Data for the various isotopes can be compared by scaling the temperature by the quantum parameter. Measurements (by others) on both radiation damaged crystalline ({ital c}-H{sub 2}) and undamaged amorphous ({ital a}-H{sub 2}) solids at the atom recombination coefficients are used to extract the atom hop frequency. In {ital c}-H{sub 2}, we find that the atom and molecule hopping rates are almost identical. Other data on crystalline solids, taken by NMR techniques on ortho to para conversion in solid T{sub 2}, yield model dependent atom hop rates. The atom and molecule hopping rates still agree even though the recombination coefficients no longer follow a simple thermally activated form. The recombination coefficients (and hence hopping rates) for crystalline solids differ from those of amorphous solids.

  4. Absolute Rates of the Solution-Phase Addition of Atomic Hydrogen to a Vinyl Ether and a Vinyl Ester: Effect of Oxygen Substitution on Hydrogen Atom Reactivity with Olefins

    SciTech Connect

    Tanner, D D.; Kandanarachchi, P; Das, N. C.; Franz, James A.

    2003-04-08

    The reactions of vinyl butyl ether and vinyl butyrate with atomic hydrogen and deuterium lead to addition at the terminal position of the olefins. This observation is consistent with the reactions carried out earlier with other olefins. Both of the absolute rates of addition to vinylbutyl ether and vinyl butyrate, in acetone and hexane, were measured at several temperatures. The relative rates are consistent with only modest stabilization of the transition state of the radical adduct by the R-O substituent compared with that of hydrogen atom addition to 1-octene. The relative rates measured in acetone and hexane indicate no significant differential solvation of the ground state relative to the transition structures of the hydrogen atom addition. The kinetics reveal that the early transition states for hydrogen atom addition exhibit little selectivity (vinyl ether versus simple olefin) in either the abstraction of hydrogen R to the oxygen or by terminal addition to the olefinic ether and reflects the modest influence of the increased enthalpy of reaction associated with resonance stabilization by the oxygen substituent at the developing radical site.

  5. Excitation of atomic hydrogen by protons and helium ions

    SciTech Connect

    Theodosiou, C.E.

    1980-12-01

    The Vainshtein-Presnyakov-Sobel'man approximation (VPSA) is extended for heavy projectiles and applied to calculating cross sections for direct excitation of atomic hydrogen by proton and He/sup +/ impact. The contribution of the projectile-target core interaction to the transition matrix element is included here for the first time. In addition an effective charge zeta is introduced to minimize the effect of neglecting certain terms in the Schroedinger equation of the collision system; this term-neglecting process is inherent to the VPSA. It is found that the projectile-target core interaction contribution is, as expected for heavy projectiles, small for calculating total cross sections but becomes significant for differential cross sections and increasing scattering angles. Inclusion of the effective charge raises the cross sections at lower-impact energies. The developed formulation is applied to excitation of atomic hydrogen to the n=2, 3, 4, and 5 levels and comparison is made with the available experimental values for total and differential cross sections. The agreement is very good when the relative velocity is larger than approx.0.6upsilon/sub 0/(upsilon/sub 0/=..cap alpha..c=2.188 x 10/sup -8/ cm s/sup -1/). The present results are also compared with the ones obtained by typical alternative theoretical approaches of varying sophistication.

  6. Excitation of atomic hydrogen by protons and helium ions

    NASA Astrophysics Data System (ADS)

    Theodosiou, Constantine E.

    1980-12-01

    The Vainshtein-Presnyakov-Sobel'man approximation (VPSA) is extended for heavy projectiles and applied to calculating cross sections for direct excitation of atomic hydrogen by proton and He+ impact. The contribution of the projectile-target core interaction to the transition matrix element is included here for the first time. In addition an effective charge ζ is introduced to minimize the effect of neglecting certain terms in the Schrödinger equation of the collision system; this term-neglecting process is inherent to the VPSA. It is found that the projectile-target core interaction contribution is, as expected for heavy projectiles, small for calculating total cross sections but becomes significant for differential cross sections and increasing scattering angles. Inclusion of the effective charge raises the cross sections at lower-impact energies. The developed formulation is applied to excitation of atomic hydrogen to the n=2,3,4, and 5 levels and comparison is made with the available experimental values for total and differential cross sections. The agreement is very good when the relative velocity is larger than ~0.6v0(v0=αc=2.188×10-8 cm s-1). The present results are also compared with the ones obtained by typical alternative theoretical approaches of varying sophistication.

  7. Tabulation of the bound-state energies of atomic hydrogen

    NASA Astrophysics Data System (ADS)

    Horbatsch, M.; Hessels, E. A.

    2016-02-01

    We present tables for the bound-state energies for atomic hydrogen. The tabulated energies include the hyperfine structure and thus this work extends the work of Mohr et al. [P. J. Mohr et al., Rev. Mod. Phys. 84, 1527 (2012)], 10.1103/RevModPhys.84.1527, which excludes the hyperfine structure. The tabulation includes corrections of the hyperfine structure due to the anomalous moment of the electron, due to the finite mass of the proton, and due to off-diagonal matrix elements of the hyperfine Hamiltonian. These corrections are treated incorrectly in most other works. Simple formulas valid for all quantum numbers are presented for the hyperfine corrections. The tabulated energies have uncertainties of less than 1 kHz for all states. This accuracy is possible because of the recent precision measurement [R. Pohl et al., Nature (London) 466, 213 (2010)], 10.1038/nature09250 of the proton radius. The effect of this radius on the energy levels is also tabulated and the energies are compared to precision measurements of atomic hydrogen energy intervals.

  8. 1,2-shifts of hydrogen atoms in aryl radicals

    SciTech Connect

    Brooks, M.A.; Scott, L.T.

    1999-06-16

    An energy barrier on the order of 60 kcal/mol is predicted for the 1,2-shift of hydrogen atoms in aryl radicals. Such rearrangements are, therefore, not expected to occur under ordinary laboratory conditions, but they should be prevalent in the aryl radicals formed during combustion, flash vacuum pyrolysis, and other high-temperature gas-phase processes. As a demonstration of this rearrangement, the 2-benzo[c]phenanthryl radical (1) was generated by flash vacuum pyrolysis of the corresponding aryl bromide. A 1,2-shift of hydrogen out of the sterically congested cover region of 1, followed by cyclization and rearomatization of the resulting radical, is proposed to explain the observation of benzo[ghi]fluoranthene as the dominant monomeric product formed. Under the same conditions, [1,3,4,5-{sup 2}H{sub 4}]-2-bromobenzo[c]phenanthrene gives [1,2,3,4-{sup 2}H{sub 4}]-benzo[ghi]fluoranthene as the dominant monomeric product, in accord with the expectation of a deuterium atom 1,2-shift.

  9. Atomic hydrogen for low temperature atomic hydrogen masers and in-vacuum dissociators for VLG-11 series masers

    NASA Technical Reports Server (NTRS)

    Vessot, R. F. C.

    1984-01-01

    The operation of a cryogenically-cooled hydrogen maser using an RF plasma dissociator operating at liquid nitrogen temperature (77K) in confunction with a state selector magnet whose dimensions are suitable for slow atoms is studied. The focusing characteristics for a hexapole state selector magnet with maximum fields at the pole tips, provide a maximum acceptance angle for atoms at the most probable velocity in the beam. By thermally isolating the RF circuitry from the dissociator glassware, only dielectric losses in the glass and the energy coupled to the plasma will result in the boil-off of liquid nitrogen. It is estimated that this is about one watt and thus a loss rate of approximately .022 liters pr hour is anticipated.

  10. Pulsed EPR characterization of encapsulated atomic hydrogen in octasilsesquioxane cages.

    PubMed

    Mitrikas, George

    2012-03-21

    Hydrogen atoms encapsulated in molecular cages are potential candidates for quantum computing applications. They provide the simplest two-spin system where the 1s electron spin, S = 1/2, is hyperfine-coupled to the proton nuclear spin, I = 1/2, with a large isotropic hyperfine coupling (A = 1420.40575 MHz for a free atom). While hydrogen atoms can be trapped in many matrices at cryogenic temperatures, it has been found that they are exceptionally stable in octasilsesquioxane cages even at room temperature [Sasamori et al., Science, 1994, 256, 1691]. Here we present a detailed spin-lattice and spin-spin relaxation study of atomic hydrogen encapsulated in Si(8)O(12)(OSiMe(2)H)(8) using X-band pulsed EPR spectroscopy. The spin-lattice relaxation times T(1) range between 1.2 s at 20 K and 41.8 μs at room temperature. The temperature dependence of the relaxation rate shows that for T < 60 K the spin-lattice relaxation is best described by a Raman process with a Debye temperature of θ(D) = 135 K, whereas for T > 100 K a thermally activated process with activation energy E(a) = 753 K (523 cm(-1)) prevails. The phase memory time T(M) = 13.9 μs remains practically constant between 200 and 300 K and is determined by nuclear spin diffusion. At lower temperatures T(M) decreases by an order of magnitude and exhibits two minima at T = 140 K and T = 60 K. The temperature dependence of T(M) between 20 and 200 K is attributed to dynamic processes that average inequivalent hyperfine couplings, e.g. rotation of the methyl groups of the cage organic substituents. The hyperfine couplings of the encapsulated proton and the cage (29)Si nuclei are obtained through numerical simulations of field-swept FID-detected EPR spectra and HYSCORE experiments, respectively. The results are discussed in terms of existing phenomenological models based on the spherical harmonic oscillator and compared to those of endohedral fullerenes. PMID:22323086

  11. Quantitative aspects of ESR and spin trapping of hydroxyl radicals and hydrogen atoms in gamma-irradiated aqueous solutions

    SciTech Connect

    Carmichael, A.J.; Makino, K.; Riesz, P.

    1984-11-01

    The efficiency of 5,5-dimethylpyrroline-1-N-oxide (DMPO) and ..cap alpha..-(4-pyridyl-1-oxide)-N-tert-butylnitrone (POBN) to spin trap hydroxyl radicals and hydrogen atoms, respectively, was studied in ..gamma..-irradiated solutions where the radical yields are accurately known. The effects of dose, spin trap concentration, and pH and of the stability of the spin adducts on the spin-trapping efficiency were investigated. In degassed or N/sub 2/-saturated solutions the spin-trapping efficiencies were 35% for DMPO and hydroxyl radicals and 14% for POBN and hydrogen atoms. The low spin-trapping efficiency of DMPO may be explained by the reaction of hydroxyl radicals to abstract hydrogen from the DMPO molecule to produce carbon radicals as well as addition to the N=C double bond to form nitroxide radicals. For POBN the low spin-trapping efficiency for hydrogen atoms is explained in terms of addition reactions of hydrogen atoms to the aromatic ring and the pyridinium and nitrone oxygens.

  12. Hydrogen Attachment/Abstraction Dissociation (HAD) of Gas-Phase Peptide Ions for Tandem Mass Spectrometry.

    PubMed

    Takahashi, Hidenori; Sekiya, Sadanori; Nishikaze, Takashi; Kodera, Kei; Iwamoto, Shinichi; Wada, Motoi; Tanaka, Koichi

    2016-04-01

    Dissociation of gas-phase peptide ions through interaction with low-energy hydrogen (H) radical (∼0.15 eV) was observed with a quadrupole ion trap mass spectrometry. The H radical generated by thermal dissociation of H2 molecules passing through a heated tungsten capillary (∼2000 °C) was injected into the ion trap containing target peptide ions. The fragmentation spectrum showed abundant c-/z- and a-/x-type ions, attributable to H attachment/abstraction to/from peptide ion. Because the low-energy neutral H radical initiated the fragmentation, the charge state of the precursor ion was maintained during the dissociation. As a result, precursor ions of any charge state, including singly charged positive and negative ions, could be analyzed for amino acid sequence. The sequence coverage exceeding 90% was obtained for both singly protonated and singly deprotonated substance P peptide. This mass spectrometry also preserved labile post-translational modification bonds. The modification sites of triply phosphorylated peptide (kinase domain of insulin receptor) were identified with the sequence coverage exceeding 80%. PMID:27002918

  13. Design of Transversal Phase Space Meter for Atomic Hydrogen Beam Source

    NASA Astrophysics Data System (ADS)

    Belov, A. S.

    2016-02-01

    For optimization of polarized atomic beam sources apparatus it is important to have detailed information about characteristics of sources of hydrogen atoms, especially, taking into account present intensity limitations of polarized atomic beam sources. Usually, longitudinal velocity distribution of hydrogen atoms produced by RF dissociator is measured while transversal phase space of unpolarized atomic hydrogen beams was not measured up to now. In this work we report and discuss a design of transversal phase space meter for pulsed atomic hydrogen beam source. The meter design is based on “two slits” method which is well known from ion beam technique. Specific feature of the meter are movable sensitive detector of hydrogen atoms and molecules.

  14. The ground state properties of spin-aligned atomic hydrogen, deuterium, and tritium

    NASA Technical Reports Server (NTRS)

    Etters, R. D.; Dugan, J. V., Jr.; Palmer, R. W.

    1975-01-01

    The internal energy, pressure, and compressibility of ground-state, spin-aligned atomic hydrogen, deuterium, and tritium are calculated assuming that all pair interactions occur via the atomic triplet (spin-aligned) potential. The conditions required to obtain atomic hydrogen and its isotopes in bulk are discussed; such a development would be of value in propulsion systems because of the light mass and energetic recombination of atomic hydrogen. Results show that atomic triplet hydrogen and deuterium remain gaseous at 0 K, and that tritium forms a liquid with a binding energy of approximately -0.75 K per atom at a molar volume of 130 cu cm per mole. The pair distribution function for these systems is calculated, and the predicted superfluid behavior of atomic triplet hydrogen and tritium is briefly discussed.

  15. Positron impact excitations of hydrogen atom embedded in weakly coupled plasmas: Formation of Rydberg atoms

    SciTech Connect

    Rej, Pramit; Ghoshal, Arijit

    2014-09-15

    Formation of Rydberg atoms due to 1s→nlm excitations of hydrogen, for arbitrary n, l, m, by positron impact in weakly coupled plasma has been investigated using a distorted-wave theory in the momentum space. The interactions among the charged particles in the plasma have been represented by Debye-Huckel potentials. Making use of a simple variationally determined wave function for the hydrogen atom, it has been possible to obtain the distorted-wave scattering amplitude in a closed analytical form. A detailed study has been made on the effects of plasma screening on the differential and total cross sections in the energy range 20–300 eV of incident positron. For the unscreened case, our results agree nicely with some of the most accurate results available in the literature. To the best of our knowledge, such a study on the differential and total cross sections for 1s→nlm inelastic positron-hydrogen collisions for arbitrary n, l, m in weakly coupled plasmas is the first reported in the literature.

  16. Generation of atomic H in a hydrogen matrix by tritium decay

    NASA Technical Reports Server (NTRS)

    Zeleznik, F. J.

    1976-01-01

    Webeler's (1976) experimental results for the generation of atomic hydrogen in a hydrogen matrix by tritium decay are reexamined with a variant of Rosen's (1976) mathematical treatment. The analysis retains Rosen's equations for the number densities of trapped and mobile hydrogen atoms, but replaces his enthalpy equation with an equation for the directly measured temperature. Theoretical expressions are derived for the dependence of storage time, recombination time, and maximum density of trapped hydrogen atoms as a function of temperature for a given tritium concentration. A comparison of predictions for the maximum trapped atomic hydrogen number density as a function of storage time reveals that Rosen's estimate for the maximum number density of hydrogen atoms for the zero magnetic field case is a little more optimistic than the estimate obtained in the paper.

  17. Presolvated Electron Reaction with Methylacetoacetate: Electron Localization, Proton-Deuteron Exchange, and H-atom Abstraction

    PubMed Central

    Petrovici, Alex; Adhikary, Amitava; Kumar, Anil; Sevilla, Michael D.

    2015-01-01

    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 methylacetoacetate (MAA, CH3-CO-CH2-CO-OCH3) at 77 K and subsequent reactions of the anion radical (CH3-CO•−-CH2-CO-OCH3) in the temperature range (77 to ca. 170 K) 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-CO-OCH3. The ESR spectrum of CH3-C(•)OH-CH2-CO-OCH3 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-CO-OCH3 in D2O glass shows only the line components due to proton hyperfine couplings of CH3 group. This is expected since the methylen protons in MAA are readily exchangeable in D2O. On stepwise annealing to higher temperatures (ca. 150 to 170 K), CH3-C(•)OH-CH2-CO-OCH3 undergoes bimolecular H-atom abstraction from MAA to form the more stable radical, CH3-CO-CH•-CO-OCH3. Theoretical calculations using density functional theory (DFT) support the radical assignments. PMID:25255751

  18. Phase Space Structures Explain Hydrogen Atom Roaming in Formaldehyde Decomposition.

    PubMed

    Mauguière, Frédéric A L; Collins, Peter; Kramer, Zeb C; Carpenter, Barry K; Ezra, Gregory S; Farantos, Stavros C; Wiggins, Stephen

    2015-10-15

    We re-examine the prototypical roaming reaction--hydrogen atom roaming in formaldehyde decomposition--from a phase space perspective. Specifically, we address the question "why do trajectories roam, rather than dissociate through the radical channel?" We describe and compute the phase space structures that define and control all possible reactive events for this reaction, as well as provide a dynamically exact description of the roaming region in phase space. Using these phase space constructs, we show that in the roaming region, there is an unstable periodic orbit whose stable and unstable manifolds define a conduit that both encompasses all roaming trajectories exiting the formaldehyde well and shepherds them toward the H2···CO well. PMID:26499774

  19. Muon transfer from hydrogen and deuterium atoms to neon

    SciTech Connect

    Jacot-Guillarmod, R. )

    1995-03-01

    The muon exchange reactions from the ground state of muonic protium and deuterium atoms to neon are studied. Measurements have been performed in binary gas mixtures at room temperature. The transfer rate from thermalized muonic deuterium is found to exceed by about an order of magnitude the one from muonic protium. On the other hand, an energy dependence of the rate from [mu][ital d] is revealed, while none is observed from [mu][ital p]. The intensity patterns of the muonic Lyman series of neon resulting from the muon exchange differ from one hydrogen isotope to the other, the most obvious discrepancy being the presence of the muonic Ne(7-1) line after transfer from [mu][ital d], whereas this line is absent by transfer from [mu][ital p]. This indicates that the muon is transferred to the level [ital n][sub [ital p

  20. Cold Collision Frequency Shift in Two-Dimensional Atomic Hydrogen

    SciTech Connect

    Ahokas, J.; Jaervinen, J.; Vasiliev, S.

    2007-01-26

    We report a measurement of the cold collision frequency shift in atomic hydrogen gas adsorbed on the surface of superfluid {sup 4}He at T(less-or-similar sign)90 mK. Using two-photon electron and nuclear magnetic resonance in 4.6 T field we separate the resonance line shifts due to the dipolar and exchange interactions, both proportional to surface density {sigma}. We find the clock shift {delta}{nu}{sub c}=-1.0(1)x10{sup -7} Hz cm{sup -2}x{sigma}, which is about 100 times smaller than the value predicted by the mean field theory and known scattering lengths in the three-dimensional case.

  1. Inelastic cross sections for positron scattering from atomic hydrogen

    SciTech Connect

    Weber, M.; Hofmann, A.; Raith, W.; Sperber, W.; Jacobsen, F.; Lynn, K.G.

    1994-12-31

    Positronium formation (Ps) cross sections for positrons impinging on atomic hydrogen were measured in the impact energy range from 13eV to 255eV at the High Intensity Positron (HIP) beam at Brookhaven National Laboratory (BNL). The Ps-formation cross section was found to rise rapidly from the threshold at 6.8eV to a maximum value of (2.98 {plus_minus} 0.18) {times} 10{sup {minus}16} cm{sup 2} for {approx} 15eV positrons. By 75eV it drops below the detection limit of 0.17 {times} 10{sup {minus}16} cm{sup 2} which is the present level of statistical uncertainty. The experiment was modified to enable the measurement of doubly differential scattering cross sections.

  2. Entropy and complexity analysis of hydrogenic Rydberg atoms

    SciTech Connect

    Lopez-Rosa, S.; Toranzo, I. V.; Dehesa, J. S.; Sanchez-Moreno, P.

    2013-05-15

    The internal disorder of hydrogenic Rydberg atoms as contained in their position and momentum probability densities is examined by means of the following information-theoretic spreading quantities: the radial and logarithmic expectation values, the Shannon entropy, and the Fisher information. As well, the complexity measures of Cramer-Rao, Fisher-Shannon, and Lopez Ruiz-Mancini-Calvet types are investigated in both reciprocal spaces. The leading term of these quantities is rigorously calculated by use of the asymptotic properties of the concomitant entropic functionals of the Laguerre and Gegenbauer orthogonal polynomials which control the wavefunctions of the Rydberg states in both position and momentum spaces. The associated generalized Heisenberg-like, logarithmic and entropic uncertainty relations are also given. Finally, application to linear (l= 0), circular (l=n- 1), and quasicircular (l=n- 2) states is explicitly done.

  3. Effects of atomic hydrogen and deuterium exposure on high polarization GaAs photocathodes

    SciTech Connect

    M. Baylac; P. Adderley; J. Brittian; J. Clark; T. Day; J. Grames; J. Hansknecht; M. Poelker; M. Stutzman; A. T. Wu; A. S. Terekhov

    2005-12-01

    Strained-layer GaAs and strained-superlattice GaAs photocathodes are used at Jefferson Laboratory to create high average current beams of highly spin-polarized electrons. High electron yield, or quantum efficiency (QE), is obtained only when the photocathode surface is atomically clean. For years, exposure to atomic hydrogen or deuterium has been the photocathode cleaning technique employed at Jefferson Laboratory. This work demonstrates that atomic hydrogen cleaning is not necessary when precautions are taken to ensure that clean photocathode material from the vendor is not inadvertently dirtied while samples are prepared for installation inside photoemission guns. Moreover, this work demonstrates that QE and beam polarization can be significantly reduced when clean high-polarization photocathode material is exposed to atomic hydrogen from an rf dissociator-style atomic hydrogen source. Surface analysis provides some insight into the mechanisms that degrade QE and polarization due to atomic hydrogen cleaning.

  4. Understanding the Mechanism of the Hydrogen Abstraction from Arachidonic Acid Catalyzed by the Human Enzyme 15-Lipoxygenase-2. A Quantum Mechanics/Molecular Mechanics Free Energy Simulation.

    PubMed

    Suardíaz, Reynier; Jambrina, Pablo G; Masgrau, Laura; González-Lafont, Àngels; Rosta, Edina; Lluch, José M

    2016-04-12

    Lipoxygenases (LOXs) are a family of enzymes involved in the biosynthesis of several lipid mediators. In the case of human 15-LOX, the 15-LOX-1 and 15-LOX-2 isoforms show slightly different reaction regiospecificity and substrate specificity, indicating that substrate binding and recognition may be different, a fact that could be related to their different biological role. Here, we have used long molecular dynamics simulations, QM(DFT)/MM potential energy and free energy calculations (using the newly developed DHAM method), to investigate the binding mode of the arachidonic acid (AA) substrate into 15-LOX-2 and the rate-limiting hydrogen-abstraction reaction 15-LOX-2 catalyzes. Our results strongly indicate that hydrogen abstraction from C13 in 15-LOX-2 is only consistent with the "tail-first" orientation of AA, with its carboxylate group interacting with Arg429, and that only the pro-S H13 hydrogen will be abstracted (being the pro-R H13 and H10 too far from the acceptor oxygen atom). At the B3LYP/6-31G(d) level the potential and free energy barriers for the pro-S H13 abstraction of AA by 15-LOX-2 are 18.0 and 18.6 kcal/mol, respectively. To analyze the kinetics of the hydrogen abstraction process, we determined a Markov model corresponding to the unbiased simulations along the state-discretized reaction coordinate. The calculated rates based on the second largest eigenvalue of the Markov matrices agree well with experimental measurements, and also provide the means to directly determine the pre-exponential factor for the reaction by comparing with the free energy barrier height. Our calculated pre-exponential factor is close to the value of kBT/h. On the other hand, our results suggest that the spin inversion of the complete system (including the O2 molecule) that is required to happen at some point along the full process to lead to the final hydroperoxide product, is likely to take place during the hydrogen transfer, which is a proton coupled electron transfer

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

    NASA Astrophysics Data System (ADS)

    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.

  6. In situ measurement of atomic hydrogen in the upper mesosphere

    NASA Technical Reports Server (NTRS)

    Sharp, W. E.; Kita, D.

    1987-01-01

    In situ measurements of H abundance between 73 and 93 km are reported for conditions of winter solstice, magnetic quiet, and a solar depression angle of 12 deg. The data were obtained by a rocket-borne instrument using the resonance fluorescence technique. A discharge source emitting photons at 1216 A was an integral part of the instrument. The instrument was radially deployed 80 cm by a boom from the front of the payload in order to avoid the shock created by the gas flow over the front of the payload. An attitude control system oriented the payload so that the gas flow was nearly perpendicular to the plane containing the incident and scattered photons, thus minimizing any correction for Doppler shift. The resonance radiation detector viewed a black backstop in order to minimize background radiation from the hydrogen geocorona; however, the background was not entirely eliminated. The signal-to-noise ratio was improved by summing the data in 1.8-s bins. The observed hydrogen concentration maximized at 85 km at 1.5 + or - 1.1 x 10 to the 8th atoms/cu cm.

  7. Positron scattering from hydrogen atom embedded in dense quantum plasma

    SciTech Connect

    Bhattacharya, Arka; Kamali, M. Z. M.; Ghoshal, Arijit; Ratnavelu, K.

    2013-08-15

    Scattering of positrons from the ground state of hydrogen atoms embedded in dense quantum plasma has been investigated by applying a formulation of the three-body collision problem in the form of coupled multi-channel two-body Lippmann-Schwinger equations. The interactions among the charged particles in dense quantum plasma have been represented by exponential cosine-screened Coulomb potentials. Variationally determined hydrogenic wave function has been employed to calculate the partial-wave scattering amplitude. Plasma screening effects on various possible mode of fragmentation of the system e{sup +}+H(1s) during the collision, such as 1s→1s and 2s→2s elastic collisions, 1s→2s excitation, positronium formation, elastic proton-positronium collisions, have been reported in the energy range 13.6-350 eV. Furthermore, a comparison has been made on the plasma screening effect of a dense quantum plasma with that of a weakly coupled plasma for which the plasma screening effect has been represented by the Debye model. Our results for the unscreened case are in fair agreement with some of the most accurate results available in the literature.

  8. Thioether bond formation by SPASM domain radical SAM enzymes: Cα H-atom abstraction in subtilosin A biosynthesis.

    PubMed

    Benjdia, Alhosna; Guillot, Alain; Lefranc, Benjamin; Vaudry, Hubert; Leprince, Jérôme; Berteau, Olivier

    2016-05-01

    AlbA is a radical SAM enzyme catalyzing the formation of three unusual thioether bonds in the antibiotic subtilosin A. We demonstrate here that AlbA catalyzes direct Cα H-atom abstraction and likely contains three essential [4Fe-4S] centers. This leads us to propose novel mechanistic perspectives for thioether bond catalysis by radical SAM enzymes. PMID:27087315

  9. STM and XPS study of CeO2(111) reduction by atomic hydrogen

    NASA Astrophysics Data System (ADS)

    Shahed, Syed Mohammad Fakruddin; Hasegawa, Tomo; Sainoo, Yasuyuki; Watanabe, Yoshihide; Isomura, Noritake; Beniya, Atsushi; Hirata, Hirohito; Komeda, Tadahiro

    2014-10-01

    Reduction of CeO2(111)/Ru(0001) surface by atomic hydrogen was investigated using scanning tunneling microscopy (STM) and X-ray photoelectron spectroscopy (XPS). We observed the formation of oxygen vacancy trimers and hydroxyl trimers on the stoichiometric CeO2(111) surface when it was exposed to atomic hydrogen at room temperature. The reaction of an impinging hydrogen atom with a surface oxygen atom yields a hydroxyl species, which diffuse on the surface until stabilized by the formation of OH trimers. The hydrogen atoms were located at atop sites of the oxygen atoms in the topmost surface layer. A reaction between the hopping hydrogen atom and the hydroxyl species yields a water molecule, which is desorbed from the surface leaving an oxygen defect. The oxygen vacancies were also observed as a trimer of vacancies. XPS measurements showed an increase of a reduced Ce and hydroxyl species with an amount of exposed hydrogen atoms. The former was estimated by measuring the ratio of Ce3 +/Ce4 + in the Ce 3d components. Our study shows the formation of hydroxyl trimer species in atomic scale upon atomic hydrogen exposure to CeO2(111) surface which could offer new catalytic activity.

  10. Anharmonic effects in atomic hydrogen: Superconductivity and lattice dynamical stability

    NASA Astrophysics Data System (ADS)

    Borinaga, Miguel; Errea, Ion; Calandra, Matteo; Mauri, Francesco; Bergara, Aitor

    2016-05-01

    We present first-principles calculations of metallic atomic hydrogen in the 400-600 GPa pressure range in a tetragonal structure with space group I 41/a m d , which is predicted to be its first atomic phase. Our calculations show a band structure close to the free-electron-like limit due to the high electronic kinetic energy induced by pressure. Bands are properly described even in the independent electron approximation fully neglecting the electron-electron interaction. Linear-response harmonic calculations show a dynamically stable phonon spectrum with marked Kohn anomalies. Even if the electron-electron interaction has a minor role in the electronic bands, the inclusion of electronic exchange and correlation in the density response is essential to obtain a dynamically stable structure. Anharmonic effects, which are calculated within the stochastic self-consistent harmonic approximation, harden high-energy optical modes and soften transverse acoustic modes up to a 20% in energy. Despite a large impact of anharmonicity has been predicted in several high-pressure hydrides, here the superconducting critical temperature is barely affected by anharmonicity, as it is lowered from its harmonic 318 K value only to 300 K at 500 GPa. We attribute the small impact of anharmonicity on superconductivity to the absence of softened optical modes and the fairly uniform distribution of the electron-phonon coupling among the vibrational modes.

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

    SciTech Connect

    Bonfanti, Matteo; Jackson, Bret; Hughes, Keith H.; Burghardt, Irene

    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.

  12. Quantum Control of Atomic Hydrogen Using Laser Fields

    NASA Astrophysics Data System (ADS)

    Zhang, Xingjun; Red, Eddie; Wynn, Albert, III; Weatherford, Charles

    2007-06-01

    A method for the ab initio simulation of STIRAP (stimulated Raman adiabatic passage) [1,2] laser quantum control of the energy level poulations of atomic ions will be described. The method employs a new algorithm for the solution of the time- dependent Schr"odinger equation which avoids the time-propagator and uses spectral elements in time with a spectral spatial basis.[3] This results in a set of coupled simultaneous equations and is thus an implicit stable procedure. In order to treat the continuum problem (ionization), a complex absorbing potential is used. The spectral spatial basis used is the Coulomb Sturmians.[4] As an initial application, the control of the levels of atomic hydrogen will be presented. [1] S.A. Rice and M. Zhao, Optical Control of Molecular Dynamics, Wiley, New York, 2000. [2] M. Shapiro and P. Brumer, Principles of the Quantum Control of Molecular Processes, Wiley, New York, 2003. [3] C.A. Weatherford, E. Red, and A. Wynn III, J. Mol. Structure (Theochem) 592, 47 (2002). [4] J. Avery, Hyperspherical Harmonics and Generalized Sturmians, Kluwer, Dordrecht, 2000.

  13. Hénon-Heiles interaction for hydrogen atom in phase space

    NASA Astrophysics Data System (ADS)

    da Cruz Filho, J. S.; Amorim, R. G. G.; Ulhoa, S. C.; Khanna, F. C.; Santana, A. E.; Vianna, J. D. M.

    2016-03-01

    Using elements of symmetry, as gauge invariance, several aspects of a Schrödinger equation represented in phase space are introduced and analyzed under physical basis. The hydrogen atom is explored in the same context. Then we add a Hénon-Heiles potential to the hydrogen atom in order to explore chaotic features.

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

    ERIC Educational Resources Information Center

    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…

  15. Hydrogen abstraction in the neutral molecular cluster of benzophenone and hydrogen donors formed in a supersonic free jet expansion

    SciTech Connect

    Matsushita, Yoshihisa; Kajii, Yoshizumi; Obi, Kinichi

    1992-08-06

    This paper discusses how benzophenone undergoes photoreduction to form benzophenone ketyl radical by an intracellular reaction in the benzophenone 1,4-cyclohexadiene mixed expansion in a supersonic free jet expansion. No ketyl radical fluorescence is observed when triethylamine, 2-propanol, or ethanol is the hydrogen donor; thus the normal molecular cluster activity depends on the nature of the hydrogen donor. 36 refs., 5 figs.

  16. Positron impact excitations of hydrogen atom embedded in dense quantum plasmas: Formation of Rydberg atoms

    SciTech Connect

    Rej, Pramit; Ghoshal, Arijit

    2014-11-15

    Formation of Rydberg atoms due to 1 s → nlm excitations of hydrogen by positron impact, for arbitrary n, l, m, in dense quantum plasma has been investigated using a distorted wave theory which includes screened dipole polarization potential. The interactions among the charged particles in the plasma have been represented by exponential cosine-screened Coulomb potentials. Making use of a simple variationally determined hydrogen wave function, it has been possible to obtain the distorted wave scattering amplitude in a closed analytical form. A detailed study has been made to explore the structure of differential and total cross sections in the energy range 20–300 eV of incident positron. For the unscreened case, our results agree nicely with some of the most accurate results available in the literature. To the best of our knowledge, such a study on the differential and total cross sections for 1 s → nlm inelastic positron-hydrogen collisions in dense quantum plasma is the first reported in the literature.

  17. Eley-Rideal surface chemistry: Direct reactivity of gas phase atomic hydrogen with adsorbed species

    SciTech Connect

    Weinberg, W.H.

    1996-10-01

    Selected examples of Eley-Rideal surface chemistry are presented in order to review this field. Reactions on Ru(100) only are considered. The specific examples employed are: (i) hydrogenation of oxygen atoms, (ii) hydrogenation of CO, (iii) formation of dihydrogen, and (iv) hydrogenation of formate. 80 refs., 8 figs.

  18. Hydrogen transport through oxide metal surface under atom and ion irradiation

    NASA Astrophysics Data System (ADS)

    Begrambekov, L.; Dvoychenkova, O.; Evsin, A.; Kaplevsky, A.; Sadovskiy, Ya; Schitov, N.; Vergasov, S.; Yurkov, D.

    2014-11-01

    Both the latest and earlier achieved results on gas exchange processes on metal surfaces (including stainless steel, titanium, zirconium, tungsten with deposited aluminum oxide coating) under hydrogen atom or plasma irradiation with occasional oxygen impurity are presented in the paper. Mechanisms and regularities of these processes are discussed. It is demonstrated that surface oxide layer properties as a diffusion barrier strongly depend on external influence on the surface. In particular, it is revealed that low energy hydrogen ion irradiation could slow down hydrogen desorption from metals. Hydrogen atom or ion irradiation combined with simultaneous oxygen admixture accelerates hydrogen desorption from metals.

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

    PubMed Central

    2009-01-01

    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. PMID:20298519

  20. New horizons in chemical propulsion. [processes using free radicals, atomic hydrogen, excited species, etc

    NASA Technical Reports Server (NTRS)

    Cohen, W.

