Atomic hydrogen cleaning of EUV multilayer optics

NASA Astrophysics Data System (ADS)

Graham, Samuel, Jr.; Steinhaus, Charles A.; Clift, W. Miles; Klebanoff, Leonard E.; Bajt, Sasa

2003-06-01

Recent studies have been conducted to investigate the use of atomic hydrogen as an in-situ contamination removal method for EUV optics. In these experiments, a commercial source was used to produce atomic hydrogen by thermal dissociation of molecular hydrogen using a hot filament. Samples for these experiments consisted of silicon wafers coated with sputtered carbon, Mo/Si optics with EUV-induced carbon, and bare Si-capped and Ru-B4C-capped Mo/Si optics. Samples were exposed to an atomic hydrogen source at a distance of 200 - 500 mm downstream and angles between 0-90° with respect to the source. Carbon removal rates and optic oxidation rates were measured using Auger electron spectroscopy depth profiling. In addition, at-wavelength peak reflectance (13.4 nm) was measured using the EUV reflectometer at the Advanced Light Source. Data from these experiments show carbon removal rates up to 20 Ê/hr for sputtered carbon and 40 Ê/hr for EUV deposited carbon at a distance of 200 mm downstream. The cleaning rate was also observed to be a strong function of distance and angular position. Experiments have also shown that the carbon etch rate can be increased by a factor of 4 by channeling atomic hydrogen through quartz tubes in order to direct the atomic hydrogen to the optic surface. Atomic hydrogen exposures of bare optic samples show a small risk in reflectivity degradation after extended periods. Extended exposures (up to 20 hours) of bare Si-capped Mo/Si optics show a 1.2% loss (absolute) in reflectivity while the Ru-B4C-capped Mo/Si optics show a loss on the order of 0.5%. In order to investigate the source of this reflectivity degradation, optic samples were exposed to atomic deuterium and analyzed using low energy ion scattering direct recoil spectroscopy to determine any reactions of the hydrogen with the multilayer stack. Overall, the results show that the risk of over-etching with atomic hydrogen is much less than previous studies using RF discharge cleaning while providing cleaning rates suitable for EUV lithography operations.

Atomic hydrogen cleaning of EUV multilayer optics

NASA Astrophysics Data System (ADS)

Graham, Samuel, Jr.; Steinhaus, Charles A.; Clift, W. Miles; Klebanoff, Leonard E.; Bajt, Sasa

2003-06-01

Recent studies have been conducted to investigate the use of atomic hydrogen as an in-situ contamination removal method for EUV optics. In these experiments, a commercial source was used to produce atomic hydrogen by thermal dissociation of molecular hydrogen using a hot filament. Samples for these experiments consisted of silicon wafers coated with sputtered carbon, Mo/Si optics with EUV-induced carbon, and bare Si-capped and Ru-B4C-capped Mo/Si optics. Samples were exposed to an atomic hydrogen source at a distance of 200 - 500 mm downstream and angles between 0-90° with respect to the source. Carbon removal rates and optic oxidation rates were measured using Auger electron spectroscopy depth profiling. In addition, at-wavelength peak reflectance (13.4 nm) was measured using the EUV reflectometer at the Advanced Light Source. Data from these experiments show carbon removal rates up to 20 Å/hr for sputtered carbon and 40 Å/hr for EUV deposited carbon at a distance of 200 mm downstream. The cleaning rate was also observed to be a strong function of distance and angular position. Experiments have also shown that the carbon etch rate can be increased by a factor of 4 by channeling atomic hydrogen through quartz tubes in order to direct the atomic hydrogen to the optic surface. Atomic hydrogen exposures of bare optic samples show a small risk in reflectivity degradation after extended periods. Extended exposures (up to 20 hours) of bare Si-capped Mo/Si optics show a 1.2% loss (absolute) in reflectivity while the Ru-B4C-capped Mo/Si optics show a loss on the order of 0.5%. In order to investigate the source of this reflectivity degradation, optic samples were exposed to atomic deuterium and analyzed using low energy ion scattering direct recoil spectroscopy to determine any reactions of the hydrogen with the multilayer stack. Overall, the results show that the risk of over-etching with atomic hydrogen is much less than previous studies using RF discharge cleaning while providing cleaning rates suitable for EUV lithography operations.

The Effect of Vicinal Versus Geminal Substitution of Hydrogen by Chlorine: Microwave Spectra and Molecular Structures of the Complexes of 1-CHLORO-1-FLUOROETHYLENE and (E)-1-CHLORO-2-FLUOROETHYLENE with Hydrogen Fluoride

NASA Astrophysics Data System (ADS)

Leung, Helen O.; Marshall, Mark D.; Lee, Alex J.; Bozzi, Aaron T.; Cohen, Paul M.; Lam, Mable

2010-06-01

Previous work in our laboratory has demonstrated that increasing the degree of fluorine substitution in complexes of fluoroethylenes with protic acids results in a weaker primary hydrogen-bonding interaction. This has been interpreted as arising from a decrease in the nucleophilicity of the hydrogen bond-accepting fluorine atom as a consequence of the inductive, electron-withdrawing nature of the additional fluorine atoms. We have recently extended these studies to investigate the effects of substitution with the less electronegative, but more polarizable chlorine atom. Through analysis of their 6-21 GHz Fourier transform microwave spectra, molecular structures are obtained for the complexes of 1-chloro-1-fluoroethylene and the (E) isomer of 1-chloro-2-fluoroethylene with hydrogen fluoride. The structures are compared with each other and with their difluoroethylene counterparts.

When hydroquinone meets methoxy radical: Hydrogen abstraction reaction from the viewpoint of interacting quantum atoms.

PubMed

Petković, Milena; Nakarada, Đura; Etinski, Mihajlo

2018-05-25

Interacting Quantum Atoms methodology is used for a detailed analysis of hydrogen abstraction reaction from hydroquinone by methoxy radical. Two pathways are analyzed, which differ in the orientation of the reactants at the corresponding transition states. Although the discrepancy between the two barriers amounts to only 2 kJ/mol, which implies that the two pathways are of comparable probability, the extent of intra-atomic and inter-atomic energy changes differs considerably. We thus demonstrated that Interacting Quantum Atoms procedure can be applied to unravel distinct energy transfer routes in seemingly similar mechanisms. Identification of energy components with the greatest contribution to the variation of the overall energy (intra-atomic and inter-atomic terms that involve hydroquinone's oxygen and the carbon atom covalently bound to it, the transferring hydrogen and methoxy radical's oxygen), is performed using the Relative energy gradient method. Additionally, the Interacting Quantum Fragments approach shed light on the nature of dominant interactions among selected fragments: both Coulomb and exchange-correlation contributions are of comparable importance when considering interactions of the transferring hydrogen atom with all other atoms, whereas the exchange-correlation term dominates interaction between methoxy radical's methyl group and hydroquinone's aromatic ring. This study represents one of the first applications of Interacting Quantum Fragments approach on first order saddle points. © 2018 Wiley Periodicals, Inc. © 2018 Wiley Periodicals, Inc.

Benefits of rapid solidification processing of modified LaNi{sub 5} alloys by high pressure gas atomization for battery applications

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

Anderson, I.E.; Pecharsky, V.K.; Ting, J.

1997-12-31

A high pressure gas atomization approach to rapid solidification has been employed to investigate simplified processing of Sn modified LaNi{sub 5} powders that can be used for advanced Ni/metal hydride (Ni/MH) batteries. The current industrial practice involves casting large ingots followed by annealing and grinding and utilizes a complex and costly alloy design. This investigation is an attempt to produce powders for battery cathode fabrication that can be used in an as-atomized condition without annealing or grinding. Both Ar and He atomization gas were tried to investigate rapid solidification effects. Sn alloy additions were tested to promote subambient pressure absorption/desorptionmore » of hydrogen at ambient temperature. The resulting fine, spherical powders were subject to microstructural analysis, hydrogen gas cycling, and annealing experiments to evaluate suitability for Ni/MH battery applications. The results demonstrate that a brief anneal is required to homogenize the as-solidified microstructure of both Ar and He atomized powders and to achieve a suitable hydrogen absorption behavior. The Sn addition also appears to suppress cracking during hydrogen gas phase cycling in particles smaller than about 25 {micro}m. These results suggest that direct powder processing of a LaNi{sub 5{minus}x}Sn{sub x} alloy has potential application in rechargeable Ni/MH batteries.« less

Benefits of rapid solidification processing of modified LaNi{sub 5} alloys by high pressure gas atomization for battery applications

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

Anderson, I.E.; Pecharsky, V.K.; Ting, J.

1998-07-01

A high pressure gas atomization approach to rapid solidification has been employed to investigate simplified processing of Sn modified LaNi{sub 5} powders that can be used for advanced Ni/metal hydride (Ni/MH) batteries. The current industrial practice involves casting large ingots followed by annealing and grinding and utilizes a complex and costly alloy design. This investigation is an attempt to produce powders for battery cathode fabrication that can be used in an as-atomized condition without annealing or grinding. Both Ar and He atomization gas were tried to investigate rapid solidification effects. Sn alloy additions were tested to promote subambient pressure absorption/desorptionmore » of hydrogen at ambient temperature. The resulting fine, spherical powders were subject to microstructural analysis, hydrogen gas cycling, and annealing experiments to evaluate suitability for Ni/MH battery applications. The results demonstrate that a brief anneal is required to homogenize the as-solidified microstructure of both Ar and He atomized powders and to achieve a suitable hydrogen absorption behavior. The Sn addition also appears to suppress cracking during hydrogen gas phase cycling in particles smaller than about 25{micro}m. These results suggest that direct powder processing of a LaNi{sub 5{minus}x}Sn{sub x} alloy has potential application in rechargeable Ni/MH batteries.« less

A density functional theory study on the effect of zero-point energy corrections on the methanation profile on Fe(100).

PubMed

Govender, Ashriti; Ferré, Daniel Curulla; Niemantsverdriet, J W Hans

2012-04-23

The thermodynamics and kinetics of the surface hydrogenation of adsorbed atomic carbon to methane, following the reaction sequence C+4H(-->/<--)CH+3H(-->/<--)CH(2)+2H(-->/<--)CH(3)+H(-->/<--)CH(4), are studied on Fe(100) by means of density functional theory. An assessment is made on whether the adsorption energies and overall energy profile are affected when zero-point energy (ZPE) corrections are included. The C, CH and CH(2) species are most stable at the fourfold hollow site, while CH(3) prefers the twofold bridge site. Atomic hydrogen is adsorbed at both the twofold bridge and fourfold hollow sites. Methane is physisorbed on the surface and shows neither orientation nor site preference. It is easily desorbed to the gas phase once formed. The incorporation of ZPE corrections has a very slight, if any, effect on the adsorption energies and does not alter the trends with regards to the most stable adsorption sites. The successive addition of hydrogen to atomic carbon is endothermic up to the addition of the third hydrogen atom resulting in the methyl species, but exothermic in the final hydrogenation step, which leads to methane. The overall methanation reaction is endothermic when starting from atomic carbon and hydrogen on the surface. Zero-point energy corrections are rarely provided in the literature. Since they are derived from C-H bonds with characteristic vibrations on the order of 2500-3000 cm(-1), the equivalent ZPE of 1/2 hν is on the order of 0.2-0.3 eV and its effect on adsorption energy can in principle be significant. Particularly in reactions between CH(x) and H, the ZPE correction is expected to be significant, as additional C-H bonds are formed. In this instance, the methanation reaction energy of +0.77 eV increased to +1.45 eV with the inclusion of ZPE corrections, that is, less favourable. Therefore, it is crucial to include ZPE corrections when reporting reactions involving hydrogen-containing species. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

Nature of bonding and cooperativity in linear DMSO clusters: A DFT, AIM and NCI analysis.

PubMed

Venkataramanan, Natarajan Sathiyamoorthy; Suvitha, Ambigapathy

2018-05-01

This study aims to cast light on the nature of interactions and cooperativity that exists in linear dimethyl sulfoxide (DMSO) clusters using dispersion corrected density functional theory. In the linear DMSO, DMSO molecules in the middle of the clusters are bound strongly than at the terminal. The plot of the total binding energy of the clusters vs the cluster size and mean polarizabilities vs cluster size shows an excellent linearity demonstrating the presence of cooperativity effect. The computed incremental binding energy of the clusters remains nearly constant, implying that DMSO addition at the terminal site can happen to form an infinite chain. In the linear clusters, two σ-hole at the terminal DMSO molecules were found and the value on it was found to increase with the increase in cluster size. The quantum theory of atoms in molecules topography shows the existence of hydrogen and SO⋯S type in linear tetramer and larger clusters. In the dimer and trimer SO⋯OS type of interaction exists. In 2D non-covalent interactions plot, additional peaks in the regions which contribute to the stabilization of the clusters were observed and it splits in the trimer and intensifies in the larger clusters. In the trimer and larger clusters in addition to the blue patches due to hydrogen bonds, additional, light blue patches were seen between the hydrogen atom of the methyl groups and the sulphur atom of the nearby DMSO molecule. Thus, in addition to the strong H-bonds, strong electrostatic interactions between the sulphur atom and methyl hydrogens exists in the linear clusters. Copyright © 2018 Elsevier Inc. All rights reserved.

Thermal O-H Bond Activation of Water as Mediated by Heteronuclear [Al2Mg2O5]•+: Evidence for Oxygen-Atom Scrambling.

PubMed

Geng, Caiyun; Li, Jilai; Weiske, Thomas; Schwarz, Helmut

2018-06-25

Mechanistic insight into the thermal O-H bond activation of water by the cubane-like, prototypical heteronuclear oxide cluster [Al 2 Mg 2 O 5 ] •+ has been derived from a combined experimental/computational study. Experiments in the highly diluted gas phase using Fourier transform ion-cyclotron resonance mass spectrometry show that hydrogen-atom abstraction from water by the cluster cation [Al 2 Mg 2 O 5 ] •+ occurs at ambient conditions accompanied by the liberation of an OH • radical. Due to a complete randomization of all oxygen atoms prior to fragmentation about 83% of the oxygen atoms of the hydroxyl radical released originate from the oxide cluster itself. The experimental findings are supported by detailed high-level quantum chemical calculations. The theoretical analysis reveals that the transfer of a formal hydrogen atom from water to the metal-oxide cation can proceed mechanistically via proton- or hydrogen-atom transfer exploiting different active sites of the cluster oxide. In addition to the unprecedented oxygen-atom scrambling, one of the more general and quite unexpected findings concerns the role of spin density at the hydrogen-acceptor oxide atom. While this feature is so crucial for [M-O] + /CH 4 couples, it is much less important in the O-H bond activation of water.

Failure of hydrogenation in protecting polycyclic aromatic hydrocarbons from fragmentation

NASA Astrophysics Data System (ADS)

Gatchell, M.; Stockett, M. H.; de Ruette, N.; Chen, T.; Giacomozzi, L.; Nascimento, R. F.; Wolf, M.; Anderson, E. K.; Delaunay, R.; Vizcaino, V.; Rousseau, P.; Adoui, L.; Huber, B. A.; Schmidt, H. T.; Zettergren, H.; Cederquist, H.

2015-11-01

A recent study of soft x-ray absorption in native and hydrogenated coronene cations, C24H12+m +m =0 -7 , led to the conclusion that additional hydrogen atoms protect (interstellar) polycyclic aromatic hydrocarbon (PAH) molecules from fragmentation [Reitsma et al., Phys. Rev. Lett. 113, 053002 (2014), 10.1103/PhysRevLett.113.053002]. The present experiment with collisions between fast (30-200 eV) He atoms and pyrene (C16H10+m + , m =0 , 6, and 16) and simulations without reference to the excitation method suggests the opposite. We find that the absolute carbon-backbone fragmentation cross section does not decrease but increases with the degree of hydrogenation for pyrene molecules.

Molecular interaction of (ethanol)2-water heterotrimers.

PubMed

Mejía, Sol M; Espinal, Juan F; Restrepo, Albeiro; Mondragón, Fanor

2007-08-23

The potential energy surface of the (ethanol)2-water heterotrimers for the trans and gauche conformers of ethanol was studied using density functional theory. The same approximation was used for characterizing representative clusters of (ethanol)3, (methanol)3, and (methanol)2-water. Trimerization energies and enthalpies as well as the analysis of geometric parameters suggest that the structures with a cyclic pattern in the three hydrogen bonds of the type O-H---O (primary hydrogen bonds), where all molecules are proton donor-acceptor at the same time, are more stable than those with just two primary hydrogen bonds. Additionally, we propose the formation of "secondary hydrogen bonds" between hydrogen atoms of the methyl group of ethanol and the oxygen atom of water or other ethanol molecule (C-H---O), which were found to be weaker than the primary hydrogen bonds.

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 the vertical EA of the aryl radical or the vertical IE of the hydrogen atom donor. PMID:19061320

ALMA Shows that Gas Reservoirs of Star-forming Disks over the Past 3 Billion Years Are Not Predominantly Molecular

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

Cortese, Luca; Catinella, Barbara; Janowiecki, Steven, E-mail: luca.cortese@uwa.edu.au

Cold hydrogen gas is the raw fuel for star formation in galaxies, and its partition into atomic and molecular phases is a key quantity for galaxy evolution. In this Letter, we combine Atacama Large Millimeter/submillimeter Array and Arecibo single-dish observations to estimate the molecular-to-atomic hydrogen mass ratio for massive star-forming galaxies at z ∼ 0.2 extracted from the HIGHz survey, i.e., some of the most massive gas-rich systems currently known. We show that the balance between atomic and molecular hydrogen in these galaxies is similar to that of local main-sequence disks, implying that atomic hydrogen has been dominating the coldmore » gas mass budget of star-forming galaxies for at least the past three billion years. In addition, despite harboring gas reservoirs that are more typical of objects at the cosmic noon, HIGHz galaxies host regular rotating disks with low gas velocity dispersions suggesting that high total gas fractions do not necessarily drive high turbulence in the interstellar medium.« less

Investigation of Kp- and Kd-atom formation and their collisional processes with hydrogen and deuterium targets by the classical-trajectory Monte Carlo method

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

Raeisi, G. M.; Department of Physics, Shahrekord University, Shahrekord 115; Kalantari, S. Z.

The classical-trajectory Monte Carlo method has been used to study the capture of negative kaons by hydrogen and deuterium atoms; subsequently, the elastic scattering, Stark mixing, and Coulomb deexcitation cross sections of Kp and Kd atoms have been determined. The results for kaonic atom formation confirm the initial conditions that have been parametrically applied by most atomic cascade models. Our results show that Coulomb deexcitation in Kp and Kd atoms with {Delta}n>1 is important in addition to n=1. We have shown that the contribution of molecular structure effects to the cross sections of the collisional processes is larger than themore » isotopic effects of the targets. We have also compared our results with the semiclassical approaches.« less

Tunneling in hydrogen and deuterium atom addition to CO at low temperatures

NASA Astrophysics Data System (ADS)

Andersson, Stefan; Goumans, T. P. M.; Arnaldsson, Andri

2011-09-01

The hydrogen and deuterium atom addition reactions of CO to form HCO and DCO are addressed by Harmonic Quantum Transition State Theory calculations. Special attention is paid to the reactions at very low temperatures (5-20 K) where it is found that quantum tunneling leads to substantial rates of reaction. This supports experiments in the solid phase, which conclude that these reactions are driven by tunneling at low temperatures. The calculated kinetic isotope effect of kD/ kH = 1/250 is found to be lower than the experimentally deduced value of 0.08 for the surface reaction. Possible reasons for this discrepancy are discussed.

Manganese complex-catalyzed oxidation and oxidative kinetic resolution of secondary alcohols by hydrogen peroxide† †Electronic supplementary information (ESI) available: Tables S1–S4 and additional data: NMR spectra of the products, GC and HPLC chromatograms in the OKR of secondary alcohols, key geometric information for DFT, etc. See DOI: 10.1039/c7sc00891k Click here for additional data file.

PubMed Central

Miao, Chengxia; Li, Xiao-Xi; Lee, Yong-Min; Xia, Chungu; Wang, Yong

2017-01-01

The highly efficient catalytic oxidation and oxidative kinetic resolution (OKR) of secondary alcohols has been achieved using a synthetic manganese catalyst with low loading and hydrogen peroxide as an environmentally benign oxidant in the presence of a small amount of sulfuric acid as an additive. The product yields were high (up to 93%) for alcohol oxidation and the enantioselectivity was excellent (>90% ee) for the OKR of secondary alcohols. Mechanistic studies revealed that alcohol oxidation occurs via hydrogen atom (H-atom) abstraction from an α-CH bond of the alcohol substrate and a two-electron process by an electrophilic Mn–oxo species. Density functional theory calculations revealed the difference in reaction energy barriers for H-atom abstraction from the α-CH bonds of R- and S-enantiomers by a chiral high-valent manganese–oxo complex, supporting the experimental result from the OKR of secondary alcohols. PMID:29163900

DFT study of hydrogen production from formic acid decomposition on Pd-Au alloy nanoclusters

NASA Astrophysics Data System (ADS)

Liu, D.; Gao, Z. Y.; Wang, X. C.; Zeng, J.; Li, Y. M.