    1973-01-01

    After a review of the work of the late-Fifties on free radicals for propulsion, it is concluded that atomic hydrogen would provide a potentially large increase in specific impulse. Work conducted to find an approach for isolating atomic hydrogen is considered. Other possibilities for obtaining propellants of greatly increased capability might be connected with the technology for the generation of activated states of gases, metallic hydrogen, fuels obtained from other planets, and laser transfer of energy.

  1. Single charge exchange between hydrogen-like projectiles and hydrogen atom: the post version of the BDW-4B approximation

    NASA Astrophysics Data System (ADS)

    Azizan, Sh; Shojaei, F.; Fathi, R.

    2016-04-01

    The post version of the four-body Born distorted wave method (BDW-4B) is applied to calculate the total cross section for single electron exchange in the collision of hydrogen-like projectiles with hydrogen atom. The post form of transition amplitude is obtained in terms of two-dimensional real integrals which can be computed numerically. This second-order theory which satisfies the correct boundary conditions is used for the collision of {{H}}, {{H}}{{{e}}}+, {{L}}{{{i}}}2+, {{{B}}}4+, {{{C}}}5+ with hydrogen atoms at intermediate and high impact energies. The validity of our results is assessed in comparison with available experimental data and other theories.

  2. Temperature and site dependence of the rate of hydrogen and deuterium abstraction by methyl radicals in methanol glasses

    SciTech Connect

    Doba, T.; Ingold, K.U.; Siebrand, W.; Wildman, T.A.

    1984-07-19

    Rate constants are reported for hydrogen and deuterium abstraction by methyl radicals in CH/sub 3/OH and CD/sub 3/OD glasses in the ranges 5-89 and 77-97 K, respectively. At each temperature, they show a distribution due to a variation of radical trapping sites. The rate constants of this distribution are analyzed theoretically to yield a quantitative relation between tunneling rate and equilibrium tunneling distance. 20 references, 2 figures.

  3. Hydrogen storage as a hydride. Citations from the International Aerospace Abstracts data base

    NASA Technical Reports Server (NTRS)

    Zollars, G. F.

    1980-01-01

    These citations from the international literature concern the storage of hydrogen in various metal hydrides. Binary and intermetallic hydrides are considered. Specific alloys discussed are iron titanium, lanthanium nickel, magnesium copper and magnesium nickel among others.

  4. Atomic mechanism and prediction of hydrogen embrittlement in iron.

    PubMed

    Song, Jun; Curtin, W A

    2013-02-01

    Hydrogen embrittlement in metals has posed a serious obstacle to designing strong and reliable structural materials for many decades, and predictive physical mechanisms still do not exist. Here, a new H embrittlement mechanism operating at the atomic scale in α-iron is demonstrated. Direct molecular dynamics simulations reveal a ductile-to-brittle transition caused by the suppression of dislocation emission at the crack tip due to aggregation of H, which then permits brittle-cleavage failure followed by slow crack growth. The atomistic embrittlement mechanism is then connected to material states and loading conditions through a kinetic model for H delivery to the crack-tip region. Parameter-free predictions of embrittlement thresholds in Fe-based steels over a range of H concentrations, mechanical loading rates and H diffusion rates are found to be in excellent agreement with experiments. This work provides a mechanistic, predictive framework for interpreting experiments, designing structural components and guiding the design of embrittlement-resistant materials. PMID:23142843

  5. On emission from a hydrogen-like atom

    NASA Astrophysics Data System (ADS)

    Skobelev, V. V.

    2016-02-01

    A solution of the Dirac equation for an electron in the field of a point nucleus ( Ze) has been obtained as an eigenfunction of the Schrödinger Hamiltonian and the spin projection operator Σ3. With the use of this solution, the probability W (ν) of the emission of a neutrino per unit time from a hydrogen-like atom, (Ze)* to (Ze) + ν bar ν, has been calculated for the first time in the first order of the parameter Ze ≪ 1. The probability W (ν) appears to be rather small, and the corresponding lifetime τ(ν) = [ W (ν)]-1 is much larger than the age of the Universe; correspondingly, this process cannot affect the balance of low-energy neutrinos. The smallness of W (ν) is due not only to the presence of the obvious "weak" factor ( Gm p 2 )2( m/ mp)4 in the expression for W (ν), but also primarily to the "electromagnetic" factor ( Zα)12, which can be revealed only in a particular calculation. It has been argued within quantum electrodynamics with the mentioned wavefunctions that photon emission, ( Ze)* → ( Ze) + γ, can be absent (analysis of photon emission requires the further development of the method), whereas axion emission, ( Ze)* → ( Ze) + a, can occur, although the last two effects have not been considered in detail.

  6. Ionization of the hydrogen atom by intense ultrashort laser pulses

    NASA Astrophysics Data System (ADS)

    Borbély, S.; Tőkési, K.; Nagy, L.

    2008-03-01

    The ionization of atomic hydrogen in intense laser fields is studied theoretically by both quantum-mechanical and classical approaches. In the quantum-mechanical treatment we apply a momentum-space strong-field approximation (MSSFA) and the Coulomb potential is taken into account as a perturbation. The classical calculations are performed within the framework of the classical trajectory Monte Carlo method. The energy and angular distributions of the ionization probabilities of the photoelectrons are presented for different laser pulses. While for the case of low electron energies larger discrepancies can be observed between the theories in the double-differential ionization probabilities, at high electron energies the agreement is excellent. This indicates that the generation of low-energy electrons is of quantum type and it is strongly influenced by the Coulomb potential, while the production of high-energy electrons is of classical type and it is less influenced by the Coulomb interaction. Our MSSFA results are in good agreement with the most reliable calculations based on a numerical solution of the time-dependent Schrödinger equation for high momentum transfers.

  7. Calculation of muon transfer from muonic hydrogen to atomic oxygen

    SciTech Connect

    Dupays, Arnaud; Lepetit, Bruno; Beswick, J. Alberto; Rizzo, Carlo; Bakalov, Dimitar

    2003-06-01

    The muon-transfer probabilities between muonic hydrogen and an oxygen atom are calculated in a constrained geometry one-dimensional model for collision energies between 10{sup -6} and 10{sup 3} eV. For relative translational energies below 10{sup -1} eV, for which the de Broglie wavelength (>1 Aa) is much larger than the characteristic distance of the potential interaction ({approx}0.1 Aa), the problem corresponds to an ultracold collision. The close-coupling time-independent quantum equations are written in terms of hyperspherical coordinates and a diabatic-by-sectors basis set. The muon-transfer probabilities are qualitatively interpreted in terms of a model involving two Landau-Zener crossings together with the threshold energy dependence. Based on this analysis, a simple procedure to estimate the energy dependence of the muon-transfer rate in three dimensions is proposed. These estimated rates are discussed in the light of previous model calculations and available experimental data for this process. It is concluded that the high transfer rates at epithermal energies inferred from experiments are unlikely to be correct.

  8. Charge exchange and ionization in hydrogen atom-fully stripped ion collisions in Debye plasmas

    SciTech Connect

    Zhang, H.; Wang, J. G.; He, B.; Qiu, Y. B.; Janev, R. K.

    2007-05-15

    The processes of charge exchange and ionization in collisions of ground state hydrogen atom with fully stripped ions in a weakly coupled plasma are studied by the classical trajectory Monte Carlo method in the collision energy range 10-900 keV/amu. The interparticle interactions are described by the Debye-Hueckel model with inclusion of dynamical effects associated with the projectile velocity. The microcanonical distribution of initial state electronic coordinates and momenta has been determined by inclusion of plasma screening effects. The cross section dependencies on plasma parameters and ion charge and velocity are investigated. It is shown that plasma effects on charge exchange and ionization cross sections are significant and particularly pronounced at low collision velocities. The results of systematic cross section calculations for different values of Debye screening length (in the range 1-50a{sub 0}) and ion charges (in the range 1-14) are presented.

  9. Trapping hydrogen atoms from a neon-gas matrix: a theoretical simulation.

    PubMed

    Bovino, S; Zhang, P; Kharchenko, V; Dalgarno, A

    2009-08-01

    Hydrogen is of critical importance in atomic and molecular physics and the development of a simple and efficient technique for trapping cold and ultracold hydrogen atoms would be a significant advance. In this study we simulate a recently proposed trap-loading mechanism for trapping hydrogen atoms released from a neon matrix. Accurate ab initio quantum calculations are reported of the neon-hydrogen interaction potential and the energy- and angular-dependent elastic scattering cross sections that control the energy transfer of initially cold atoms are obtained. They are then used to construct the Boltzmann kinetic equation, describing the energy relaxation process. Numerical solutions of the Boltzmann equation predict the time evolution of the hydrogen energy distribution function. Based on the simulations we discuss the prospects of the technique. PMID:19673557

  10. Electron transfer and multi-atom abstraction reactions between atomic metal anions and NO, NO2 and SO2

    NASA Astrophysics Data System (ADS)

    Butson, J. M.; Curtis, S.; Mayer, P. M.

    2016-05-01

    The atomic metal anions Fe-, Cs-, Cu- and Ag- were reacted with NO, NO2 and SO2 to form intact NO-, NO2- and SO2- with no fragmentation. Yields for the molecular anions ranged from 4 to 97% and were found to correlate to the exothermicity of the electron transfer process. Sequential oxygen atom extraction was found to take place between the metal anions and NO and NO2. Reactions between NO2 and Fe- resulted in FeO-, FeO2- and FeO3- while reactions of Cu- with NO2 resulted in CuO- and CuO2-. Reactions of Cu- and Ag- with NO resulted in CuO- and AgO- respectively.

  11. (abstract) Development of Sorbent Bed Assembly for a Periodic 10K Solid Hydrogen Cryocooler

    NASA Technical Reports Server (NTRS)

    Wade, L. A.; Bowman, R. C., Jr.; Gilkinson, D. R.; Sywulka, P. H.

    1993-01-01

    A closed-cycle 10K sorption cryocooler is being fabricated for microgravity testing during a future space shuttle mission. A critical component of this cryogenic refrigerator is the metal hydride sorbent bed assembly (SBA). The SBA uses hydrides which absorb hydrogen gas at low pressure, (i.e., about 0.25 MPa from liquid hydrogen at 25K and below 0.2 kPa from solid hydrogen near 10K) and subsequently delivers hydrogen at nearly 10 MPa to a storage reservoir to repeat the Joule-Thomson (J-T) expansion process. The SBA includes three independent hydride beds where two contain LaNi(sub 4.8)Sn(sub 0.2) alloy and the third ZrNi. Detailed descriptions will be given for the three beds, which have specialized design features to enhance performance at each step of operation. In particular, two beds must rapidly absorb hydrogen in order for the J-T cold stage to reach 10K within two minutes from a 65K holding temperature. Performance characterization results will be compared to model analyses of the SBA.

  12. Adhesion properties of hydrogen on Sb(111) probed by helium atom scattering

    NASA Astrophysics Data System (ADS)

    Kraus, P.; Gösweiner, Ch.; Tamtögl, A.; Apolloner, F.; Ernst, W. E.

    2016-06-01

    We have carried out a series of helium atom scattering measurements in order to characterise the adsorption properties of hydrogen on antimony(111). Molecular hydrogen does not adsorb at temperatures above 110 K in contrast to pre-dissociated atomic hydrogen. Depending on the substrate temperature, two different adlayer phases of atomic hydrogen on Sb(111) occur. At low substrate temperatures (110 K), the deposited hydrogen layer does not show any ordering while we observe a perfectly ordered (1× 1) H/Sb(111) structure for deposition at room temperature. Furthermore, the amorphous hydrogen layer deposited at low temperature forms an ordered overlayer upon heating the crystal to room temperature. Hydrogen starts to desorb at Tm = 430 \\text{K} which corresponds to a desorption energy of Edes=(1.33+/-0.06) \\text{eV} . Using measurements of the helium reflectivity during hydrogen exposure at different surface temperatures, we conclude that the initial sticking coefficient of atomic hydrogen on Sb(111) decreases with increasing surface temperature. Furthermore, the scattering cross-section for the diffuse scattering of helium from hydrogen on Sb(111) is determined as Σ = (12 +/- 1) \\unicode{8491}2 .

  13. Applications of photoinduced electron transfer and hydrogen abstraction reactions to chemical and electrochemical conversion processes. Final report, March 1, 1981-February 28, 1984

    SciTech Connect

    Not Available

    1984-01-01

    Goal has been to study light-driven electron transfer and hydrogen atom abstraction processes with emphasis on reactions giving rise to net chemical or electrochemical conversion. The work focused on studies using substrates excitable with visible light - ranging from metal complexes, porphyrins and metalloporphyrins to dyes and ketones - and quencher-mediators capable of acting as electron donors or acceptors by virtue of having multiple closely spaced redox levels. The work can be conveniently divided into five major areas: Generation and Reaction of Reducing and Oxidizing Radicals and Radical Ions in Photoelectrochemical Cells; Studies of Weitz-type Quenchers Having Stable One-electron Redox Products; Two-electron Oxidative and Reductive Quenching Processes with Weitz-type Systems in Solution and Organized Media; Photoredox Reactions of Indigo Dyes; and Modification of Photochemical Reactivity by Formation of Amylose Inclusion Complexes in Aqueous and Partially Aqueous Solutions.

  14. Applications of photoinduced electron transfer and hydrogen abstraction reactions to chemical and electrochemical conversion processes. Progress report, March 1, 1981-September 1, 1982

    SciTech Connect

    Whitten, D.G.

    1982-01-01

    The major goal of this research as outlined in our proposal is to study light-driven electron transfer and hydrogen atom abstraction processes with a particular emphasis on reactions giving rise to net chemical or electrochemical conversion. During the past eighteen months we have obtained results of some significance in each of the five areas which are discussed individually in the report: (1) generation and reaction of reducing and oxidizing radicals and radical ions in photoelectrochemical cells; (2) studies of Weitz-type quenchers having stable one-electron redox products; (3) two-electron oxidative and reductive quenching processes with Weitz-type systems in solution and organized media; (4) photoredox reactions of indigo dyes; and (5) modification of photochemical reactivity by formation of amylose inclusion complexes in aqueous and partially aqueous solutions.

  15. Applications of photoinduced electron transfer and hydrogen abstraction reactions to chemical and electrochemical conversion processes. Part I. Progress report, March 1, 1981-July 1, 1983

    SciTech Connect

    Whitten, D.G.

    1983-01-01

    Goal is to study light-driven electron transfer and hydrogen atom abstraction processes with emphasis on reactions giving rise to net chemical or electrochemical conversion. The original proposal focused on studies using substrates excitable with visible light - ranging from metal complexes, porphyrins and metalloporphyrins to dyes and ketones - and quencher-mediators capable of acting as electron donors or acceptors by virtue of having multiple closely spaced redox levels. During the past eighteen months results were obtained in five areas: generation and reaction of reducing and oxidizing radicals and radical ions in photoelectrochemical cells; studies of Weitz-type quenchers having stable one-electron redox products; two-electron oxidative and reductive quenching processes with Weitz-type systems in solution and organized media; photoredox reactions of indigo dyes; and modification of photochemical reactivity by formation of amylose inclusion complexes in aqueous and partially aqueous solutions.

  16. Hydrogen fluoride and deuterium fluoride lasers. Citations from the International Aerospace Abstracts data base

    NASA Technical Reports Server (NTRS)

    Mauk, S. C.

    1980-01-01

    Research cited from the international literature adresses various aspects of hydrogen fluoride and deuterium fluoride lasers. Topics covered include flows, laser outputs, molecular relaxation, molecular rotation, energy conversion efficiency, reaction kinetics, and laser materials. Continous wave and pulsed laser are considered. This updated bibliography contains 283 citations, 53 of which are new additions to the previous edition.

  17. Characterization of intramolecular hydrogen bonds by atomic charges and charge fluxes.

    PubMed

    Baranović, Goran; Biliškov, Nikola; Vojta, Danijela

    2012-08-16

    The electronic charge redistribution and the infrared intensities of the two types of intramolecular hydrogen bonds, O-H···O and O-H···π, of o-hydroxy- and o-ethynylphenol, respectively, together with a set of related intermolecular hydrogen bond complexes are described in terms of atomic charges and charge fluxes derived from atomic polar tensors calculated at the B3LYP/cc-pVTZ level of theory. The polarizable continuum model shows that both the atomic charges and charge fluxes are strongly dependent on solvent. It is shown that their values for the OH bond in an intramolecular hydrogen bond are not much different from those for the "free" OH bond, but the changes are toward the values found for an intermolecular hydrogen bond. The intermolecular hydrogen bond is characterized not only by the decreased atomic charge but also by the enlarged charge flux term of the same sign producing thus an enormous increase in IR intensity. The overall behavior of the charges and fluxes of the hydrogen atom in OH and ≡CH bonds agree well with the observed spectroscopic characteristics of inter- and intramolecular hydrogen bonding. The main reason for the differences between the two types of the hydrogen bond lies in the molecular structure because favorable linear proton donor-acceptor arrangement is not possible to achieve within a small molecule. The calculated intensities (in vacuo and in polarizable continuum) are only in qualitative agreement with the measured data. PMID:22809455

  18. Electron, proton and hydrogen-atom transfers in photosynthetic water oxidation.

    PubMed Central

    Tommos, Cecilia

    2002-01-01

    When photosynthetic organisms developed so that they could use water as an electron source to reduce carbon dioxide, the stage was set for efficient proliferation. Algae and plants spread globally and provided the foundation for our atmosphere and for O(2)-based chemistry in biological systems. Light-driven water oxidation is catalysed by photosystem II, the active site of which contains a redox-active tyrosine denoted Y(Z), a tetramanganese cluster, calcium and chloride. In 1995, Gerald Babcock and co-workers presented the hypothesis that photosynthetic water oxidation occurs as a metallo-radical catalysed process. In this model, the oxidized tyrosine radical is generated by coupled proton/electron transfer and re-reduced by abstracting hydrogen atoms from substrate water or hydroxide-ligated to the manganese cluster. The proposed function of Y(Z) requires proton transfer from the tyrosine site upon oxidation. The oxidation mechanism of Y(Z) in an inhibited and O(2)-evolving photosystem II is discussed. Domino-deprotonation from Y(Z) to the bulk solution is shown to be consistent with a variety of data obtained on metal-depleted samples. Experimental data that suggest that the oxidation of Y(Z) in O(2)-evolving samples is coupled to proton transfer in a hydrogen-bonding network are described. Finally, a dielectric-dependent model for the proton release that is associated with the catalytic cycle of photosystem II is discussed. PMID:12437877

  19. Open-shell pair interaction energy decomposition analysis (PIEDA): Formulation and application to the hydrogen abstraction in tripeptides

    NASA Astrophysics Data System (ADS)

    Green, Mandy C.; Fedorov, Dmitri G.; Kitaura, Kazuo; Francisco, Joseph S.; Slipchenko, Lyudmila V.

    2013-02-01

    An open-shell extension of the pair interaction energy decomposition analysis (PIEDA) within the framework of the fragment molecular orbital (FMO) method is developed. The open-shell PIEDA method allows the analysis of inter- and intramolecular interactions in terms of electrostatic, exchange-repulsion, charge-transfer, dispersion, and optional polarization energies for molecular systems with a radical or high-spin fragment. Taking into account the low computational cost and scalability of the FMO and PIEDA methods, the new scheme provides a means to characterize the stabilization of radical and open-shell sites in biologically relevant species. The open-shell PIEDA is applied to the characterization of intramolecular interactions in capped trialanine upon hydrogen abstraction (HA) at various sites on the peptide. Hydrogen abstraction reaction is the first step in the oxidative pathway initiated by reactive oxygen or nitrogen species, associated with oxidative stress. It is found that HA results in significant geometrical reorganization of the trialanine peptide. Depending on the HA site, terminal interactions in the radical fold conformers may become weaker or stronger compared to the parent molecule, and often change the character of the non-covalent bonding from amide stacking to hydrogen bonding.

  20. Signatures of Quantum-Tunneling Diffusion of Hydrogen Atoms on Water Ice at 10 K

    NASA Astrophysics Data System (ADS)

    Kuwahata, K.; Hama, T.; Kouchi, A.; Watanabe, N.

    2015-09-01

    Reported here is the first observation of the tunneling surface diffusion of a hydrogen (H) atom on water ice. Photostimulated desorption and resonance-enhanced multiphoton ionization methods were used to determine the diffusion rates at 10 K on amorphous solid water and polycrystalline ice. H-atom diffusion on polycrystalline ice was 2 orders of magnitude faster than that of deuterium atoms, indicating the occurrence of tunneling diffusion. Whether diffusion is by tunneling or thermal hopping also depends on the diffusion length of the atoms and the morphology of the surface. Our findings contribute to a better understanding of elementary physicochemical processes of hydrogen on cosmic ice dust.

  1. Signatures of Quantum-Tunneling Diffusion of Hydrogen Atoms on Water Ice at 10 K.

    PubMed

    Kuwahata, K; Hama, T; Kouchi, A; Watanabe, N

    2015-09-25

    Reported here is the first observation of the tunneling surface diffusion of a hydrogen (H) atom on water ice. Photostimulated desorption and resonance-enhanced multiphoton ionization methods were used to determine the diffusion rates at 10 K on amorphous solid water and polycrystalline ice. H-atom diffusion on polycrystalline ice was 2 orders of magnitude faster than that of deuterium atoms, indicating the occurrence of tunneling diffusion. Whether diffusion is by tunneling or thermal hopping also depends on the diffusion length of the atoms and the morphology of the surface. Our findings contribute to a better understanding of elementary physicochemical processes of hydrogen on cosmic ice dust. PMID:26451552

  2. Flow-tube kinetics study of the reaction between ground-state hydrogen atoms and nitromethane

    SciTech Connect

    Ko, Taeho; Flaherty, W.F.; Fontijn, A. )

    1991-09-05

    The kinetics of the H + CH{sub 3}NO{sub 2} reaction have been studied by using a discharge-flow resonance-fluorescence technique. H atoms are produced from microwave discharges through NH{sub 3}Ar mixtures. The data in the 360-570 K range are well fitted by the empirical expression k(T) = 7.8 {times} 10{sup {minus}12} exp(-1878K/T) cm{sup 3} molecule{sup {minus}1} s{sup {minus}1}. Precision of the data varies from {plus minus} 6 to {plus minus} 11%, and the resulting accuracy is estimated to be better than {+-} 20%, where both figures represent 2{sigma} statistical confidence intervals. Results of some experiments where h{sub 2} was discharged indicate that the channel leading to OH and CH{sub 3}NO is significant for the reaction. A comparison of the kinetics of several reactions where a methyl-group hydrogen is abstracted by H atoms indicates that such a channel is not important in the present work but could become significant at elevated temperatures. To confirm the accuracy achieved with the present apparatus, measurements on the H + C{sub 6}H{sub 6} reaction have been made in the 410-530 K range and are compared to results from other studies.

  3. Ab Initio Vibrational Levels For HO2 and Vibrational Splittings for Hydrogen Atom Transfer

    NASA Technical Reports Server (NTRS)

    Barclay, V. J.; Dateo, Christopher E.; Hamilton, I. P.; Arnold, James O. (Technical Monitor)

    1994-01-01

    We calculate vibrational levels and wave functions for HO2 using the recently reported ab initio potential energy surface of Walch and Duchovic. There is intramolecular hydrogen atom transfer when the hydrogen atom tunnels through a T-shaped saddle point separating two equivalent equilibrium geometries, and correspondingly, the energy levels are split. We focus on vibrational levels and wave functions with significant splitting. The first three vibrational levels with splitting greater than 2/cm are (15 0), (0 7 1) and (0 8 0) where V(sub 2) is the O-O-H bend quantum number. We discuss the dynamics of hydrogen atom transfer; in particular, the O-O distances at which hydrogen atom transfer is most probable for these vibrational levels. The material of the proposed presentation was reviewed and the technical content will not reveal any information not already in the public domain and will not give any foreign industry or government a competitive advantage.

  4. Influence of cathode material on generation of energetic hydrogen atoms in a glow discharge

    SciTech Connect

    Cvetanovic, N.; Obradovic, B. M.; Kuraica, M. M.

    2011-01-01

    In this paper influence of cathode material on formation of fast hydrogen atoms in an abnormal glow discharge is investigated using Balmer alpha emission spectroscopy. Energetic H atoms are generated in charge exchange reactions of hydrogen ions that are accelerated in the electric field, and also formed in the backscattering process at the cathode surface. Copper and graphite cathodes were used. Investigation was performed in two orthogonal directions of observation in pure hydrogen and argon-hydrogen mixture. The shapes of the profiles are examined together with the space intensity distribution of Balmer alpha line. Reduced atom reflection from graphite was manifested in the spectroscopic result, in accordance to the field acceleration model. The effect was evident only at high ion energies. This is explained by energy dependence of reflection coefficient for H atoms.

  5. DNA damage by the sulfate radical anion: hydrogen abstraction from the sugar moiety versus one-electron oxidation of guanine.

    PubMed

    Roginskaya, Marina; Mohseni, Reza; Ampadu-Boateng, Derrick; Razskazovskiy, Yuriy

    2016-07-01

    The products of oxidative damage to double-stranded (ds) DNA initiated by photolytically generated sulfate radical anions SO4(•-) were analyzed using reverse-phase (RP) high-performance liquid chromatography (HPLC). Relative efficiencies of two major pathways were compared: production of 8-oxoguanine (8oxoG) and hydrogen abstraction from the DNA 2-deoxyribose moiety (dR) at C1,' C4,' and C5' positions. The formation of 8oxoG was found to account for 87% of all quantified lesions at low illumination doses. The concentration of 8oxoG quickly reaches a steady state at about one 8oxoG per 100 base pairs due to further oxidation of its products. It was found that another guanine oxidation product identified as 2-amino-5-(2'-alkylamino)-4H-imidazol-4-one (X) was released in significant quantities from its tentative precursor 2-amino-5-[(2'-deoxy-β-d-erythro-pentofuranosyl)amino]-4H-imidazol-4-one (dIz) upon treatment with primary amines in neutral solutions. The linear dose dependence of X release points to the formation of dIz directly from guanine and not through oxidation of 8oxoG. The damage to dR was found to account for about 13% of the total damage, with majority of lesions (33%) originating from the C4' oxidation. The contribution of C1' oxidation also turned out to be significant (17% of all dR damages) despite of the steric problems associated with the abstraction of the C1'-hydrogen. However, no evidence of base-to-sugar free valence transfer as a possible alternative to direct hydrogen abstraction at C1' was found. PMID:27043476

  6. Erwin Schrödinger, Wave Mechanics, and the Hydrogen Atom

    NASA Astrophysics Data System (ADS)

    de Lange, Owen L.

    1996-06-01

    A brief account is given of some of the main events in Erwin Schrödinger's life, the circumstances leading to his discovery of wave mechanics in 1925-1926, and the application of this mechanics to a model of the hydrogen atom. Two methods of solving this model are outlined, namely, Sommerfeld's polynomial method and Schrödinger's shift operator method. The relation to Pauli's analysis of the quantum-mechanical hydrogen atom is also discussed.

  7. Muon transfer from muonic atoms of hydrogen isotopes to He nuclei

    SciTech Connect

    Bystritskii, V.M.

    1995-05-01

    The entire body of experimental results on muon transfer from {mu} atoms of hydrogen isotopes to helium nuclei is discussed and subjected to comparative analysis. A program of further investigations aimed at obtaining more precise and detailed information about the characteristics of {mu}-atomic and {mu}-molecular processes in mixtures of hydrogen isotopes and helium is proposed. 34 refs., 5 figs., 1 tab.

  8. Detection of hot muonic hydrogen atoms emitted in vacuum using x-rays

    SciTech Connect

    Jacot-Guillarmod, R. ); Bailey, J.M. ); Beer, G.A.; Knowles, P.E.; Mason, G.R.; Olin, A. ); Beveridge, J.L.; Marshall, G.M. ); Brewer, J.H.; Forster, B.M. ); Huber, T.M. ); Kammel, P

    1992-01-01

    Negative muons are stopped in solid layers of hydrogen and neon. Muonic hydrogen atoms can drift to the neon layer where the muon is immediately transferred. It was found that the time structure of the muonic neon X-rays follows the exponential law where the rate is the same as the disappearance rate of [mu][sup -]p atoms. The pp[mu]-formation rate and the muon transfer rate to deuterium are deduced.

  9. Estimated rate constants for hydrogen abstraction from N-heterocyclic carbene-borane complexes by an alkyl radical.

    PubMed

    Solovyev, Andrey; Ueng, Shau-Hua; Monot, Julien; Fensterbank, Louis; Malacria, Max; Lacôte, Emmanuel; Curran, Dennis P

    2010-07-01

    Rate constants for hydrogen abstraction by a nonyl radical from 20 complexes of N-heterocyclic carbenes and boranes (NHC-boranes) have been determined by the pyridine-2-thioneoxycarbonyl (PTOC) competition kinetic method at a single concentration point. The rate constants range from <1 x 10(4) to 8 x 10(4) M(-1) s(-1). They show little dependence on the electronic properties of the carbene core, but there is a trend for increasing rate constants with decreasing size of the carbene N-substituents. Two promising new reagents with small N-substituents (R = Me) have been identified. PMID:20536158

  10. Mechanism of the formation of hydrogen tetroxide and peroxide via low-temperature interaction between hydrogen atoms and molecular oxygen

    NASA Astrophysics Data System (ADS)

    Levanov, A. V.; Isaikina, O. Ya.; Antipenko, E. E.; Lunin, V. V.

    2014-09-01

    A mechanism and kinetic model for the synthesis of peroxide radical condensate via the low-temperature interaction of hydrogen atoms with O2 molecules is proposed. The main components of the reaction, hydrogen tetroxide H2O4 and hydrogen peroxide H2O2, are formed in a low-temperature liquid layer formed near the cold surface during synthesis. Molecules of H2O4 and H2O2 are stabilized by transitioning to the solid phase. The dependences of the ratio on the ratio of concentrations of H and O2 in the gas phase, calculated on the basis of the model, are consistent with the experimental data.

  11. Atomic-Scale Mechanism for Hydrogenation of o-Cresol on Pt Catalysis

    NASA Astrophysics Data System (ADS)

    Li, Yaping; Liu, Zhimin; Xue, Wenhua; Crossley, Steven; Jentoft, Friederike; Wang, Sanwu

    Biofuels derived from lignocellulosic biomass have received significant attention lately due to increasing environmental concerns. With first-principles density-functional theory and ab initio molecular dynamic simulations, we investigated the atomic-scale mechanism of o-cresol hydrogenation on the Pt(111) surface. The formation of 2-methyl-cyclohexanone (the intermediate product) was found to involve two steps. The first step is the dehydrogenation, that is, the H atom in the hydroxyl group moves to the Pt surface. The second step is the hydrogenation, that is, the H atoms on Pt react with the carbon atoms in the aromatic ring. The first step involves a smaller barrier, suggesting that dehydrogenation occurs first, followed by hydrogenation of the ring. In particular, tautomerization is found to occur via a two-step process over the catalyst. On the other hand, 2-methyl-cyclohexanol (the final product) is produced through two paths. One is direct hydrogenation of the aromatic ring. Another pathway includes partial hydrogenation of the ring, dehydrogenation of -OH group, finally hydrogenation of remaining C atoms and the O atom. Our theoretical results agree well with the experimental observations. Supported by DOE (DE-SC0004600). This research used the supercomputer resources of NERSC, XSEDE, TACC.

  12. Constructive and destructive interferences of Stark resonances induced by an ac field in atomic hydrogen

    SciTech Connect

    Pawlak, Mariusz; Bylicki, Miroslaw; Moiseyev, Nimrod; Sindelka, Milan

    2010-12-15

    We study theoretically the problem of a hydrogen atom exposed both to a static dc field and to a monochromatic ac field. We show that, in the presence of an ac field, a constructive (or destructive) interference occurs between the excited (Rydberg) Stark resonance states and the hydrogenic ground state. This mechanism is responsible for dramatic enhancement (or suppression) of the corresponding photoionization rates.

  13. Hydrogen sulphide in cardiovascular system: A cascade from interaction between sulphur atoms and signalling molecules.

    PubMed

    Wang, Ming-Jie; Cai, Wen-Jie; Zhu, Yi-Chun

    2016-05-15

    As a gasotransmitter, hydrogen sulphide exerts its extensive physiological and pathophysiological effects in mammals. The interaction between sulphur atoms and signalling molecules forms a cascade that modulates cellular functions and homeostasis. In this review, we focus on the signalling mechanism underlying the effect of hydrogen sulphide in the cardiovascular system and metabolism as well as the biological relevance to human diseases. PMID:27071836

  14. The simplicity of perfect atoms: Degeneracies in supersymmetric hydrogen

    DOE PAGESBeta

    Rube, Tomas; Wacker, Jay G.

    2011-06-07

    In this study, supersymmetric QED hydrogen-like bound states are remarkably similar to nonsupersymmetric hydrogen, including an accidental degeneracy of the fine structure and is broken by the Lamb shift. This article classifies the states, calculates the leading order spectrum, and illustrates the results in several limits. The relation to other nonrelativistic bound states is explored.

  15. The simplicity of perfect atoms: Degeneracies in supersymmetric hydrogen

    SciTech Connect

    Rube, Tomas; Wacker, Jay G.

    2011-06-15

    Supersymmetric QED hydrogen-like bound states are remarkably similar to nonsupersymmetric hydrogen, including an accidental degeneracy of the fine structure and is broken by the Lamb shift. This article classifies the states, calculates the leading order spectrum, and illustrates the results in several limits. The relation to other nonrelativistic bound states is explored.

  16. Kinetic and Mechanistic Studies of Carbon-to-Metal Hydrogen Atom Transfer Involving Os-Centered Radicals: Evidence for Tunneling

    SciTech Connect

    Lewandowska-Androlojc, Anna; Grills, David C.; Zhang, Jie; Bullock, R. Morris; Miyazawa, Akira; Kawanishi, Yuji; Fujita, Etsuko

    2014-03-05

    We have investigated the kinetics of novel carbon-to-metal hydrogen atom transfer reactions, in which homolytic cleavage of a C-H bond is accomplished by a single metal-centered radical. Studies by means of time-resolved IR spectroscopic measurements revealed efficient hydrogen atom transfer from xanthene, 9,10-dihydroanthracene and 1,4-cyclohexadiene to Cp(CO)2Os• and (n5-iPr4C5H)(CO)2Os• radicals, formed by photoinduced homolysis of the corresponding osmium dimers. The rate constants for hydrogen abstraction from these hydrocarbons were found to be in the range 1.54 × 105 M 1 s 1 -1.73 × 107 M 1 s-1 at 25 °C. For the first time, kinetic isotope effects for carbon-to-metal hydrogen atom transfer were determined. Large primary kinetic isotope effects of 13.4 ± 1.0 and 16.6 ± 1.4 were observed for the hydrogen abstraction from xanthene to form Cp(CO)2OsH and (n5-iPr4C5H)(CO)2OsH, respectively, at 25 °C. Temperature-dependent measurements of the kinetic isotope effects over a 60 -C temperature range were carried out to obtain the difference in activation energies and the pre-exponential factor ratio. For hydrogen atom transfer from xanthene to (n5-iPr4C5H)(CO)2Os•, the (ED - EH) = 3.25 ± 0.20 kcal/mol and AH/AD = 0.056 ± 0.018 values are greater than the semi-classical limits and thus suggest a quantum mechanical tunneling mechanism. The work at BNL was carried out under contract DE-AC02-98CH10886 with the U.S. Department of Energy and supported by its Division of Chemical Sciences, Geosciences & Biosciences, Office of Basic Energy Sciences. RMB also thanks the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences for support. Pacific Northwest National Laboratory is operated by Battelle for the U.S. Department of Energy.

  17. Quantum chemistry and dynamics of the abstraction reaction of H atoms from formaldehyde

    NASA Astrophysics Data System (ADS)

    Siaï, A.; Oueslati, I.; Kerkeni, Boutheïna

    2016-08-01

    This work reports a reduced dimensionality rate constant calculation of the H-abstraction reaction from formaldehyde. Quantum scattering calculations are performed treating explicitly the bonds being broken and formed. Geometry optimisations and frequency calculations are done at the MP2/cc-pVTZ level while energies are calculated with the CCSD(T) method. An analytical potential energy surface was developed from a relatively small number of grid points. When compared to semi-classical approaches, the quantum scattering calculations show that quantum tunnelling yields large contributions at low temperatures. At 200 K, we note a difference of about 5 orders of magnitude between transition state theory (TST) and quantum rate constants. Our predicted results show that the quantum and the CVT/SCT rate constants are in reasonable agreement with the available experiment at high temperatures, but that the last one gives better agreement to experimental results at low temperatures.

  18. Rapid RNA Strand Scission Following C2′-Hydrogen Atom Abstraction

    PubMed Central

    Paul, Rakesh; Greenberg, Marc M.

    2015-01-01

    C2′-Nucleotide radicals have been proposed as key intermediates in direct strand break formation in RNA exposed to ionizing radiation. Uridin-2′-yl radical (1) was independently generated in single- and double-stranded RNA via photolysis of a ketone precursor. Direct stand breaks result from heterolytic cleavage of the adjacent C3′-carbon–oxygen bond. Trapping of 1 by O2 or β-mercaptoethanol (1 M) does not compete with strand scission, indicating that phosphate elimination is >106 s−1. Uracil loss also does not compete with strand scission. When considered in conjunction with reports that nucleobase radicals produce 1, this chemistry explains why RNA is significantly more susceptible to strand scission by ionizing radiation (hydroxyl radical) than is DNA. PMID:25580810

  19. Kinetics of Hydrogen Atom Abstraction from Substrate by an Active Site Thiyl Radical in Ribonucleotide Reductase

    PubMed Central

    2015-01-01

    Ribonucleotide reductases (RNRs) catalyze the conversion of nucleotides to deoxynucleotides in all organisms. Active E. coli class Ia RNR is an α2β2 complex that undergoes reversible, long-range proton-coupled electron transfer (PCET) over a pathway of redox active amino acids (β-Y122 → [β-W48] → β-Y356 → α-Y731 → α-Y730 → α-C439) that spans ∼35 Å. To unmask PCET kinetics from rate-limiting conformational changes, we prepared a photochemical RNR containing a [ReI] photooxidant site-specifically incorporated at position 355 ([Re]-β2), adjacent to PCET pathway residue Y356 in β. [Re]-β2 was further modified by replacing Y356 with 2,3,5-trifluorotyrosine to enable photochemical generation and spectroscopic observation of chemically competent tyrosyl radical(s). Using transient absorption spectroscopy, we compare the kinetics of Y· decay in the presence of substrate and wt-α2, Y731F-α2 ,or C439S-α2, as well as with 3′-[2H]-substrate and wt-α2. We find that only in the presence of wt-α2 and the unlabeled substrate do we observe an enhanced rate of radical decay indicative of forward radical propagation. This observation reveals that cleavage of the 3′-C–H bond of substrate by the transiently formed C439· thiyl radical is rate-limiting in forward PCET through α and has allowed calculation of a lower bound for the rate constant associated with this step of (1.4 ± 0.4) × 104 s–1. Prompting radical propagation with light has enabled observation of PCET events heretofore inaccessible, revealing active site chemistry at the heart of RNR catalysis. PMID:25353063

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

    NASA Technical Reports Server (NTRS)

    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.

  1. Evolution of Structure-Reactivity Correlations for the Hydrogen Abstraction Reaction by Chlorine Atom

    SciTech Connect

    Poutsma, Marvin L

    2013-01-01

    Empirical structure-reactivity correlations are developed for log k298, the gas-phase rate constants for the reaction (Cl + HCR3 ClH + CR3 ). It has long been recognized that correlation with rH is weak. The poor performance of the linear Evans-Polanyi formulation s illustrated and was little improved by adding a quadratic term, e.g., by making its slope smoothly dependent on rH [ ( rH rHmin) / ( rHmax rHmin)]. The polar effect ( -Cl---H---CR3 +) has also been long discussed but there is no formalization of this dependence based on widely available independent variable(s). Using the sum of Hammett constants for the R substituents also gave at best modest correlations, either for para or for its dissection into F (field/inductive) and R (resonance) effects. Much greater success was achieved by combining these approaches with the preferred independent variable set being either [( rH)2, rH, F, and R] or [ , rH, F, and R]. For 64 rate constants which span 7 orders of magnitude, these correlation formulations give r2 > 0.87 and a mean unsigned deviation of <0.5 log k units, with even better performance if primary secondary, and tertiary reaction centers are treated separately.

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

    PubMed

    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. PMID:27386545

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

    PubMed Central

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

    2016-01-01

    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. PMID:27386545

  4. Identification of titanium-hydrogen complexes with up to four hydrogen atoms in silicon

    NASA Astrophysics Data System (ADS)

    Scheffler, L.; Kolkovsky, Vl.; Weber, J.

    2015-02-01

    Using high-resolution Laplace deep level transient spectroscopy studies, several TiH-related complexes (E40', E170, E170', and E260) were observed in wet-chemically etched and H-plasma treated n-type Si. We assign E40' and E170 to two different configurations of Ti with one H atom. Both of them are shown to behave as single donor states with an activation enthalpy of EC - 0.07 eV (E40') and EC - 0.34 eV (E170) in the upper half of Si. E170' with an activation energy of EC - 0.37 eV is correlated with the donor state of the TiiH2 defect, whereas E260 is attributed to the donor state of TiiH3. Besides the TiH defects, the presence of electrically inactive TiH4 is reported. No titanium-hydrogen-related levels were observed in p-type Si.

  5. Identification of titanium-hydrogen complexes with up to four hydrogen atoms in silicon

    SciTech Connect

    Scheffler, L.; Kolkovsky, Vl. Weber, J.

    2015-02-28

    Using high-resolution Laplace deep level transient spectroscopy studies, several TiH-related complexes (E40′, E170, E170′, and E260) were observed in wet-chemically etched and H-plasma treated n-type Si. We assign E40′ and E170 to two different configurations of Ti with one H atom. Both of them are shown to behave as single donor states with an activation enthalpy of E{sub C} − 0.07 eV (E40′) and E{sub C} − 0.34 eV (E170) in the upper half of Si. E170′ with an activation energy of E{sub C} − 0.37 eV is correlated with the donor state of the Ti{sub i}H{sub 2} defect, whereas E260 is attributed to the donor state of Ti{sub i}H{sub 3}. Besides the TiH defects, the presence of electrically inactive TiH{sub 4} is reported. No titanium-hydrogen-related levels were observed in p-type Si.

  6. Trapping of hydrogen atoms inside small beryllium clusters and their ions

    NASA Astrophysics Data System (ADS)

    Naumkin, F. Y.; Wales, D. J.

    2016-08-01

    Structure, stability and electronic properties are evaluated computationally for small Ben (n = 5-9) cluster cages accommodating atomic H inside and forming core-shell species. These parameters are predicted to vary significantly upon insertion of H, for ionic derivatives, and with the system size. In particular, the energy barrier for H-atom exit from the cage changes significantly for ions compared to the neutral counterparts. The corresponding effects predicted for cage assemblies suggest the possibility of efficient charge-control of hydrogen release. This, together with a high capacity for storing hydrogen in extended such assemblies might indicate a possible way towards feasible hydrogen-storage solutions.

  7. Low-damage processing of CdTe(110) surfaces using atomic hydrogen

    NASA Astrophysics Data System (ADS)

    Luo, Y.; Slater, D. A.; Osgood, R. M., Jr.

    1995-07-01

    We present the results of an AES, XPS, and LEED study of the reaction of oxide and contaminant overlayers on the CdTe(110) surface with atomic hydrogen. Exposure of an oxidized surface to a flux of atomic hydrogen produced by ``cracking'' ambient molecular hydrogen on a hot tungsten filament results in a rapid, quantitative removal of the oxide overlayer with substrate temperatures as low as 300 K to produce a stoichiometric surface free of contaminants which has sufficient surface order to produce a sharp (1×1) LEED pattern.

  8. Two-dimensional B- B NMR spectroscopy: coupling through bridging hydrogen atoms

    SciTech Connect

    Gaines, D.F.; Edvenson, G.M.; Hill, T.G.; Adams, B.R.

    1987-06-03

    Application of B- B two-dimensional correlated spectroscopy (COSY) to a variety of boranes and substituted boranes has shown coupling between B nuclei linked by bridging hydrogen atoms to be more common than previously observed. Coupling between the hydrogen-bridged boron nuclei in decaborane(14), 2-(CH3)B5H8, B4H10, (Me2N)2B4H8, ( -Me2NCH2)B5H8, and ( -Me3CCH=N)B5H8 are reported. The factors that contribute to the detection of coupling between hydrogen-bridged boron atoms are discussed.

  9. In situ study of erosion and deposition of amorphous hydrogenated carbon films by exposure to a hydrogen atom beam

    SciTech Connect

    Markelj, Sabina; Pelicon, Primoz; Cadez, Iztok; Schwarz-Selinger, Thomas; Jacob, Wolfgang

    2012-07-15

    This paper reports on the first dual-beam experiment employing a hydrogen atom beam for sample exposure and an ion beam for analysis, enabling in situ and real-time studies of hydrogen atom interaction with materials. The erosion of an amorphous hydrogenated carbon (a-C:H) layer by deuterium atoms at 580 K sample temperature was studied and the uptake of deuterium during the erosion process was measured in real time. The deuterium areal density increased at the beginning to 7.3 Multiplication-Sign 10{sup 15} D cm{sup -2}, but then stabilized at a constant value of 5.5 Multiplication-Sign 10{sup 15} D cm{sup -2}. Formation of a polymer-like deposit on an a-C:H layer held at room temperature and subjected to the deuterium atom beam was observed and also studied in situ. For both erosion and deposition studies an a-{sup 13}C:H layer on top of an Si substrate was used as a sample, making the experiments isotopically fully specified and thereby differentiating the deposited from the original layer and the interacting D atoms from H atoms present in the layer and in the residual vacuum. From the deposition study it was shown that carbon in the deposited layer originates from carbon-carrying species in the background vacuum that interact with hydrogen atoms. The areal density of the carbon at the surface was determined from the energy shift of the Si edge in the Rutherford backscattering spectrum. The cross section for {sup 7}Li on D at 4.3 MeV Li ion energy and at a recoil angle of 30 Degree-Sign was also determined to be (236 {+-} 16) Multiplication-Sign 10{sup -27} cm{sup 2}/sr. This is a factor of 3 {+-} 0.2 times higher than the Rutherford elastic cross section.

  10. Theoretical Prediction of Rate Constants for Hydrogen Abstraction by OH, H, O, CH3, and HO2 Radicals from Toluene.

    PubMed

    Li, Shu-Hao; Guo, Jun-Jiang; Li, Rui; Wang, Fan; Li, Xiang-Yuan

    2016-05-26

    Hydrogen abstraction from toluene by OH, H, O, CH3, and HO2 radicals are important reactions in oxidation process of toluene. Geometries and corresponding harmonic frequencies of the reactants, transition states as well as products involved in these reactions are determined at the B3LYP/6-31G(2df,p) level. To achieve highly accurate thermochemical data for these stationary points on the potential energy surfaces, the Gaussian-4(G4) composite method was employed. Torsional motions are treated either as free rotors or hindered rotors in calculating partion functions to determine thermodynamic properties. The obtained standard enthalpies of formation for reactants and some prodcuts are shown to be in excellent agreement with experimental data with the largest error of 0.5 kcal mol(-1). The conventional transition state theory (TST) with tunneling effects was adopted to determine rate constants of these hydrogen abstraction reactions based on results from quantum chemistry calculations. To faciliate its application in kinetic modeling, the obtained rate constants are given in Arrhenius expression: k(T) = AT(n) exp(-EaR/T). The obtained reaction rate constants also agree reasonably well with available expermiental data and previous theoretical values. Branching ratios of these reactions have been determined. The present reaction rates for these reactions have been used in a toluene combustion mechanism, and their effects on some combustion properties are demonstrated. PMID:27164019

  11. Methanol dimer formation drastically enhances hydrogen abstraction from methanol by OH at low temperature.

    PubMed

    Siebrand, Willem; Smedarchina, Zorka; Martínez-Núñez, Emilio; Fernández-Ramos, Antonio

    2016-08-10

    The kinetics of the reaction of methanol with hydroxyl radicals is revisited in light of the reported new kinetic data, measured in cold expansion beams. The rate constants exhibit an approximately 10(2)-fold increase when the temperature decreases from 200 to 50 K, a result that cannot be fully explained by tunneling, as we confirm by new calculations. These calculations also show that methanol dimers are much more reactive to hydroxyl than monomers and imply that a dimer concentration of about 30% of the equilibrium concentration can account quantitatively for the observed rates. The assumed presence of dimers is supported by the observation of cluster formation in these and other cold beams of molecules subject to hydrogen bonding. The calculations imply an important caveat with respect to the use of cold expansion beams for the study of interstellar chemistry. PMID:27479134

  12. Characterization of hot hydrogen-atom reactions by kinetic spectrography.

    NASA Technical Reports Server (NTRS)

    Tomalesky, R. E.; Sturm, J. E.

    1971-01-01

    The flash photolysis of hydrogen iodide in the presence of nitrous oxide, carbon dioxide, and water has been investigated by kinetic spectroscopy. Although the fraction of hydrogen iodide dissociated was very large, the only observable intermediate was imidogen. It was demonstrated that the rapid removal of imidogen and the apparent absence of hydroxyl radicals in each case is a result of the following two reactions, respectively: (1) NH + HI yields NH2 + I; and (2) OH + HI yields H2O + I.

  13. Laser Diagnostics of Atomic Hydrogen and Oxygen Production in RF and Microwave Plasma Discharges

    NASA Astrophysics Data System (ADS)

    Preppernau, Bryan Lee

    1993-01-01

    The research for this thesis involved the application of two-photon allowed laser-induced fluorescence (TALIF) to the study of atomic hydrogen and oxygen production in industrial scale radio-frequency and microwave plasma discharge apparatus. Absolute atomic hydrogen concentration profiles were measured in a Gaseous Electronics Conference Reference Cell installed at Wright-Patterson AFB, Ohio operating with a simple H_2 discharge. Two -dimensional atomic hydrogen concentration profiles were also measured in an ASTEX HPMM microwave plasma diamond deposition reactor during actual diamond growth. In addition, absolute atomic oxygen concentrations were measured in the ASTEX system. Particular attention was paid to refining the concentration calibration technique and in determining a correction to account for the collisional quenching of excited state fluorescence in high pressure gases.

  14. Atomically isolated nickel species anchored on graphitized carbon for efficient hydrogen evolution electrocatalysis.

    PubMed

    Fan, Lili; Liu, Peng Fei; Yan, Xuecheng; Gu, Lin; Yang, Zhen Zhong; Yang, Hua Gui; Qiu, Shilun; Yao, Xiangdong

    2016-01-01

    Hydrogen production through electrochemical process is at the heart of key renewable energy technologies including water splitting and hydrogen fuel cells. Despite tremendous efforts, exploring cheap, efficient and durable electrocatalysts for hydrogen evolution still remains as a great challenge. Here we synthesize a nickel-carbon-based catalyst, from carbonization of metal-organic frameworks, to replace currently best-known platinum-based materials for electrocatalytic hydrogen evolution. This nickel-carbon-based catalyst can be activated to obtain isolated nickel atoms on the graphitic carbon support when applying electrochemical potential, exhibiting highly efficient hydrogen evolution performance with high exchange current density of 1.2 mA cm(-2) and impressive durability. This work may enable new opportunities for designing and tuning properties of electrocatalysts at atomic scale for large-scale water electrolysis. PMID:26861684

  15. Atomically isolated nickel species anchored on graphitized carbon for efficient hydrogen evolution electrocatalysis

    NASA Astrophysics Data System (ADS)

    Fan, Lili; Liu, Peng Fei; Yan, Xuecheng; Gu, Lin; Yang, Zhen Zhong; Yang, Hua Gui; Qiu, Shilun; Yao, Xiangdong

    2016-02-01

    Hydrogen production through electrochemical process is at the heart of key renewable energy technologies including water splitting and hydrogen fuel cells. Despite tremendous efforts, exploring cheap, efficient and durable electrocatalysts for hydrogen evolution still remains as a great challenge. Here we synthesize a nickel-carbon-based catalyst, from carbonization of metal-organic frameworks, to replace currently best-known platinum-based materials for electrocatalytic hydrogen evolution. This nickel-carbon-based catalyst can be activated to obtain isolated nickel atoms on the graphitic carbon support when applying electrochemical potential, exhibiting highly efficient hydrogen evolution performance with high exchange current density of 1.2 mA cm-2 and impressive durability. This work may enable new opportunities for designing and tuning properties of electrocatalysts at atomic scale for large-scale water electrolysis.

  16. Atomically isolated nickel species anchored on graphitized carbon for efficient hydrogen evolution electrocatalysis

    PubMed Central

    Fan, Lili; Liu, Peng Fei; Yan, Xuecheng; Gu, Lin; Yang, Zhen Zhong; Yang, Hua Gui; Qiu, Shilun; Yao, Xiangdong

    2016-01-01

    Hydrogen production through electrochemical process is at the heart of key renewable energy technologies including water splitting and hydrogen fuel cells. Despite tremendous efforts, exploring cheap, efficient and durable electrocatalysts for hydrogen evolution still remains as a great challenge. Here we synthesize a nickel–carbon-based catalyst, from carbonization of metal-organic frameworks, to replace currently best-known platinum-based materials for electrocatalytic hydrogen evolution. This nickel-carbon-based catalyst can be activated to obtain isolated nickel atoms on the graphitic carbon support when applying electrochemical potential, exhibiting highly efficient hydrogen evolution performance with high exchange current density of 1.2 mA cm−2 and impressive durability. This work may enable new opportunities for designing and tuning properties of electrocatalysts at atomic scale for large-scale water electrolysis. PMID:26861684

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

    PubMed

    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

  18. (abstract) Line Mixing Behavior of Hydrogen-Broadened Ammonia Under Jovian Atmospheric Conditions

    NASA Technical Reports Server (NTRS)

    Spilker, Thomas R.

    1994-01-01

    Laboratory spectral data reported last year have been used to investigate the line mixing behavior of hydrogen-broadened ammonia inversion lines. The data show that broadening parameters appearing in the modified Ben-Reuven opacity formalism of Berge and Gulkis (1976) cannot maintain constant values over pressure ranges that include low to moderate pressures and high pressures. Also, they cannot change drastically in value, as in the Spilker (1990) revision of the Berge and Gulkis formalism. It has long been recognized that at low pressures, less than about 1 bar of a Jovian atmospheric mixture, a VVW formalism yields more accurate predictions of ammonia opacity than Ben-Reuven formalisms. At higher pressures the Ben-Reuven formalisms are more accurate. Since the Ben-Reuven lineshape collapses to a VVW lineshape in the low pressure limit, this low pressure inaccuracy of the Ben-Reuven formalisms is surprising. By incorporating various behavior, a new formalism is produced that is more accurate than previous formalisms, particularly in the critical 'transition region' from 0.5 to 2 bars, and that can be used without discontinuity from pressures of zero to hundreds of bars. The new formalism will be useful in such applications as interpretation of radio astronomical and radio occultation data on giant planet atmospheres, and radiative transfer modeling of those atmospheres.

  19. Numerology, hydrogenic levels, and the ordering of excited states in one-electron atoms

    NASA Astrophysics Data System (ADS)

    Armstrong, Lloyd, Jr.

    1982-03-01

    We show that the observed ordering of Rydberg states of one-electron atoms can be understood by assuming that these states are basically hydrogenic in nature. Much of the confusion concerning this point is shown to arise from the failure to differentiate between hydrogenic ordering as the nuclear charge approaches infinity, and hydrogenic ordering for an effective charge of one. The origin of κ ordering of Rydberg levels suggested by Sternheimer is considered within this picture, and the predictions of κ ordering are compared with those obtained by assuming hydrogenic ordering.

  20. Electric dipole polarizabilities at imaginary frequencies for hydrogen, the alkali-metal, alkaline-earth, and noble gas atoms

    SciTech Connect

    Derevianko, Andrei Porsev, Sergey G. Babb, James F.

    2010-05-15

    The electric dipole polarizabilities evaluated at imaginary frequencies for hydrogen, the alkali-metal atoms, the alkaline-earth atoms, and the noble gases are tabulated along with the resulting values of the atomic static polarizabilities, the atom-surface interaction constants, and the dispersion (or van der Waals) constants for the homonuclear and the heteronuclear diatomic combinations of the atoms.

  1. Symmetry in chemistry from the hydrogen atom to proteins

    PubMed Central

    Kellman, Michael E.

    1996-01-01

    The last 2 decades have seen discoveries in highly excited states of atoms and molecules of phenomena that are qualitatively different from the “planetary” model of the atom, and the near-rigid model of molecules, characteristic of these systems in their low-energy states. A unified view is emerging in terms of approximate dynamical symmetry principles. Highly excited states of two-electron atoms display “molecular” behavior of a nonrigid linear structure undergoing collective rotation and vibration. Highly excited states of molecules described in the “standard molecular model” display normal mode couplings, which induce bifurcations on the route to molecular chaos. New approaches such as rigid–nonrigid correlation, vibrons, and quantum groups suggest a unified view of collective electronic motion in atoms and nuclear motion in molecules. PMID:8962040

  2. Positron scattering from hydrogen atom with screened Coulomb potentials

    SciTech Connect

    Ghoshal, Arijit; Nayek, Sujay; Kamali, M. Z. M.; Ratnavelu, K.

    2014-03-05

    Elastic positron-hydrogen collisions with screened Coulomb potentials have been investigated using a second-order distorted wave Born approximation in the momentum space. Two types of potentials have been considered, namely, static screened Coulomb potential and exponential cosine-screened Coulomb potential. Using a simple variationally determined hydrogenic wave function it has been possible to obtain the scattering amplitude in a closed form. A detailed study has been made on the differential and total cross sections in the energy range 20–300 eV.

  3. Kinetics investigation of the hydrogen abstraction reaction between CH3SS and CN radicals.

    PubMed

    Yan, Liu; Wenliang, Wang; Zhongwen, Liu; Hongjiang, Ren

    2016-01-01

    The reaction mechanisms and rates for the H abstraction reactions between CH3SS and CN radicals in the gas phase were investigated with density functional theory (DFT) methods. The geometries, harmonic vibrational frequencies, and energies of all stationary points were obtained at B3PW91/6-311G(d,p) level of theory. Relationships between the reactants, intermediates, transition states and products were confirmed, with the frequency and the intrinsic reaction coordinate (IRC) analysis at the same theoretical level. High accurate energy information was provided by the G3(MP2) method combined with the standard statistical thermodynamics. Gibbs free energies at 298.15 K for all of the reaction steps were reported, and were used to describe the profile diagrams of the potential energy surface. The rate constants were evaluated with both the classical transition state theory and the canonical variational transition state theory, in which the small-curvature tunneling correction was included. A total number of 9 intermediates (IMs) and 17 transition states (TSs) were obtained. It is shown that IM1 is the most stable intermediate by the largest energy release, and the channel of CH3SS + CN → IM3 → TS10  → P1(CH2SS + HCN) is the dominant reaction with the lowest energy barrier of 144.7 kJ mol(-1). The fitted Arrhenius expressions of the calculated CVT/SCT rate constants for the rate-determining step of the favorable channel is k =7.73 × 10(6)  T (1.40)exp(-14,423.8/T) s(-1) in the temperature range of 200-2000 K. The apparent activation energy E a(app.) for the main channel is -102.5 kJ mol(-1), which is comparable with the G3(MP2) energy barrier of -91.8 kJ mol(-1) of TS10 (relative to the reactants). PMID:26781664

  4. Controlling Hydrogen Activation, Spillover, and Desorption with Pd-Au Single-Atom Alloys.

    PubMed

    Lucci, Felicia R; Darby, Matthew T; Mattera, Michael F G; Ivimey, Christopher J; Therrien, Andrew J; Michaelides, Angelos; Stamatakis, Michail; Sykes, E Charles H

    2016-02-01

    Key descriptors in hydrogenation catalysis are the nature of the active sites for H2 activation and the adsorption strength of H atoms to the surface. Using atomically resolved model systems of dilute Pd-Au surface alloys and density functional theory calculations, we determine key aspects of H2 activation, diffusion, and desorption. Pd monomers in a Au(111) surface catalyze the dissociative adsorption of H2 at temperatures as low as 85 K, a process previously expected to require contiguous Pd sites. H atoms preside at the Pd sites and desorb at temperatures significantly lower than those from pure Pd (175 versus 310 K). This facile H2 activation and weak adsorption of H atom intermediates are key requirements for active and selective hydrogenations. We also demonstrate weak adsorption of CO, a common catalyst poison, which is sufficient to force H atoms to spill over from Pd to Au sites, as evidenced by low-temperature H2 desorption. PMID:26747698

  5. Origin of the smaller conductances of Rh, Pb, and Co atomic junctions in hydrogen environment

    SciTech Connect

    Li, Xue; Chen, Mingyan; Ye, Xiang; Xie, Yi-qun; Ke, San-huang

    2015-02-14

    We study theoretically the structural and electronic origins of the smaller conductances (one conductance quantum, G{sub 0}, and smaller) of Rh, Pb, and Co metal atomic junctions (MAJs) in a hydrogen environment, as were measured in recent experiments. For the Rh MAJs, the 1G{sub 0} conductance is attributed to a stable contact bridged by a single hydrogen molecule whose antibonding state provides a single transport channel. For the Pb and Co MAJs the 1G{sub 0} conductance is, however, ascribed to a linear atomic chain adsorbing two dissociated H atoms, which largely reduces the density of states at the Fermi energy with respect to the pure ones. On the other hand, the small conductances of 0.3G{sub 0} (Rh) and 0.2G{sub 0} (Co) are due to H-decorated atomic chains connected to electrodes by a H atom.

  6. Hydrogen-induced atomic rearrangement in MgPd{sub 3}

    SciTech Connect

    Kohlmann, H. . E-mail: h.kohlmann@mx.uni-saarland.de; Renaudin, G.; Yvon, K.; Wannek, C.; Harbrecht, B.

    2005-04-15

    The hydrogenation behavior of MgPd{sub 3} has been studied by in situ X-ray powder diffraction and by neutron powder diffraction. At room temperature and p {approx}500kPa hydrogen pressure its structure is capable of incorporating up to one hydrogen atom per formula unit ({alpha}-MgPd{sub 3}H{sub {approx}}{sub 1}), thereby retaining a tetragonal ZrAl{sub 3}-type metal atom arrangement. Upon heating to 750K in a hydrogen atmosphere of 610kPa it transforms into a cubic modification with AuCu{sub 3}-type metal atom arrangement ({beta}-MgPd{sub 3}H{sub {approx}}{sub 0.7}). Neutron diffraction on the deuteride reveals an anion deficient anti-perovskite-type structure ({beta}-MgPd{sub 3}D{sub 0.67}, a=398.200(7)pm) in which octahedral sites surrounded exclusively by palladium atoms are occupied by deuterium. Complete removal of hydrogen (480K, 1Pa) stabilizes a new binary modification ({beta}-MgPd{sub 3}, a=391.78(2)pm) crystallizing with a primitive cubic AuCu{sub 3}-type structure. Mechanical treatment (grinding) transforms both {alpha} and {beta} modifications of MgPd{sub 3} into a cubic face-centered solid solution Mg{sub 0.25}Pd{sub 0.75} showing a random distribution of magnesium and palladium atoms.

  7. Doppler broadening of atomic-hydrogen lines in DC and capacitively coupled RF plasmas

    NASA Astrophysics Data System (ADS)

    Akhtar, Kamran; Scharer, J. E.; Mills, R. L.

    2007-10-01

    The extraordinary broadening of Balmer lines of hydrogen admixed with Ar or He as opposed to Xe in DC glow and capacitively coupled rf discharges is studied over a wide range of pressure and gas compositions. High-resolution optical emission spectroscopy is performed parallel to (end-on) and perpendicular (side-on) to the electrode axis along with Langmuir probe measurements of plasma density and electron temperature for the RF capacitive discharge case. A broad and symmetric (Gaussian) Balmer emission line corresponding to 20-60 eV hydrogen atom temperatures is observed in Ar/H2 and He/H2 plasmas. Energy is transferred selectively to hydrogen atoms whereas the atoms of admixed He and Ar gases remain cold (<0.5 eV). In the field acceleration model [e.g., Cvetanovic et. al. J. App. Phys., Vol. 97, 033302-1, 2005] there apparently is no preferred species to which energy is coupled and according to the model one should observe enhanced temperatures of hydrogen and helium atoms in He/H2 discharges where the atomic mass is more comparable (4:1). We also briefly examine the experimental results using the Resonance Transfer Model of hydrogen heating [Mills et. al IEEE Trans. Plasma Sci., 31, 338, 2003] as the source of broadening.

  8. Exotic atoms: Muonic atoms into vacuum from solid hydrogen. Technical progress report, February 1, 1994--January 31, 1995

    SciTech Connect

    Kunselman, R.

    1993-12-31

    The experiments use various solid hydrogen layers to form various muonic hydrogen isotopes that escape into vacuum. The method relies on transfer of the muon from protium to either a deuteron or a triton. The resulting muonic deuterium or muonic tritium will not immediately thermalize because of the very low elastic cross sections, and may be emitted from the surface of the layer. Measurements which detect decay electrons, muonic x-rays, and fusion products have been used to study the processes. A target has been constructed which exploits muonic atom emission in order to learn more about the energy dependence of transfer and muon molecular formation.

  9. Kinetic and product distribution analysis of the reaction of atomic hydrogen with vinyl chloride

    SciTech Connect

    Barat, R.B.; Bozzelli, J.W.

    1992-03-19

    An elementary reaction mechanism has been developed to model the experimentally observed loss of vinyl chloride by reaction with atomic hydrogen, as well as the observed products. At the low-pressure, room temperature experimental conditions the consumption of C{sub 2}H{sub 3}Cl by reaction with H occurs primarily by nonipso attack by H on the =CH{sub 2} group to form (CH{sub 3}C{center_dot}HCl){sup {double_dagger}}. This energized complex then undergoes an H shift to form (C{center_dot}H{sub 2}CH{sub 2}Cl){sup {double_dagger}}, which decomposes to form Cl + CH{sub 2}=CH{sub 2}. Collisional stabilization of the original adduct is also important. Abstraction of Cl by H is negligible in these conditions. The authors` mechanism is based on quantum Rice-Ramsperger-Kassel (QRRK) analysis of the reactions of the energized adducts from the separately considered ipso and nonipso additions. The authors also utilized transition-state theory for the isomerization reaction, evaluated with literature rate constants and barriers. The authors extend the QRRK calculations to higher pressures and temperatures for use by the modeling community. A mechanistic pathway is presented to explain the formation of the various reaction products observed. 26 refs., 13 figs., 7 tabs.

  10. Coulomb deexcitation of muonic hydrogen in collisions with atoms of hydrogen isotopes

    SciTech Connect

    Kravtsov, A.V.; Mikhailov, A.I.

    1995-05-01

    The asymptotic theory of nonadiabatic transitions is used to treat Coulomb deexcitation of muonic hydrogen in hydrogen, including the effect of electron shielding of the charge of the target nucleus. The rates are calculated for an isotopically pure target and for a mixture of hydrogen isotopes. For a mixture of isotopes the rates of direct and inverse charge exchange with deexcitation are also calculated. 13 refs., 3 figs., 6 tabs.

  11. A New Time-Dependent Scattering Theory: Application to the Capture of Antiprotons by Hydrogen Atoms and Helium Atoms

    SciTech Connect

    Tong, X. M.; Hino, K.; Toshima, N.

    2008-08-08

    We present a theoretical method for Coulomb three-body rearrangement collisions solving a Chew-Goldberger-type integral equation directly. The scattering boundary condition is automatically satisfied by adiabatically switching on the interaction between the projectile and target. Hence the outgoing wave function is obtained without the tedious procedure of adjusting the total wave function in the asymptotic region. All the dynamical information can be derived from the scattering wave function obtained on pseudo-spectral grids numerically. Using this method, we obtained the state-specified capture cross sections when antiprotons collide with hydrogen atoms or helium atoms. Differing from the capture processes of antiprotons by hydrogen atoms, the anomalous bumpy structures are revealed in the total angular momentum dependent capture cross sections by helium atoms. Further analysis shows that the bumps arise from the partial channel closing due to the removal of the energy degeneracy in the antiprotonic helium atom. The ejected electron energy distributions are also provided for the comparison with future experiments.

  12. Quantum reflection: Focusing of hydrogen atoms with a concave mirror

    SciTech Connect

    Berkhout, J.J.; Luiten, O.J.; Setija, I.D.; Hijmans, T.W.; Mizusaki, T.; Walraven, J.T.M. Van der Waals Laboratorium, Universiteit van Amsterdam, Valckenierstraat 65/67, 1018 XE Amsterdam, The Netherlands )

    1989-10-16

    We use a concave spherical mirror to focus at 18-mm-diam beam of H atoms down to 0.5 mm. The mirror consists of a fused-quartz substrate polished to optical precision and coated with a liquid-{sup 4}He film to obtain high reflectivity. The temperature dependence of the focused beam intensity enables us to study the influence of the dynamic surface roughness on the reflection of the H atoms. Both zero-point fluctuations and thermal excitations turn out to be of importance. A monolayer of {sup 3}He does not significantly affect the results.

  13. Hydrogenation-induced atomic stripes on the 2 H -MoS2 surface

    NASA Astrophysics Data System (ADS)

    Han, Sang Wook; Yun, Won Seok; Lee, J. D.; Hwang, Y. H.; Baik, J.; Shin, H. J.; Lee, Wang G.; Park, Young S.; Kim, Kwang S.

    2015-12-01

    We report that the hydrogenation of a single crystal 2 H -MoS2 induces a novel-intermediate phase between 2H and 1T phases on its surface, i.e., the large-area, uniform, robust, and surface array of atomic stripes through the intralayer atomic-plane gliding. The total energy calculations confirm that the hydrogenation-induced atomic stripes are energetically most stable on the MoS2 surface between the semiconducting 2H and metallic 1T phase. Furthermore, the electronic states associated with the hydrogen ions, which is bonded to sulfur anions on both sides of the MoS2 surface layer, appear in the vicinity of the Fermi level (EF) and reduces the band gap. This is promising in developing the monolayer-based field-effect transistor or vanishing the Schottky barrier for practical applications.