2017-12-01

Recently, it has been reported that the hydrogen production rate of formic acid decomposition can be significantly increased using Pd-Au binary alloy nano-catalysts [Wang et al. J. Mater. Chem. A 1 (2013) 12721-12725]. To explain the reaction mechanism of this alloy catalysis method, formic acid decomposition reactions on pure Pd and Pd-Au alloy nanoclusters are studied via density functional theory simulations. The simulation results indicate that the addition of inert element Au would not influence formic acid decomposition on Pd surface sites of Pd-Au alloy nanoclusters. On the other hand, the existence of Au surface sites brings relative weak hydrogen atom adsorption. On Pd-Au alloy nanoclusters, the dissociated hydrogen atoms from formic acid are easier to combine as hydrogen molecules than that on pure Pd clusters. Via the synergetic effect between Pd and Au, both formic acid decomposition and hydrogen production are events with large probability, which eventually results in high hydrogen production rate.

First-principles studies of hydrogen interaction with ultrathin Mg and Mg-based alloy films

NASA Astrophysics Data System (ADS)

Yoon, Mina; Weitering, Hanno H.; Zhang, Zhenyu

2011-01-01

The search for technologically and economically viable storage solutions for hydrogen fuel would benefit greatly from research strategies that involve systematic property tuning of potential storage materials via atomic-level modification. Here, we use first-principles density-functional theory to investigate theoretically the structural and electronic properties of ultrathin Mg films and Mg-based alloy films and their interaction with atomic hydrogen. Additional delocalized charges are distributed over the Mg films upon alloying them with 11.1% of Al or Na atoms. These extra charges contribute to enhance the hydrogen binding strength to the films. We calculated the chemical potential of hydrogen in Mg films for different dopant species and film thickness, and we included the vibrational degrees of freedom. By comparing the chemical potential with that of free hydrogen gas at finite temperature (T) and pressure (P), we construct a hydrogenation phase diagram and identify the conditions for hydrogen absorption or desorption. The formation enthalpies of metal hydrides are greatly increased in thin films, and in stark contrast to its bulk phase, the hydride state can only be stabilized at high P and T (where the chemical potential of free H2 is very high). Metal doping increases the thermodynamic stabilities of the hydride films and thus significantly helps to reduce the required pressure condition for hydrogen absorption from H2 gas. In particular, with Na alloying, hydrogen can be absorbed and/or desorbed at experimentally accessible T and P conditions.

Name that compound: The numbers game for CFCs, HFCs, HCFCs, and Halons

DOE Data Explorer

Blasing, T. J.; Jones, Sonja

2012-02-01

Chlorofluorocarbons (CFCs) contain Carbon and some combination of Fluorine and Chlorine atoms. Hydrofluorocarbons (HFCs) contain Hydrogen, Fluorine, and Carbon (no chlorine). Hydrochlorofluorocarbons (HCFCs) contain Hydrogen, Chlorine, Fluorine, and Carbon atoms. Hydrobromofluorocarbons (HBFCs) contain Hydrogen, Bromine, Fluorine, and Carbon atoms. Perfluorocarbons contain Fluorine, Carbon, and Bromine atoms, and some contain Chlorine and/or Hydrogen atoms. These compounds are often designated by a combination of letters and numbers (e.g., CFC-11, HCFC-142b). In the latter example, the lower-case b refers to an isomer, which has no relationship to the chemical formula (C2H3F2Cl), but designates a particular structural arrangement of the atoms included. For example, HCFC-142b identifies the isomer in which all three hydrogen atoms are attached to the same carbon atom, and the structural formula is written as CH3CF2Cl. By contrast, HCFC-142 (without the b) refers to an arrangement in which one carbon atom is attached to two hydrogen atoms and one chlorine atom, while the other carbon atom is attached to the third hydrogen atom and two fluorine atoms. Hence, it has a different structural formula (CH2ClCHF2).

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.

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.

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.

Properties of Resistive Hydrogen Sensors as a Function of Additives of 3 D-Metals Introduced in the Volume of Thin Nanocrystalline SnO2 Films

NASA Astrophysics Data System (ADS)

Sevast'yanov, E. Yu.; Maksimova, N. K.; Potekaev, A. I.; Sergeichenko, N. V.; Chernikov, E. V.; Almaev, A. V.; Kushnarev, B. O.

2017-11-01

Analysis of the results of studying electrical and gas sensitive characteristics of the molecular hydrogen sensors based on thin nanocrystalline SnO2 films coated with dispersed Au layers and containing Au+Ni and Au+Co impurities in the bulk showed that the characteristics of these sensors are more stable under the prolonged exposure to hydrogen in comparison with Au/SnO2:Sb, Au films modified only with gold. It has been found that introduction of the nickel and cobalt additives increases the band bending at the grain boundaries of tin dioxide already in freshly prepared samples, which indicates an increase in the density Ni of the chemisorbed oxygen. It is important that during testing, the band bending eφs at the grain boundaries of tin dioxide additionally slightly increases. It can be assumed that during crystallization of films under thermal annealing, the 3d-metal atoms in the SnO2 volume partially segregate on the surface of microcrystals and form bonds with lattice oxygen, the superstoichiometric tin atoms are formed, and the density Ni increases. If the bonds of oxygen with nickel and cobalt are stronger than those with tin, then, under the prolonged tests, atomic hydrogen will be oxidized not by lattice oxygen, but mainly by the chemisorbed one. In this case, stability of the sensors' characteristics increases.

Modelling of adsorption and intercalation of hydrogen on/into tungsten disulphide multilayers and multiwall nanotubes.

PubMed

Martínez, José I; Laikhtman, Alex; Moon, Hoi Ri; Zak, Alla; Alonso, Julio A

2018-05-07

Understanding the interaction of hydrogen with layered materials is crucial in the fields of sensors, catalysis, fuel cells and hydrogen storage, among others. Density functional theory, improved by the introduction of van der Waals dispersion forces, provides an efficient and practical workbench to investigate the interaction of molecular and atomic hydrogen with WS 2 multilayers and nanotubes. We find that H 2 physisorbs on the surface of those materials on top of W atoms, while atomic H chemisorbs on top of S atoms. In the case of nanotubes, the chemisorption strength is sensitive to the nanotube diameter. Diffusion of H 2 on the surface of WS 2 encounters quite small activation barriers whose magnitude helps to explain previous and new experimental results for the observed dependence of the hydrogen concentration with temperature. Intercalation of H 2 between adjacent planar WS 2 layers reveals an endothermic character. Intercalating H atoms is energetically favorable, but the intercalation energy does not compensate for the cost of dissociating the molecules. When H 2 molecules are intercalated between the walls of a double wall nanotube, the rigid confinement induces the dissociation of the confined molecules. A remarkable result is that the presence of a full H 2 monolayer adsorbed on top of the first WS 2 layer of a WS 2 multilayer system strongly facilitates the intercalation of H 2 between WS 2 layers underneath. This opens up an additional gate to intercalation processes.

Symmetry analysis of the behavior of the family R6M23 compounds upon hydrogenation

NASA Astrophysics Data System (ADS)

Kuna, Agnieszka; Sikora, Wiesława

2011-06-01

Symmetry analysis was applied in this work to discuss the behavior of the family R6M23 compounds upon hydrogenation (deuteration), where different structural transformations and magnetic properties, depending on the type of R and M atoms and hydrogen (deuterium) concentrations, have been found. The crystallographic structure of these compounds is described by the Fm3m space group and contain 116 atoms per unit cell occupying the positions 24e(R), 4b, 24d, 32f1 and 32f2(M). Additionally in the elementary cell, there could be up to 100 atoms of hydrogen (or deuterium) occupying the interstitial positions 4a, 32f3, 96j1 and 96k1. The symmetry analysis in the frame of the theory of space groups and their representation gives the opportunity to find all possible transformations from high symmetry parent structure to the structures with symmetry belonging to one of its subgroups. For a given transformation it indicates possible displacements of atoms from initial positions in the parent structure, ordering of hydrogen over interstitial sites and also ordering of magnetic moments, described by the smallest possible number of free parameters. The analysis was carried out by means of the MODY computer program for vectors k = (0; 0; 0) and k = (0; 0; 1) describing the changes of translational symmetry and all positions occupied by the R, M and D atoms.

Non-thermal hydrogen atoms in the terrestrial upper thermosphere.

PubMed

Qin, Jianqi; Waldrop, Lara

2016-12-06

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

Non-thermal hydrogen atoms in the terrestrial upper thermosphere

PubMed Central

Qin, Jianqi; Waldrop, Lara

2016-01-01

Model predictions of the distribution and dynamical transport of hydrogen atoms in the terrestrial atmosphere have long-standing discrepancies with ultraviolet remote sensing measurements, indicating likely deficiencies in conventional theories regarding this crucial atmospheric constituent. Here we report the existence of non-thermal hydrogen atoms that are much hotter than the ambient oxygen atoms in the upper thermosphere. Analysis of satellite measurements indicates that the upper thermospheric hydrogen temperature, more precisely the mean kinetic energy of the atomic hydrogen population, increases significantly with declining solar activity, contrary to contemporary understanding of thermospheric behaviour. The existence of hot hydrogen atoms in the upper thermosphere, which is the key to reconciling model predictions and observations, is likely a consequence of low atomic oxygen density leading to incomplete collisional thermalization of the hydrogen population following its kinetic energization through interactions with hot atomic or ionized constituents in the ionosphere, plasmasphere or magnetosphere. PMID:27922018

Composition and properties of the so-called 'diamond-like' amorphous carbon films

NASA Technical Reports Server (NTRS)

Angus, J. C.; Stultz, J. E.; Shiller, P. J.; Macdonald, J. R.; Mirtich, M. J.

1984-01-01

The composition of amorphous 'diamond-like' films made by direct low energy ion beam deposition, R.F. discharge and sputtering was determined by nuclear reaction analysis, IR spectroscopy and microcombustion chemical analysis. The nuclear reaction analysis showed very similar hydrogen depth profiles for all three types of samples. The atomic ratio of hydrogen to carbon was approximately 0.2 at the film surface and rose to approximately 1.0 at a depth of 500 A. The integrated intensity of the C-H stretching band at about 2900 per cm indicates that the amount of chemically bonded hydrogen is less than the total hydrogen content. Combustion analysis confirmed the overall atomic ratio of hydrogen to carbon determined by nuclear reaction analysis. The chemical state of the non-bonded hydrogen was not determined; however, the effective diffusion coefficient computed from the hydrogen depth profile was extremely low. This indicates either that the films are exceedingly impermeable or that the non-bonded hydrogen requires an additional activated step to leave the films, e.g., desorption or chemical reaction.