  14. Perturbed wavefunctions of the excited states of hydrogen atom in Stark effect

    SciTech Connect

    Sapra, G.K.; Bhasin, V.S.; Kothari, L.S. . Dept. of Physics Astrophysics)

    1994-03-15

    The authors extend the procedure originally suggested by Dalgarno and Lewis in studying the second-order Stark effect for the ground-state hydrogen atom to the excited states. They solve the perturbation equations for the excited states of hydrogen atom placed in an external electric field to obtain expressions for the perturbed wavefunctions. Here the emphasis is on studying in detail the nature of the perturbed wavefunction rather than energy shifts as investigated in most of the attempts made so far. The effect of the electric field on these wavefunctions is analyzed and the values of the electric polarizability of the hydrogen atom in the excited states obtained in this way are compared with the earlier work.

  15. A massive cloud of cold atomic hydrogen in the outer Galaxy.

    PubMed

    Knee, L B; Brunt, C M

    2001-07-19

    A large fraction of the mass of the interstellar medium in our Galaxy is in the form of warm (103-104 K) and cool (50-100 K) atomic hydrogen (H i) gas. Cold (10-30 K) regions are thought to be dominated by dense clouds of molecular hydrogen. Cold H i is difficult to observe, and therefore our knowledge of its abundance and distribution in the interstellar medium is poor. The few known clouds of cold H i are much smaller in size and mass than typical molecular clouds. Here we report the discovery that the H i supershell GSH139-03-69 is very cold (10 K). It is about 2 kiloparsecs in size and as massive as the largest molecular complexes. The existence of such an immense structure composed of cold atomic hydrogen in the interstellar medium runs counter to the prevailing view that cold gas resides almost exclusively in clouds dominated by molecular hydrogen. PMID:11460155

  16. Performance evaluation of the SAO VLG-11 atomic hydrogen masers

    NASA Technical Reports Server (NTRS)

    Levine, M. W.; Vessot, R. F.; Mattison, E. M.

    1978-01-01

    A new generation of frequency standards, the VLG-11 hydrogen maser, has been designed and built at the Smithsonian Astrophysical Observatory (SAO). A comprehensive series of environmental and short-term stability tests on three VLG-11 masers has been completed and evaluated. The test results reported here show substantial improvements over previous hydrogen masers in measured sensitivity to variations in ambient temperature, barometric pressure, and magnetic fields. The maser frequency stability, as represented by the two-sample (Allan) variance, has been measured for averaging times ranging from 1 to 100,00 seconds. The variance is lower than 1 x 10 to the -15th for averaging intervals between 1400 and 20,000 seconds. For times shorter than 4000 seconds, the measured stability data agree remarkably well with theoretical values calculated from thermal noise mechanisms and the 'noise within the linewidth' regime is clearly discernable in the data.

  17. LOX/Hydrogen Coaxial Injector Atomization Test Program

    NASA Technical Reports Server (NTRS)

    Zaller, M.

    1990-01-01

    Quantitative information about the atomization of injector sprays is needed to improve the accuracy of computational models that predict the performance and stability margin of liquid propellant rocket engines. To obtain this data, a facility for the study of spray atomization is being established at NASA-Lewis to determine the drop size and velocity distributions occurring in vaporizing liquid sprays at supercritical pressures. Hardware configuration and test conditions are selected to make the cold flow simulant testing correspond as closely as possible to conditions in liquid oxygen (LOX)/gaseous H2 rocket engines. Drop size correlations from the literature, developed for liquid/gas coaxial injector geometries, are used to make drop size predictions for LOX/H2 coaxial injectors. The mean drop size predictions for a single element coaxial injector range from 0.1 to 2000 microns, emphasizing the need for additional studies of the atomization process in LOX/H2 engines. Selection of cold flow simulants, measured techniques, and hardware for LOX/H2 atomization simulations are discussed.

  18. LOX/hydrogen coaxial injector atomization test program

    NASA Technical Reports Server (NTRS)

    Zaller, M.

    1990-01-01

    Quantitative information about the atomization of injector sprays is needed to improve the accuracy of computational models that predict the performance and stability margin of liquid propellant rocket engines. To obtain this data, a facility for the study of spray atomization is being established at NASA-Lewis to determine the drop size and velocity distributions occurring in vaporizing liquid sprays at supercritical pressures. Hardware configuration and test conditions are selected to make the cold flow simulant testing correspond as closely as possible to conditions in liquid oxygen (LOX)/gaseous H2 rocket engines. Drop size correlations from the literature, developed for liquid/gas coaxial injector geometries, are used to make drop size predictions for LOX/H2 coaxial injectors. The mean drop size predictions for a single element coaxial injector range from 0.1 to 2000 microns, emphasizing the need for additional studies of the atomization process in LOX/H2 engines. Selection of cold flow simulants, measurement techniques, and hardware for LOX/H2 atomization simulations are discussed.

  19. Hydrogen Embrittlement of Metals: Atomic hydrogen from a variety of sources reduces the ductility of many metals.

    PubMed

    Rogers, H C

    1968-03-01

    Hydrogen interacts with many metals to reduce their ductility (2) and frequently their strength also. It enters metals in the atomic form, diffusing very rapidly even at normal temperatures. During melting and fabrication, as well as during use, there are various ways in which metals come in contact with hydrogen and absorb it. The absorbed hydrogen may react irreversibly with oxides or carbides in some metals to produce a permanently degraded structure. It may also recombine at internal surfaces of defects of various types to form gaseous molecular hydrogen under pressures sufficiently high to form metal blisters when the recombination occurs near the outer surface. In other metals, brittle hydrides that lower the mechanical properties of the metal are formed. Another type of embrittlement is reversible, depending on the presence of hydrogen in the metal lattice during deformation for its occurrence. Under some conditions the failure may be delayed for long periods. A number of different mechanisms have been postulated to explain reversible embrittlement. According to some theories hydrogen interferes with the processes of plastic deformation in metals, while according to others it enhances the tendency for cracking. PMID:17775040

  20. Transport-theoretic model for the electron-proton-hydrogen atom aurora. I. Theory

    SciTech Connect

    Basu, B.; Jasperse, J.R; Strickland, D.J.

    1993-12-01

    The first self-consistent transport-theoretic model for the combined electron-proton-hydrogen atom aurora is presented. This is needed for accurate modeling of the diffuse aurora, particularly in the midnight sector, for which a statistical study indicates that the proton contribution to the total auroral energy flux is (on the average) about 20 to 25% of that of the electrons. As a result, the ionization yield as well as the yields of many emission features will be underestimated (on the average) by about the same percentage if the proton-hydrogen atom contributions are neglected. The model presented here can also be used to study a pure electron aurora or a pure proton-hydrogen atom aurora by choosing the appropriate boundary conditions, namely, by setting the incident flux of one or the other particle population equal to zero. In the latter case, the new feature of the present model is the rigorous transport-theoretic treatment of the contributions to ionization rates and to emission rates and yields from the secondary electrons produced by protons and hydrogen atoms. A coupled set of three linear transport equations is presented. Protons and hydrogen atoms are coupled only to each other through charge-changing (charge exchange and stripping) collisions, while the electrons are coupled to both protons and hydrogen atoms through the secondary electrons that they produce. Source functions for the secondary electrons produced by the three primary particle populations are compared and contrasted, and the numerical methods for solving the coupled transport equations are described. Finally, formulas for calculating pertinent aurora-related quantities from the particle fluxes are given. 66 refs., 9 figs., 2 tabs.

  1. Two-photon ionization of atomic hydrogen with elliptically polarized light

    NASA Technical Reports Server (NTRS)

    Kassaee, A.; Rustgi, M. L.; Long, S. A. T.

    1988-01-01

    The theory of two-photon ionization of a hydrogenic state in the nonrelativistic dipole approximation is generalized for elliptically polarized light. An application to the metastable 2S state of atomic hydrogen is made. Significant differences in the angular distribution of the outgoing electrons are found depending upon the polarization of the photons. It is claimed that two-photon ionization employing elliptically polarized photons from lasers may provide an additional test for the theories of multiphoton ionization.

  2. Hydrogen atom migration in the oxidation of aldehydes - O(3P) + H2CO

    NASA Technical Reports Server (NTRS)

    Dupuis, M.; Lester, W. A., Jr.

    1984-01-01

    An ab initio study of hydrogen atom migration in methylenebis(oxy)H2CO2(3B2) to form triplet formic acid HCOOH (3A1) is reported. From HF, MCHF, and CI calculated energy barriers, the activation energy is estimated to be no less than 30 kcal/mol. It is concluded that the hydrogen migration channel is not accessible in recent room temperature experiments on the O(3P) + H2CO reaction.

  3. α-Hydrogen Abstraction by •OH and •SH Radicals from Amino Acids and Their Peptide Derivatives.

    PubMed

    Chan, Bun; Karton, Amir; Easton, Christopher J; Radom, Leo

    2016-04-12

    We have used computational quantum chemistry to investigate the thermochemistry of α-hydrogen abstraction from the full set of amino acids normally found in proteins, as well as their peptide forms, by •OH and •SH radicals. These reactions, with their reasonable complexity in the electronic structure (at the α-carbon), are chosen as a consistent set of models for conducting a fairly robust assessment of theoretical procedures. Our benchmarking investigation shows that, in general, the performance for the various classes of theoretical methods improves in the order nonhybrid DFT → hybrid DFT → double-hybrid DFT → composite procedures. More specifically, we find that the DSD-PBE-P86 double-hybrid DFT procedure yields the best agreement with our high-level W1X-2 vibrationless barriers and reaction energies for this particular set of systems. A significant observation is that, when one considers relative instead of absolute values for the vibrationless barriers and reaction energies, even nonhybrid DFT procedures perform fairly well. To exploit this feature in a cost-effective manner, we have examined a number of multilayer schemes for the calculation of reaction energies and barriers for the abstraction reactions. We find that accurate values can be obtained when a "core" of glycine plus the abstracting radical is treated by DSD-PBE-P86, and the substituent effects are evaluated with M06-2X. Inspection of the set of calculated thermochemical data shows that the correlation between the free energy barriers and reaction free energies is strongest when the reactions are either endergonic or nearly thermoneutral. PMID:26950040

  4. A time-of-flight spectrometer for detection of low-energy hydrogen atoms

    NASA Astrophysics Data System (ADS)

    van Toledo, W.; de Bree, A. R.; van Buuren, R.; de Kluiver, H.; Donné, A. J. H.

    1990-01-01

    This article deals with an application of the technique of converting hydrogen atoms into negative ions on a low-work-function surface, which is similar to the method nowadays utilized in H- surface sources. This conversion technique is the basis for a time-of-flight spectrometer, for which a proof of principle has recently been established. The conversion takes place on a tungsten (110) crystal target that is covered with cesium. By mounting this target in the detector part of the spectrometer, this apparatus is made sensitive to hydrogen atoms that have energy in the range 10-1000 eV. This feature makes the spectrometer a very powerful and unique tool for detection of low-energy hydrogen atoms. It is, for instance, capable of detecting low-energy hydrogen atoms that are emitted from the edge of a tokamak plasma, and therefore it can yield information on the hydrogen recycling inside the tokamak and hence on the energy balance of the plasma. In the paper we discuss the principle of the detection method, along with a presentation of some time-of-flight spectra that have been obtained from a tokamak plasma.

  5. Enhanced stability of hydrogen atoms at the graphene/graphane interface of nanoribbons

    NASA Astrophysics Data System (ADS)

    Ao, Z. M.; Hernández-Nieves, A. D.; Peeters, F. M.; Li, S.

    2010-12-01

    The thermal stability of graphene/graphane nanoribbons (GGNRs) is investigated using density functional theory. It is found that the energy barriers for the diffusion of hydrogen atoms on the zigzag and armchair interfaces of GGNRs are 2.86 and 3.17 eV, respectively, while the diffusion barrier of an isolated H atom on pristine graphene was only ˜0.3 eV. These results unambiguously demonstrate that the thermal stability of GGNRs can be enhanced significantly by increasing the hydrogen diffusion barriers through graphene/graphane interface engineering. This may provide new insights for viable applications of GGNRs.

  6. Photoelectron momentum distributions of the hydrogen atom driven by multicycle elliptically polarized laser pulses

    NASA Astrophysics Data System (ADS)

    Murakami, Mitsuko; Chu, Shih-I.

    2016-02-01

    Photoelectron momentum distributions (PMDs) of the hydrogen atom driven by multicycle elliptically polarized strong laser fields are studied in detail, based on the numerical solution of the time-dependent Schrödinger equation and the Volkov wave propagation. Both short and long driving pulses of the 800-nm field are considered, as well as the ellipticity dependence, to describe the mechanism of symmetry breaking in the hydrogen-atom PMD. Moreover, we demonstrate that the value of a retardation angle in the longitudinal PMD can depend on the order of above-threshold ionization spectra.

  7. Solvation and kinetic isotope effects in H and D abstraction reactions from formate ions by D, H, and Mu atoms in aqueous solutions.

    SciTech Connect

    Lossack, A. M.; Roduner, E.; Bartels, D. M.; Chemistry; Univ. of Stuttgart

    2001-01-01

    Electron paramagnetic resonance free induction decay attenuation and muon spin rotation measurements were performed in the temperature range of liquid water for the reactions of the hydrogen isotopes D, H, and Mu with undeuterated and deuterated formate ions. Accurate rate constants were determined, and excellent Arrhenius behavior represented bywas found in all cases. Ab initio calculations at the MP2 and the QCISD level with the aug-cc-pvDZ basis set reveal that the reaction has no electronic barrier in the gas phase. This contrasts with quite sizeable activation energies observed in aqueous solution, and it suggests that the barrier is entirely solvent induced. Calculations at the above mentioned ab initio level using a polarized dielectric continuum for the solvated reaction system restore a realistic barrier and confirm this interpretation. It is shown that the solvent effect is a consequence of a pronounced change of polarization of the system along the reaction path. It may be more appropriate to describe the reaction as a consecutive electron-proton transfer rather than an H atom abstraction.

  8. Adsorption and recombination of hydrogen atoms on a model graphite surface. [in interstellar space

    NASA Technical Reports Server (NTRS)

    Aronowitz, S.; Chang, S.

    1985-01-01

    The adsorption and recombination of atomic hydrogen on a model graphite grain have been examined in a series of calculations in which a modified, iterative, extended Hueckel program was used. The hydrogen atom is found to be chemisorbed at a site with a zero-point binding energy of 0.7 eV and at an equilibrium distance of 2.25 A above the site. Despite a barrier of about 0.4 eV between adjacent sites, calculations suggest that at temperatures as low as 10 K, an H atom will tunnel through to adjacent sites in less than one nanosecond. However, a potential barrier to the recombination of two hydrogen atoms has been found which displays high sensitivity to the mutual arrangement of the two hydrogen atoms with respect to the graphite surface. Results show that at very low temperatures, recombinations can occur only by tunneling. Consistent with experiment, the region in which H2 begins to form exhibits a repulsive potential with respect to possible chemisorption of the incipient H2 entity.

  9. Hydrogen atom recombination on tungsten at high temperature: Experiment and Molecular Dynamics Simulation

    NASA Astrophysics Data System (ADS)

    Rutigliano, M.; Santoro, D.; Balat-Pichelin, M.

    2014-10-01

    Atom recombination at wall is a phenomenon involved in many plasma experiments and also in present tokamaks and future fusion plasma reactors like ITER. This exothermic surface reaction is catalyzed by the material and depends on its composition and temperature. In the MESOX experimental set-up, several methods were developed for the measurement of the recombination parameters. In this paper, a method developed for the experimental evaluation of the recombination coefficient of atomic hydrogen γH on tungsten at high temperature is presented using two series of atomic lines (Hα and He or Hβ and H2) and the results obtained for surface temperature up to 1350 K are given. A Molecular Dynamics Simulation has been done for the recombination of hydrogen atoms on tungsten in conditions close to the experimental ones using a semi-classical collisional method. Modeling results are compared to the experimental data for two surface temperature values and a fairly good agreement was obtained.

  10. Planar hydrogen-like atom in inhomogeneous magnetic fields: Exactly or quasi-exactly solvable models

    NASA Astrophysics Data System (ADS)

    Liu, Liyan; Hao, Qinghai

    2015-05-01

    We use a simple mathematical method to solve the problem of a two-dimensional hydrogen-like atom in the inhomogeneous magnetic fields B = ( k/ r)z and B = ( k/ r 3)z. We construct a Hamiltonian that takes the same form as the Hamiltonian of a hydrogen-like atom in the homogeneous magnetic fields and obtain the energy spectrum by comparing the Hamiltonians. The results show that the whole spectrum of the atom in the magnetic field B = ( k/ r)z can be obtained, and the problem is exactly solvable in this case. We find analytic solutions of the Schrödinger equation for the atom in the magnetic field B = ( k/ r 3)z for particular values of the magnetic strength k and thus present a quasi-exactly solvable model.

  11. Possibility of nonexistence of hot and superhot hydrogen atoms in electrical discharges

    SciTech Connect

    Loureiro, J.; Amorim, J.

    2010-09-15

    Recently, the existence of extremely energetic hydrogen atoms in electrical discharges has been proposed in the literature with large controversy, from the analysis of the anomalous broadening of hydrogen Balmer lines. In this paper, the velocity distribution of H atoms and the profiles of the emitting atom lines created by the exothermic reaction H{sub 2}{sup +}+H{sub 2}{yields}H{sub 3}{sup +}+H+{Delta}E are calculated, as a function of the internal energy defect {Delta}E. The shapes found for the non-Maxwell-Boltzmann distributions resulting in non-Gaussian line profiles raise serious arguments against the existence of hot and superhot H atoms as it has been proposed, at least with those temperatures.

  12. Role of hydrogen in the chemical vapor deposition growth of MoS2 atomic layers

    NASA Astrophysics Data System (ADS)

    Li, Xiao; Li, Xinming; Zang, Xiaobei; Zhu, Miao; He, Yijia; Wang, Kunlin; Xie, Dan; Zhu, Hongwei

    2015-04-01

    Hydrogen plays a crucial role in the chemical vapor deposition (CVD) growth of graphene. Here, we have revealed the roles of hydrogen in the two-step CVD growth of MoS2. Our study demonstrates that hydrogen acts as the following: (i) an inhibitor of the thermal-induced etching effect in the continuous film growth process; and (ii) a promoter of the desulfurization reaction by decreasing the S/Mo atomic ratio and the oxidation reaction of the obtained MoSx (0 < x < 2) films. A high hydrogen content of more than 100% in argon forms nano-sized circle-like defects and damages the continuity and uniformity of the film. Continuous MoS2 films with a high crystallinity and a nearly perfect S/Mo atomic ratio were finally obtained after sulfurization annealing with a hydrogen content in the range of 20%-80%. This insightful understanding reveals the crucial roles of hydrogen in the CVD growth of MoS2 and paves the way for the controllable synthesis of two-dimensional materials.Hydrogen plays a crucial role in the chemical vapor deposition (CVD) growth of graphene. Here, we have revealed the roles of hydrogen in the two-step CVD growth of MoS2. Our study demonstrates that hydrogen acts as the following: (i) an inhibitor of the thermal-induced etching effect in the continuous film growth process; and (ii) a promoter of the desulfurization reaction by decreasing the S/Mo atomic ratio and the oxidation reaction of the obtained MoSx (0 < x < 2) films. A high hydrogen content of more than 100% in argon forms nano-sized circle-like defects and damages the continuity and uniformity of the film. Continuous MoS2 films with a high crystallinity and a nearly perfect S/Mo atomic ratio were finally obtained after sulfurization annealing with a hydrogen content in the range of 20%-80%. This insightful understanding reveals the crucial roles of hydrogen in the CVD growth of MoS2 and paves the way for the controllable synthesis of two-dimensional materials. Electronic supplementary

  13. Minima in generalized oscillator strengths for initially excited hydrogen-like atoms

    NASA Technical Reports Server (NTRS)

    Matsuzawa, M.; Omidvar, K.; Inokuti, M.

    1976-01-01

    Generalized oscillator strengths for transitions from an initially excited state of a hydrogenic atom to final states (either discrete or continuum) have complicated structures, including minima and shoulders, as functions of the momentum transfer. Extensive calculations carried out in the present work have revealed certain systematics of these structures. Some implications of the minima to the energy dependence of the inner-shell ionization cross section of heavy atoms by proton impact are discussed.

  14. Nucleon polarizabilities: From Compton scattering to hydrogen atom

    NASA Astrophysics Data System (ADS)

    Hagelstein, Franziska; Miskimen, Rory; Pascalutsa, Vladimir

    2016-05-01

    We review the current state of knowledge of the nucleon polarizabilities and of their role in nucleon Compton scattering and in hydrogen spectrum. We discuss the basic concepts, the recent lattice QCD calculations and advances in chiral effective-field theory. On the experimental side, we review the ongoing programs aimed to measure the nucleon (scalar and spin) polarizabilities via the Compton scattering processes, with real and virtual photons. A great part of the review is devoted to the general constraints based on unitarity, causality, discrete and continuous symmetries, which result in model-independent relations involving nucleon polarizabilities. We (re-)derive a variety of such relations and discuss their empirical value. The proton polarizability effects are presently the major sources of uncertainty in the assessment of the muonic hydrogen Lamb shift and hyperfine structure. Recent calculations of these effects are reviewed here in the context of the "proton-radius puzzle". We conclude with summary plots of the recent results and prospects for the near-future work.

  15. Path integral calculation of thermal rate constants within the quantum instanton approximation: Application to the H+CH4-->H2+CH3 hydrogen abstraction reaction in full Cartesian space

    NASA Astrophysics Data System (ADS)

    Zhao, Yi; Yamamoto, Takeshi; Miller, William H.

    2004-02-01

    The quantum instanton approximation for thermal rate constants of chemical reactions [Miller, Zhao, Ceotto, and Yang, J. Chem. Phys. 119, 1329 (2003)], which is modeled after the earlier semiclassical instanton approach, is applied to the hydrogen abstraction reaction from methane by a hydrogen atom, H+CH4→H2+CH3, using a modified and recalibrated version of the Jordan-Gilbert potential surface. The quantum instanton rate is evaluated using path integral Monte Carlo approaches based on the recently proposed implementation schemes [Yamamoto and Miller, J. Chem. Phys. 120, 3086 (2004)]. The calculations were carried out using the Cartesian coordinates of all the atoms (thus involving 18 degrees of freedom), thereby taking explicit account of rotational effects of the whole system and also allowing the equivalent treatment of the four methane hydrogens. To achieve such a treatment, we present extended forms of the path integral estimators for relevant quantities that may be used for general N-atom systems with any generalized reaction coordinates. The quantum instanton rates thus obtained for the temperature range T=200-2000 K show good agreement with available experimental data, which gives support to the accuracy of the underlying potential surface used.

  16. Path integral calculation of thermal rate constants within the quantum instanton approximation: application to the H + CH4 --> H2 + CH3 hydrogen abstraction reaction in full Cartesian space.

    PubMed

    Zhao, Yi; Yamamoto, Takeshi; Miller, William H

    2004-02-15

    The quantum instanton approximation for thermal rate constants of chemical reactions [Miller, Zhao, Ceotto, and Yang, J. Chem. Phys. 119, 1329 (2003)], which is modeled after the earlier semiclassical instanton approach, is applied to the hydrogen abstraction reaction from methane by a hydrogen atom, H + CH4 --> H2 + CH3, using a modified and recalibrated version of the Jordan-Gilbert potential surface. The quantum instanton rate is evaluated using path integral Monte Carlo approaches based on the recently proposed implementation schemes [Yamamoto and Miller, J. Chem. Phys. 120, 3086 (2004)]. The calculations were carried out using the Cartesian coordinates of all the atoms (thus involving 18 degrees of freedom), thereby taking explicit account of rotational effects of the whole system and also allowing the equivalent treatment of the four methane hydrogens. To achieve such a treatment, we present extended forms of the path integral estimators for relevant quantities that may be used for general N-atom systems with any generalized reaction coordinates. The quantum instanton rates thus obtained for the temperature range T = 200-2000 K show good agreement with available experimental data, which gives support to the accuracy of the underlying potential surface used. PMID:15268462

  17. Applications of photoinduced electron transfer and hydrogen abstraction reactions to chemical and electrochemical conversion processes. Progress report, September 1, 1982-August 1, 1985

    SciTech Connect

    Whitten, D.G.

    1985-01-01

    The studies carried out have focused on photoinduced electron transfer and hydrogen atom abstraction processes. The main thrust over the past three years has been on a study of light induced electron transfer reactions and in particular on fates of the energy rich radical ions formed in electron transfer quenching of excited states. In particular we have studied these reactions under conditions - light absorbing substrates, quenchers, media - where net chemical conversion is favored over the usual back electron transfer to return to starting materials. The first part of the progress report focuses on our efforts to control reactivity by the use of specific substrates or quenchers which favor net chemical conversion. The second part describes our studies using reaction media - in this case amylose which preferentially complexes hydrophobic molecules in aqueous solution - to alter the rates of primary and secondary photophysical events associated with light induced electron transfer and other photoreactions. Our most extensive investigations of electron transfer reactions have involved the photoreduction of indigo dyes by electron donors. We have found that three representative indigo dyes, thioindigo, N,N'-diacetylindigo and oxalylindigo, all undergo photobleaching reactions with a variety of potential reductance ranging from alcohols to amines, such as triethylamine and N-benzyl-1, 4-dihydronicotinamide. 25 refs.

  18. Zirconium-nickel crystals—hydrogen accumulators: Dissolution and penetration of hydrogen atoms in alloys

    NASA Astrophysics Data System (ADS)

    Matysina, Z. A.; Zaginaichenko, S. Yu.; Shchur, D. V.; Gabdullin, M. T.; Kamenetskaya, E. A.

    2016-07-01

    The calculation of the free energy, thermodynamic equilibrium equations, and kinetic equations of the intermetallic compound Zr2NiH x has been carried out based on molecular-kinetic concepts. The equilibrium hydrogen concentration depending on the temperature, pressure, and energy parameters has been calculated. The absorption-desorption of hydrogen has been studied, and the possibility of the realization of the hysteresis effect has been revealed. The kinetics of the dissolution and permeability of hydrogen is considered, the time dependence of these values has been found, and conditions for the extremum character of their time dependence have been determined. Relaxation times of the dissolution and permeability of hydrogen into the alloy have been calculated. The calculation results are compared with the experimental data available in the literature.

  19. Hydrogen transport diagnostics by atomic and molecular emission line profiles simultaneously measured for large helical device

    SciTech Connect

    Fujii, K.; Shikama, T.; Hasuo, M.; Goto, M.; Morita, S.

    2013-01-15

    We observe the Balmer-{alpha}, -{beta}, and -{gamma} lines of hydrogen atoms and Q branches of the Fulcher-{alpha} band of hydrogen molecules simultaneously with their polarization resolved for large helical device. From the fit including the line splits and the polarization dependences by the Zeeman effect, the emission locations, intensities, and the temperatures of the atoms and molecules are determined. The emission locations of the hydrogen atoms are determined outside but close to the last closed flux surface (LCFS). The results are consistent with a previous work (Phys. Plasmas 12, 042501 (2005)). On the other hand, the emission locations of the molecules are determined to be in the divertor legs, which is farer from those of the atoms. The kinetic energy of the atoms is 1 {approx} 20 eV, while the rotational temperature of molecules is {approx}0.04 eV. Additionally, substantial wings, which originate from high velocity atoms and are not reproduced by the conventional spectral analysis, are observed in the Balmer line profiles. We develop a one-dimensional model to simulate the transport of the atoms and molecules. The model reproduces the differences of the emission locations of the atoms and molecules when their initial temperatures are assumed to be 3 eV and 0.04 eV, respectively. From the model, the wings of the Balmer-{alpha} line is attributed to the high velocity atoms exist deep inside the LCFS, which are generated by the charge exchange collisions with hot protons there.

  20. Dry soldering with hot filament produced atomic hydrogen

    DOEpatents

    Panitz, Janda K. G.; Jellison, James L.; Staley, David J.

    1995-01-01

    A system for chemically transforming metal surface oxides to metal that is especially, but not exclusively, suitable for preparing metal surfaces for dry soldering and solder reflow processes. The system employs one or more hot, refractory metal filaments, grids or surfaces to thermally dissociate molecular species in a low pressure of working gas such as a hydrogen-containing gas to produce reactive species in a reactive plasma that can chemically reduce metal oxides and form volatile compounds that are removed in the working gas flow. Dry soldering and solder reflow processes are especially applicable to the manufacture of printed circuit boards, semiconductor chip lead attachment and packaging multichip modules. The system can be retrofitted onto existing metal treatment ovens, furnaces, welding systems and wave soldering system designs.

  1. Dry soldering with hot filament produced atomic hydrogen

    DOEpatents

    Panitz, J.K.G.; Jellison, J.L.; Staley, D.J.

    1995-04-25

    A system is disclosed for chemically transforming metal surface oxides to metal that is especially, but not exclusively, suitable for preparing metal surfaces for dry soldering and solder reflow processes. The system employs one or more hot, refractory metal filaments, grids or surfaces to thermally dissociate molecular species in a low pressure of working gas such as a hydrogen-containing gas to produce reactive species in a reactive plasma that can chemically reduce metal oxides and form volatile compounds that are removed in the working gas flow. Dry soldering and solder reflow processes are especially applicable to the manufacture of printed circuit boards, semiconductor chip lead attachment and packaging multichip modules. The system can be retrofitted onto existing metal treatment ovens, furnaces, welding systems and wave soldering system designs. 1 fig.

  2. STEM Imaging of Single Pd Atoms in Activated Carbon Fibers Considered for Hydrogen Storage

    SciTech Connect

    Van Benthem, Klaus; Bonifacio, Cecile S; Contescu, Cristian I; Pennycook, Stephen J; Gallego, Nidia C

    2011-01-01

    Aberration corrected scanning transmission electron microscopy was used to demonstrate the feasibility of imaging individual Pd atoms that are highly dispersed throughout the volume of activated carbon fibers. Simultaneous acquisition of high-angle annular dark-field and bright-field images allows correlation of the location of single Pd atoms with microstructural features of the carbon host material. Sub-Angstrom imaging conditions revealed that 18 wt% of the total Pd content is dispersed as single Pd atoms in three re-occurring local structural arrangements. The identified structural configurations may represent effective storage sites for molecular hydrogen through Kubas complex formation as discussed in detail in the preceding article.

  3. Low-energy measurements of electron capture by multicharged ions from excited hydrogen atoms

    SciTech Connect

    Havener, C.C. ); Haque, M.A. ); Smith, A.C.H. ); Urbain, X. ); Zeijlmans van Emmichoven, P.A. Joint Institute for Heavy Ion Research, Holifield Heavy Ion Research Facility, Oak Ridge, Tennessee 37831-6374 )

    1993-06-05

    For very low collision energies electron capture from excited hydrogen by multicharged ions is characterized by enormous cross sections, the predicted maximum being comparable to the geometric size of the Rydberg atom. The ion-atom merged-beams technique is being used to study these collisions for the variety of charge states and the wide range of energies (0.1 to 1000 eV/amu) accessible to the apparatus. A neutral D beam containing a Rydberg atom population proportional to 1/n[sup 3] is produced by collisional electron detachment of 8 keV D[sup [minus

  4. Low-energy measurements of electron capture by multicharged ions from excited hydrogen atoms

    SciTech Connect

    Havener, C.C. ); Haque, M.A. ); Smith, A.C.H. ); Urbain, X. ); Zeijlmans van Emmichoven, P.A. Joint Inst. for Heavy Ion Research, Oak Ridge, TN (United Sta

    1992-01-01

    For very low collision energies electron capture from excited hydrogen by multicharged ions is characterized by enormous cross sections, the predicted maximum being comparable to the geometric size of the Rydberg atom. The ion-atom merged-beams technique is being used to study these collisions for the variety of charge states and the wide range of energies (0.1 to 1000 eV/amu) accessible to the apparatus. A neutral D beam containing a Rydberg atom population proportional to 1/n[sup 3] is produced by collisional electron detachment of 8 key D[sup [minus

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

    NASA Astrophysics Data System (ADS)

    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.

  6. Laboratory Measurements of Charge Transfer on Atomic Hydrogen at Thermal Energies

    NASA Technical Reports Server (NTRS)

    Havener, C. C.; Vane, C. R.; Krause, H. F.; Stancil, P. C.; Mroczkowski, T.; Savin, D. W.

    2002-01-01

    We describe our ongoing program to measure velocity dependent charge transfer (CT) cross sections for selected ions on atomic hydrogen using the ion-aloin merged-beams apparatus at Oak Ridge Natioiial Laboralory. Our focus is on those ions for which CT plays an important role in determining the ionization structure, line emis sion, and thermal structure of observed cosmic photoionized plasmas.

  7. Compensation of logarithmic corrections in calculating the fine structure of levels in hydrogen-like atoms

    SciTech Connect

    Boikova, N. A. Tyukhtyaev, Yu. N.; Faustov, R. N.

    2011-01-15

    Special features of the quasipotential approach to calculating logarithmic (in the fine-structure constant) contributions to the fine splitting of energy levels in hydrogen-like atoms are analyzed. The boundaries of the region of applicability of the Fell technique are indicated, and the order of corrections beyond this region is estimated.

  8. Irregular wave functions of a hydrogen atom in a uniform magnetic field

    NASA Technical Reports Server (NTRS)

    Wintgen, D.; Hoenig, A.

    1989-01-01

    The highly excited irregular wave functions of a hydrogen atom in a uniform magnetic field are investigated analytically, with wave function scarring by periodic orbits considered quantitatively. The results obtained confirm that the contributions of closed classical orbits to the spatial wave functions vanish in the semiclassical limit. Their disappearance, however, is slow. This discussion is illustrated by numerical examples.

  9. Determination of the Relative Atomic Masses of Metals by Liberation of Molecular Hydrogen

    ERIC Educational Resources Information Center

    Waghorne, W. Earle; Rous, Andrew J.

    2009-01-01

    Students determine the relative atomic masses of calcium, magnesium, and aluminum by reaction with hydrochloric acid and measurement of the volume of hydrogen gas liberated. The experiment demonstrates stoichiometry and illustrates clearly that mass of the reagent is not the determinant of the amounts in chemical reactions. The experiment is…

  10. Effects of laser radiation field on energies of hydrogen atom in plasmas

    NASA Astrophysics Data System (ADS)

    Bahar, M. K.

    2015-09-01

    In this study, for the first time, the Schrödinger equation with more general exponential cosine screened Coulomb (MGECSC) potential is solved numerically in the presence of laser radiation field within the Ehlotzky approximation using the asymptotic iteration method. The MGECSC potential includes four different potential forms in consideration of different sets of the parameters in the potential. By applying laser field, the total interaction potential of hydrogen atom embedded in plasmas converts to double well-type potential. The plasma screening effects under the influence of laser field as well as confinement effects of laser field on hydrogen atom in Debye and quantum plasmas are investigated by solving the Schrödinger equation with the laser-dressed MGECSC potential. It is resulted that since applying a monochromatic laser field on hydrogen atom embedded in a Debye and quantum plasma causes to shift in the profile of the total interaction potential, the confinement effects of laser field on hydrogen atom in plasmas modeled by the MGECSC potential change localizations of energy states.

  11. The nature of the hydrogen bond: A synthesis from the interacting quantum atoms picture

    NASA Astrophysics Data System (ADS)

    Martín Pendás, A.; Blanco, M. A.; Francisco, E.