Accurate calculation of dynamic Stark shifts and depopulation rates of Rydberg energy levels induced by blackbody radiation. Hydrogen, helium, and alkali-metal atoms

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

Farley, J.W.; Wing, W.H.

1981-05-01

A highly excited (Rydberg) atom bathed in blackbody radiation is perturbed in two ways. A dynamic Stark shift is induced by the off-resonant components of the blackbody radiation. Additionally, electric-dipole transitions to other atomic energy levels are induced by the resonant components of the blackbody radiation. This depopulation effect shortens the Rydberg-state lifetime, thereby broadening the energy level. Calculations of these two effects in many states of hydrogen, helium, and the alkali-metal atoms Li, Na, K, Rb, and Cs are presented for T = 300 K. Contributions from the entire blackbody spectrum and from both discrete and continuous perturbing statesmore » are included. The accuracy is considerably greater than that of previous estimates.« less

Manganese complex-catalyzed oxidation and oxidative kinetic resolution of secondary alcohols by hydrogen peroxide.

PubMed

Miao, Chengxia; Li, Xiao-Xi; Lee, Yong-Min; Xia, Chungu; Wang, Yong; Nam, Wonwoo; Sun, Wei

2017-11-01

The highly efficient catalytic oxidation and oxidative kinetic resolution (OKR) of secondary alcohols has been achieved using a synthetic manganese catalyst with low loading and hydrogen peroxide as an environmentally benign oxidant in the presence of a small amount of sulfuric acid as an additive. The product yields were high (up to 93%) for alcohol oxidation and the enantioselectivity was excellent (>90% ee) for the OKR of secondary alcohols. Mechanistic studies revealed that alcohol oxidation occurs via hydrogen atom (H-atom) abstraction from an α-CH bond of the alcohol substrate and a two-electron process by an electrophilic Mn-oxo species. Density functional theory calculations revealed the difference in reaction energy barriers for H-atom abstraction from the α-CH bonds of R - and S -enantiomers by a chiral high-valent manganese-oxo complex, supporting the experimental result from the OKR of secondary alcohols.

Superthermal electron processes in the upper atmosphere of Uranus: Aurora and electroglow

NASA Technical Reports Server (NTRS)

Waite, J. H., Jr.; Chandler, M. O.; Yelle, R. V.; Sandel, B. R.

1987-01-01

Strong ultraviolet emissions from the upper atmosphere of Uranus suggest that both auroral and electroglow phenomena are of significant aeronomical consequences in the structure of the upper atmosphere. Combined modeling and data analysis were performed to determine the effect of electroglow and auroral phenomena on the global heat and atomic hydrogen budgets in the Uranus upper atmosphere. The results indicate that the auroral and electroglow heat sources are not adequate to explain the high exospheric temperature observed at Uranus, but that the atomic hydrogen supplied by these processes is more than sufficient to explain the observations. The various superthermal electron distributions modeled have significantly different efficiencies for the various processes such as UV emission, heating, ionization, and atomic hydrogen production, and produce quite different H2 band spectra. However, additional information on the UV spectra and global parameters is needed before modeling can be used to distinguish between the possible mechanisms for electroglow.

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.

A Simple Relativistic Bohr Atom

ERIC Educational Resources Information Center

Terzis, Andreas F.

2008-01-01

A simple concise relativistic modification of the standard Bohr model for hydrogen-like atoms with circular orbits is presented. As the derivation requires basic knowledge of classical and relativistic mechanics, it can be taught in standard courses in modern physics and introductory quantum mechanics. In addition, it can be shown in a class that…

STM observation of the chemical reaction of atomic hydrogen on the N-adsorbed Cu(001) surface

NASA Astrophysics Data System (ADS)

Hattori, Takuma; Yamada, Masamichi; Komori, Fumio

2017-01-01

Chemical reaction of atomic hydrogen with the N-adsorbed Cu(001) surfaces was investigated at room temperature by scanning tunnel microscopy. At the low exposure of atomic hydrogen, it reacted with the N atoms and turned to be the NH species on the surface. The reaction rate is proportional to the amount of the unreacted N atoms. By increasing the exposure of atomic hydrogen from this condition, the amount of nitrogen species on the surface decreased. This is attributed to the formation of ammonia and its desorption from the surface. The NH species on the surface turn to NH3 through the surface NH2 species by atomic hydrogen. Coexistence of the clean Cu surface enhances the rate of ammonia formation owing to atomic hydrogen migrating on the clean surface.

Tunable electronic properties of partially edge-hydrogenated armchair boron-nitrogen-carbon nanoribbons.

PubMed

Alaal, Naresh; Medhekar, Nikhil; Shukla, Alok

2018-04-18

We employ a first-principles calculations based density-functional-theory (DFT) approach to study the electronic properties of partially and fully edge-hydrogenated armchair boron-nitrogen-carbon (BNC) nanoribbons (ABNCNRs), with widths between 0.85 nm to 2.3 nm. Due to the partial passivation of edges, the electrons, which do not participate in the bonding, form new energy states located near the Fermi-level. Because of these additional bands, some ABNCNRs exhibit metallic behavior, which is quite uncommon in armchair nanoribbons. Our calculations reveal that metallic behavior is observed for the following passivation patterns: (i) when the B atom from one edge and the N atom from another edge are unpassivated. (ii) when the N atoms from both the edges are unpassivated. (iii) when the C atom from one edge and the N atom from another edge are unpassivated. Furthermore, spin-polarization is also observed for certain passivation schemes, which is also quite uncommon for armchair nanoribbons. Thus, our results suggest that the ABNCNRs exhibit a wide range of electronic and magnetic properties in that the fully edge-hydrogenated ABNCNRs are direct band gap semiconductors, while the partially edge-hydrogenated ones are either semiconducting, or metallic, while simultaneously exhibiting spin polarization, based on the nature of passivation. We also find that the ribbons with larger widths are more stable as compared to the narrower ones.

Electron impact ionization of metastable 2P-state hydrogen atoms in the coplanar geometry

NASA Astrophysics Data System (ADS)

Dhar, S.; Nahar, N.

Triple differential cross sections (TDCS) for the ionization of metastable 2P-state hydrogen atoms by electrons are calculated for various kinematic conditions in the asymmetric coplanar geometry. In this calculation, the final state is described by a multiple-scattering theory for ionization of hydrogen atoms by electrons. Results show qualitative agreement with the available experimental data and those of other theoretical computational results for ionization of hydrogen atoms from ground state, and our first Born results. There is no available other theoretical results and experimental data for ionization of hydrogen atoms from the 2P state. The present study offers a wide scope for the experimental study for ionization of hydrogen atoms from the metastable 2P state.

Hydrogen rearrangements in the fragmentation of anthracene by low-energy electron impact

NASA Astrophysics Data System (ADS)

van der Burgt, Peter J. M.; Dunne, Melissa; Gradziel, Marcin L.

2018-02-01

We have measured mass spectra for positive ions produced by low-energy electron impact on anthracene using a reflectron time-of-flight mass spectrometer. The electron impact energy has been varied from 0 to 100 eV in steps of 0.5 eV. Ion yield curves of most of the fragment ions have been determined by fitting groups of adjacent peaks in the mass spectra with sequences of normalized Gaussians. Appearance energies for all these ions have been determined, and we report the first direct measurement of the triple ionization energy of anthracene at 45.5±0.5 eV. The groups of fragments containing 8-13 carbon atoms provide evidence for hydrogen rearrangements during the fragmentation, involving retention or loss of one or two additional hydrogen atoms. Groups of fragments with 6 and 7 carbon atoms clearly show the presence of doubly-charged fragments. The smaller fragments with 1-4 carbon atoms all show broadened peaks, and these fragments may be partly or mostly due to energetic charge-separation fragmentations of doubly-charged anthracene.

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.

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

Detering, B.A.; Kong, P.C.; Thomas, C.P.

This paper describes the experimental demonstration of a process for direct conversion of methane to acetylene in a thermal plasma. The process utilizes a thermal plasma to dissociate methane and form an equilibrium mixture of acetylene followed by a supersonic expansion of the hot gas to preserve the produced acetylene in high yield. The high translational velocities and rapid cooling result in an overpopulation of atomic hydrogen which persists throughout the expansion process. The presence of atomic hydrogen shifts the equilibrium composition by inhibiting complete pyrolysis of methane and acetylene to solid carbon. This process has the potential to reducemore » the cost of producing acetylene from natural gas. Acetylene and hydrogen produced by this process could be used directly as industrial gases, building blocks for synthesis of industrial chemicals, or oligomerized to long chain liquid hydrocarbons for use as fuels. This process produces hydrogen and ultrafine carbon black in addition to acetylene.« less

Reversible depression in the T{sub c} of thin Nb films due to enhanced hydrogen adsorption

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

Jisrawi, N.M.; Ruckman, M.W.; Thurston, T.R.

The effect of large hydrogen concentrations ({approx}30{percent} atomic), on the superconducting transition temperature T{sub c} of Nb films is discussed. The hydrogen is incorporated in solutionlike phases which occur at these concentrations because the ({alpha} to {beta}) hydride transition in these films is suppressed. X-ray-diffraction data show an asymmetric expansion of the [110] Nb interplanar spacing. This can be as high as a 6{endash}8thinsp{percent} expansion perpendicular to the plane of the film for the addition of {approximately}70{percent} hydrogen, with only a 1{endash}2thinsp{percent} change in the plane of the film. T{sub c} is depressed to a value near 50{percent} of thatmore » of the undoped film with about 30{percent} atomic hydrogen, and returns to its initial value when the hydrogen is removed. A discussion is given of how both disorder and changes in the electronic structure can affect T{sub c}. {copyright} {ital 1998} {ital The American Physical Society}« less

Reintroducing electrostatics into macromolecular crystallographic refinement: application to neutron crystallography and DNA hydration.

PubMed

Fenn, Timothy D; Schnieders, Michael J; Mustyakimov, Marat; Wu, Chuanjie; Langan, Paul; Pande, Vijay S; Brunger, Axel T

2011-04-13

Most current crystallographic structure refinements augment the diffraction data with a priori information consisting of bond, angle, dihedral, planarity restraints, and atomic repulsion based on the Pauli exclusion principle. Yet, electrostatics and van der Waals attraction are physical forces that provide additional a priori information. Here, we assess the inclusion of electrostatics for the force field used for all-atom (including hydrogen) joint neutron/X-ray refinement. Two DNA and a protein crystal structure were refined against joint neutron/X-ray diffraction data sets using force fields without electrostatics or with electrostatics. Hydrogen-bond orientation/geometry favors the inclusion of electrostatics. Refinement of Z-DNA with electrostatics leads to a hypothesis for the entropic stabilization of Z-DNA that may partly explain the thermodynamics of converting the B form of DNA to its Z form. Thus, inclusion of electrostatics assists joint neutron/X-ray refinements, especially for placing and orienting hydrogen atoms. Copyright © 2011 Elsevier Ltd. All rights reserved.

Reintroducing Electrostatics into Macromolecular Crystallographic Refinement: Application to Neutron Crystallography and DNA Hydration

PubMed Central

Fenn, Timothy D.; Schnieders, Michael J.; Mustyakimov, Marat; Wu, Chuanjie; Langan, Paul; Pande, Vijay S.; Brunger, Axel T.

2011-01-01

Summary Most current crystallographic structure refinements augment the diffraction data with a priori information consisting of bond, angle, dihedral, planarity restraints and atomic repulsion based on the Pauli exclusion principle. Yet, electrostatics and van der Waals attraction are physical forces that provide additional a priori information. Here we assess the inclusion of electrostatics for the force field used for all-atom (including hydrogen) joint neutron/X-ray refinement. Two DNA and a protein crystal structure were refined against joint neutron/X-ray diffraction data sets using force fields without electrostatics or with electrostatics. Hydrogen bond orientation/geometry favors the inclusion of electrostatics. Refinement of Z-DNA with electrostatics leads to a hypothesis for the entropic stabilization of Z-DNA that may partly explain the thermodynamics of converting the B form of DNA to its Z form. Thus, inclusion of electrostatics assists joint neutron/X-ray refinements, especially for placing and orienting hydrogen atoms. PMID:21481775

HI-to-H2 Transitions in the Perseus Molecular Cloud

NASA Astrophysics Data System (ADS)

Bialy, Shmuel; Sternberg, Amiel; Lee, Min-Young; Le Petit, Franck; Roueff, Evelyne

2015-08-01

We use the Sternberg et al. theory for interstellar atomic to molecular hydrogen (H i-to-H2) conversion to analyze H i-to-H2 transitions in five (low-mass) star-forming and dark regions in the Perseus molecular cloud, B1, B1E, B5, IC348, and NGC1333. The observed H i mass surface densities of 6.3-9.2 {M}⊙ {{pc}}-2 are consistent with H i-to-H2 transitions dominated by H i-dust shielding in predominantly atomic envelopes. For each source, we constrain the dimensionless parameter α G, and the ratio {I}{UV}/n, of the FUV intensity to hydrogen gas density. We find α G values from 5.0 to 26.1, implying characteristic atomic hydrogen densities 11.8-1.8 cm-3, for {I}{UV}≈ 1 appropriate for Perseus. Our analysis implies that the dusty H i shielding layers are probably multiphased, with thermally unstable UNM gas in addition to cold CNM within the 21 cm kinematic radius.

New frontiers of atomic layer etching

NASA Astrophysics Data System (ADS)

Sherpa, Sonam D.; Ranjan, Alok

2018-03-01

Interest in atomic layer etching (ALE) has surged recently because it offers several advantages over continuous or quasicontinuous plasma etching. These benefits include (1) independent control of ion energy, ion flux, and radical flux, (2) flux-independent etch rate that mitigates the iso-dense loading effects, and (3) ability to control the etch rate with atomic or nanoscale precision. In addition to these benefits, we demonstrate an area-selective etching for maskless lithography as a new frontier of ALE. In this paper, area-selective etching refers to the confinement of etching into the specific areas of the substrate. The concept of area-selective etching originated during our studies on quasi-ALE of silicon nitride which consists of sequential exposure of silicon nitride to hydrogen and fluorinated plasma. The findings of our studies reported in this paper suggest that it may be possible to confine the etching into specific areas of silicon nitride without using any mask by replacing conventional hydrogen plasma with a localized source of hydrogen ions.

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.

Electronic and magnetic properties of MoSe2 armchair nanoribbons controlled by the different edge structures

NASA Astrophysics Data System (ADS)

Zhang, Hui; Zhao, Xu; Gao, Yonghui; Wang, Haiyang; Wang, Tianxing; Wei, Shuyi

2018-03-01

Tow-dimensional materials obviously have potential applications in next-generation nanodevices because of their extraordinary physical and chemical properties and the demands of the market. Using first-principle calculation based on density functional theory, we explore electronic and magnetic properties of the different nanoribbons with various edge structures, namely, with hydrogenation or not. In addition, we also calculate the binding energy to analyze the stability of the nanoribbon. Our calculations tell us that the passivated nanoribbons have the positive binding energies, which indicates the passivated nanoribbons are relative stable and hydrogenation can improve the stability of the bare nanoribbons due to the reduction of the dangling bonds. Among of them, full hydrogenation has the highest stability. We find all the nanoribbons with full and without hydrogenation are nonmagnetic semiconductors. It is worth mentioning that hydrogenation can induce the bare nanoribbons to transform gradually from indirect band gap semiconductor to direct band gap semiconductor, even to half-metal. In addition, the magnetic moment of the bare nanoribbon change bit by bit as the rate of hydrogenation increases. When the edge atoms are fully hydrogenated, the magnetic moment return to zero. What's more, our research results still confirm that electronic and magnetic properties of the nanorribons without and with different edge passivation are mainly contributed by the atoms at the edges. These studies about MoSe2 nanoribbons will shed light on the further development of the relevant nanodevices in versatile applications, such as spintronics and energy harvesting.

Acetylene chain reaction on hydrogenated boron nitride monolayers: a density functional theory study.

PubMed

Ponce-Pérez, R; Cocoletzi, Gregorio H; Takeuchi, Noboru

2017-11-28

Spin-polarized first-principles total-energy calculations have been performed to investigate the possible chain reaction of acetylene molecules mediated by hydrogen abstraction on hydrogenated hexagonal boron nitride monolayers. Calculations have been done within the periodic density functional theory (DFT), employing the PBE exchange correlation potential, with van der Waals corrections (vdW-DF). Reactions at two different sites have been considered: hydrogen vacancies on top of boron and on top of nitrogen atoms. As previously calculated, at the intermediate state of the reaction, when the acetylene molecule is attached to the surface, the adsorption energy is of the order of -0.82 eV and -0.20 eV (measured with respect to the energy of the non interacting molecule-substrate system) for adsorption on top of boron and nitrogen atoms, respectively. After the hydrogen abstraction takes place, the system gains additional energy, resulting in adsorption energies of -1.52 eV and -1.30 eV, respectively. These results suggest that the chain reaction is energetically favorable. The calculated minimum energy path (MEP) for hydrogen abstraction shows very small energy barriers of the order of 5 meV and 22 meV for the reaction on top of boron and nitrogen atoms, respectively. Finally, the density of states (DOS) evolution study helps to understand the chain reaction mechanism. Graphical abstract Acetylene chain reaction on hydrogenated boron nitride monolayers.

Reversible Inter- and Intramolecular Carbon-Hydrogen Activation, Hydrogen Addition, and Catalysis by the Unsaturated Complex Pt(IPr)(SnBu(t)3)(H).

PubMed

Koppaka, Anjaneyulu; Captain, Burjor

2016-03-21

The complex Pt(IPr)(SnBu(t)3)(H) (1) was obtained from the reaction of Pt(COD)2 with Bu(t)3SnH and IPr [IPr = N,N'-bis(2,6-diisopropylphenyl)imidazol-2-ylidene]. Complex 1 undergoes exchange reactions with deuterated solvents (C6D6, toluene-d8, and CD2Cl2), where the hydride ligand and the methyl hydrogen atoms on the isopropyl group of the IPr ligand have been replaced by deuterium atoms. Complex 1 reacts with H2 gas reversibly at room temperature to yield the complex Pt(IPr)(SnBu(t)3)(H)3 (2). Complex 2 also undergoes exchange reactions with deuterated solvents as in 1 to deuterate the hydride ligands and the methyl hydrogen atoms on the isopropyl group of the IPr ligand. Complex 1 catalyzes the hydrogenation of styrene to ethylbenzene at room temperature. The reaction of 1 with 1 equiv of styrene at -20 °C yields the η(2)-coordinated product Pt(IPr)(SnBu(t)3)(η(2)-CH2CHPh)(H) (3), and with 2 equiv of styrene, it forms Pt(IPr)(η(2)-CH2CHPh)2 (4).

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

Dubey, P., E-mail: purushd@barc.gov.in; Sharma, V. K.; Mitra, S.

Synthetic hydroxyapatite (HAp) is an important material in biomedical engineering due to its excellent biocompatibility and bioactivity. Here we report dynamics of cetyltrimethylammonium bromide (CTAB) in HAp composite, prepared by co-precipitation method, as studied by quasielastic neutron scattering (QENS) technique. It is found that the observed dynamics involved two time scales associated with fast torsional motion and segmental motion of the CTAB monomers. In addition to segmental motion of the hydrogen atoms, few undergo torsional motion as well. Torsional dynamics was described by a 2-fold jump diffusion model. The segmental dynamics of CTAB has been described assumimg the hydrogen atomsmore » undergoing diffusion inside a sphere of confined volume. While the diffusivity is found to increase with temperature, the spherical volumes within which the hydrogen atoms are undergoing diffusion remain almost unchanged.« less

Ultrafine hydrogen storage powders

DOEpatents

Anderson, Iver E.; Ellis, Timothy W.; Pecharsky, Vitalij K.; Ting, Jason; Terpstra, Robert; Bowman, Robert C.; Witham, Charles K.; Fultz, Brent T.; Bugga, Ratnakumar V.

2000-06-13

A method of making hydrogen storage powder resistant to fracture in service involves forming a melt having the appropriate composition for the hydrogen storage material, such, for example, LaNi.sub.5 and other AB.sub.5 type materials and AB.sub.5+x materials, where x is from about -2.5 to about +2.5, including x=0, and the melt is gas atomized under conditions of melt temperature and atomizing gas pressure to form generally spherical powder particles. The hydrogen storage powder exhibits improved chemcial homogeneity as a result of rapid solidfication from the melt and small particle size that is more resistant to microcracking during hydrogen absorption/desorption cycling. A hydrogen storage component, such as an electrode for a battery or electrochemical fuel cell, made from the gas atomized hydrogen storage material is resistant to hydrogen degradation upon hydrogen absorption/desorption that occurs for example, during charging/discharging of a battery. Such hydrogen storage components can be made by consolidating and optionally sintering the gas atomized hydrogen storage powder or alternately by shaping the gas atomized powder and a suitable binder to a desired configuration in a mold or die.