    2006-11-01

    The interacting quantum atoms approach [IQA, as presented by Blanco et al., J. Chem. Theory Comput. 1, 1096 (2005)] is applied to standard hydrogen bonded dimers. IQA is an interpretation tool based on a real space energy decomposition scheme fully consistent with the quantum theory of atoms in molecules. It provides a partition of every physical term present in the Hamiltonian into atomic and interatomic contributions. The procedure is orbital-free and self-contained, needing neither external references nor artificial intermediate states. Binding is the result of a competition between the destabilizing deformations suffered by the interacting fragments upon interaction and the stabilizing interaction energy itself. According to IQA, there is no incompatibility between the prevalent electrostatic image of hydrogen bonded systems and that favoring important covalent contributions. Depending on how we gather the different energetic terms, we may recover electrostatic or covalent pictures from the same underlying quantum mechanical description. Our results show that the nonclassical contributions to hydrogen bonding are spatially localized, involving only the H atom and its two nearest neighbors. IQA is well suited as a comparative tool. Its thin energetic decomposition allows us to recover exactly (or to a very good approximation) the quantities of the most widely used energy decomposition schemes. Such a comparison sheds light on the virtues and faults of the different methods and on the origin of the 50years old debate regarding the covalent/electrostatic nature of the hydrogen bond.

  12. Moøller polarimetry with polarized atomic hydrogen at MESA

    SciTech Connect

    Bartolomé, P. Aguar; Aulenbacher, K.; Tyukin, V.

    2013-11-07

    A new generation of parity violation (PV) electron scattering experiments are planned to be carried out at the Institut für Kernphysik in Mainz. These experiments will be performed at low energies of 100-200 MeV using the new accelerator MESA (Mainz Energy recovering Superconducting Accelerator). One of the main challenges of such experiments is to achieve an accuracy in beam polarization measurements that must be below 0.5%. This very high accuracy can be reached using polarized atomic hydrogen gas, stored in an ultra-cold magnetic trap, as the target for electron beam polarimetry based on Mo/ller scattering. Electron spin-polarized atomic hydrogen can be stored at high densities of 10{sup 16} cm{sup −2}, over relatively long time periods, in a high magnetic field (8T) and at low temperatures (0.3K). The gradient force splits the ground state of the hydrogen into four states with different energies. Atoms in the low energy states are trapped in the strong magnetic field region whereas the high energy states are repelled and pumped away. The physics of ultra-cold atomic hydrogen in magnetic traps and the status of the Mainz Hydro-Mo/ller project will be presented.

  13. Effects of laser radiation field on energies of hydrogen atom in plasmas

    SciTech Connect

    Bahar, M. K.

    2015-09-15

    In this study, for the first time, the Schrödinger equation with more general exponential cosine screened Coulomb (MGECSC) potential is solved numerically in the presence of laser radiation field within the Ehlotzky approximation using the asymptotic iteration method. The MGECSC potential includes four different potential forms in consideration of different sets of the parameters in the potential. By applying laser field, the total interaction potential of hydrogen atom embedded in plasmas converts to double well-type potential. The plasma screening effects under the influence of laser field as well as confinement effects of laser field on hydrogen atom in Debye and quantum plasmas are investigated by solving the Schrödinger equation with the laser-dressed MGECSC potential. It is resulted that since applying a monochromatic laser field on hydrogen atom embedded in a Debye and quantum plasma causes to shift in the profile of the total interaction potential, the confinement effects of laser field on hydrogen atom in plasmas modeled by the MGECSC potential change localizations of energy states.

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

    SciTech Connect

    Bonfanti, Matteo; Jackson, Bret; Hughes, Keith H.; Burghardt, Irene

    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.

  15. Irregular wave functions of a hydrogen atom in a uniform magnetic field

    SciTech Connect

    Wintgen, D. Max-Planck-Institut fuer Kernphysik, Postfach 103980, D-6900 Heidelberg, ); Honig, A. )

    1989-10-02

    We study the irregular wave functions of a highly excited hydrogen atom in a uniform magnetic field. The scarring of wave functions by periodic orbits is quantitatively investigated. The shape of unperturbed scars is in good agreement with recent semiclassical predictions.

  16. Photoelectron momentum spectra for multiphoton ionization of Hydrogen atoms by intense laser pulses

    NASA Astrophysics Data System (ADS)

    Ovchinnikov, Serge; Macek, Joseph

    2007-06-01

    Full three-dimensional electron momentum distribution for multiphoton ionization of Hydrogen atoms by intense laser pulses are calculated by solving the time-dependent solutions of Schr"odinger equation on a three-dimensional lattice in a scaled coordinate representation (CSLTDSE). This approach allows one to circumvent many difficulties related to the propagation of wave function to macroscopic distances.

  17. Inelastic scattering of electrons by metastable hydrogen atoms in a laser field

    NASA Astrophysics Data System (ADS)

    Buica, Gabriela

    2015-09-01

    The inelastic scattering of fast electrons by metastable hydrogen atoms in the presence of a linearly polarized laser field is theoretically studied in the domain of field intensities below 1010 W/cm2. The interaction of the hydrogen atom with the laser field is described by first-order time-dependent perturbation theory, while the projectile electrons interacting with the laser field are described by the Gordon-Volkov wave functions. An analytic expression is obtained for the differential scattering cross section in the first-order Born approximation for laser-assisted inelastic e--H (2 s ) scattering for the 2 s →n l excitation. Detailed analytical and numerical results are presented for inelastic scattering accompanied by one-photon absorption, and the angular dependence and resonance structure of the differential cross sections are discussed for the 2 s →4 l excitation of metastable hydrogen.

  18. Construction of the isocopalane skeleton: application of a desulfinylative 1,7-hydrogen atom transfer strategy.

    PubMed

    Xiao, Xiong; Xu, ZhongYu; Zeng, Qian-Ding; Chen, Xi-Bo; Ji, Wen-Hao; Han, Ying; Wu, PeiYing; Ren, Jiangmeng; Zeng, Bu-Bing

    2015-06-01

    Two attractive chirons, aldehyde 6 and chloride 7, exhibiting functionalized ent-spongiane-type tricyclic skeletons (ABC ring system), have been constructed and their absolute configurations have been studied by NMR spectroscopy and confirmed by single-crystal X-ray diffraction. Both of these chirons are derived from commercially available andrographolide in good yield. Aldehyde 6 is obtained through a novel K2 S2 O8 -catalyzed aquatic ring-closing reaction of allylic sodium sulfonate and intramolecular 1,7-hydrogen atom transfer process. Further mechanistic investigations demonstrate that the 1,7-hydrogen atom transfer is a free-radical process, whereby hydrogen migrates from C18 to C17, as evidenced by double-18- deuterium-labeled isotope experiments. Prospective applications of these two chiral sources are also discussed. PMID:25907201

  19. Carrier-envelope phase effects in few-cycle ionisation of atomic hydrogen

    NASA Astrophysics Data System (ADS)

    Kielpinski, David; Wallace, W. C.; Pullen, M. G.; Ghafur, O.; Laban, D. E.; Palmer, A. J.; Hanne, G. F.; Grum-Grzhimailo, A. N.; Bartschat, K.; Ivanov, I. A.; Kheifets, A. S.; Tong, X.-M.; Quiney, H. M.; Litvinyuk, I. V.; Sang, R. T.

    2012-06-01

    The control of strong-field photoionization with laser carrier-envelope phase (CEP) is the key enabling technique for attosecond science. Currently, quantitatively accurate ab initio simulations of this process can only be carried out for atomic hydrogen. We have observed CEP effects in the above-threshold ionisation of atomic hydrogen for the first time. The modulation due to CEP is mapped over a wide range of laser intensity and electron energy. The data is compared with ab initio simulations for the time dependent Schr"odinger equation carried out using three separate methodologies, as well as a semi-ab initio simulation method. We find reasonable agreement between experiment and all simulations over the entire sampled parameter space. Our results point the way toward accurate calibration of absolute laser CEP by means of the uniquely calculable hydrogen system.

  20. Hydrogen atom initiated chemistry. [chemical evolution in planetary atmospheres

    NASA Technical Reports Server (NTRS)

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

    1979-01-01

    H Atoms have been created by the photolysis of H2S. These then initiated reactions in mixtures involving acetylene-ammonia-water and ethylene-ammonia-water. In the case of the acetylene system, the products consisted of two amino acids, ethylene and a group of primarily cyclic thio-compounds, but no free sulfur. In the case of the ethylene systems, seven amino acids, including an aromatic one, ethane, free sulfur, and a group of solely linear thio-compounds were produced. Total quantum yields for the production of amino acids were about 3 x 10 to the -5th and about 2 x 10 to the -4th with ethylene and acetylene respectively as carbon substrates. Consideration is given of the mechanism for the formation of some of the products and implications regarding planetary atmosphere chemistry, particularly that of Jupiter, are explored.

  1. Graphene oxide/metal nanocrystal multilaminates as the atomic limit for safe and selective hydrogen storage

    NASA Astrophysics Data System (ADS)

    Cho, Eun Seon; Ruminski, Anne M.; Aloni, Shaul; Liu, Yi-Sheng; Guo, Jinghua; Urban, Jeffrey J.

    2016-02-01

    Interest in hydrogen fuel is growing for automotive applications; however, safe, dense, solid-state hydrogen storage remains a formidable scientific challenge. Metal hydrides offer ample storage capacity and do not require cryogens or exceedingly high pressures for operation. However, hydrides have largely been abandoned because of oxidative instability and sluggish kinetics. We report a new, environmentally stable hydrogen storage material constructed of Mg nanocrystals encapsulated by atomically thin and gas-selective reduced graphene oxide (rGO) sheets. This material, protected from oxygen and moisture by the rGO layers, exhibits exceptionally dense hydrogen storage (6.5 wt% and 0.105 kg H2 per litre in the total composite). As rGO is atomically thin, this approach minimizes inactive mass in the composite, while also providing a kinetic enhancement to hydrogen sorption performance. These multilaminates of rGO-Mg are able to deliver exceptionally dense hydrogen storage and provide a material platform for harnessing the attributes of sensitive nanomaterials in demanding environments.

  2. Graphene oxide/metal nanocrystal multilaminates as the atomic limit for safe and selective hydrogen storage

    DOE PAGESBeta

    Cho, Eun Seon; Ruminski, Anne M.; Aloni, Shaul; Liu, Yi-Sheng; Guo, Jinghua; Urban, Jeffrey J.

    2016-02-23

    Interest in hydrogen fuel is growing for automotive applications; however, safe, dense, solid-state hydrogen storage remains a formidable scientific challenge. Metal hydrides offer ample storage capacity and do not require cryogens or exceedingly high pressures for operation. However, hydrides have largely been abandoned because of oxidative instability and sluggish kinetics. We report a new, environmentally stable hydrogen storage material constructed of Mg nanocrystals encapsulated by atomically thin and gas-selective reduced graphene oxide (rGO) sheets. This material, protected from oxygen and moisture by the rGO layers, exhibits exceptionally dense hydrogen storage (6.5 wt% and 0.105 kg H2 per litre in themore » total composite). As rGO is atomically thin, this approach minimizes inactive mass in the composite, while also providing a kinetic enhancement to hydrogen sorption performance. In conclusion, these multilaminates of rGO-Mg are able to deliver exceptionally dense hydrogen storage and provide a material platform for harnessing the attributes of sensitive nanomaterials in demanding environments.« less

  3. Graphene oxide/metal nanocrystal multilaminates as the atomic limit for safe and selective hydrogen storage

    PubMed Central

    Cho, Eun Seon; Ruminski, Anne M.; Aloni, Shaul; Liu, Yi-Sheng; Guo, Jinghua; Urban, Jeffrey J.

    2016-01-01

    Interest in hydrogen fuel is growing for automotive applications; however, safe, dense, solid-state hydrogen storage remains a formidable scientific challenge. Metal hydrides offer ample storage capacity and do not require cryogens or exceedingly high pressures for operation. However, hydrides have largely been abandoned because of oxidative instability and sluggish kinetics. We report a new, environmentally stable hydrogen storage material constructed of Mg nanocrystals encapsulated by atomically thin and gas-selective reduced graphene oxide (rGO) sheets. This material, protected from oxygen and moisture by the rGO layers, exhibits exceptionally dense hydrogen storage (6.5 wt% and 0.105 kg H2 per litre in the total composite). As rGO is atomically thin, this approach minimizes inactive mass in the composite, while also providing a kinetic enhancement to hydrogen sorption performance. These multilaminates of rGO-Mg are able to deliver exceptionally dense hydrogen storage and provide a material platform for harnessing the attributes of sensitive nanomaterials in demanding environments. PMID:26902901

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

    SciTech Connect

    Lee, June Key E-mail: hskim7@jbnu.ac.kr; Hyeon, Gil Yong; Tawfik, Wael Z.; Choi, Hee Seok; Ryu, Sang-Wan; Jeong, Tak; Jung, Eunjin; Kim, Hyunsoo E-mail: hskim7@jbnu.ac.kr

    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.

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

    NASA Astrophysics Data System (ADS)

    Lee, June Key; Hyeon, Gil Yong; Tawfik, Wael Z.; Choi, Hee Seok; Ryu, Sang-Wan; Jeong, Tak; Jung, Eunjin; Kim, Hyunsoo

    2015-05-01

    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.

  6. Graphene oxide/metal nanocrystal multilaminates as the atomic limit for safe and selective hydrogen storage.

    PubMed

    Cho, Eun Seon; Ruminski, Anne M; Aloni, Shaul; Liu, Yi-Sheng; Guo, Jinghua; Urban, Jeffrey J

    2016-01-01

    Interest in hydrogen fuel is growing for automotive applications; however, safe, dense, solid-state hydrogen storage remains a formidable scientific challenge. Metal hydrides offer ample storage capacity and do not require cryogens or exceedingly high pressures for operation. However, hydrides have largely been abandoned because of oxidative instability and sluggish kinetics. We report a new, environmentally stable hydrogen storage material constructed of Mg nanocrystals encapsulated by atomically thin and gas-selective reduced graphene oxide (rGO) sheets. This material, protected from oxygen and moisture by the rGO layers, exhibits exceptionally dense hydrogen storage (6.5 wt% and 0.105 kg H2 per litre in the total composite). As rGO is atomically thin, this approach minimizes inactive mass in the composite, while also providing a kinetic enhancement to hydrogen sorption performance. These multilaminates of rGO-Mg are able to deliver exceptionally dense hydrogen storage and provide a material platform for harnessing the attributes of sensitive nanomaterials in demanding environments. PMID:26902901

  7. The possibility of constructing the hydrogen scale of the absolute atomic masses of the elements

    NASA Astrophysics Data System (ADS)

    Kuz'min, I. I.

    2009-12-01

    The paper presents a scheme for the experimental-empirical construction of the existing chemical, physical, and carbon scales of the relative nonintegral atomic masses of the elements. The quantitative interrelation between the nonintegral relative atomic masses, their minimized fractional positive and negative natural deviations from integral numbers, and their integral parts are reproduced mathematically. Nonisotopic fractional deviations are shown to be a consequence of methodological side effects of the scheme for theoretical processing of the data of thorough physical and chemical measurements performed by Stas and Aston in constructing scales of relative atomic masses. In conformity with the Prout hypothesis, the absolute atomic mass unit and the corresponding Avogadro’s number value are suggested for the construction of the hydrogen scale of absolute atomic masses of nonisotopic elements, individual isotopes, and isotope-containing elements.

  8. Hydrogen Abstraction Reactions from Phenolic Compounds by Peroxyl Radicals: Multireference Character and Density Functional Theory Rate Constants.

    PubMed

    Galano, Annia; Muñoz-Rugeles, Leonardo; Alvarez-Idaboy, Juan Raul; Bao, Junwei Lucas; Truhlar, Donald G

    2016-07-14

    An assessment of multireference character in transition states is considered to be an important component in establishing the expected reliability of various electronic structure methods. In the present work, the multireference characters of the transition states and the forming and breaking of bonds for a large set of hydrogen abstraction reactions from phenolic compounds by peroxyl radicals have been analyzed using the T1, M, B1, and GB1 diagnostics. The extent of multireference character depends on the system and on the conditions under which the reaction takes place, and some systematic trends are observed. In particular, the multireference character is found to be reduced by solvation, the size of the phenolic compound, and deprotonation in aqueous solution. However, the deviations of calculated rate constants from experimental ones are not correlated with the extent of multireference character. The performance of single-determinant density functional theory was investigated for the kinetics of these reactions by comparing calculated rate constants to experimental data; the results from these analyses showed that the M05 functional performs well for the task at hand. PMID:26378461

  9. Electronic spin-flipping collisions of hydrogen atoms

    SciTech Connect

    Zygelman, B.

    2010-03-15

    We present a unified multichannel approach to calculate electron spin-exchange and spin-flipping transition cross sections for collisions of H with H, H with T, and T with T. We use the theory to calculate the hyperfine quenching cross sections for collision energies that range from 1 mK to thermal temperatures. We show that spin-flipping transitions are induced by the splitting of the b {sup 3{Sigma}}{sub u} Born-Oppenheimer potential via the long-range magnetic interactions among electrons. We find that the spin-flipping cross sections in the tritium dimer are about a magnitude larger than that predicted by mass scaling the H-H cross sections. For the former, we show that the spin-exchange cross sections are several magnitudes larger, at cold temperatures, than that of the hydrogen system. We compare the results of the multichannel approach with those obtained using approximate methods such as the degenerate internal-state, the elastic, and Born approximations and discuss their respective range of validity.

  10. Benchmarking all-atom simulations using hydrogen exchange

    PubMed Central

    Skinner, John J.; Yu, Wookyung; Gichana, Elizabeth K.; Baxa, Michael C.; Hinshaw, James R.; Freed, Karl F.; Sosnick, Tobin R.

    2014-01-01

    Long-time molecular dynamics (MD) simulations are now able to fold small proteins reversibly to their native structures [Lindorff-Larsen K, Piana S, Dror RO, Shaw DE (2011) Science 334(6055):517–520]. These results indicate that modern force fields can reproduce the energy surface near the native structure. To test how well the force fields recapitulate the other regions of the energy surface, MD trajectories for a variant of protein G are compared with data from site-resolved hydrogen exchange (HX) and other biophysical measurements. Because HX monitors the breaking of individual H-bonds, this experimental technique identifies the stability and H-bond content of excited states, thus enabling quantitative comparison with the simulations. Contrary to experimental findings of a cooperative, all-or-none unfolding process, the simulated denatured state ensemble, on average, is highly collapsed with some transient or persistent native 2° structure. The MD trajectories of this protein G variant and other small proteins exhibit excessive intramolecular H-bonding even for the most expanded conformations, suggesting that the force fields require improvements in describing H-bonding and backbone hydration. Moreover, these comparisons provide a general protocol for validating the ability of simulations to accurately capture rare structural fluctuations. PMID:25349413

  11. Local atomic structure modulations activate metal oxide as electrocatalyst for hydrogen evolution in acidic water

    PubMed Central

    Li, Yu Hang; Liu, Peng Fei; Pan, Lin Feng; Wang, Hai Feng; Yang, Zhen Zhong; Zheng, Li Rong; Hu, P.; Zhao, Hui Jun; Gu, Lin; Yang, Hua Gui

    2015-01-01

    Modifications of local structure at atomic level could precisely and effectively tune the capacity of materials, enabling enhancement in the catalytic activity. Here we modulate the local atomic structure of a classical but inert transition metal oxide, tungsten trioxide, to be an efficient electrocatalyst for hydrogen evolution in acidic water, which has shown promise as an alternative to platinum. Structural analyses and theoretical calculations together indicate that the origin of the enhanced activity could be attributed to the tailored electronic structure by means of the local atomic structure modulations. We anticipate that suitable structure modulations might be applied on other transition metal oxides to meet the optimal thermodynamic and kinetic requirements, which may pave the way to unlock the potential of other promising candidates as cost-effective electrocatalysts for hydrogen evolution in industry. PMID:26286479

  12. Stabilizing a Platinum1 Single-Atom Catalyst on Supported Phosphomolybdic Acid without Compromising Hydrogenation Activity.

    PubMed

    Zhang, Bin; Asakura, Hiroyuki; Zhang, Jia; Zhang, Jiaguang; De, Sudipta; Yan, Ning

    2016-07-11

    In coordination chemistry, catalytically active metal complexes in a zero- or low-valent state often adopt four-coordinate square-planar or tetrahedral geometry. By applying this principle, we have developed a stable Pt1 single-atom catalyst with a high Pt loading (close to 1 wt %) on phosphomolybdic acid(PMA)-modified active carbon. This was achieved by anchoring Pt on the four-fold hollow sites on PMA. Each Pt atom is stabilized by four oxygen atoms in a distorted square-planar geometry, with Pt slightly protruding from the oxygen planar surface. Pt is positively charged, absorbs hydrogen easily, and exhibits excellent performance in the hydrogenation of nitrobenzene and cyclohexanone. It is likely that the system described here can be extended to a number of stable SACs with superior catalytic activities. PMID:27240266

  13. Measurements of positron scattering by hydrogen, alkali metal, and other atoms

    NASA Astrophysics Data System (ADS)

    Stein, T. S.; Harte, M.; Jiang, J.; Kauppila, W. E.; Kwan, C. K.; Li, H.; Zhou, S.

    1998-08-01

    Recent developments in measurements of total and positronium (Ps) formation cross sections for positrons (in the energy range of 1-300 eV) scattered by hydrogen, alkali metal, and other atoms are reviewed. Measurements and calculations of total and Ps formation cross section ( QPs's) for positrons scattered by hydrogen atoms are in very good agreement, and for the most part there is also good agreement for sodium, potassium, and rubidium atoms, but there is a puzzling discrepancy between measured and recently calculated QPs's for sodium. Preliminary measurements of QPs's for Mg show a very rapid rise to a large maximum value less than 2 eV above the Ps formation threshold energy (0.8 eV) which may be related to the proximity of that threshold to zero energy. It appears that structure observed in e +-Ar and Kr QPs measurements may be related to capture of inner-subshell electrons.

  14. Light emission induced by an XUV laser pulse interacting resonantly with atomic hydrogen

    NASA Astrophysics Data System (ADS)

    Li, Qingyi; Zhang, Zhiyuan; Zhang, Yunfeng; Li, Suyu; Guo, Fuming; Yang, Yujun

    2016-01-01

    The resonant interaction between XUV ultra-short laser pulses and atomic hydrogen is systematically studied by numerically solving the time-dependent Schrödinger equation in this paper. Triple-peak structures are found to appear in the harmonics emitted provided that the incident laser is resonant with the 1 s-2p transition of the hydrogen atom. Moreover, the energy difference between neighboring peaks is the same and turns out to be proportional to the peak field strength E 0. Based on the theory of strong field approximation, and taking the interactions of the 1 s-2p bound energy levels into consideration, theoretical interpretations of the phenomena mentioned are successfully presented. This work provides a possible approach for generating XUV radiation with a tunable frequency via the interaction between atoms and XUV laser pulses.

  15. Local atomic structure modulations activate metal oxide as electrocatalyst for hydrogen evolution in acidic water.

    PubMed

    Li, Yu Hang; Liu, Peng Fei; Pan, Lin Feng; Wang, Hai Feng; Yang, Zhen Zhong; Zheng, Li Rong; Hu, P; Zhao, Hui Jun; Gu, Lin; Yang, Hua Gui

    2015-01-01

    Modifications of local structure at atomic level could precisely and effectively tune the capacity of materials, enabling enhancement in the catalytic activity. Here we modulate the local atomic structure of a classical but inert transition metal oxide, tungsten trioxide, to be an efficient electrocatalyst for hydrogen evolution in acidic water, which has shown promise as an alternative to platinum. Structural analyses and theoretical calculations together indicate that the origin of the enhanced activity could be attributed to the tailored electronic structure by means of the local atomic structure modulations. We anticipate that suitable structure modulations might be applied on other transition metal oxides to meet the optimal thermodynamic and kinetic requirements, which may pave the way to unlock the potential of other promising candidates as cost-effective electrocatalysts for hydrogen evolution in industry. PMID:26286479

  16. Semiclassical study of the quenching of excited-state fluorine atom by hydrogen molecule - Comparison between reactive and nonreactive processes

    NASA Technical Reports Server (NTRS)

    Yuan, J.-M.; Skuse, B. M.; Jaffe, R. L.; Komornicki, A.; Morokuma, K.; George, T. F.

    1980-01-01

    Semiclassical calculations are carried out for the quenching of excited-state fluorine atom by collinear collisions with hydrogen molecule. The overall quenching probability is the sum of two contributions: the reactive quenching probability associated with the formation of hydrogen fluoride and the nonreactive quenching probability leading to ground-state fluorine atom and hydrogen molecule. The reactive probability is greater in the threshold region of the collision energy, whereas the nonreactive probability dominates for energies above the threshold region.

  17. Solid Hydrogen Experiments for Atomic Propellants: Particle Formation, Imaging, Observations, and Analyses

    NASA Technical Reports Server (NTRS)

    Palaszewski, Bryan

    2005-01-01

    This report presents particle formation observations and detailed analyses of the images from experiments that were conducted on the formation of solid hydrogen particles in liquid helium. Hydrogen was frozen into particles in liquid helium, and observed with a video camera. The solid hydrogen particle sizes and the total mass of hydrogen particles were estimated. These newly analyzed data are from the test series held on February 28, 2001. Particle sizes from previous testing in 1999 and the testing in 2001 were similar. Though the 2001 testing created similar particles sizes, many new particle formation phenomena were observed: microparticles and delayed particle formation. These experiment image analyses are some of the first steps toward visually characterizing these particles, and they allow designers to understand what issues must be addressed in atomic propellant feed system designs for future aerospace vehicles.

  18. Solid Hydrogen Experiments for Atomic Propellants: Particle Formation Energy and Imaging Analyses

    NASA Technical Reports Server (NTRS)

    Palaszewski, Bryan

    2002-01-01

    This paper presents particle formation energy balances and detailed analyses of the images from experiments that were conducted on the formation of solid hydrogen particles in liquid helium during the Phase II testing in 2001. Solid particles of hydrogen were frozen in liquid helium and observed with a video camera. The solid hydrogen particle sizes and the total mass of hydrogen particles were estimated. The particle formation efficiency is also estimated. Particle sizes from the Phase I testing in 1999 and the Phase II testing in 2001 were similar. Though the 2001 testing created similar particles sizes, many new particle formation phenomena were observed. These experiment image analyses are one of the first steps toward visually characterizing these particles and it allows designers to understand what issues must be addressed in atomic propellant feed system designs for future aerospace vehicles.

  19. Adsorption of atomic hydrogen at a nanostructured electrode of polyacrylate-capped Pt nanoparticles in polyelectrolyte.

    PubMed

    Markarian, Marie Zabel; El Harakeh, Maysaa; Halaoui, Lara I

    2005-06-16

    Atomic hydrogen electrosorption is reported at crystallite sites of polyacrylate-capped Pt nanoparticles (d = 2.5 +/- 0.6 nm), by assembling nanostructured electrodes of polyacrylate-Pt nanocrystallites layer-by-layer in a cationic polyelectrolyte, poly(diallyldimethylammonium chloride). Cyclic voltammetry in 1 M H2SO4 revealed a strongly adsorbed hydrogen state and a weakly adsorbed hydrogen state assigned to adsorption at (100) and (110) sites of the modified nanocrystallites, respectively. Resolving hydrogen adsorption states signifies that surface capping by the carboxylate groups is not irreversibly blocking hydrogen adsorption sites at the modified Pt nanoparticle surface. Adsorption peak currents increased with increasing the number of layers up to 16 bilayers, indicating the feasibility of nanoparticle charging via interparticle charge hopping and the accessibility of adsorption states within the thickness of the nanoparticle/polyelectrolyte multilayers. Despite similarity in hydrogen adsorption in the cyclic voltammorgrams in 1 M H2SO4, negative shifts in adsorption potentials were measured at the nanocrystallite Pt-polyelectrolyte multilayers relative to a polycrystalline bulk Pt surface. This potential shift is attributed to a kinetic limitation in the reductive hydrogen adsorption as a result of the Pt nanoparticle surface modification and the polyelectrolyte environment. PMID:16852426

  20. Two-center effect on low-energy electron emission in collisions of 1-MeV/u bare ions with atomic hydrogen, molecular hydrogen, and helium. I. Atomic hydrogen

    NASA Astrophysics Data System (ADS)

    Tribedi, Lokesh C.; Richard, P.; Gulyás, L.; Rudd, M. E.; Moshammer, R.

    2001-06-01

    We have investigated ionization mechanisms in fast ion-atom collisions by measuring the low-energy electron emission cross sections in a pure three-body collision involving bare carbon ions (v=6.35 a.u.) colliding with atomic hydrogen targets. The measurements have also been extended to molecular hydrogen and helium targets. In this paper we provide the energy and angular distributions of double differential cross sections of low-energy electron emission for atomic hydrogen targets. The Slevin rf source with a high degree of dissociation was used to produce the atomic H target. It is found that the two-center effect has a major influence on the observed large forward-backward angular asymmetry. A detailed comparison is presented with calculations based on the continuum distorted-wave (CDW) and CDW-EIS (eikonal initial-state) approximations. Both the continuum distorted-wave calculations provide a very good understanding of the data, whereas the first Born calculation predicts almost symmetric forward-backward distributions that do not agree with the data. The two-center effect is slightly better represented by the CDW calculations compared to the CDW-EIS calculation. The total cross sections are, however, in good agreement with the theories used. The results for molecular hydrogen and helium will be discussed in the following paper.

  1. Towards an improved measurement of the proton size from precision spectroscopy of atomic hydrogen

    NASA Astrophysics Data System (ADS)

    Maisenbacher, Lothar; Beyer, Axel; Khabarova, Ksenia; Matveev, Arthur; Pohl, Randolf; Udem, Thomas; Hänsch, Theodor W.; Kolachevsky, Nikolai

    2015-05-01

    Precision spectroscopy of atomic hydrogen has long been successfully used to provide stringent tests on fundamental theories and precisely determine physical constants. The current limit originates from the uncertainty in the value of the proton r.m.s.charge radius rp. Moreover, the value of rp extracted from laser spectroscopy of muonic hydrogen is ten times more accurate than any other determination, but disagrees by 7 σ with the recommended CODATA 2010 value. Here, we report on our progress towards an improved absolute frequency measurement of the 2S-4P (one-photon) transition in atomic hydrogen, which combined with the much more precisely known 1S-2S transition frequency allows a more precise extraction of rp from electronic hydrogen. To suppress the first order Doppler shift, we use a cryogenic beam of atoms optically excited to the 2S state and actively stabilized counter-propagating laser beams. Interference effects due to spontaneous emission were studied and we show how to experimentally suppress the corresponding line center shifts.

  2. Single Pd atoms in activated carbon fibers and their contribution to hydrogen storage

    SciTech Connect

    Contescu, Cristian I; van Benthem, Klaus; Li, Sa; Bonifacio, Cecile S; Pennycook, Stephen J; Jena, Puru; Gallego, Nidia C

    2011-01-01

    Palladium-modified activated carbon fibers (Pd-ACF) were synthesized by meltspinning, carbonization and activation of an isotropic pitch carbon precursor premixed with an organometallic Pd compound. The hydrogen uptake at 25 oC and 20 bar on Pd- ACF exceeded the expected capacity based solely on Pd hydride formation and hydrogen physisorption on the microporous carbon support. Aberration-corrected scanning transmission electron microscopy (STEM) with sub- ngstrom spatial resolution provided unambiguous identification of isolated Pd atoms occurring in the carbon matrix that coexist with larger Pd particles. First principles calculations revealed that each single Pd atom can form Kubas-type complexes by binding up to three H2 molecules in the pressure range of adsorption measurements. Based on Pd atom concentration determined from STEM images, the contribution of various mechanisms to the excess hydrogen uptake measured experimentally was evaluated. With consideration of Kubas binding as a viable mechanism (along with hydride formation and physisorption to carbon support) the role of hydrogen spillover in this system may be smaller than previously thought.

  3. Analytical transition-matrix treatment of electric multipole polarizabilities of hydrogen-like atoms

    SciTech Connect

    Kharchenko, V.F.

    2015-04-15

    The direct transition-matrix approach to the description of the electric polarization of the quantum bound system of particles is used to determine the electric multipole polarizabilities of the hydrogen-like atoms. It is shown that in the case of the bound system formed by the Coulomb interaction the corresponding inhomogeneous integral equation determining an off-shell scattering function, which consistently describes virtual multiple scattering, can be solved exactly analytically for all electric multipole polarizabilities. Our method allows to reproduce the known Dalgarno–Lewis formula for electric multipole polarizabilities of the hydrogen atom in the ground state and can also be applied to determine the polarizability of the atom in excited bound states. - Highlights: • A new description for electric polarization of hydrogen-like atoms. • Expression for multipole polarizabilities in terms of off-shell scattering functions. • Derivation of integral equation determining the off-shell scattering function. • Rigorous analytic solving the integral equations both for ground and excited states. • Study of contributions of virtual multiple scattering to electric polarizabilities.

  4. Selective adsorption of atomic hydrogen on a h-BN thin film

    SciTech Connect

    Koswattage, Kaveenga Rasika; Shimoyama, Iwao; Baba, Yuji; Sekiguchi, Tetsuhiro; Nakagawa, Kazumichi

    2011-07-07

    The adsorption of atomic hydrogen on hexagonal boron nitride (h-BN) is studied using two element-specific spectroscopies, i.e., near-edge x-ray absorption fine structure (NEXAFS) spectroscopy and x-ray photoelectron spectroscopy (XPS). B K-edge NEXAFS spectra show a clear change in the energy region of the {pi}{sup *} band before and after reaction with atomic deuterium. On the other hand, N K-edge NEXAFS spectra show only a little change. B 1s XPS spectra show a distinct component at the low binding energy side of a main component, while N 1s XPS spectra show peak broadening at the high binding energy side. These experimental results are analyzed by the discrete variational X{alpha} method with a core-hole effect and are explained by a model in which hydrogen atoms are preferentially adsorbed on the B sites of h-BN. Based on the experimental and theoretical results, we propose a site-selective property of BN material on adsorption of atomic hydrogen.

  5. Selective adsorption of atomic hydrogen on a h-BN thin film.

    PubMed

    Koswattage, Kaveenga Rasika; Shimoyama, Iwao; Baba, Yuji; Sekiguchi, Tetsuhiro; Nakagawa, Kazumichi

    2011-07-01

    The adsorption of atomic hydrogen on hexagonal boron nitride (h-BN) is studied using two element-specific spectroscopies, i.e., near-edge x-ray absorption fine structure (NEXAFS) spectroscopy and x-ray photoelectron spectroscopy (XPS). B K-edge NEXAFS spectra show a clear change in the energy region of the π* band before and after reaction with atomic deuterium. On the other hand, N K-edge NEXAFS spectra show only a little change. B 1s XPS spectra show a distinct component at the low binding energy side of a main component, while N 1s XPS spectra show peak broadening at the high binding energy side. These experimental results are analyzed by the discrete variational Xα method with a core-hole effect and are explained by a model in which hydrogen atoms are preferentially adsorbed on the B sites of h-BN. Based on the experimental and theoretical results, we propose a site-selective property of BN material on adsorption of atomic hydrogen. PMID:21744913

  6. Single-Atom Pd₁/Graphene Catalyst Achieved by Atomic Layer Deposition: Remarkable Performance in Selective Hydrogenation of 1,3-Butadiene.