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.

Polymeric Materials With Additives for Durability and Radiation Shielding in Space

NASA Technical Reports Server (NTRS)

Kiefer, Richard

2011-01-01

Polymeric materials are attractive for use in space structures because of their light weight and high strength In addition, polymers are made of elements with low atomic numbers (Z), primarily carbon (C), hydrogen (H), oxygen (0), and nitrogen (N) which provide the best shielding from galactic cosmic rays (GCR) (ref. 1). Galactic cosmic rays are composed primarily of nuclei (i.e., fully ionized atoms) plus a contribution of about 2% from electrons and positrons. There is a small but significant component of GCR particles with high charge (Z > 10) and high energy (E >100 GeV) (ref. 2). These so-called HZE particles comprise only 1 to 2% of the cosmic ray fluence but they interact with very high specific ionization and contribute 50% of the long- term dose to humans. The best shield for this radiation would be liquid hydrogen, which is not feasible. For this reason, hydrogen-containing polymers make the most effective practical shields. Moreover, neutrons are formed in the interactions of GCR particles with materials. Neutrons can only lose energy by collisions or reactions with a nucleus since they are uncharged. This is a process that is much less probable than the Coulombic interactions of charged particles. Thus, neutrons migrate far from the site of the reaction in which they were formed. This increases the probability of neutrons reaching humans or electronic equipment. Fast neutrons (> 1 MeV) can interact with silicon chips in electronic equipment resulting in the production of recoil ions which can cause single event upsets (SEU) in sensitive components (ref. 3). Neutrons lose energy most effectively by elastic collisions with light atoms, particularly hydrogen atoms. Therefore, hydrogen-containing polymers are not only effective in interacting with GCR particles; they are also effective in reducing the energy of the neutrons formed in the interactions.

Hydrogen transfer reactions of interstellar Complex Organic Molecules

NASA Astrophysics Data System (ADS)

Álvarez-Barcia, S.; Russ, P.; Kästner, J.; Lamberts, T.

2018-06-01

Radical recombination has been proposed to lead to the formation of complex organic molecules (COMs) in CO-rich ices in the early stages of star formation. These COMs can then undergo hydrogen addition and abstraction reactions leading to a higher or lower degree of saturation. Here, we have studied 14 hydrogen transfer reactions for the molecules glyoxal, glycoaldehyde, ethylene glycol, and methylformate and an additional three reactions where CHnO fragments are involved. Over-the-barrier reactions are possible only if tunneling is invoked in the description at low temperature. Therefore the rate constants for the studied reactions are calculated using instanton theory that takes quantum effects into account inherently. The reactions were characterized in the gas phase, but this is expected to yield meaningful results for CO-rich ices due to the minimal alteration of reaction landscapes by the CO molecules. We found that rate constants should not be extrapolated based on the height of the barrier alone, since the shape of the barrier plays an increasingly larger role at decreasing temperature. It is neither possible to predict rate constants based only on considering the type of reaction, the specific reactants and functional groups play a crucial role. Within a single molecule, though, hydrogen abstraction from an aldehyde group seems to be always faster than hydrogen addition to the same carbon atom. Reactions that involve heavy-atom tunneling, e.g., breaking or forming a C-C or C-O bond, have rate constants that are much lower than those where H transfer is involved.

Hirshfeld atom refinement for modelling strong hydrogen bonds.

PubMed

Woińska, Magdalena; Jayatilaka, Dylan; Spackman, Mark A; Edwards, Alison J; Dominiak, Paulina M; Woźniak, Krzysztof; Nishibori, Eiji; Sugimoto, Kunihisa; Grabowsky, Simon

2014-09-01

High-resolution low-temperature synchrotron X-ray diffraction data of the salt L-phenylalaninium hydrogen maleate are used to test the new automated iterative Hirshfeld atom refinement (HAR) procedure for the modelling of strong hydrogen bonds. The HAR models used present the first examples of Z' > 1 treatments in the framework of wavefunction-based refinement methods. L-Phenylalaninium hydrogen maleate exhibits several hydrogen bonds in its crystal structure, of which the shortest and the most challenging to model is the O-H...O intramolecular hydrogen bond present in the hydrogen maleate anion (O...O distance is about 2.41 Å). In particular, the reconstruction of the electron density in the hydrogen maleate moiety and the determination of hydrogen-atom properties [positions, bond distances and anisotropic displacement parameters (ADPs)] are the focus of the study. For comparison to the HAR results, different spherical (independent atom model, IAM) and aspherical (free multipole model, MM; transferable aspherical atom model, TAAM) X-ray refinement techniques as well as results from a low-temperature neutron-diffraction experiment are employed. Hydrogen-atom ADPs are furthermore compared to those derived from a TLS/rigid-body (SHADE) treatment of the X-ray structures. The reference neutron-diffraction experiment reveals a truly symmetric hydrogen bond in the hydrogen maleate anion. Only with HAR is it possible to freely refine hydrogen-atom positions and ADPs from the X-ray data, which leads to the best electron-density model and the closest agreement with the structural parameters derived from the neutron-diffraction experiment, e.g. the symmetric hydrogen position can be reproduced. The multipole-based refinement techniques (MM and TAAM) yield slightly asymmetric positions, whereas the IAM yields a significantly asymmetric position.

Regioselective Ni-Catalyzed Carboxylation of Allylic and Propargylic Alcohols with Carbon Dioxide.

PubMed

Chen, Yue-Gang; Shuai, Bin; Ma, Cong; Zhang, Xiu-Jie; Fang, Ping; Mei, Tian-Sheng

2017-06-02

An efficient Ni-catalyzed reductive carboxylation of allylic alcohols with CO 2 has been successfully developed, providing linear β,γ-unsaturated carboxylic acids as the sole regioisomer with generally high E/Z stereoselectivity. In addition, the carboxylic acids can be generated from propargylic alcohols via hydrogenation to give allylic alcohol intermediates, followed by carboxylation. A preliminary mechanistic investigation suggests that the hydrogenation step is made possible by a Ni hydride intermediate produced by a hydrogen atom transfer from water.

Investigation of steric influences on hydrogen-bonding motifs in cyclic ureas by using X-ray, neutron, and computational methods.

PubMed

McCormick, Laura J; McDonnell-Worth, Ciaran; Platts, James A; Edwards, Alison J; Turner, David R

2013-11-01

A series of urea-derived heterocycles, 5N-substituted hexahydro-1,3,5-triazin-2-ones, has been prepared and their structures have been determined for the first time. This family of compounds only differ in their substituent at the 5-position (which is derived from the corresponding primary amine), that is, methyl (1), ethyl (2), isopropyl (3), tert-butyl (4), benzyl (5), N,N-(diethyl)ethylamine (6), and 2-hydroxyethyl (7). The common heterocyclic core of these molecules is a cyclic urea, which has the potential to form a hydrogen-bonding tape motif that consists of self-associative R₂²(8) dimers. The results from X-ray crystallography and, where possible, Laue neutron crystallography show that the hydrogen-bonding motifs that are observed and the planarity of the hydrogen bonds appear to depend on the steric hindrance at the α-carbon atom of the N substituent. With the less-hindered substituents, methyl and ethyl, the anticipated tape motif is observed. When additional methyl groups are added onto the α-carbon atom, as in the isopropyl and tert-butyl derivatives, a different 2D hydrogen-bonding motif is observed. Despite the bulkiness of the substituents, the benzyl and N,N-(diethyl)ethylamine derivatives have methylene units at the α-carbon atom and, therefore, display the tape motif. The introduction of a competing hydrogen-bond donor/acceptor in the 2-hydroxyethyl derivative disrupts the tape motif, with a hydroxy group interrupting the N-H···O=C interactions. The geometry around the hydrogen-bearing nitrogen atoms, whether planar or non-planar, has been confirmed for compounds 2 and 5 by using Laue neutron diffraction and rationalized by using computational methods, thus demonstrating that distortion of O-C-N-H torsion angles occurs to maintain almost-linear hydrogen-bonding interactions. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

PubMed

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

2009-08-07

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.

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.

Molecular dynamics simulations of hydrogen diffusion in aluminum

DOE PAGES

Zhou, X. W.; El Gabaly, F.; Stavila, V.; ...

2016-03-23

In this study, hydrogen diffusion impacts the performance of solid-state hydrogen storage materials and contributes to the embrittlement of structural materials under hydrogen-containing environments. In atomistic simulations, the diffusion energy barriers are usually calculated using molecular statics simulations where a nudged elastic band method is used to constrain a path connecting the two end points of an atomic jump. This approach requires prior knowledge of the “end points”. For alloy and defective systems, the number of possible atomic jumps with respect to local atomic configurations is tremendous. Even when these jumps can be exhaustively studied, it is still unclear howmore » they can be combined to give an overall diffusion behavior seen in experiments. Here we describe the use of molecular dynamics simulations to determine the overall diffusion energy barrier from the Arrhenius equation. This method does not require information about atomic jumps, and it has additional advantages, such as the ability to incorporate finite temperature effects and to determine the pre-exponential factor. As a test case for a generic method, we focus on hydrogen diffusion in bulk aluminum. We find that the challenge of this method is the statistical variation of the results. However, highly converged energy barriers can be achieved by an appropriate set of temperatures, output time intervals (for tracking hydrogen positions), and a long total simulation time. Our results help elucidate the inconsistencies of the experimental diffusion data published in the literature. The robust approach developed here may also open up future molecular dynamics simulations to rapidly study diffusion properties of complex material systems in multidimensional spaces involving composition and defects.« less

Direct quantitative measurement of the C═O⋅⋅⋅H–C bond by atomic force microscopy

PubMed Central

Kawai, Shigeki; Nishiuchi, Tomohiko; Kodama, Takuya; Spijker, Peter; Pawlak, Rémy; Meier, Tobias; Tracey, John; Kubo, Takashi; Meyer, Ernst; Foster, Adam S.