    PubMed

    Yan, Huan; Cheng, Hao; Yi, Hong; Lin, Yue; Yao, Tao; Wang, Chunlei; Li, Junjie; Wei, Shiqiang; Lu, Junling

    2015-08-26

    We reported that atomically dispersed Pd on graphene can be fabricated using the atomic layer deposition technique. Aberration-corrected high-angle annular dark-field scanning transmission electron microscopy and X-ray absorption fine structure spectroscopy both confirmed that isolated Pd single atoms dominantly existed on the graphene support. In selective hydrogenation of 1,3-butadiene, the single-atom Pd1/graphene catalyst showed about 100% butenes selectivity at 95% conversion at a mild reaction condition of about 50 °C, which is likely due to the changes of 1,3-butadiene adsorption mode and enhanced steric effect on the isolated Pd atoms. More importantly, excellent durability against deactivation via either aggregation of metal atoms or carbonaceous deposits during a total 100 h of reaction time on stream was achieved. Therefore, the single-atom catalysts may open up more opportunities to optimize the activity, selectivity, and durability in selective hydrogenation reactions. PMID:26268551

  7. Accounting for conformational flexibility and torsional anharmonicity in the H + CH{sub 3}CH{sub 2}OH hydrogen abstraction reactions: A multi-path variational transition state theory study

    SciTech Connect

    Meana-Pañeda, Rubén; Fernández-Ramos, Antonio

    2014-05-07

    This work reports a detailed theoretical study of the hydrogen abstraction reactions from ethanol by atomic hydrogen. The calculated thermal rate constants take into account torsional anharmonicity and conformational flexibility, in addition to the variational and tunneling effects. Specifically, the kinetics calculations were performed by using multi-path canonical variational transition state theory with least-action path tunneling corrections, to which we have added the two-dimensional non-separable method to take into account torsional anharmonicity. The multi-path thermal rate constant is expressed as a sum over conformational reaction channels. Each of these channels includes all the transition states that can be reached by internal rotations. The results show that, in the interval of temperatures between 250 and 2500 K, the account for multiple paths leads to higher thermal rate constants with respect to the single path approach, mainly at low and at high temperatures. In addition, torsional anharmonicity enhances the slope of the Arrhenius plot in this range of temperatures. Finally, we show that the incorporation of tunneling into the hydrogen abstraction reactions substantially changes the contribution of each of the transition states to the conformational reaction channel.

  8. The contribution of dissociative processes to the production of atomic lines in hydrogen plasmas

    NASA Technical Reports Server (NTRS)

    Kunc, J. A.

    1985-01-01

    The contribution of molecular dissociative processes to the production of atomic lines is considered for a steady-state hydrogen plasma. If the contribution of dissociative processes is dominant, a substantial simplification in plasma diagnostics can be achieved. Numerical calculations have been performed for the production of Balmer alpha, beta, and gamma lines in hydrogen plasmas with medium and large degrees of ionization (x greater than about 0.0001) and for electron temperatures of 5000-45,000 K and electron densities of 10 to the 10th to 10 to the 16th/cu cm.

  9. Rydberg hydrogen atom near a metallic surface: Stark regime and ionization dynamics

    SciTech Connect

    Inarrea, Manuel; Salas, J. Pablo; Lanchares, Victor; Pascual, Ana Isabel; Palacian, Jesus F.; Yanguas, Patricia

    2007-11-15

    We investigate the classical dynamics of a hydrogen atom near a metallic surface in the presence of a uniform electric field. To describe the atom-surface interaction we use a simple electrostatic image model. Owing to the axial symmetry of the system, the z-component of the canonical angular momentum P{sub {phi}} is an integral and the electronic dynamics is modeled by a two degrees of freedom Hamiltonian in cylindrical coordinates. The structure and evolution of the phase space as a function of the electric field strength is explored extensively by means of numerical techniques of continuation of families of periodic orbits and Poincare surfaces of section. We find that, due to the presence of the electric field, the atom is strongly polarized through two consecutive pitchfork bifurcations that strongly change the phase space structure. Finally, by means of the phase space transition state theory and the classical spectral theorem, the ionization dynamics of the atom is studied.

  10. Charge transfer in slow collisions between hydrogen atoms and metal surfaces

    NASA Astrophysics Data System (ADS)

    Bahrim, B.; Thumm, U.

    2002-05-01

    We have developed a new two-center close-coupling approach [1] for slow ion (atom)-surface collision in which the continuum of metal conduction-band states is discretized by using Weyl wave packets [2] to represent the motion of the active electron in the metal subspace. Results for the time evolution of the atomic and metallic population amplitudes for a hydrogen atom in colliding at perpendicular incidence with an model aluminum surface are shown and discussed. For the n=2 hydrogenic manifold, we have obtained converged atomic populations amplitudes by including all projectile levels up to the n=5 manifold and 480 Weyl wave packets in the close-coupling expansion. We will discuss the electron dynamics in particular in view of possible dephasing effects (in distance and time) and recurrence effects that may arrise due to our continuum discretization in term of a finite number of localized Weyl packets. [1] B. Bahrim and U. Thumm, Surf. Sci. 451, 1 (2000), and to appear in Phys. Rev. A. [2] B.H. Bransden and M.R.C. McDowell, "Charge Exchange and the Theory of Ion-Atom Collisions" Clarendon Press (Oxford 1992). Supported by NSF and by the Division of Chemical Sciences, Office of Basic Energy Sciences, Office of Energy Research, U.S. DOE

  11. Nonadiabatic couplings in low-energy collisions of hydrogen ground-state atoms

    SciTech Connect

    Wolniewicz, L.

    2003-10-01

    The effect of nonadiabatic couplings on low-energy s-wave scattering of two hydrogen atoms is investigated. Coupling matrix elements are computed in a wide range of internuclear distances. The resulting scattering equations are numerically unstable and therefore are integrated only approximately. Computations are performed for H, D, and T atoms. The phase shifts in the zero velocity limit are inversely proportional to the nuclear reduced mass {delta}{sub 0}{approx_equal}0.392/{mu}. This leads to infinite scattering lengths.

  12. CHEMI-IONIZATION IN SOLAR PHOTOSPHERE: INFLUENCE ON THE HYDROGEN ATOM EXCITED STATES POPULATION

    SciTech Connect

    Mihajlov, Anatolij A.; Ignjatovic, Ljubinko M.; Sreckovic, Vladimir A.; Dimitrijevic, Milan S. E-mail: mihajlov@ipb.ac.rs

    2011-03-15

    In this paper, the influence of chemi-ionization processes in H*(n {>=} 2) + H(1s) collisions, as well as the influence of inverse chemi-recombination processes on hydrogen atom excited-state populations in solar photosphere, are compared with the influence of concurrent electron-atom and electron-ion ionization and recombination processes. It has been found that the considered chemi-ionization/recombination processes dominate over the relevant concurrent processes in almost the whole solar photosphere. Thus, it is shown that these processes and their importance for the non-local thermodynamic equilibrium modeling of the solar atmosphere should be investigated further.

  13. (2+1) laser-induced fluorescence of spin-polarized hydrogen atoms.

    PubMed

    Bougas, Lykourgos; Sofikitis, Dimitris; Everest, Michael A; Alexander, Andrew J; Rakitzis, T Peter

    2010-11-01

    We report the measurement of the spin polarization of hydrogen (SPH) atoms by (2+1) laser-induced fluorescence, produced via the photodissociation of thermal HBr molecules with circularly polarized 193 nm light. This scheme, which involves two-photon laser excitation at 205 nm and fluorescence at 656 nm, offers an experimentally simpler polarization-detection method than the previously reported vacuum ultraviolet detection scheme, allowing the detection of SPH atoms to be performed more straightforwardly, from the photodissociation of a wide range of molecules and from a variety of collision experiments. PMID:21054033

  14. Hyperfine resonance of gaseous atomic hydrogen at 4.2 K

    NASA Technical Reports Server (NTRS)

    Crampton, S. B.; Kleppner, D.; Phillips, W. D.; Weinrib, A.; Greytak, T. J.; Smith, D. A.

    1979-01-01

    The hyperfine frequency and wall shift of hydrogen atoms at 4.2 K stored in a bulb coated with solid H2 were measured. The phase shift per wall collision is -0.29(1) rad. The adsorption energy of H on H2 is 9(2) K, and the adsorption time at 4.2 K is approximately 30 nsec. Transverse and longitudinal relaxation times have been measured, and atomic densities greater than 10 to the 14th/cu cm have been observed.

  15. Magnetic state selection in atomic frequency and time standards. [hydrogen masers

    NASA Technical Reports Server (NTRS)

    Peters, H. E.

    1982-01-01

    Atomic standards such as those based upon cesium and hydrogen rely upon magnetic state selection to obtain population inversion in the hyperfine transition levels. Use of new design approaches and improved magnetic materials has made it possible to fabricate improved state selectors of small size, and thus the efficiency of utilization of beam flux is greatly improved and the size and weight of the standard is reduced. The sensitivity to magnetic perturbations is also decreased, so that the accuracy and stability of the standard is improved. Several new state selector designs are illustrated and the application to standards utilizing different atomic species is analyzed.

  16. Nonadiabatic coupling in cold collisions of spin-polarized metastable hydrogen atoms

    SciTech Connect

    Forrey, Robert C.; Dalgarno, Alex; Vanne, Yulian V.; Saenz, Alejandro; Froelich, Piotr

    2007-11-15

    Previous calculations of low-temperature cross sections for collisions between spin-polarized metastable hydrogen atoms are improved to include nonadiabatic radial and angular coupling at large interatomic separations. The electrostatic dipole-quadrupole interaction produces nonadiabatic radial coupling between (2s,2p) and (2p,2p) states, while the Coriolis interaction produces nonadiabatic angular coupling. Both of these long-range contributions are handled in a space-fixed atomic gauge that is particularly convenient for a spin-polarized system. The improved theoretical results are compared with an existing experiment.

  17. Interstitial modification of palladium nanoparticles with boron atoms as a green catalyst for selective hydrogenation.

    PubMed

    Chan, Chun Wong Aaron; Mahadi, Abdul Hanif; Li, Molly Meng-Jung; Corbos, Elena Cristina; Tang, Chiu; Jones, Glenn; Kuo, Winson Chun Hsin; Cookson, James; Brown, Christopher Michael; Bishop, Peter Trenton; Tsang, Shik Chi Edman

    2014-01-01

    Lindlar catalysts comprising of palladium/calcium carbonate modified with lead acetate and quinoline are widely employed industrially for the partial hydrogenation of alkynes. However, their use is restricted, particularly for food, cosmetic and drug manufacture, due to the extremely toxic nature of lead, and the risk of its leaching from catalyst surface. In addition, the catalysts also exhibit poor selectivities in a number of cases. Here we report that a non-surface modification of palladium gives rise to the formation of an ultra-selective nanocatalyst. Boron atoms are found to take residence in palladium interstitial lattice sites with good chemical and thermal stability. This is favoured due to a strong host-guest electronic interaction when supported palladium nanoparticles are treated with a borane tetrahydrofuran solution. The adsorptive properties of palladium are modified by the subsurface boron atoms and display ultra-selectivity in a number of challenging alkyne hydrogenation reactions, which outclass the performance of Lindlar catalysts. PMID:25523894

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

    NASA Technical Reports Server (NTRS)

    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.

  19. Hydrogen atom in a magnetic field: Ghost orbits, catastrophes, and uniform semiclassical approximations

    SciTech Connect

    Main, J.; Wunner, G.

    1997-03-01

    Applying closed-orbit theory to the recurrence spectra of the hydrogen atom in a magnetic field, one can interpret most, but not all, structures semiclassically in terms of closed classical orbits. In particular, conventional closed-orbit theory fails near bifurcations of orbits where semiclassical amplitudes exhibit unphysical divergences. Here we analyze the role of ghost orbits living in complex phase space. The ghosts can explain resonance structures in the spectra of the hydrogen atom in a magnetic field at positions where no real orbits exist. For three different types of catastrophes, viz. fold, cusp, and butterfly catastrophes, we construct uniform semiclassical approximations and demonstrate that these solutions are completely determined by classical parameters of the real orbits and complex ghosts. {copyright} {ital 1997} {ital The American Physical Society}

  20. Proton scattering by a hydrogen atom in an effectively two-body model

    SciTech Connect

    Pupyshev, V. V.

    2013-02-15

    It is assumed that the total potential of proton interaction with a hydrogen atom is the sum of the short-range nuclear soft-core Reid potential and the long-range Thomas-Fermi potential. A quantum mechanical analysis of low-energy features of the phase shift and cross section for elastic proton scattering on a hydrogen atom is given for the case of zero total angular momentum. The calculations performed in the present study within a nonlinear version of the variable-phase approach ultimately revealed that, because of a long-range character of the asymptotic behavior of the Thomas-Fermi potential, the respective cross section at low energies oscillates but has a finite number of zeros.

  1. Interstitial modification of palladium nanoparticles with boron atoms as a green catalyst for selective hydrogenation

    NASA Astrophysics Data System (ADS)

    Chan, Chun Wong Aaron; Mahadi, Abdul Hanif; Li, Molly Meng-Jung; Corbos, Elena Cristina; Tang, Chiu; Jones, Glenn; Kuo, Winson Chun Hsin; Cookson, James; Brown, Christopher Michael; Bishop, Peter Trenton; Tsang, Shik Chi Edman

    2014-12-01

    Lindlar catalysts comprising of palladium/calcium carbonate modified with lead acetate and quinoline are widely employed industrially for the partial hydrogenation of alkynes. However, their use is restricted, particularly for food, cosmetic and drug manufacture, due to the extremely toxic nature of lead, and the risk of its leaching from catalyst surface. In addition, the catalysts also exhibit poor selectivities in a number of cases. Here we report that a non-surface modification of palladium gives rise to the formation of an ultra-selective nanocatalyst. Boron atoms are found to take residence in palladium interstitial lattice sites with good chemical and thermal stability. This is favoured due to a strong host-guest electronic interaction when supported palladium nanoparticles are treated with a borane tetrahydrofuran solution. The adsorptive properties of palladium are modified by the subsurface boron atoms and display ultra-selectivity in a number of challenging alkyne hydrogenation reactions, which outclass the performance of Lindlar catalysts.

  2. LETTER TO THE EDITOR: A formula for line strengths of hydrogenic atoms

    NASA Astrophysics Data System (ADS)

    Watson, James K. G.

    2006-07-01

    It is shown that the line strength for the transition n' <--> n of a hydrogenic atom with nuclear charge Z is (in atomic units) S_{n^{\\prime}n}=2Z \\langle n^{\\prime},0\\vert r\\vert n,0\\rangle \\langle n,0\\vert r^2\\vert n^{\\prime},0\\rangle, where the 0s in the matrix elements are the values of the quantum number l. This agrees with the expression for the hydrogen intensities originally given by McLean (1932 Nature 129 25). Expressions for the general l-diagonal matrix elements of r and r2 are given in terms of hypergeometric functions, and their asymptotic approximations for large n and relatively small c = n' - n are shown to agree with the asymptotic formula for the oscillator strength.

  3. Ionization of an Highly Excited Hydrogen atom in parallel Electric and Magnetic fields

    NASA Astrophysics Data System (ADS)

    Topçu, T.&Ürker; Robicheaux, Francis

    2006-05-01

    In a recent paper, Mitchell et al [Phys. Rev. Lett. 92, 073001 (2004)] investigated the ionization of a classical hydrogen atom in parallel electric and magnetic fields. They reported epistrophic self- similar pulse trains of ionized electrons attributed to the classical chaos induced by the magnetic field. We study hydrogen atom in an excited state with n˜80 in parallel external fields as an example of an open, chaotic quantum system in the time domain. We investigate the effect of interference between the outgoing pulse trains which is absent in the classical picture. We look at interference effect as a function of the energy since Schr"odinger equation does not scale as the classical equations of motion do. We compare and contrast our quantum results with the classical results of Mitchell et al.

  4. A fuzzy-atom analysis of electron delocalization on hydrogen bonds.

    PubMed

    Guillaumes, L; Salvador, P; Simon, S

    2014-02-13

    The extent of electron delocalization is quantified for set of cyclic complexes exhibiting two or more hydrogen bonds (HBs). In particular, the delocalization index (DI) between the atoms directly involved in the HB, and the ING (a normalized n-center delocalization index) have been evaluated using several fuzzy-atom schemes, namely Becke, Becke-ρ, Hirshfeld, and Hirshfeld-Iterative. The results have been compared with the widely used Quantum Theory of Atoms in Molecules (QTAIM) atomic definition. The DI values are found to correlate very well with geometrical or topological descriptors widely used in the literature to characterize HB systems. Among all fuzzy-atom methods, the ones that can better accommodate the different partial ionic character of the bonds perform particularly well. The best performing fuzzy-atom scheme for both pairwise and n-center electron delocalization is found to be the Becke-ρ method, for which similar results to QTAIM model are obtained with a much reduced computational cost. These results open up a wide range of applications of such electron delocalization descriptors based on fuzzy-atoms for noncovalent interactions in more complex and larger systems. PMID:24444143

  5. Measurement of cross sections for the scattering of p{mu} and d{mu} atoms on hydrogen and deuterium

    SciTech Connect

    Bystritskii, V.M.

    1995-04-01

    A brief review is given of all experiments on measurement of cross sections for the scattering of p{mu} atoms on hydrogen and for the scattering of d{mu} atoms on hydrogen or deuterium. The experimental results are analyzed and compared both with one another and with the results of calculations. In order to clarify the nature of discrepancies between the results of certain experiments and to obtain more precise information about the cross sections for the above processes, a program is proposed for further experimental investigation of the scattering of muonic atoms by hydrogen isotopes. 23 refs., 4 figs., 3 tabs.

  6. On the Origin of Cometary C2 and C3: Hydrogen Atom Migration in Diacetylene?

    NASA Astrophysics Data System (ADS)

    Heymann, Dieter

    2008-06-01

    The photolysis of C10H2 in air-saturated hexane by 253.6 nm photons yields the polyyne C8H2 in approximately 5% of all C10H2 disappearances; perhaps due to the migration of the hydrogen atom on Γ1 (I use the symbol Γn to designate the specific carbon atom number n in the chain; Γ1 is carbon atom 1) to Γ3 in the electronically excited C10H*2 molecule followed by the rupture of the Γ2-Γ3 carbon-carbon bond. C6H2 and C12H2 were not seen to form. This new result strengthens the hypothesis that hydrogen migration along carbon chains of photon-excited polyynes followed by the rupture of one carbon bond could be very common among these compounds. It is suggested here that diacetylene forms photochemically from acetylene in the cometary coma followed by the swift photochemical formation of C2 from diacetylene by hydrogen migration from Γ1 to Γ3 followed by the rupture of the Γ2-Γ3 carbon-carbon bond. Hydrogen migration from Γ1 to Γ4 in excited diacetylene followed by the rupture of the Γ3-Γ4 carbon bond might form cometary C3. Neither C2 nor C3 were detected in the current study. Their formation by hydrogen migration is therefore hypothetical but the case for C2 is observationally stronger than for C3. Removal of air from the solution increased the disappearance rate of C10H2 by a factor of almost 103, which implies that the excited molecule is in a triplet state with an estimated lifetime of 160 μs.

  7. Lower bounds to energies for cusped-gaussian wavefunctions. [hydrogen atom ground state

    NASA Technical Reports Server (NTRS)

    Eaves, J. O.; Walsh, B. C.; Steiner, E.

    1974-01-01

    Calculations for the ground states of H, He, and Be, conducted by Steiner and Sykes (1972), show that the inclusion of a very small number of cusp functions can lead to a substantial enhancement of the quality of the Gaussian basis used in molecular wavefunction computations. The properties of the cusped-Gaussian basis are investigated by a calculation of lower bounds concerning the ground state energy of the hydrogen atom.

  8. Breit and Quantum Electrodynamics Energy Contributions in Multielectron Atoms from the Relativistic Screened Hydrogenic Model

    NASA Astrophysics Data System (ADS)

    Di Rocco, Héctor O.; Lanzini, Fernando

    2016-04-01

    The correction to the Coulomb repulsion between two electrons due to the exchange of a transverse photon, referred to as the Breit interaction, as well as the main quantum electrodynamics contributions to the atomic energies (self-energy and vacuum polarization), are calculated using the recently formulated relativistic screened hydrogenic model. Comparison with the results of multiconfiguration Dirac-Hartree-Fock calculations and experimental X- ray energies is made.

  9. Spectrum of the hydrogen atom in Snyder space in a semiclassical approximation

    NASA Astrophysics Data System (ADS)

    Ivetić, B.; Mignemi, S.; Samsarov, A.

    2016-03-01

    We study the spectrum of the hydrogen atom in Snyder space in a semiclassical approximation based on a generalization of the Born-Sommerfeld quantization rule. While the corrections to the standard quantum mechanical spectrum arise at first order in the Snyder parameter for the l =0 states, they are of second order for l ≠0 . This can be understood as due to the different topology of the regions of integration in phase space.

  10. Doubly excited states of the hydrogen negative ion and helium atom in astrophysical plasmas

    SciTech Connect

    Jiang Pinghui; Kar, Sabyasachi; Zhou, Y.

    2013-01-15

    The nonthermal effects on the doubly excited resonance states of the hydrogen negative ion and helium atom are investigated in Lorentzian astrophysical plasma environments using highly correlated Hylleraas-type wave functions in the framework of the stabilization method. Resonance parameters (resonance position and width) are reported for the first time as functions of the spectral index and plasma parameter. The screening effects are more pronounced in the stronger screening region.

  11. Distortion effects in electron excitation of hydrogen atoms by impact of heavy ions

    SciTech Connect

    Ramirez, C.A.; Rivarola, R.D.

    1995-12-01

    Electron excitation from the fundamental state of hydrogen atoms by impact of bare ions is studied at intermediate and high collision velocities. Total cross sections for final {ital np} states by impact of protons, alpha particles, and He{sup +} ions are calculated using the symmetric eikonal approximation and compared with experimental data. This comparison supports the existence of distortion effects recently predicted by Bugacov and co-workers [Phys. Rev. A {bold 47}, 1052 (1993)]. The validity of scaling laws is analyzed.

  12. Disappearance of correlations in the atom motion upon hydrogen intercalation into ReO3 lattice

    NASA Astrophysics Data System (ADS)

    Timoshenko, Janis; Kuzmin, Alexei; Purans, Juris

    2016-05-01

    The influence of hydrogen intercalation on the local structure of rhenium trioxide is studied in-situ by the Re L3-edge EXAFS spectroscopy and analysed using a novel approach, based on the use of evolutionary algorithm and wavelet transform. The proposed method allows us to perform accurate EXAFS analysis within the multiple-scattering approach taking into account contributions from outer coordination shells and to access the information on correlations in atomic thermal motion.

  13. Absolute rate of the reaction of hydrogen atoms with ozone from 219-360 K

    NASA Technical Reports Server (NTRS)

    Lee, J. H.; Michael, J. V.; Payne, W. A.; Stief, L. J.

    1978-01-01

    Absolute rate constants for the reaction of atomic hydrogen with ozone were obtained over the temperature range 219-360 K by the flash photolysis-resonance fluorescence technique. The results can be expressed in Arrhenius form by K = (1.33 plus or minus 0.32)x10 to the minus 10 power exp (-449 plus or minus 58/T) cu cm/molecule/s (two standard deviations). The present work is compared to two previous determinations and is discussed theoretically.

  14. Dissociative excitation as the source of neutral atoms in hydrogen discharges

    SciTech Connect

    McNeill, D.H.

    1980-01-01

    Electron impact dissociative excitation of H/sub 2/ molecules is identified as the origin of the narrow width and structure of Balmer lines observed in various low density hydrogen discharges. On the basis of this data and estimates of the rates of competing processes in plasmas, dissociative excitation, together with other molecular reactions, is proposed as the source of neutral atoms and protons in these discharges.

  15. Hydrogen atom donor compounds as contrast enhancers for black-and-white photothermographic and thermographic elements

    DOEpatents

    Harring, Lori S.; Simpson, Sharon M.; Sansbury, Francis H.

    1997-01-01

    Hydrogen atom donor compounds are useful as contrast enhancers when used in combination with (i) hindered phenol developers, and (ii) trityl hydrazide and/or formyl-phenyl hydrazine co-developers, to produce ultra-high contrast black-and-white photothermographic and thermographic elements. The photothermographic and thermographic elements may be used as a photomask in a process where there is a subsequent exposure of an ultraviolet or short wavelength visible radiation-sensitive imageable medium.

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

    SciTech Connect

    Bauschlicher, Charles W. Jr.; Ricca, Alessandra E-mail: Alessandra.Ricca-1@nasa.gov

    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.

  17. Europa - Ultraviolet emissions and the possibility of atomic oxygen and hydrogen clouds

    NASA Technical Reports Server (NTRS)

    Wu, F.-M.; Judge, D. L.; Carlson, R. W.

    1978-01-01

    Emission signals from Europa with wavelength below 800 A were detected by the Pioneer 10 ultraviolet photometer. In the present paper, improved procedures for data reduction are used to determine the spatial region as well as the intensity of the suggested emission sources. The observations indicate a cloud with a radius of about 1.5 Jupiter radii and an apparent brightness of approximately 10 rayleighs for a wavelength of 500 A. It is argued that neutral oxygen atoms, along with neutral hydrogen, are produced through dissociation of water ice on the surface of Europa by particle impact. Electron impact ionization excitation of oxygen atoms in the resulting cloud then gives rise to the observed emission. The present source brightness and cloud radius results are used to estimate an oxygen column density of the order of 10 trillion per sq cm, while the density of atomic hydrogen is at most 100 billion per sq cm and 1 trillion per sq cm for molecular hydrogen.

  18. Fate of accidental symmetries of the relativistic hydrogen atom in a spherical cavity

    NASA Astrophysics Data System (ADS)

    Al-Hashimi, M. H.; Shalaby, A. M.; Wiese, U.-J.

    2015-11-01

    The non-relativistic hydrogen atom enjoys an accidental SO(4) symmetry, that enlarges the rotational SO(3) symmetry, by extending the angular momentum algebra with the Runge-Lenz vector. In the relativistic hydrogen atom the accidental symmetry is partially lifted. Due to the Johnson-Lippmann operator, which commutes with the Dirac Hamiltonian, some degeneracy remains. When the non-relativistic hydrogen atom is put in a spherical cavity of radius R with perfectly reflecting Robin boundary conditions, characterized by a self-adjoint extension parameter γ, in general the accidental SO(4) symmetry is lifted. However, for R =(l + 1) (l + 2) a (where a is the Bohr radius and l is the orbital angular momentum) some degeneracy remains when γ = ∞ or γ =2/R. In the relativistic case, we consider the most general spherically and parity invariant boundary condition, which is characterized by a self-adjoint extension parameter. In this case, the remnant accidental symmetry is always lifted in a finite volume. We also investigate the accidental symmetry in the context of the Pauli equation, which sheds light on the proper non-relativistic treatment including spin. In that case, again some degeneracy remains for specific values of R and γ.

  19. Confinement effects of magnetic field on two-dimensional hydrogen atom in plasmas

    NASA Astrophysics Data System (ADS)

    Bahar, M. K.; Soylu, A.

    2015-05-01

    In this study, for the first time, the Schrödinger equation with more general exponential cosine screened Coulomb (MGECSC) potential is solved numerically in the presence and in the absence of an external magnetic field within two-dimensional formalism using the asymptotic iteration method. The MGECSC potential includes four different potential forms when considering different sets of the parameters in the potential. The plasma screening effects in the weak and strong magnetic field regimes as well as the confinement effects of magnetic field on the two-dimensional hydrogen atom in Debye and quantum plasmas are investigated by solving the corresponding equations. It is found that applying a uniform magnetic field on the hydrogen atom embedded in a plasma leads to change in the profile of the total interaction potential. Thus, confinement effects of magnetic field on hydrogen atom embedded in Debye and quantum plasmas modeled by a MGECSC potential lead to shift bound state energies. This effect would be important to isolate the plasma from the external environment in the experimental applications of plasma physics.

  20. Polarized Atomic Hydrogen Beam Tests in the Michigan Ultra-Cold Jet Target

    NASA Astrophysics Data System (ADS)

    Kageya, T.; Blinov, B. B.; Denbow, J. M.; Kandes, M. C.; Krisch, A. D.; Kulkarni, D. A.; Lehman, M. A.; Luppov, V. G.; Morozov, V. S.; Murray, J. R.; Peters, C. C.; Raymond, R. S.; Ross, M. R.; Yonehara, K.; Borisov, N. S.; Fimushkin, V. V.; Kleppner, D.; Grishin, V. N.; Mysnik, A. L.

    2001-04-01

    To study spin effects in high energy collisions, we are developing an ultra-cold high-density jet target of proton-spin-polarized hydrogen atoms (Michigan Jet Target). The target uses a 12 Tesla magnetic field and a 0.3 K separation cell coated with superfluid helium-4 to produce a slow monochromatic electron-spin-polarized atomic hydrogen beam; an rf transition unit then converts this into a proton-spin-polarized beam, which is focused by a superconducting sextupole into the interaction region. The Jet produced, at the detector, a spin-polarized atomic hydrogen beam with a measured intensity of about 1.7 10^15 H s-1 and a FWHM area of less than 0.13 cm^2. This intensity corresponds to a free jet density of about 1.3 10^12 H cm-3 with a proton polarization of about 50%. When the transition RF unit is installed, we expect a proton polarization higher than 90%.

  1. Polarized Atomic Hydrogen Beam Tests in the Mark-II Ultra-Cold Jet Target.

    NASA Astrophysics Data System (ADS)

    Luppov, V. G.; Blinov, B. B.; Gladycheva, S. E.; Kageya, T.; Kantsyrev, D. Yu.; Krisch, A. D.; Murray, J. R.; Neumann, J. J.; Raymond, R. S.; Borisov, N. S.; Kleppner, D.; Davidenko, A. M.; Grishin, V. N.

    2000-04-01

    To study spin effects in high energy collisions, we are developing an ultra-cold high-density jet target of proton-spin-polarized hydrogen atoms (Mark-II). The target uses a 12 Tesla magnetic field and a 0.3 K separation cell coated with superfluid helium-4 to produce a slow monochromatic electron-spin-polarized atomic hydrogen beam; an rf transition unit then converts this into a proton-spin-polarized beam, which is focused by a superconducting sextupole into the interaction region. Recently, the Jet produced a measured electron-spin-polarized atomic hydrogen beam of about 10^15 H s-1 into a 0.3 cm^2 area at the detector. This intensity corresponds to the free jet density of about 10^11 H cm-3 with a proton polarization of about 50%. So far, the intensity is limited by the high insulation vacuum pressure due to the evaporation of the separation cell's helium film. The beam's angular and radial distributions were measured. A test of a new superfluid-^4He-coated parabolic mirror, attached to the separation cell, appeared to increase the beam intensity by a factor of about 3, as expected.

  2. Confinement effects of magnetic field on two-dimensional hydrogen atom in plasmas

    SciTech Connect

    Bahar, M. K.; Soylu, A.

    2015-05-15

    In this study, for the first time, the Schrödinger equation with more general exponential cosine screened Coulomb (MGECSC) potential is solved numerically in the presence and in the absence of an external magnetic field within two-dimensional formalism using the asymptotic iteration method. The MGECSC potential includes four different potential forms when considering different sets of the parameters in the potential. The plasma screening effects in the weak and strong magnetic field regimes as well as the confinement effects of magnetic field on the two-dimensional hydrogen atom in Debye and quantum plasmas are investigated by solving the corresponding equations. It is found that applying a uniform magnetic field on the hydrogen atom embedded in a plasma leads to change in the profile of the total interaction potential. Thus, confinement effects of magnetic field on hydrogen atom embedded in Debye and quantum plasmas modeled by a MGECSC potential lead to shift bound state energies. This effect would be important to isolate the plasma from the external environment in the experimental applications of plasma physics.

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

    NASA Astrophysics Data System (ADS)

    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.

  4. A ``local observables'' method for wave mechanics applied to atomic hydrogen

    NASA Astrophysics Data System (ADS)

    Bowman, Peter J.

    2008-12-01

    An alternative method of deriving the values of the observables of atomic systems is presented. Rather than using operators and eigenvalues the local variables method uses the continuity equation together with current densities derived from wave functions that are solutions of the Dirac or Pauli equation. The method is applied to atomic hydrogen using the usual language of quantum mechanics rather than that of geometric algebra with which the method is often associated. The picture of the atom that emerges is one in which the electron density as a whole is rotating about a central axis. The results challenge some assumptions of conventional quantum mechanics. Electron spin is shown to be a property of the dynamical motion of the electron and not an intrinsic property of the electron, the ground state of hydrogen is shown to have an orbital angular momentum of ℏ, and excited states are shown to have angular momenta that are different from the eigenvalues of the usual quantum mechanical operators. The uncertainty relations are found not to be applicable to the orthogonal components of the angular momentum. No double electron spin gyromagnetic ratio is required to account for the observed magnetic moments, and the behavior of the atom in a magnetic field is described entirely in kinetic terms.

  5. Hydrogen atoms under magnification: direct observation of the nodal structure of Stark states.

    PubMed

    Stodolna, A S; Rouzée, A; Lépine, F; Cohen, S; Robicheaux, F; Gijsbertsen, A; Jungmann, J H; Bordas, C; Vrakking, M J J

    2013-05-24

    To describe the microscopic properties of matter, quantum mechanics uses wave functions, whose structure and time dependence is governed by the Schrödinger equation. In atoms the charge distributions described by the wave function are rarely observed. The hydrogen atom is unique, since it only has one electron and, in a dc electric field, the Stark Hamiltonian is exactly separable in terms of parabolic coordinates (η, ξ, φ). As a result, the microscopic wave function along the ξ coordinate that exists in the vicinity of the atom, and the projection of the continuum wave function measured at a macroscopic distance, share the same nodal structure. In this Letter, we report photoionization microscopy experiments where this nodal structure is directly observed. The experiments provide a validation of theoretical predictions that have been made over the last three decades. PMID:23745864

  6. High-multipole excitations of hydrogen-like atoms by twisted photons near a phase singularity

    NASA Astrophysics Data System (ADS)

    Afanasev, Andrei; Carlson, Carl E.; Mukherjee, Asmita

    2016-07-01

    We calculate transition amplitudes and cross sections for excitation of hydrogen-like atoms by the twisted photon states, or photon states with angular momentum projection on the direction of propagation exceeding ℏ. If the target atom is located at distances of the order of atomic size near the phase singularity in the vortex center, the transition rates into the states with orbital angular momentum {l}f\\gt 1 become comparable with the rates for electric dipole transitions. It is shown that when the transition rates are normalized to the local photon flux, the resulting cross sections for {l}f\\gt 1 are singular near the optical vortex center. The relation to the ‘quantum core’ concept introduced by Berry and Dennis is discussed.

  7. Infrared studies of ortho-para conversion at Cl-atom and H-atom impurity centers in cryogenic solid hydrogen

    NASA Astrophysics Data System (ADS)

    Raston, P. L.; Kettwich, S. C.; Anderson, D. T.

    2010-05-01

    We report infrared spectroscopic studies of H2 ortho-para (o/p) conversion in solid hydrogen doped with Cl-atoms at 2K while the Cl +H2 (v=1)→HCl+H infrared-induced chemical reaction is occurring. The Cl-atom doped hydrogen crystals are synthesized using 355nm in situ photodissociation of Cl2 precursor molecules. For hydrogen solids with high ortho-H2 fractional concentrations (Xo=0.55), the o/p conversion kinetics is dominated by Cl-atom catalyzed conversion with a catalyzed conversion rate constant Kcc=1.16(11)min-1 and the process is rate-limited by ortho-H2 quantum diffusion. For hydrogen crystals with low ortho-H2 concentrations (Xo=0.03), single-exponential decay of the ortho-H2 concentration with time is observed which is attributed to H-atom catalyzed o/p conversion by the H-atoms produced during the infrared-induced Cl +H2 reaction. The measured H-atom catalyzed o/p conversion kinetics indicates the H-atoms are mobile under these conditions in agreement with previous ESR measurements.

  8. Isotope Dependence and Quantum Effects on Atomic Hydrogen Diffusion in Liquid Water.

    PubMed

    Walker, J A; Mezyk, S P; Roduner, E; Bartels, D M

    2016-03-01

    Relative diffusion coefficients were determined in water for the D, H, and Mu isotopes of atomic hydrogen by measuring their diffusion-limited spin-exchange rate constants with Ni(2+) as a function of temperature. H and D atoms were generated by pulse radiolysis of water and measured by time-resolved pulsed EPR. Mu atoms are detected by muonium spin resonance. To isolate the atomic mass effect from solvent isotope effect, we measured all three spin-exchange rates in 90% D2O. The diffusion depends on the atomic mass, demonstrating breakdown of Stokes-Einstein behavior. The diffusion can be understood using a combination of water "cavity diffusion" and "hopping" mechanisms, as has been proposed in the literature. The H/D isotope effect agrees with previous modeling using ring polymer molecular dynamics. The "quantum swelling" effect on muonium due to its larger de Broglie wavelength does not seem to slow its "hopping" diffusion as much as predicted in previous work. Quantum effects of both the atom mass and the water librations have been modeled using RPMD and a qTIP4P/f quantized flexible water model. These results suggest that the muonium diffusion is very sensitive to the Mu versus water potential used. PMID:26623663

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

    SciTech Connect

    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 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.

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

    NASA Astrophysics Data System (ADS)

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

    2015-12-01

    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.

  11. Atomic and electronic structure of hydrogen on ZnO (1bar 100) surface: ab initio hybrid calculations

    NASA Astrophysics Data System (ADS)

    Usseinov, A. B.; Kotomin, E. A.; Zhukovskii, Yu F.; Purans, J.; Sorokin, A. V.; Akilbekov, A. T.

    2013-12-01

    Hydrogen atoms unavoidably incorporated into ZnO during growth of bulk samples and thin films considerably affect their electrical conductivity. The results of first principles hybrid LCAO calculations are discussed for hydrogen atoms in the bulk and on the non-polar ZnO (1bar 100) surface. The incorporation energy, the atomic relaxation, the electronic density redistribution and the electronic structure modifications are compared for the surface adsorption and bulk interstitial H positions. It is shown that hydrogen has a strong binding with the surface O ions (2.7 eV) whereas its incorporation into bulk is energetically unfavorable. Surface hydrogen atoms are very shallow donors, thus, contributing to the electronic conductivity.

  12. Atom-by-atom simulations of chemical vapor deposition of nanoporous hydrogenated silicon nitride

    NASA Astrophysics Data System (ADS)

    Houska, J.; Klemberg-Sapieha, J. E.; Martinu, L.

    2010-04-01

    Amorphous hydrogenated silicon nitride (SiNH) materials prepared by plasma-enhanced chemical vapor deposition (PECVD) are of high interest because of their suitability for diverse applications including optical coatings, gas/vapor permeation barriers, corrosion resistant, and protective coatings and numerous others. In addition, they are very suitable for structurally graded systems such as those with a graded refractive index. In parallel, modeling the PECVD process of SiN(H) of an a priori given SiN(H) ratio by atomistic calculations represents a challenge due to: (1) different (and far from constant) sticking coefficients of individual elements, and (2) expected formation of N2 (and H2) gas molecules. In the present work, we report molecular-dynamics simulations of particle-by-particle deposition process of SiNH films from SiHx and N radicals. We observe formation of a mixed zone (damaged layer) in the initial stages of film growth, and (under certain conditions) formation of nanopores in the film bulk. We investigate the effect of various PECVD process parameters (ion energy, composition of the SiHx+N particle flux, ion fraction in the particle flux, composition of the SiHx radicals, angle of incidence of the particle flux) on both (1) deposition characteristics, such as sticking coefficients, and (2) material characteristics, such as dimension of the nanopores formed. The results provide detailed insight into the complex relationships between these process parameters and the characteristics of the deposited SiNH materials and exhibit an excellent agreement with the experimentally observed results.

  13. Kinetics of the hydrogen abstraction *CH3 + alkane --> CH4 + alkyl reaction class: an application of the reaction class transition state theory.

    PubMed

    Kungwan, Nawee; Truong, Thanh N

    2005-09-01

    Kinetics of the hydrogen abstraction reaction (*)CH(3) + CH(4) --> CH(4) + (*)CH(3) is studied by a direct dynamics method. Thermal rate constants in the temperature range of 300-2500 K are evaluated by the canonical variational transition state theory (CVT) incorporating corrections from tunneling using the multidimensional semiclassical small-curvature tunneling (SCT) method and from the hindered rotations. These results are used in conjunction with the Reaction Class Transition State Theory/Linear Energy Relationship (RC-TST/LER) to predict thermal rate constants of any reaction in the hydrogen abstraction class of (*)CH(3) + alkanes. Our analyses indicate that less than 40% systematic errors on the average exist in the predicted rate constants using the RC-TST/LER method while comparing to explicit rate calculations the differences are less than 100% or a factor of 2 on the average. PMID:16834150

  14. Atomic Regime in Which the Magnetic Interaction Dominates the Coulomb Interaction for Highly Excited States of Hydrogen

    PubMed Central

    Mueller, Ronald O.; Hughes, Vernon W.

    1974-01-01

    The atomic regime in which the interaction of the electron with an external magnetic field dominates the Coulomb interaction with the nucleus, relevant to pulsars, can be realized at laboratory magnetic fields for discrete autoionized states of hydrogen, at energies above the ionization limit. Approximate wave functions, energy levels, and electric dipole transition probabilities are presented for hydrogen, and an atomic beam absorption spectroscopy experiment at 50 kG is proposed to study this new regime. PMID:16578723

  15. Selective hydrogenation of 1,3-butadiene on platinum–copper alloys at the single-atom limit

    SciTech Connect

    Lucci, Felicia R.; Liu, Jilei; Marcinkowski, Matthew D.; Yang, Ming; Allard, Lawrence F.; Flytzani-Stephanopoulos, Maria; Sykes, E. Charles H.

    2015-10-09

    Platinum is ubiquitous in the production sectors of chemicals and fuels; however, its scarcity in nature and high price will limit future proliferation of platinum-catalysed reactions. One definite approach to conserve platinum involves understanding the smallest number of platinum atoms needed to catalyse a reaction, then designing catalysts with the minimal platinum ensembles. Here we design and test a new generation of platinum–copper nanoparticle catalysts for the selective hydrogenation of 1,3-butadiene,, an industrially important reaction. Isolated platinum atom geometries enable hydrogen activation and spillover but are incapable of C–C bond scission that leads to loss of selectivity and catalyst deactivation. γ-Alumina-supported single-atom alloy nanoparticle catalysts with <1 platinum atom per 100 copper atoms are found to exhibit high activity and selectivity for butadiene hydrogenation to butenes under mild conditions, demonstrating transferability from the model study to the catalytic reaction under practical conditions.

  16. Selective hydrogenation of 1,3-butadiene on platinum-copper alloys at the single-atom limit

    NASA Astrophysics Data System (ADS)

    Lucci, Felicia R.; Liu, Jilei; Marcinkowski, Matthew D.; Yang, Ming; Allard, Lawrence F.; Flytzani-Stephanopoulos, Maria; Sykes, E. Charles H.

    2015-10-01

    Platinum is ubiquitous in the production sectors of chemicals and fuels; however, its scarcity in nature and high price will limit future proliferation of platinum-catalysed reactions. One promising approach to conserve platinum involves understanding the smallest number of platinum atoms needed to catalyse a reaction, then designing catalysts with the minimal platinum ensembles. Here we design and test a new generation of platinum-copper nanoparticle catalysts for the selective hydrogenation of 1,3-butadiene,, an industrially important reaction. Isolated platinum atom geometries enable hydrogen activation and spillover but are incapable of C-C bond scission that leads to loss of selectivity and catalyst deactivation. γ-Alumina-supported single-atom alloy nanoparticle catalysts with <1 platinum atom per 100 copper atoms are found to exhibit high activity and selectivity for butadiene hydrogenation to butenes under mild conditions, demonstrating transferability from the model study to the catalytic reaction under practical conditions.

  17. Selective hydrogenation of 1,3-butadiene on platinum-copper alloys at the single-atom limit.

    PubMed

    Lucci, Felicia R; Liu, Jilei; Marcinkowski, Matthew D; Yang, Ming; Allard, Lawrence F; Flytzani-Stephanopoulos, Maria; Sykes, E Charles H

    2015-01-01

    Platinum is ubiquitous in the production sectors of chemicals and fuels; however, its scarcity in nature and high price will limit future proliferation of platinum-catalysed reactions. One promising approach to conserve platinum involves understanding the smallest number of platinum atoms needed to catalyse a reaction, then designing catalysts with the minimal platinum ensembles. Here we design and test a new generation of platinum-copper nanoparticle catalysts for the selective hydrogenation of 1,3-butadiene,, an industrially important reaction. Isolated platinum atom geometries enable hydrogen activation and spillover but are incapable of C-C bond scission that leads to loss of selectivity and catalyst deactivation. γ-Alumina-supported single-atom alloy nanoparticle catalysts with <1 platinum atom per 100 copper atoms are found to exhibit high activity and selectivity for butadiene hydrogenation to butenes under mild conditions, demonstrating transferability from the model study to the catalytic reaction under practical conditions. PMID:26449766

  18. Selective hydrogenation of 1,3-butadiene on platinum–copper alloys at the single-atom limit

    PubMed Central

    Lucci, Felicia R.; Liu, Jilei; Marcinkowski, Matthew D.; Yang, Ming; Allard, Lawrence F.; Flytzani-Stephanopoulos, Maria; Sykes, E. Charles H.

    2015-01-01

    Platinum is ubiquitous in the production sectors of chemicals and fuels; however, its scarcity in nature and high price will limit future proliferation of platinum-catalysed reactions. One promising approach to conserve platinum involves understanding the smallest number of platinum atoms needed to catalyse a reaction, then designing catalysts with the minimal platinum ensembles. Here we design and test a new generation of platinum–copper nanoparticle catalysts for the selective hydrogenation of 1,3-butadiene,, an industrially important reaction. Isolated platinum atom geometries enable hydrogen activation and spillover but are incapable of C–C bond scission that leads to loss of selectivity and catalyst deactivation. γ-Alumina-supported single-atom alloy nanoparticle catalysts with <1 platinum atom per 100 copper atoms are found to exhibit high activity and selectivity for butadiene hydrogenation to butenes under mild conditions, demonstrating transferability from the model study to the catalytic reaction under practical conditions. PMID:26449766

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

    ERIC Educational Resources Information Center

    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…

  20. Photoreduction of benzophenone by acetonitrile: correlation of rates of hydrogen abstraction from RH with the ionization potentials of the radicals R

    SciTech Connect

    Naguib, Y.M.A.; Steel, C.; Cohen, S.G.; Young, M.A.

    1987-05-21

    Triplet benzophenone (/sup 4/K) abstracts a hydrogen from acetonitrile with a rate constant of 130 +/- 30 M/sup -1/ s/sup -1/. Despite this low rate constant acetonitrile is not really an inert solvent and at low light fluxes, where T-T annihilation is not a major fate of the triplet, a major decay path for /sup 4/K is hydrogen abstraction with resulting pinacol (K/sub 2/H/sub 2/) formation (phi/sub K/sub 2/H/sub 2/ approx. = 0.1 at t = 0). Both K/sub 2/H/sub 2/ formation and /sup 3/K lifetime rapidly decrease with irradiation due to the light absorbing transients (LAT's) which are formed along with K/sub 7/H/sub 2/ from ketyl radicals (KH). The rate constants per hydrogen (k/sub H/) for abstraction from R-H by the electrophilic /sup 3/K correlate well with the ionization potentials (IP) of the corresponding radicals (R).

  1. Hydrogen atom distribution and hydrogen induced site depopulation for the La{sub 2-x}Mg{sub x}Ni{sub 7}-H system

    SciTech Connect

    Guzik, Matylda N.; Hauback, Bjorn C.; Yvon, Klaus

    2012-02-15

    La{sub 2-x}Mg{sub x}Ni{sub 7} and its hydrides/deuterides were investigated by high resolution synchrotron powder X-ray and neutron diffraction. Upon deuteration the single phase sample of the intermetallic compound with the refined composition La{sub 1.63}Mg{sub 0.37}Ni{sub 7} (space group: P6{sub 3}/mmc) expands isotropically, in contrast to the Mg free phase. The hydrogen uptake, {approx}9 D/f.u., is higher than in La{sub 2}Ni{sub 7}D{sub 6.5}. The refined composition accounts for La{sub 1.63}Mg{sub 0.37}Ni{sub 7}D{sub 8.8} (beta-phase). Rietveld refinements using the neutron and synchrotron diffraction data suggest that deuterium atoms occupy 5 different interstitial sites within both AB{sub 2} and AB{sub 5} slabs, either in an ordered or a disordered way. All determined D sites have an occupancy >50% and the shortest D-D contact is 1.96(3) A. It is supposed that a competition between the tendency to form directional bonds and repulsive D-D (H-H) interactions is the most important factor that influences the distribution of deuterium atoms in this structure. A hitherto unknown second, alpha-phase with composition La{sub 1.63}Mg{sub 0.37}Ni{sub 7}D{sub 0.56}, crystallizing with the same hexagonal symmetry as La{sub 1.63}Mg{sub 0.37}Ni{sub 7}D{sub 8.8}, has been discovered. The unit cell parameters for this D-poor phase differ slightly from those of the intermetallic. Alpha-phase displays only one D site (4f, space group: P6{sub 3}/mmc) occupied >50%, which is not populated in the D-rich beta-phase. This hydrogen/deuterium induced site depopulation can be explained by repulsive D-D (H-H) interactions that are likely to influence non-occupancy of certain interstices in metal lattice when absorbing hydrogen. - Graphical abstract: The detailed D atoms arrangement in La{sub 1.63}Mg{sub 0.37}Ni{sub 7}D{sub 8.8} differs significantly from the previously reported La{sub 1.5}Mg{sub 0.5}Ni{sub 7}D{sub 8.9(9.1)}. The present model consists of only five deuterium sites as

  2. Density functional study of manganese atom adsorption on hydrogen-terminated armchair boron nitride nanoribbons

    NASA Astrophysics Data System (ADS)

    Abdullahi, Yusuf Zuntu; Rahman, Md. Mahmudur; Shuaibu, Alhassan; Abubakar, Shamsu; Zainuddin, Hishamuddin; Muhida, Rifki; Setiyanto, Henry

    2014-08-01

    In this paper, we have investigated stable structural, electric and magnetic properties of manganese (Mn) atom adsorption on armchair hydrogen edge-terminated boron nitride nanoribbon (A-BNNRs) using first principles method based on density-functional theory with the generalized gradient approximation. Calculation shows that Mn atom situated on the ribbons of A-BNNRs is the most stable configuration, where the bonding is more pronounced. The projected density of states (PDOS) of the favored configuration has also been computed. It has been found that the covalent bonding of boron (B), nitrogen (N) and Mn is mainly contributed by s, d like-orbitals of Mn and partially occupied by the 2p like-orbital of N. The difference in energy between the inner and the edge adsorption sites of A-BNNRs shows that Mn atoms prefer to concentrate at the edge sites. The electronic structures of the various configurations are wide, narrow-gap semiconducting and half-metallic, and the magnetic moment of Mn atoms are well preserved in all considered configurations. This has shown that the boron nitride (BN) sheet covered with Mn atoms demonstrates additional information on its usefulness in future spintronics, molecular magnet and nanoelectronics devices.

  3. Collisional radiative average atom code based on a relativistic Screened Hydrogenic Model

    NASA Astrophysics Data System (ADS)

    Benita, A. J.; Mínguez, E.; Mendoza, M. A.; Rubiano, J. G.; Gil, J. M.; Rodríguez, R.; Martel, P.

    2015-03-01

    A steady-state and time-dependent collisional-radiative ''average-atom'' (AA) model (ATMED CR) is presented for the calculation of atomic and radiative properties of plasmas for a wide range of laboratory and theoretical conditions: coronal, local thermodynamic equilibrium or nonlocal thermodynamic equilibrium, optically thin or thick plasmas and photoionized plasmas. The radiative and collisional rates are a set of analytical approximations that compare well with more sophisticated quantum treatment of atomic rates that yield fast calculations. The atomic model is based on a new Relativistic Screened Hydrogenic Model (NRSHM) with a set of universal screening constants including nlj-splitting that has been obtained by fitting to a large database of ionization potentials and excitation energies compiled from the National Institute of Standards and Technology (NIST) database and the Flexible Atomic Code (FAC). The model NRSHM has been validated by comparing the results with ionization energies, transition energies and wave functions computed using sophisticated self-consistent codes and experimental data. All the calculations presented in this work were performed using ATMED CR code.

  4. Stable isolated metal atoms as active sites for photocatalytic hydrogen evolution.

    PubMed

    Xing, Jun; Chen, Jian Fu; Li, Yu Hang; Yuan, Wen Tao; Zhou, Ying; Zheng, Li Rong; Wang, Hai Feng; Hu, P; Wang, Yun; Zhao, Hui Jun; Wang, Yong; Yang, Hua Gui

    2014-02-17

    The process of using solar energy to split water to produce hydrogen assisted by an inorganic semiconductor is crucial for solving our energy crisis and environmental problems in the future. However, most semiconductor photocatalysts would not exhibit excellent photocatalytic activity without loading suitable co-catalysts. Generally, the noble metals have been widely applied as co-catalysts, but always agglomerate during the loading process or photocatalytic reaction. Therefore, the utilization efficiency of the noble co-catalysts is still very low on a per metal atom basis if no obvious size effect exists, because heterogeneous catalytic reactions occur on the surface active atoms. Here, for the first time, we have synthesized isolated metal atoms (Pt, Pd, Rh, or Ru) stably by anchoring on TiO2 , a model photocatalystic system, by a facile one-step method. The isolated metal atom based photocatalysts show excellent stability for H2 evolution and can lead to a 6-13-fold increase in photocatalytic activity over the metal clusters loaded on TiO2 by the traditional method. Furthermore, the configurations of isolated atoms as well as the originality of their unusual stability were analyzed by a collaborative work from both experiments and theoretical calculations. PMID:24403011

  5. Photochemical effects in 243-nm two-photon excitation of atomic hydrogen in flames.

    PubMed

    Goldsmith, J E

    1989-03-15

    This paper describes photochemical effects observed during two-photon 1S-2S excitation of atomic hydrogen in flames using 243-nm laser radiation. An I(4) intensity dependence is observed in regions of the flame where the natural atomic concentration is low, suggesting an I(2) photochemical production mechanism, which we believe is due to two-photon excitation of water molecules, which then predissociate to form H and OH fragments. In a measurement of OH created in the flame by the 243-nm beam, we observe the same I(2) intensity dependence with the laser detuned from the atomic hydrogen 1S-2S resonance, but an apparent I(3.4) dependence is observed when the laser is tuned to the resonance. We believe that a second photochemical mechanism contributes at the resonance, namely, two-photon excitation of H, followed by collisional energy transfer to water molecules, which then fall apart into H and OH fragments. We model this process and show that a combination of I(2) and I(4) dependences can lead to an intensity dependence that mimics a single I(3.4) dependence over a limited range of intensities. PMID:20548641

  6. Achievement of high atomic hydrogen densities in cylindrical rf plasmas with magnetic field

    NASA Astrophysics Data System (ADS)

    Fantz, Ursel; Briefi, Stefan

    2014-10-01

    Cylindrical rf plasmas in hydrogen with and without an axial magnetic field of up to 120 G are investigated in the pressure range of 0.3 to 10 Pa. The atomic hydrogen density is determined with optical emission spectroscopy, analyzing the Balmer lines and the molecular radiation (Fulcher band). The results obtained by using different coil geometries (4 to 6 turn windings and Nagoya type antenna) as well as different diameters (10 cm and 25 cm) of a quartz, aluminum oxide or aluminum nitride cylinder are compared. RF powers of up to 600 W at a frequency of 13.56 MHz are available for the 10 cm configuration, whereas up to 70 kW power at 1 MHz are used for the 25 cm cylinder. Density ratios of atoms to molecules of up to 0.3 are achieved in both configurations, whereby the achievement in the high power setup is limited by neutral depletion. The influence of the wall material on the atomic densities, and thus the recombination coefficient, will be pointed out.

  7. Branching ratios for the decay of n = 3 hydrogen atoms in axial and transverse electric fields

    SciTech Connect

    Rouze, N.; Havener, C.C.; Westerveld, W.B.; Risley, A.J.S.

    1986-01-01

    The branching ratios for the n = 3 to n = 2 Balmer- decay of hydrogen atoms in axial and transverse electric fields in the range 0--1000 V/cm have been calculated with use of a density-matrix formalism to take into account the time evolution of the atomic states in the presence of an electric field. The branching ratios are useful when the production of 2s hydrogen atoms is measured with the use of an electric field and when it is desired to correct for cascade contributions from the n = 3 level. The total n = 3 to n = 2 branching ratio is found to depend on each of the 14 independent quantities which determine the axially symmetric n = 3 density matrix, thus emphasizing the need to determine the complete density matrix including the off-diagonal coherence terms. If the off-diagonal density-matrix elements are not known, it is preferable to use transverse electric fields since, in this configuration, the contributions to the branching ratios from the off-diagonal terms are less than with axial electric fields. For transverse fields of approximately 200 V/cm, the contribution from the off-diagonal terms are nearly zero.

  8. Exposure of GaAs to atomic hydrogen for cleaning prior to NEA photocathode activation

    SciTech Connect

    Sinclair, C.K.; Poelker, B.M.; Price, J.S.

    1998-12-31

    Creating an atomically clean semiconductor surface is an essential step in preparing negative electron affinity (NEA) photoemission cathodes. While bulk GaAs can be satisfactorily cleaned by chemical etching and in situ heat cleaning, many high polarization electron source materials are either much too thin, or have oxides and carbides which are too tightly bound, to be cleaned by these methods. Some polarized source candidate materials may be degraded during the heat cleaning step. It is well established that the exposure of many III-V, II-VI, and elemental semiconductors to atomic hydrogen, typically at elevated temperatures, produces semiconductor surfaces free of contamination. Furthermore, this cleaning, possibly followed by thermal annealing, leaves surfaces which show sharp LEED patterns, indicating good stoichiometry and surface order. Atomic hydrogen cleaning should eliminate the chemical etching step, and might reduce the temperature and/or temperature-time product presently used in forming NEA cathodes. The process is readily adaptable to in situ use in ultrahigh vaccum.

  9. Electromagnetic Shifts of Energy Levels of a Hydrogen Atom in Idealized Cavities.

    NASA Astrophysics Data System (ADS)

    Burzan, Dragisa

    Available from UMI in association with The British Library. Requires signed TDF. Energy level shifts are evaluated for the 2p-2s transition for a hydrogen atom in various confining geometries with idealized perfectly conducting metallic boundaries in all cases. The minimal coupling Hamiltonian formalism is employed in the non-relativistic approximation in the Coulomb gauge to calculate the level shifts. Bethe's work for the Lamb shift in free space for the hydrogen atom is used as the model for working out the transverse level shifts in the various confining geometries. The Stark effect arising from the interaction of an atom with its image in the metal is used to evaluate the longitudinal level shift. The analysis is carried out by first quantizing the electro-magnetic field in a general cavity after a discussion is presented in the introduction of the relation of this work to that of other authors on related topics. The theory is then developed in detail in the various special confining geometries starting with case of the parallelopiped and its limiting cases of two plates and one plate respectively. The confining geometries of a finite and infinite cylinder are considered next followed by that of sphere. Detailed numerical results are presented in each of the various special cases with graphs and tables after extensive computation. The conclusions of the thesis are summarized separately.

  10. Experimental investigations of reactions of hot hydrogen atoms with molecular hydrogen and water

    SciTech Connect

    Adelman, D.E.

    1993-01-01

    The state-to-state integral rate constants were measured for the three reactions: (1) D + H[sub 2](vj) [yields] HD(v[prime] = 0,1,2;j) + H at E[sub rel] = 1.4 and 0.8 eV and (2) H + D[sub 2] [yields] HD(v[prime] = 1,j[prime]) + D at E[sub rel] = 2.2 and 2.5 eV, and (3) H + D[sub 2]O [yields] HD(v[prime],j[prime]), + OD at E[sub rel] = 2.7 eV. The reagents were either in the ground state, (v = 0,j), or for the D + H[sub 2] work prepared in the first excited vibrational state, (v = 1, j = 1), by stimulated Raman pumping. Translationally hot D(H) atoms were generated by UV photolysis of D(H)I. Resonance-enhanced multiphoton ionization and time-of-flight mass spectrometry were employed to detect the nascent HD product in a quantum-state-specific manner. For the reaction D + H[sub 2] we find that vibrational excitation of the H[sub 2] reagent results in: (1) substantial HD rotational excitation for each product vibrational state, (2) a [open quotes]heating[close quotes] of the vibrational product state distribution, and (3) almost no change in the total rate into HD(v[prime] = 0,1,2;j[prime]). The experimental results are consistent with a model in which internal energy of the reagents is conserved. Good to excellent agreement is found between the experiment and recent quantum-mechanical (QM) scattering calculations. The reaction H + D[sub 2] [yields] HD(v[prime] = 1,j[prime]) + D was studied at high collision energies. These experiments provide data that will be useful for determining the importance of the Jahn-Teller effect in reactive scattering systems and to the development of theoretical techniques in which the ground and first excited electronic surfaces are included in QM calculations. For the reaction H + D[sub 2]O, approximately 35% (12% in vibration, 23% in rotation) of the available energy is partitioned into the internal modes of the HD product.

  11. Repulsive tip tilting as the dominant mechanism for hydrogen bond-like features in atomic force microscopy imaging

    NASA Astrophysics Data System (ADS)

    Lee, Alex J.; Sakai, Yuki; Kim, Minjung; Chelikowsky, James R.

    2016-05-01

    Experimental atomic force microscopy (AFM) studies have reported distinct features in regions with little electron density for various organic systems. These unexpected features have been proposed to be a direct visualization of intermolecular hydrogen bonding. Here, we apply a computational method using ab initio real-space pseudopotentials along with a scheme to account for tip tilting to simulate AFM images of the 8-hydroxyquinoline dimer and related systems to develop an understanding of the imaging mechanism for hydrogen bonds. We find that contrast for the observed "hydrogen bond" feature comes not from the electrostatic character of the bonds themselves but rather from repulsive tip tilting induced by neighboring electron-rich atoms.

  12. Charge exchange of hydrogen atoms with multiply charged ions in a hot plasma

    NASA Astrophysics Data System (ADS)

    Abramov, V. A.; Baryshnikov, F. F.; Lisitsa, V. S.

    1980-08-01

    The symmetry properties of the hydrogen atom were used to calculate the charge exchange cross sections sigma of hydrogen with the nuclei of multiply charged ions, while allowance was made for the degeneration of final states. If the transitions between these states produced by rotation of the internuclear axis are taken into account, there is a qualitative change in the dependence of sigma on v for low values of v (a gradual decrease in the cross section instead of the exponential one in the Landau-Zener model) and also a considerable increase in the peak cross section. The cross sections are calculated for a wide range of velocities and charge values-Z. The distribution of final states over orbital angular momenta is found.

  13. Multiply Confined Nickel Nanocatalysts Produced by Atomic Layer Deposition for Hydrogenation Reactions.

    PubMed

    Gao, Zhe; Dong, Mei; Wang, Guizhen; Sheng, Pei; Wu, Zhiwei; Yang, Huimin; Zhang, Bin; Wang, Guofu; Wang, Jianguo; Qin, Yong

    2015-07-27

    To design highly efficient catalysts, new concepts for optimizing the metal-support interactions are desirable. Here we introduce a facile and general template approach assisted by atomic layer deposition (ALD), to fabricate a multiply confined Ni-based nanocatalyst. The Ni nanoparticles are not only confined in Al2 O3 nanotubes, but also embedded in the cavities of Al2 O3 interior wall. The cavities create more Ni-Al2 O3 interfacial sites, which facilitate hydrogenation reactions. The nanotubes inhibit the leaching and detachment of Ni nanoparticles. Compared with the Ni-based catalyst supported on the outer surface of Al2 O3 nanotubes, the multiply confined catalyst shows a striking improvement of catalytic activity and stability in hydrogenation reactions. Our ALD-assisted template method is general and can be extended for other multiply confined nanoreactors, which may have potential applications in many heterogeneous reactions. PMID:26150352

  14. Solar wind heating beyond 1 AU. [interplanetary atomic hydrogen gas effect on protons and electrons

    NASA Technical Reports Server (NTRS)

    Holzer, T. E.; Leer, E.

    1973-01-01

    The effect of an interplanetary atomic hydrogen gas on solar wind proton, electron and alpha-particle temperatures beyond 1 AU is considered. It is shown that the proton temperature (and probably also the alpha-particle temperature) reaches a minimum between 2 AU and 4 AU, depending on values chosen for solar wind and interstellar gas parameters. Heating of the electron gas depends primarily on the thermal coupling of the protons and electrons. For strong coupling, the electron temperature reaches a minimum between 4 AU and 8 AU, but for weak coupling (Coulomb collisions only), the electron temperature continues to decrease throughout the inner solar system. A spacecraft travelling to Jupiter should be able to observe the heating effect of the solar wind-interplanetary hydrogen interaction, and from such observations it may be possible of infer some properties of the interstellar neutral gas.

  15. Use of predissociation to enhance the atomic hydrogen ion fraction in ion sources

    DOEpatents

    Kim, Jinchoon

    1979-01-01

    A duopigatron ion source is modified by replacing the normal oxide-coated wire filament cathode of the ion source with a hot tungsten oven through which hydrogen gas is fed into the arc chamber. The hydrogen gas is predissociated in the hot oven prior to the arc discharge, and the recombination rate is minimized by hot walls inside of the arc chamber. With the use of the above modifications, the atomic H.sub.1.sup.+ ion fraction output can be increased from the normal 50% to greater than 70% with a corresponding decrease in the H.sub.2.sup.+ and H.sub.3.sup.+ molecular ion fraction outputs from the ion source.

  16. Compact solid-state laser source for 1S-2S spectroscopy in atomic hydrogen

    SciTech Connect

    Kolachevsky, N.; Alnis, J.; Bergeson, S. D.; Haensch, T. W.

    2006-02-15

    We demonstrate a compact solid-state laser source for high-resolution two-photon spectroscopy of the 1S-2S transition in atomic hydrogen. The source emits up to 20 mW at 243 nm and consists of a 972 nm diode laser, a tapered amplifier, and two doubling stages. The diode laser is actively stabilized to a high-finesse cavity. We compare the new source to the stable 486 nm dye laser used in previous experiments and record 1S-2S spectra using both systems. With the solid-state laser system, we demonstrate a resolution of the hydrogen spectrometer of 6x10{sup 11}, which is promising for a number of high-precision measurements in hydrogenlike systems.

  17. Atom-economical synthesis of γ-valerolactone with self-supplied hydrogen from methanol.

    PubMed

    Li, Zheng; Tang, Xing; Jiang, Yetao; Wang, Yanjun; Zuo, Miao; Chen, Wei; Zeng, Xianhai; Sun, Yong; Lin, Lu

    2015-11-25

    γ-Valerolactone (GVL), a versatile biomass derived platform molecule, was synthesized with a highest yield of 89.8% from methyl levulinate (ML) using self-supplied H2 coming from the decomposition of MeOH derived partially from ML. Cu-Cr acted as a bi-functional catalyst for both H2 production from MeOH and carbonyl hydrogenation. An extremely low amount of MeOH (29 mol% relative to ML) was initially necessary to start up the hydrocyclization of ML to GVL and MeOH, which is in turn employed as an in situ H2 source for ML hydrogenation, providing an atom-economical pathway for GVL production. PMID:26403664

  18. Exact nonrelativistic polarizabilities of the hydrogen atom with the Lagrange-mesh method

    NASA Astrophysics Data System (ADS)

    Baye, Daniel

    2012-12-01

    Exact analytical expressions of the dipole polarizabilities of the nonrelativistic hydrogen atom in spherical coordinates are derived with the help of the Lagrange-mesh numerical method. This method can provide exact energies and wave functions for well-chosen conditions of calculation. Exact dipole polarizabilities are obtained after an unambiguous rounding up to at least principal quantum numbers around n=30. The scalar polarizability of any nl level is given by n4[4n2+14+7l(l+1)]/4 and its tensor polarizability is given by -n4[3n2-9+11l(l+1)]l/4(2l+3), which allows the calculation of the polarizability of any hydrogen state nlm.

  19. Activation of extended red emission photoluminescence in carbon solids by exposure to atomic hydrogen and UV radiation

    NASA Technical Reports Server (NTRS)

    Furton, Douglas G.; Witt, Adolf N.

    1993-01-01

    We report on new laboratory results which relate directly to the observation of strongly enhanced extended red emission (ERE) by interstellar dust in H2 photodissociation zones. The ERE has been attributed to photoluminescence by hydrogenated amorphous carbon (HAC). We are demonstrating that exposure to thermally dissociated atomic hydrogen will restore the photoluminescence efficiency of previously annealed HAC. Also, pure amorphous carbon (AC), not previously photoluminescent, can be induced to photoluminesce by exposure to atomic hydrogen. This conversion of AC into HAC is greatly enhanced by the presence of UV irradiation. The presence of dense, warm atomic hydrogen and a strong UV radiation field are characteristic environmental properties of H2 dissociation zones. Our results lend strong support to the HAC photoluminescence explanation for ERE.

  20. Experimental limits on the velocities of sodium atoms sputtered from solid surfaces by hydrogen ions. [Na cloud production around Io

    NASA Technical Reports Server (NTRS)

    Stoner, J. O., Jr.

    1976-01-01

    Optical emission at 589.0 nm by sodium atoms sputtered from solid targets by hydrogen molecular ions was observed, and no accompanying broadening or shifts of this line could be detected relative to that from a laboratory lamp. This allowed an upper limit of about 500,000 cm/sec on the mean speed of ejected sodium atoms to be calculated. The results are consistent with the hypothesis that the atomic sodium cloud surrounding Io is produced by this mechanism.

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

    NASA Astrophysics Data System (ADS)

    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.

  2. Phase with pressure-induced shuttlewise deformation in dense solid atomic hydrogen

    NASA Astrophysics Data System (ADS)

    Ishikawa, Takahiro; Nagara, Hitose; Oda, Tatsuki; Suzuki, Naoshi; Shimizu, Katsuya

    2014-09-01

    A phase which shows pressure-induced shuttlewise structural deformation between orthorhombic Fddd and tetragonal I41/amd structures has been predicted in solid atomic hydrogen by means of the first-principles calculations, including harmonic zero-point energy contributions of proton motions. The Fddd structure is formed by shear distortion from the I41/amd structure, and the angle specifying the distortion changes with pressure in the range 84-96∘ around 90∘, which corresponds to I41/amd. In the shuttlewise deforming phase, the electron-phonon interaction is enhanced owing to phonon softenings, which brings about superconductivity at elevated temperatures.