2017-01-01

The hydrogen atom—the smallest and most abundant atom—is of utmost importance in physics and chemistry. Although many analysis methods have been applied to its study, direct observation of hydrogen atoms in a single molecule remains largely unexplored. We use atomic force microscopy (AFM) to resolve the outermost hydrogen atoms of propellane molecules via very weak C═O⋅⋅⋅H–C hydrogen bonding just before the onset of Pauli repulsion. The direct measurement of the interaction with a hydrogen atom paves the way for the identification of three-dimensional molecules such as DNAs and polymers, building the capabilities of AFM toward quantitative probing of local chemical reactivity. PMID:28508080

Identifying the Unique Properties of α-Bi 2Mo 3O 12 for the Activation of Propene

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

Licht, Rachel B.; Getsoian, Andrew; Bell, Alexis T.

In order to understand the remarkable activity of α-Bi 2Mo 3O 12 for selective oxidation and ammoxidation of propene, the propene activation ability of four molybdenum-based mixed metal oxides - Bi 2Mo 3O 12, PbMoO 4, Bi 2Pb 5Mo 8O 32, and MoO 3 - was investigated using density functional theory. Propene activation is considered to occur via abstraction of a hydrogen atom from the methyl group of physisorbed propene by lattice oxygen. For each material, the apparent activation energy was estimated by summing the heat of adsorption of propene, the C-H bond dissociation energy, and the hydrogen attachment energymore » (HAE) for hydrogen addition to lattice oxygen; this sum provides a lower bound for the apparent activation energy. It was found that two structural features of oxide surfaces are essential to achieve low activation barriers: under-coordinated surface cation sites enable strong propene adsorption, and suitable 5- or 6-coordinate geometries at molybdenum result in favorable HAEs. The impact of molybdenum coordination on HAE was elucidated by carrying out a molecular orbital analysis using a cluster model of the molybdate unit. This effort revealed that, in 5- and 6-coordinate molybdates, oxygen donor atoms trans to molybdenyl oxo atoms destabilize the molybdate prior to H addition but stabilize the molybdate after H addition, thereby providing an HAE ~15 kcal/mol more favorable than that on 4-coordinate molybdate oxo atoms. Bi 3+ cations in Bi 2Mo 3O 12 thus promote catalytic activity by providing both strong adsorption sites for propene and forcing molybdate into 5-coordinate geometries that lead to particularly favorable values of the HAE. (Graph Presented).« less

Identifying the Unique Properties of α-Bi 2Mo 3O 12 for the Activation of Propene

DOE PAGES

Licht, Rachel B.; Getsoian, Andrew; Bell, Alexis T.

2016-12-30

In order to understand the remarkable activity of α-Bi 2Mo 3O 12 for selective oxidation and ammoxidation of propene, the propene activation ability of four molybdenum-based mixed metal oxides - Bi 2Mo 3O 12, PbMoO 4, Bi 2Pb 5Mo 8O 32, and MoO 3 - was investigated using density functional theory. Propene activation is considered to occur via abstraction of a hydrogen atom from the methyl group of physisorbed propene by lattice oxygen. For each material, the apparent activation energy was estimated by summing the heat of adsorption of propene, the C-H bond dissociation energy, and the hydrogen attachment energymore » (HAE) for hydrogen addition to lattice oxygen; this sum provides a lower bound for the apparent activation energy. It was found that two structural features of oxide surfaces are essential to achieve low activation barriers: under-coordinated surface cation sites enable strong propene adsorption, and suitable 5- or 6-coordinate geometries at molybdenum result in favorable HAEs. The impact of molybdenum coordination on HAE was elucidated by carrying out a molecular orbital analysis using a cluster model of the molybdate unit. This effort revealed that, in 5- and 6-coordinate molybdates, oxygen donor atoms trans to molybdenyl oxo atoms destabilize the molybdate prior to H addition but stabilize the molybdate after H addition, thereby providing an HAE ~15 kcal/mol more favorable than that on 4-coordinate molybdate oxo atoms. Bi 3+ cations in Bi 2Mo 3O 12 thus promote catalytic activity by providing both strong adsorption sites for propene and forcing molybdate into 5-coordinate geometries that lead to particularly favorable values of the HAE. (Graph Presented).« less

Facile and Promising Method for Michael Addition of Indole and Pyrrole to Electron-Deficient trans-β-Nitroolefins Catalyzed by a Hydrogen Bond Donor Catalyst Feist's Acid and Preliminary Study of Antimicrobial Activity

PubMed Central

Al Majid, Abdullah M. A.; Islam, Mohammad Shahidul; Barakat, Assem; Al-Agamy, Mohamed H. M.; Naushad, Mu.

2014-01-01

The importance of cooperative hydrogen-bonding effects has been demonstrated using novel 3-methylenecyclopropane-1,2-dicarboxylic acid (Feist's acid (FA)) as hydrogen bond donor catalysts for the addition of indole and pyrrole to trans-β-nitrostyrene derivatives. Because of the hydrogen bond donor (HBD) ability, Feist's acid (FA) has been introduced as a new class of hydrogen bond donor catalysts for the activation of nitroolefin towards nucleophilic substitution reaction. It has effectively catalyzed the Michael addition of indoles and pyrrole to β-nitroolefins under optimum reaction condition to furnish the corresponding Michael adducts in good to excellent yields (up to 98%). The method is general, atom-economical, convenient, and eco-friendly and could provide excellent yields and regioselectivities. Some newly synthesized compounds were for examined in vitro antimicrobial activity and their preliminary results are reported. PMID:24574906

Sequential desorption energy of hydrogen from nickel clusters

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

Deepika,; Kumar, Rakesh, E-mail: rakesh@iitrpr.ac.in; R, Kamal Raj.

2015-06-24

We report reversible Hydrogen adsorption on Nickel clusters, which act as a catalyst for solid state storage of Hydrogen on a substrate. First-principles technique is employed to investigate the maximum number of chemically adsorbed Hydrogen molecules on Nickel cluster. We observe a maximum of four Hydrogen molecules adsorbed per Nickel atom, but the average Hydrogen molecules adsorbed per Nickel atom decrease with cluster size. The dissociative chemisorption energy per Hydrogen molecule and sequential desorption energy per Hydrogen atom on Nickel cluster is found to decrease with number of adsorbed Hydrogen molecules, which on optimization may help in economical storage andmore » regeneration of Hydrogen as a clean energy carrier.« less

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.

Tunable fictitious substituent effects on the π-π interactions of substituted sandwich benzene dimers.

PubMed

Garcia, Amee M; Determan, John J; Janesko, Benjamin G

2014-05-08

Substituent effects on the π-π interactions of aromatic rings are a topic of much recent debate. Real substituents give a complicated combination of inductive, resonant, dispersion, and other effects. To help partition these effects, we present calculations on fictitious "pure" σ donor/acceptor substituents, hydrogen atoms with nuclear charges other than 1. "Pure" σ donors with nuclear charge <1 weaken π-π stacking in the sandwich benzene dimer. This result is consistent with the electrostatic model of Hunter and Sanders, and different from real substituents. Calculated inductive effects are largely additive and transferable, consistent with a local direct interaction model. A second series of fictitious substituents, neutral hydrogen atoms with an artificially broadened nuclear charge distribution, give similar trends though with reduced additivity. These results provide an alternative perspective on substituent effects in noncovalent interactions.

LIFS atomic hydrogen density measurements at the URAGAN-3M facility

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

Volkov, E.D.; Zhmurin, P.N.; Letuchii, A.N.

1994-12-31

Molecular and atomic hydrogen behavior within a plasma column of the URAGAN-3M facility was numerically simulated for a low density regime ({bar n}{sub e} {approx_equal} 2 x 10{sup 12} cm{sup {minus}3}). Local density of hydrogen atoms in the axial region was measured by Laser-Induced Fluorescence Spectroscopy technique. A good agreement of the measurements and simulations was observed. In the regime under investigation the results of hydrogen density spectroscopic measurements were found to be greatly affected by dissociative population of hydrogen atom excited states. 2 refs., 3 figs.

Hydrogen positions in single nanocrystals revealed by electron diffraction

NASA Astrophysics Data System (ADS)

Palatinus, L.; Brázda, P.; Boullay, P.; Perez, O.; Klementová, M.; Petit, S.; Eigner, V.; Zaarour, M.; Mintova, S.

2017-01-01

The localization of hydrogen atoms is an essential part of crystal structure analysis, but it is difficult because of their small scattering power. We report the direct localization of hydrogen atoms in nanocrystalline materials, achieved using the recently developed approach of dynamical refinement of precession electron diffraction tomography data. We used this method to locate hydrogen atoms in both an organic (paracetamol) and an inorganic (framework cobalt aluminophosphate) material. The results demonstrate that the technique can reliably reveal fine structural details, including the positions of hydrogen atoms in single crystals with micro- to nanosized dimensions.

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

Comparisons are made between the NP series and the NX series of hydrogen masers. A field operable hydrogen maser (NR series) is also described. Atomic hydrogen primary frequency standards are in development stages. Standards are being developed for a hydrogen beam frequency standard and for a concertina hydrogen maser.

New Propellants and Cryofuels

NASA Technical Reports Server (NTRS)

Palasezski, Bryan; Sullivan, Neil S.; Hamida, Jaha; Kokshenev, V.

2006-01-01

The proposed research will investigate the stability and cryogenic properties of solid propellants that are critical to NASA s goal of realizing practical propellant designs for future spacecraft. We will determine the stability and thermal properties of a solid hydrogen-liquid helium stabilizer in a laboratory environment in order to design a practical propellant. In particular, we will explore methods of embedding atomic species and metallic nano-particulates in hydrogen matrices suspended in liquid helium. We will also measure the characteristic lifetimes and diffusion of atomic species in these candidate cryofuels. The most promising large-scale advance in rocket propulsion is the use of atomic propellants; most notably atomic hydrogen stabilized in cryogenic environments, and metallized-gelled liquid hydrogen (MGH) or densified gelled hydrogen (DGH). The new propellants offer very significant improvements over classic liquid oxygen/hydrogen fuels because of two factors: (1) the high energy-release, and (ii) the density increase per unit energy release. These two changes can lead to significant reduced mission costs and increased payload to orbit weight ratios. An achievable 5 to 10 percent improvement in specific impulse for the atomic propellants or MGH fuels can result in a doubling or tripling of system payloads. The high-energy atomic propellants must be stored in a stabilizing medium such as solid hydrogen to inhibit or delay their recombination into molecules. The goal of the proposed research is to determine the stability and thermal properties of the solid hydrogen-liquid helium stabilizer. Magnetic resonance techniques will be used to measure the thermal lifetimes and the diffusive motions of atomic species stored in solid hydrogen grains. The properties of metallic nano-particulates embedded in hydrogen matrices will also be studied and analyzed. Dynamic polarization techniques will be developed to enhance signal/noise ratios in order to be able to detect low concentrations of the introduced species. The required lifetimes for atomic hydrogen and other species can only be realized at low temperatures to avoid recombination of atoms before use as a fuel.