  3. Relativistic corrections for screening effects on the energies of hydrogen-like atoms embedded in plasmas

    SciTech Connect

    Poszwa, A.; Bahar, M. K.

    2015-01-15

    The influence of relativistic and plasma screening effects on energies of hydrogen-like atoms embedded in plasmas has been studied. The Dirac equation with a more general exponential cosine screened potential has been solved numerically and perturbatively, by employing the direct perturbation theory. Properties of spectra corresponding to bound states and to different sets of the potential parameters have been studied both in nonrelativistic and relativistic approximations. Binding energies, fine-structure splittings, and relativistic energy shifts have been determined as functions of parameters of the potential. The results have been compared with the ones known from the literature.

  4. Absolute differential cross sections for electron capture and loss by kilo-electron-volt hydrogen atoms

    NASA Technical Reports Server (NTRS)

    Smith, G. J.; Johnson, L. K.; Gao, R. S.; Smith, K. A.; Stebbings, R. F.

    1991-01-01

    This paper reports measurements of absolute differential cross sections for electron capture and loss for fast hydrogen atoms incident on H2, N2, O2, Ar, and He. Cross sections have been determined in the 2.0- to 5.0-keV energy range over the laboratory angular range 0.02-2 deg, with an angular, resolution of 0.02 deg. The high angular resolution allows observation of the structure at small angles in some of the cross sections. Comparison of the present results with those of other authors generally shows very good agreement.

  5. Hydrogen Gas Sensors Fabricated on Atomically Flat 4H-SiC Webbed Cantilevers

    NASA Technical Reports Server (NTRS)

    Neudeck, Philip G.; Spry, David J.; Trunek, Andrew J.; Evans, Laura J.; Chen, Liang-Yu; Hunter, Gary W.; Androjna, Drago

    2007-01-01

    This paper reports on initial results from the first device tested of a "second generation" Pt-SiC Schottky diode hydrogen gas sensor that: 1) resides on the top of atomically flat 4H-SiC webbed cantilevers, 2) has integrated heater resistor, and 3) is bonded and packaged. With proper selection of heater resistor and sensor diode biases, rapid detection of H2 down to concentrations of 20 ppm was achieved. A stable sensor current gain of 125 +/- 11 standard deviation was demonstrated during 250 hours of cyclic test exposures to 0.5% H2 and N2/air.

  6. Absorption of infrared radiation by electrons in the field of a neutral hydrogen atom

    NASA Technical Reports Server (NTRS)

    Stallcop, J. R.

    1974-01-01

    An analytical expression for the absorption coefficient is developed from a relationship between the cross-section for inverse bremsstrahlung absorption and the cross-section for electron-atom momentum transfer; it is accurate for those photon frequencies v and temperatures such that hv/kT is small. The determination of the absorption of infrared radiation by free-free transitions of the negative hydrogen ion has been extended to higher temperatures. A simple analytical expression for the absorption coefficient has been derived.

  7. Connection between the hydrogen atom and the four-dimensional oscillator

    SciTech Connect

    Chen, A.C.; Kibler, M.

    1985-06-01

    The connection between the three-dimensional hydrogen atom and a four-dimensional harmonic oscillator (or equivalently a coupled pair of two-dimensional harmonic oscillators) subjected to a constraint condition is further explored. In particular, the role the constraint condition plays in determining the phase relationship between the pair of two-dimensional oscillators is examined. Furthermore, the connection is discussed in a group-theoretical context involving the Lie algebras of SO(4), SO(3,1), E(3), SO(4,2), and Sp(8,R).

  8. Experimentally attainable example of chaotic tunneling: The hydrogen atom in parallel static electric and magnetic fields

    NASA Astrophysics Data System (ADS)

    Delande, Dominique; Zakrzewski, Jakub

    2003-12-01

    Statistics of tunneling rates in the presence of chaotic classical dynamics is discussed on a realistic example: a hydrogen atom placed in parallel, uniform, static electric, and magnetic fields, where tunneling is followed by ionization along the fields direction. Depending on the magnetic quantum number, one may observe either a standard Porter-Thomas distribution of tunneling rates or, for strong scarring by a periodic orbit parallel to the external fields, strong deviations from it. For the latter case, a simple model based on random matrix theory gives the correct distribution.

  9. Rate of the reaction of atomic hydrogen with propyne over an extended pressure and temperature range

    NASA Technical Reports Server (NTRS)

    Whytock, D. A.; Payne, W. A.; Stief, L. J.

    1976-01-01

    The technique of flash photolysis coupled with time resolved detection of H via resonance fluorescence has been used to obtain rate constants for the reaction of atomic hydrogen with propyne at temperatures from 215 to 460 K and at pressures in the range 5-600 torr. The rate constants are strongly pressure dependent and the high pressure limiting values give rise to the Arrhenius expression K = approximately 6 x 10 to the minus 11th exp(-2450T) cu cm per molecule per sec. The results are discussed and compared with those of previous studies

  10. Phase transition into the metallic state in hypothetical (without molecules) dense atomic hydrogen

    SciTech Connect

    Khomkin, A. L. Shumikhin, A. S.

    2013-10-15

    A simple physical model of the metal-dielectric (vapor-liquid) phase transition in hypothetical (without molecules) atomic hydrogen is proposed. The reason for such a transition is the quantum collective cohesive energy occurring due to quantum electron-electron exchange similar to the cohesive energy in the liquid-metal phase of alkali metals. It is found that the critical parameters of the transition are P{sub c} ∼ 41000 atm, ρ{sub c} ∼ 0.1 g/cm{sup 3}, and T{sub c} ∼ 9750 K.

  11. Interaction of atomic hydrogen with anthracene and polyacene from density functional theory

    NASA Astrophysics Data System (ADS)

    Ferullo, Ricardo M.; Castellani, Norberto J.; Belelli, Patricia G.

    2016-03-01

    The interaction of atomic hydrogen with two linear polycyclic aromatic hydrocarbons (PAHs), anthracene and polyacene (the polymer of benzene), was studied within the density functional theory (DFT). Using a proper dispersion-corrected method (DFT-D) the preferential physisorption sites were explored. The activation barrier for the bond formation between a peripheral C and the incoming H was calculated to be 58.5 and 34.1 meV with pure DFT on anthracene and polyacene at its antiferromagnetic ground state, respectively. DFT-D, although improves the description of the physisorbed state, tends to underestimate the chemisorption barriers due an artifact arising from the dispersion correction.

  12. Atomic and ionic spectrum lines below 2000A: hydrogen through argon

    SciTech Connect

    Kelly, R.L.

    1982-10-01

    A critical tabulation of observed spectral lines below 2000 angstroms has been prepared from the published literature up to July 1978. It is intended principally as an aid to those physicists and astronomers who deal with the spectra of highly stripped atoms. This report includes the first 18 elements, from hydrogen (including deuterium) through argon. The tabulation is divided into two main sections: the spectrum lines by spectrum, and a finding list. The entries for each element give the ionization species, ground state term, and ionization potential, as well as the best values of vacuum wavelength, intensity, and classification. A list of the pertinent references is appended at the end.

  13. A correlational analysis of the effects of changing environmental conditions on the NR atomic hydrogen maser

    NASA Technical Reports Server (NTRS)

    Dragonette, Richard A.; Suter, Joseph J.

    1992-01-01

    An extensive statistical analysis has been undertaken to determine if a correlation exists between changes in an NR atomic hydrogen maser's frequency offset and changes in environmental conditions. Correlation analyses have been performed comparing barometric pressure, humidity, and temperature with maser frequency offset as a function of time for periods ranging from 5.5 to 17 days. Semipartial correlation coefficients as large as -0.9 have been found between barometric pressure and maser frequency offset. Correlation between maser frequency offset and humidity was small compared to barometric pressure and unpredictable. Analysis of temperature data indicates that in the most current design, temperature does not significantly affect maser frequency offset.

  14. Focusing a beam of ultracold spin-polarized hydrogen atoms with a helium-film-coated quasiparabolic mirror

    SciTech Connect

    Luppov, V.G. Joint Institute for Nuclear Research, Dubna ); Kaufman, W.A.; Hill, K.M.; Raymond, R.S.; Krisch, A.D. )

    1993-10-11

    We formed the first atomic-optics'' beam of electron-spin-polarized hydrogen atoms using a quasiparabolic polished copper mirror coated with a hydrogen-atom-reflecting film of superfluid [sup 4]He. The mirror was located in the gradient of an 8-T solenoidal magnetic field and mounted on an ultracold cell at 350 mK. After the focusing by the mirror surface, the beam was again focused with a sextupole magnet. The mirror, which was especially designed for operation in the magnetic field gradient of our solenoid, increased the focused beam intensity by a factor of about 7.5.

  15. On the role of atomic metastability in the production of Balmer line radiation from ‘cold’ atomic hydrogen, deuterium and hydrogenic ion impurities in fusion edge plasmas

    NASA Astrophysics Data System (ADS)

    Hey, J. D.

    2012-03-01

    Published arguments, which assign an important role to atomic metastability in the production of ‘narrow’ Zeeman component radiation from the boundary region of fusion plasmas, are examined critically in relation to l-redistribution by proton and electron collisions, and mixing of unperturbed atomic states by the ion microfield and microfield gradient. It is concluded that these important processes indeed severely constrain the contribution from ‘metastable’ states to the generation of the hydrogen Balmer spectra, for electron concentrations above 1012 cm-3, as pointed out before by the present author (Hey et al 1999 J. Phys. B: At. Mol. Opt. Phys. 32 3555). The analysis of collision-induced l-redistribution represents an extension of that used previously (Hey et al 1996 Contrib. Plasma Phys. 36 583), applicable up to higher electron densities. For comparison purposes, we also consider the question of metastability of ionized helium in a low-temperature plasma, and that of some common hydrogenic impurities (C5+ and Ne9+) in a hydrogen (deuterium) fusion plasma. While for low nuclear charge Z the metastability of 2s1/2 levels is quenched by the plasma environment, it is much reduced in high-Z ions owing to the rapid increase with Z of the two-photon electric dipole (2E1) and magnetic dipole (M1) spontaneous transition rates to the ground state, whereas the role of the plasma in these cases is less important. The main new principle elaborated in this work is the sensitivity of atomic line strengths, and hence collision strengths, to perturbation by the plasma environment for transitions between fine-structure sublevels of the same principal quantum number. As the plasma microfield strength grows, ‘allowed’ transitions diminish in strength, while ‘forbidden’ transitions grow. However, owing to violation of the parity selection rule, there is an overall loss of collision strength available to transitions, resulting from the appearance of significant

  16. Controlling the spin of co atoms on pt(111) by hydrogen adsorption.

    PubMed

    Dubout, Q; Donati, F; Wäckerlin, C; Calleja, F; Etzkorn, M; Lehnert, A; Claude, L; Gambardella, P; Brune, H

    2015-03-13

    We investigate the effect of H adsorption on the magnetic properties of individual Co atoms on Pt(111) with scanning tunneling microscopy. For pristine Co atoms, we detect no inelastic features in the tunnel spectra. Conversely, CoH and CoH2 show a number of low-energy vibrational features in their differential conductance identified by isotope substitution. Only the fcc-adsorbed species present conductance steps of magnetic origin, with a field splitting identifying their effective spin as Seff=2 for CoH and 3/2 for CoH2. The exposure to H2 and desorption through tunnel electrons allow the reversible control of the spin in half-integer steps. Because of the presence of the surface, the hydrogen-induced spin increase is opposite to the spin sequence of CoHn molecules in the gas phase. PMID:25815958

  17. Resonant charge transfer of hydrogen Rydberg atoms incident at a metallic sphere

    NASA Astrophysics Data System (ADS)

    Gibbard, J. A.; Softley, T. P.

    2016-06-01

    A wavepacket propagation study is reported for the charge transfer of low principal quantum number (n = 2) hydrogen Rydberg atoms incident at an isolated metallic sphere. Such a sphere acts as a model for a nanoparticle. The three-dimensional confinement of the sphere yields discrete surface-localized ‘well-image’ states, the energies of which vary with sphere radius. When the Rydberg atom energy is degenerate with one of the quantized nanoparticle states, charge transfer is enhanced, whereas for off-resonant cases little to no charge transfer is observed. Greater variation in charge-transfer probability is seen between the resonant and off-resonant examples in this system than for any other Rydberg-surface system theoretically investigated thus far. The results presented here indicate that it may be possible to use Rydberg-surface ionization as a probe of the surface electronic structure of a nanoparticle, and nanostructures in general.

  18. Absolute rate parameters for the reaction of atomic hydrogen with hydrazine

    NASA Technical Reports Server (NTRS)

    Stief, L. J.; Payne, W. A.

    1976-01-01

    Absolute rate parameters for the reaction of atomic hydrogen with hydrazine H + N2H4 yields H2 + N2H3 have been determined in a direct manner using flash photolysis of dilute mixtures of hydrazine in helium and time dependent observation of H via resonance fluorescence. By measuring the H-atom decay under pseudo-first-order conditions, the bimolecular rate constant K sub 1 was obtained over the temperature range 228-400 K. The data were fitted with good linearity to the Arrhenius expression K sub 1 = (9.87 plus or minus 1.17) x 10 to the -12th exp(-2380 plus or minus 100/RT) cu cm/molecule/s. The data were shown to be free of any contributions from secondary reactions involving H as a reactant or product.

  19. Spontaneous light emission by atomic hydrogen: Fermi's golden rule without cheating

    NASA Astrophysics Data System (ADS)

    Debierre, V.; Durt, T.; Nicolet, A.; Zolla, F.

    2015-10-01

    Focusing on the 2 p- 1 s transition in atomic hydrogen, we investigate through first order perturbation theory the time evolution of the survival probability of an electron initially taken to be in the excited (2 p) state. We examine both the results yielded by the standard dipole approximation for the coupling between the atom and the electromagnetic field - for which we propose a cutoff-independent regularisation - and those yielded by the exact coupling function. In both cases, Fermi's golden rule is shown to be an excellent approximation for the system at hand: we found its maximal deviation from the exact behaviour of the system to be of order 10-8 /10-7. Our treatment also yields a rigorous prescription for the choice of the optimal cutoff frequency in the dipole approximation. With our cutoff, the predictions of the dipole approximation are almost indistinguishable at all times from the exact dynamics of the system.

  20. Low-energy charge transfer between C5+ and atomic hydrogen

    SciTech Connect

    Draganic, Ilija N; Havener, Charles C; Seely, D. G.

    2011-01-01

    Charge transfer with carbon ions has been identified as important in both magnetic fusion plasma devices and, more recently, in solar wind interactions with comets, planets, or neutrals in the heliosphere. A merged-beams technique is used to measure the absolute total charge-transfer cross section for C{sup 5+} and atomic H over four orders of magnitude in collision energy, from 12,000 to 0.64 eV/u. The present measurements are compared with previous measurements using an atomic hydrogen target and benchmark available classical trajectory Monte Carlo and molecular-orbital close-coupling calculations. An observed increasing cross section below 10 eV/u is attributed to trajectory effects due to the ion-induced dipole attraction between reactants.

  1. Low Energy Charge Transfer between C5+ and Atomic Hydrogen

    SciTech Connect

    Draganic, Ilija N; Seely, D. G.; Havener, Charles C

    2011-01-01

    Charge transfer (CT) with carbon ions has been identified for a long time as important in both magnetic fusion plasma devices and more recently in solar wind interactions with comets, planets, or neutrals in the heliosphere. A merged-beams technique is used to measure the absolute total charge transfer cross section for C5+ and atomic H over four orders of magnitude in collision energy, from 12,000 eV/u to 0.64 eV/u. The present measurements are compared with previous measurements using an atomic hydrogen target and benchmark available classical trajectory Monte-Carlo and molecular-orbital close-coupling calculations. An increasing cross section below 10 eV/u is attributed to trajectory effects due to the ion-induced dipole attraction between reactants.

  2. Quantitative analysis of hydrogen in SiO2/SiN/SiO2 stacks using atom probe tomography

    NASA Astrophysics Data System (ADS)

    Kunimune, Yorinobu; Shimada, Yasuhiro; Sakurai, Yusuke; Inoue, Masao; Nishida, Akio; Han, Bin; Tu, Yuan; Takamizawa, Hisashi; Shimizu, Yasuo; Inoue, Koji; Yano, Fumiko; Nagai, Yasuyoshi; Katayama, Toshiharu; Ide, Takashi

    2016-04-01

    We have demonstrated that it is possible to reproducibly quantify hydrogen concentration in the SiN layer of a SiO2/SiN/SiO2 (ONO) stack structure using ultraviolet laser-assisted atom probe tomography (APT). The concentration of hydrogen atoms detected using APT increased gradually during the analysis, which could be explained by the effect of hydrogen adsorption from residual gas in the vacuum chamber onto the specimen surface. The amount of adsorbed hydrogen in the SiN layer was estimated by analyzing another SiN layer with an extremely low hydrogen concentration (<0.2 at. %). Thus, by subtracting the concentration of adsorbed hydrogen, the actual hydrogen concentration in the SiN layer was quantified as approximately 1.0 at. %. This result was consistent with that obtained by elastic recoil detection analysis (ERDA), which confirmed the accuracy of the APT quantification. The present results indicate that APT enables the imaging of the three-dimensional distribution of hydrogen atoms in actual devices at a sub-nanometer scale.

  3. Hydrogen trapping by solute atoms in Nb--Mo(3 at. %) alloys as observed by the channeling method

    SciTech Connect

    Yagi, E.; Nakamura, S.; Kano, F.; Kobayashi, T.; Watanabe, K.; Fukai, Y.; Matsumoto, T.

    1989-01-01

    In order to elucidate the mechanism of the enhancement of the terminal solubility for hydrogen (TSH) in Nb by alloying with undersized Mo atoms, the state of hydrogen was studied by the channeling method using a nuclear reaction /sup 1/H(/sup 11/B, ..cap alpha..)..cap alpha cap alpha.. in Nb--Mo(3 at. %) alloys. At room temperature H atoms are located at sites displaced from tetrahedral (T) sites by about 0.6 A towards the nearest-neighbor lattice points, while at 373 K they are at T sites. These results give direct evidence for trapping of hydrogen by Mo atoms and strongly support the trapping model for the enhancement of the TSH in the low-concentration region of Mo atoms.

  4. Hydrogen trapping by solute atoms in Nb-Mo(3 at. %) alloys as observed by the channeling method

    NASA Astrophysics Data System (ADS)

    Yagi, Eiichi; Nakamura, Shiho; Kano, Fumihisa; Kobayashi, Takane; Watanabe, Kenji; Fukai, Yuh; Matsumoto, Takehiko

    1989-01-01

    In order to elucidate the mechanism of the enhancement of the terminal solubility for hydrogen (TSH) in Nb by alloying with undersized Mo atoms, the state of hydrogen was studied by the channeling method using a nuclear reaction 1H(11B, α)αα in Nb-Mo(3 at. %) alloys. At room temperature H atoms are located at sites displaced from tetrahedral (T) sites by about 0.6 Å towards the nearest-neighbor lattice points, while at 373 K they are at T sites. These results give direct evidence for trapping of hydrogen by Mo atoms and strongly support the trapping model for the enhancement of the TSH in the low-concentration region of Mo atoms.

  5. Perturbation Theory for a Hydrogen-like Atom Confined Within an Impenetrable Spherical Cavity

    NASA Astrophysics Data System (ADS)

    Laughlin, Cecil

    Perturbation expansions for a hydrogen-like atom confined at the centre of an impenetrable spherical cavity, of finite radius R, are discussed in a non-relativistic approximation. Properties considered include: energy, oscillator strength, dipole polarisability and nuclear shielding factor. The appropriate form of perturbation theory to employ depends on the cavity size and three different regimes are considered: small, intermediate and large. For large cavity radii, perturbation of the unconfined atom boundary condition at r=R to satisfy a Dirichlet condition results in exponentially small deviations from the unconfined atom values which are predicted to high accuracy in first order. For small R, Rayleigh-Schrödinger perturbation theory can be used, with the electron-nucleus Coulomb interaction treated as a perturbation, to generate expansions in powers of R. These expansions, whose radii of convergence are explored, provide highly accurate results even for moderately large R (depending on the state considered). The difficult intermediate range of R values is finally investigated using Rayleigh-Schrödinger perturbation theory based on known exact solutions obtained from lobes of free-atom solutions.

  6. Quantum Diffusion-Controlled Chemistry: Reactions of Atomic Hydrogen with Nitric Oxide in Solid Parahydrogen.

    PubMed

    Ruzi, Mahmut; Anderson, David T

    2015-12-17

    Our group has been working to develop parahydrogen (pH2) matrix isolation spectroscopy as a method to study low-temperature condensed-phase reactions of atomic hydrogen with various reaction partners. Guided by the well-defined studies of cold atom chemistry in rare-gas solids, the special properties of quantum hosts such as solid pH2 afford new opportunities to study the analogous chemical reactions under quantum diffusion conditions in hopes of discovering new types of chemical reaction mechanisms. In this study, we present Fourier transform infrared spectroscopic studies of the 193 nm photoinduced chemistry of nitric oxide (NO) isolated in solid pH2 over the 1.8 to 4.3 K temperature range. Upon short-term in situ irradiation the NO readily undergoes photolysis to yield HNO, NOH, NH, NH3, H2O, and H atoms. We map the postphotolysis reactions of mobile H atoms with NO and document first-order growth in HNO and NOH reaction products for up to 5 h after photolysis. We perform three experiments at 4.3 K and one at 1.8 K to permit the temperature dependence of the reaction kinetics to be quantified. We observe Arrhenius-type behavior with a pre-exponential factor of A = 0.036(2) min(-1) and Ea = 2.39(1) cm(-1). This is in sharp contrast to previous H atom reactions we have studied in solid pH2 that display definitively non-Arrhenius behavior. The contrasting temperature dependence measured for the H + NO reaction is likely related to the details of H atom quantum diffusion in solid pH2 and deserves further study. PMID:26317154

  7. Atomic-Orbital Close-Coupling Calculations Of Electron Capture From Hydrogen Atoms Into Highly Excited Rydberg States Of Multiply Charged Ions

    SciTech Connect

    Igenbergs, Katharina; Wallerberger, Markus; Aumayr, Friedrich

    2011-06-01

    Collisions of neutral hydrogen atoms with multiply charged ions have been studied in the past using the semi-classical atomic-orbital close-coupling method. We present total and state-resolved cross sections for charge exchange as well as ionization. The advent of supercomputers and parallel programming facilities now allow treatment of collision systems that have been out of reach before, because much larger basis sets involving high quantum numbers are now feasible.

  8. First-principles calculations of the interaction between hydrogen and 3d alloying atom in nickel

    NASA Astrophysics Data System (ADS)

    Liu, Wenguan; Qian, Yuan; Zhang, Dongxun; Liu, Wei; Han, Han

    2015-10-01

    Knowledge of the behavior of hydrogen (H) in Ni-based alloy is essential for the prediction of Tritium behavior in Molten Salt Reactor. First-principles calculations were performed to investigate the interaction between H and 3d transition metal (TM) alloying atom in Ni-based alloy. H prefers the octahedral interstitial site to the tetrahedral interstitial site energetically. Most of the 3d TM elements (except Zn) attract H. The attraction to H in the Ni-TM-H system can be mainly attributed to the differences in electronegativity. With the large electronegativity, H and Ni gain electrons from the other TM elements, resulting in the enhanced Ni-H bonds which are the source of the attraction to H in the Ni-TM-H system. The obviously covalent-like Cr-H and Co-H bindings are also beneficial to the attraction to H. On the other hand, the repulsion to H in the Ni-Zn-H system is due to the stable electronic configuration of Zn. We mainly utilize the results calculated in 32-atom supercell which corresponds to the case of a relatively high concentration of hydrogen. Our results are in good agreement with the experimental ones.

  9. Three-dimensional atomic mapping of hydrogenated polymorphous silicon solar cells

    NASA Astrophysics Data System (ADS)

    Chen, Wanghua; Pareige, Philippe; Roca i Cabarrocas, Pere

    2016-06-01

    Hydrogenated polymorphous silicon (pm-Si:H) is a nanostructured material consisting of silicon nanocrystals embedded in an amorphous silicon matrix. Its use as the intrinsic layer in thin film p-i-n solar cells has led to good cell properties in terms of stability and efficiency. Here, we have been able to assess directly the concentration and distribution of nanocrystals and impurities (dopants) in p-i-n solar cells, by using femtosecond laser-assisted atom probe tomography (APT). An effective sample preparation method for APT characterization is developed. Based on the difference in atomic density between hydrogenated amorphous and crystalline silicon, we are able to distinguish the nanocrystals from the amorphous matrix by using APT. Moreover, thanks to the three-dimensional reconstruction, we demonstrate that Si nanocrystals are homogeneously distributed in the entire intrinsic layer of the solar cell. The influence of the process pressure on the incorporation of nanocrystals and their distribution is also investigated. Thanks to APT we could determine crystalline fractions as low as 4.2% in the pm-Si:H films, which is very difficult to determine by standard techniques, such as X-ray diffraction, Raman spectroscopy, and spectroscopic ellipsometry. Moreover, we also demonstrate a sharp p/i interface in our solar cells.

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

    NASA Technical Reports Server (NTRS)

    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.

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

    NASA Technical Reports Server (NTRS)

    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 <5 MeV particles were due to 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. 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.

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

    NASA Technical Reports Server (NTRS)

    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.

  13. Radical-mediated dehydrogenation of bile acids by means of hydrogen atom transfer to triplet carbonyls.

    PubMed

    Miro, P; Marin, M L; Miranda, M A

    2016-03-01

    The aim of the present paper is to explore the potential of radical-mediated dehydrogenation of bile salts (BSs), which is reminiscent of the enzymatic action of hydroxysteroid dehydrogenase enzymes (HSDH). The concept has been demonstrated using triplet carbonyls that can be efficiently generated upon selective UVA-excitation. Hydrogen atom transfer (HAT) from BSs to triplet benzophenone (BP) derivatives gave rise to radicals, ultimately leading to reduction of the BP chromophore with concomitant formation of the oxo-analogs of the corresponding BSs. The direct reactivity of triplet BP with BSs in the initial step was evaluated by determining the kinetic rate constants using laser flash photolysis (LFP). The BP triplet decay was monitored (λmax = 520 nm) upon addition of increasing BS concentrations, and the obtained rate constant values indicated a reactivity of the methine hydrogen atoms in the order of C-3 < C-12 < C-7. The steady-state kinetics of the overall process, monitored through the disappearance of the typical BP absorption band at 260 nm, was much faster under N2 than under O2, also supporting the role of the oxygen-quenchable triplet in the dehydrogenation process. Furthermore, irradiation of deaerated aqueous solutions of sodium cholate in the presence of KPMe provided the oxo-analogs, 3[O],7[O]-CA, 3[O]-CA and 7[O]-CA, arising from the HAT process. PMID:26833240

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

    PubMed

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

    2016-05-01

    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. PMID:27070292

  15. Emission of hydrogen energetic neutral atoms from the Martian subsolar magnetosheath

    NASA Astrophysics Data System (ADS)

    Wang, X.-D.; Alho, M.; Jarvinen, R.; Kallio, E.; Barabash, S.; Futaana, Y.

    2016-01-01

    We have simulated the hydrogen energetic neutral atom (ENA) emissions from the subsolar magnetosheath of Mars using a hybrid model of the proton plasma charge exchanging with the Martian exosphere to study statistical features revealed from the observations of the Neutral Particle Detectors on Mars Express. The simulations reproduce well the observed enhancement of the hydrogen ENA emissions from the dayside magnetosheath in directions perpendicular to the Sun-Mars line. Our results show that the neutralized protons from the shocked solar wind are the dominant ENA population rather than those originating from the pickup planetary ions. The simulation also suggests that the observed stronger ENA emissions in the direction opposite to the solar wind convective electric field result from a stronger proton flux in the same direction at the lower magnetosheath; i.e., the proton fluxes in the magnetosheath are not cylindrically symmetric. We also confirm the observed increasing of the ENA fluxes with the solar wind dynamical pressure in the simulations. This feature is associated with a low altitude of the induced magnetic boundary when the dynamic pressure is high and the magnetosheath protons can reach to a denser exosphere, and thus, the charge exchange rate becomes higher. Overall, the analysis suggests that kinetic effects play an important and pronounced role in the morphology of the hydrogen ENA distribution and the plasma environment at Mars, in general.

  16. Partial Redistribution in Multilevel Atoms. I. Method and Application to the Solar Hydrogen Line Formation

    NASA Astrophysics Data System (ADS)

    Hubeny, I.; Lites, B. W.

    1995-12-01

    We present a robust method for solution of multilevel non-LTE line transfer problems including the effects of partial frequency redistribution (PRD). This method allows the self-consistent solution for redistribution of scattered line photons simultaneously in multiple transitions of a model atom, including the effects of resonant Raman scattering ("cross-redistribution") among lines sharing common upper levels. The method is incorporated into the framework of the widely used non-LTE complete redistribution code MULTI. We have applied this method to the problem of transfer in hydrogen lines in a plane-parallel solar model atmosphere, including cross-redistribution between the Hα and Lβ, using general redistribution functions for the Lα and Lβ lines which are not restricted by the impact approximation. The convergence properties of this method are demonstrated to be comparable to that of the equivalent complete redistribution problem. In this solar model, PRD in the Lα line produces the dominant influence on the level populations. It changes considerably the populations of the excited states of hydrogen, as well as the proton number density, in the middle and upper chromosphere, owing to modification of the Lα wing radiation. The population of the hydrogen ground state undergoes only modest changes, however. The influence of cross-redistribution and PRD in Lβ has a much smaller influence on the level populations but a considerable influence on the wing intensity of the Lβ line.

  17. Discovery of a shell of neutral atomic hydrogen surrounding the carbon star IRC+10216

    NASA Astrophysics Data System (ADS)

    Matthews, L. D.; Gérard, E.; Le Bertre, T.

    2015-05-01

    We have used the Robert C. Byrd Green Bank Telescope to perform the most sensitive search to date for neutral atomic hydrogen (H I) in the circumstellar envelope (CSE) of the carbon star IRC+10216. Our observations have uncovered a low surface brightness H I shell of diameter ˜1300 arcsec (˜0.8 pc), centred on IRC+10216. The H I shell has an angular extent comparable to the far ultraviolet-emitting astrosphere of IRC+10216 previously detected with the GALEX satellite, and its kinematics are consistent with circumstellar matter that has been decelerated by the local interstellar medium. The shell appears to completely surround the star, but the highest H I column densities are measured along the leading edge of the shell, near the location of a previously identified bow shock. We estimate a total mass of atomic hydrogen associated with the IRC+10216 CSE of M_{H I} ˜ 3× 10^{-3} M_{⊙}. This is only a small fraction of the expected total mass of the CSE (<1 per cent) and is consistent with the bulk of the stellar wind originating in molecular rather than atomic form, as expected for a cool star with an effective temperature Teff ≲ 2200 K. H I mapping of a 2° × 2° region surrounding IRC+10216 has also allowed us to characterize the line-of-sight interstellar emission in the region and has uncovered a link between diffuse FUV emission south-west of IRC+10216 and the Local Leo Cold Cloud.

  18. Imaging the South Pole-Aitken basin in backscattered neutral hydrogen atoms

    NASA Astrophysics Data System (ADS)

    Vorburger, A.; Wurz, P.; Barabash, S.; Wieser, M.; Futaana, Y.; Bhardwaj, A.; Asamura, K.

    2015-09-01

    The lunar surface is very efficient in reflecting impinging solar wind ions as energetic neutral atoms (ENAs). A global analysis of lunar hydrogen ENAs showed that on average 16% of the solar wind protons are reflected, and that the reflected fraction can range from less than 8% to more than 24%, depending on location. It is established that magnetic anomalies reduce the flux of backscattered hydrogen ENAs by screening-off a fraction of the impinging solar wind. The effects of the surface properties, such as porosity, roughness, chemical composition, and extent of weathering, were not known. In this paper, we conduct an in-depth analysis of ENA observations of the South Pole-Aitken basin to determine which of the surface properties might be responsible for the observed variation in the integral ENA flux. The South Pole-Aitken basin with its highly variable surface properties is an ideal object for such studies. It is very deep, possesses strikingly elevated concentrations in iron and thorium, has a low albedo and coincides with a cluster of strong magnetic anomalies located on the northern rim of the basin. Our analysis shows that whereas, as expected, the magnetic anomalies can account well for the observed ENA depletion at the South Pole-Aitken basin, none of the other surface properties seem to influence the ENA reflection efficiency. Therefore, the integral flux of backscattered hydrogen ENAs is mainly determined by the impinging plasma flux and ENA imaging of backscattered hydrogen captures the electrodynamics of the plasma at the surface. We cannot exclude minor effects by surface features. We create two maps of surface reflected ENAs at the South Pole-Aitken basin. We compare these ENA maps to elevation, albedo, composition and magnetic field maps. The ENA maps only significantly correlate with the magnetic field map. ENA imaging captures solely the electrodynamics of the plasma at the surface.

  19. Production of high brightness H- beam by charge exchange of hydrogen atom beam in sodium jet

    SciTech Connect

    Davydenko, V.; Zelenski, A.; Ivanov, A.; Kolmogorov, A.

    2010-11-16

    Production of H{sup -} beam for accelerators applications by charge exchange of high brightness hydrogen neutral beam in a sodium jet cell is experimentally studied in joint BNL-BINP experiment. In the experiment, a hydrogen-neutral beam with 3-6 keV energy, equivalent current up to 5 A and 200 microsecond pulse duration is used. The atomic beam is produced by charge exchange of a proton beam in a pulsed hydrogen target. Formation of the proton beam is performed in an ion source by four-electrode multiaperture ion-optical system. To achieve small beam emittance, the apertures in the ion-optical system have small enough size, and the extraction of ions is carried out from the surface of plasma emitter with a low transverse ion temperature of {approx}0.2 eV formed as a result of plasma jet expansion from the arc plasma generator. Developed for the BNL optically pumped polarized ion source, the sodium jet target with recirculation and aperture diameter of 2 cm is used in the experiment. At the first stage of the experiment H{sup -} beam with 36 mA current, 5 keV energy and {approx}0.15 cm {center_dot} mrad normalized emittance was obtained. To increase H{sup -} beam current ballistically focused hydrogen neutral beam will be applied. The effects of H{sup -} beam space-charge and sodium-jet stability will be studied to determine the basic limitations of this approach.

  20. Catalytic doping of phosphorus and boron atoms on hydrogenated amorphous silicon films

    NASA Astrophysics Data System (ADS)

    Seto, Junichi; Ohdaira, Keisuke; Matsumura, Hideki

    2016-04-01

    We investigate the low-temperature doping of phosphorus (P) and boron (B) atoms on hydrogenated amorphous silicon (a-Si:H) films by catalytic doping (Cat-doping). The conductivity of a-Si:H films increases as catalyzer temperature (T cat) increases, and the increase in conductivity is accompanied by a significant reduction in activation energy obtained from the Arrhenius plot of the conductivity. Secondary ion mass spectrometry (SIMS) measurement reveals that Cat-doped P and B atoms exist within ˜10-15 nm from the a-Si:H film surface, indicating that the shallow doping of P and B atoms is realized on a-Si:H films similarly to the case of Cat-doping on crystalline Si (c-Si) wafers. We also confirm no additional film deposition during Cat-doping. These results suggest that decomposed species are effectively doped on a-Si:H films similarly to the case of Cat-doping on c-Si.