Crystal structure of a new amine nitrate: 4-dimethylaminopyridinium nitrate (C{sub 7}H{sub 11}N{sub 2})NO{sub 3}

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

Benhassan, D., E-mail: houcine-naili@yahoo.com; Rekik, W.; Naïli, H.

2015-12-15

The title compound (C{sub 7}H{sub 11}N{sub 2})NO{sub 3} (I) was obtained by the slow evaporation method at room temperature. Its crystal structure consists of organic cations (C{sub 7}H{sub 11}N{sub 2}){sup +} and nitrate anions (NO{sub 3}){sup –} linked by two types of hydrogen bonds. Each monoprotonated nitrogen atom, called bifurcated, is engaged in two N–H···O hydrogen bonds with two symmetric oxygen atoms. In addition, the crystal structure stability is established by C–H···O hydrogen bonds that ensure the formation of infinite layers, parallel to (001) plane. These layers are related together through π···π interactions established between aromatic amines.

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

Lee, Gyeong Won; Shim, Jaewon; Jung, Young-Dae, E-mail: ydjung@hanyang.ac.kr

The influence of renormalization plasma screening on the entanglement fidelity for the elastic electron-atom scattering is investigated in partially ionized dense hydrogen plasmas. The partial wave analysis and effective interaction potential are employed to obtain the scattering entanglement fidelity in dense hydrogen plasmas as functions of the collision energy, the Debye length, and the renormalization parameter. It is found that the renormalization plasma shielding enhances the scattering entanglement fidelity. Hence, we show that the transmission of the quantum information can be increased about 10% due to the renormalization shielding effect in dense hydrogen plasmas. It is also found that themore » renormalization shielding effect on the entanglement fidelity for the electron-atom collision increases with an increase of the collision energy. In addition, the renormalization shielding function increases with increasing collision energy and saturates to the unity with an increase of the Debye length.« less

Atomic hydrogen storage method and apparatus

NASA Technical Reports Server (NTRS)

Woollam, J. A. (Inventor)

1978-01-01

Atomic hydrogen, for use as a fuel or as an explosive, is stored in the presence of a strong magnetic field in exfoliated layered compounds such as molybdenum disulfide or an elemental layer material such as graphite. The compound is maintained at liquid helium temperatures and the atomic hydrogen is collected on the surfaces of the layered compound which are exposed during delamination (exfoliation). The strong magnetic field and the low temperature combine to prevent the atoms of hydrogen from recombining to form molecules.

Atomic hydrogen storage method and apparatus

NASA Technical Reports Server (NTRS)

Woollam, J. A. (Inventor)

1980-01-01

Atomic hydrogen, for use as a fuel or as an explosive, is stored in the presence of a strong magnetic field in exfoliated layered compounds such as molybdenum disulfide or an elemental layer material such as graphite. The compounds maintained at liquid helium temperatures and the atomic hydrogen is collected on the surfaces of the layered compound which are exposed during delamination (exfoliation). The strong magnetic field and the low temperature combine to prevent the atoms of hydrogen from recombining to form molecules.

Atomic hydrogen storage. [cryotrapping and magnetic field strength

NASA Technical Reports Server (NTRS)

Woollam, J. A. (Inventor)

1980-01-01

Atomic hydrogen, for use as a fuel or as an explosive, is stored in the presence of a strong magnetic field in exfoliated layered compounds such as molybdenum disulfide or an elemental layer material such as graphite. The compound is maintained at liquid temperatures and the atomic hydrogen is collected on the surfaces of the layered compound which are exposed during delamination (exfoliation). The strong magnetic field and the low temperature combine to prevent the atoms of hydrogen from recombining to form molecules.

Hydrogenation and Deuteration of C{sub 2}H{sub 2} and C{sub 2}H{sub 4} on Cold Grains: A Clue to the Formation Mechanism of C{sub 2}H{sub 6} with Astronomical Interest

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

Kobayashi, Hitomi; Kawakita, Hideyo; Hidaka, Hiroshi

We quantitatively investigated the hydrogen addition reactions of acetylene (C{sub 2}H{sub 2}) and ethylene (C{sub 2}H{sub 4}) on amorphous solid water (ASW) at 10 and 20 K relevant to the formation of ethane (C{sub 2}H{sub 6}) on interstellar icy grains. We found that the ASW surface enhances the reaction rates for C{sub 2}H{sub 2} and C{sub 2}H{sub 4} by approximately a factor of 2 compared to those on the pure-solid C{sub 2}H{sub 2} and C{sub 2}H{sub 4} at 10 K, probably due to an increase in the sticking coefficient and adsorption energy of the H atoms on ASW. In contrastmore » to the previous proposal that the hydrogenation rate of C{sub 2}H{sub 4} is orders of magnitude larger than that of C{sub 2}H{sub 2}, the present results show that the difference in hydrogenation rates of C{sub 2}H{sub 2} and C{sub 2}H{sub 4} is only within a factor of 3 on both the surfaces of pure solids and ASW. In addition, we found the small kinetic isotope effect for hydrogenation/deuteration of C{sub 2}H{sub 2} and C{sub 2}H{sub 4} at 10 K, despite the requirement of quantum tunneling. At 20 K, the reaction rate of deuteration becomes even larger than that of hydrogenation. These unusual isotope effects might originate from a slightly larger number density of D atoms than H atoms on ASW at 20 K. The hydrogenation of C{sub 2}H{sub 2} is four times faster than CO hydrogenation and can produce C{sub 2}H{sub 6} efficiently through C{sub 2}H{sub 4} even in the environment of a dark molecular cloud.« less

Kinetic theory of weakly ionized dilute gas of hydrogen-like atoms of the first principles of quantum statistics and dispersion laws of eigenwaves

NASA Astrophysics Data System (ADS)

Slyusarenko, Yurii V.; Sliusarenko, Oleksii Yu.

2017-11-01

We develop a microscopic approach to the construction of the kinetic theory of dilute weakly ionized gas of hydrogen-like atoms. The approach is based on the statements of the second quantization method in the presence of bound states of particles. The basis of the derivation of kinetic equations is the method of reduced description of relaxation processes. Within the framework of the proposed approach, a system of common kinetic equations for the Wigner distribution functions of free oppositely charged fermions of two kinds (electrons and cores) and their bound states—hydrogen-like atoms— is obtained. Kinetic equations are used to study the spectra of elementary excitations in the system when all its components are non-degenerate. It is shown that in such a system, in addition to the typical plasma waves, there are longitudinal waves of matter polarization and the transverse ones with a behavior characteristic of plasmon polaritons. The expressions for the dependence of the frequencies and Landau damping coefficients on the wave vector for all branches of the oscillations discovered are obtained. Numerical evaluation of the elementary perturbation parameters in the system on an example of a weakly ionized dilute gas of the 23Na atoms using the D2-line characteristics of the natrium atom is given. We note the possibility of using the results of the developed theory to describe the properties of a Bose condensate of photons in the diluted weakly ionized gas of hydrogen-like atoms.

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

NASA Astrophysics Data System (ADS)

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

2017-09-01

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

Launch Vehicle Performance for Bipropellant Propulsion Using Atomic Propellants With Oxygen

NASA Technical Reports Server (NTRS)

Palaszewski, Bryan

2000-01-01

Atomic propellants for bipropellant launch vehicles using atomic boron, carbon, and hydrogen were analyzed. The gross liftoff weights (GLOW) and dry masses of the vehicles were estimated, and the 'best' design points for atomic propellants were identified. Engine performance was estimated for a wide range of oxidizer to fuel (O/F) ratios, atom loadings in the solid hydrogen particles, and amounts of helium carrier fluid. Rocket vehicle GLOW was minimized by operating at an O/F ratio of 1.0 to 3.0 for the atomic boron and carbon cases. For the atomic hydrogen cases, a minimum GLOW occurred when using the fuel as a monopropellant (O/F = 0.0). The atomic vehicle dry masses are also presented, and these data exhibit minimum values at the same or similar O/F ratios as those for the vehicle GLOW. A technology assessment of atomic propellants has shown that atomic boron and carbon rocket analyses are considered to be much more near term options than the atomic hydrogen rockets. The technology for storing atomic boron and carbon has shown significant progress, while atomic hydrogen is not able to be stored at the high densities needed for effective propulsion. The GLOW and dry mass data can be used to estimate the cost of future vehicles and their atomic propellant production facilities. The lower the propellant's mass, the lower the overall investment for the specially manufactured atomic propellants.

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.

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

Automated extraction of single H atoms with STM: tip state dependency

NASA Astrophysics Data System (ADS)

Møller, Morten; Jarvis, Samuel P.; Guérinet, Laurent; Sharp, Peter; Woolley, Richard; Rahe, Philipp; Moriarty, Philip

2017-02-01

The atomistic structure of the tip apex plays a crucial role in performing reliable atomic-scale surface and adsorbate manipulation using scanning probe techniques. We have developed an automated extraction routine for controlled removal of single hydrogen atoms from the H:Si(100) surface. The set of atomic extraction protocols detect a variety of desorption events during scanning tunneling microscope (STM)-induced modification of the hydrogen-passivated surface. The influence of the tip state on the probability for hydrogen removal was examined by comparing the desorption efficiency for various classifications of STM topographs (rows, dimers, atoms, etc). We find that dimer-row-resolving tip apices extract hydrogen atoms most readily and reliably (and with least spurious desorption), while tip states which provide atomic resolution counter-intuitively have a lower probability for single H atom removal.

Method for the hydrogenation of poly-si

DOEpatents

Wang, Qi

2013-11-12

A method for hydrogenating poly-si. Poly-si is placed into the interior of a chamber. A filament is placed into the interior of a chamber. The base pressure of the interior of the chamber is evacuated, preferably to 10.sup.-6 Torr or less. The poly-si is heated for a predetermined poly-si heating time. The filament is heated by providing an electrical power to the filament. Hydrogen is supplied into the pressurized interior of the chamber comprising the heated poly-si and the heated filament. Atomic hydrogen is produced by the filament at a rate whereby the atomic hydrogen surface density at the poly-si is less than the poly-si surface density. Preferably, the poly-si is covered from the atomic hydrogen produced by the heated filament for a first predetermined covering time. Preferably, the poly-si is then uncovered from the atomic hydrogen produced by the heated filament for a first hydrogenation time.

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.

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.

First-principles study of the solid solution of hydrogen in lanthanum

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

Schoellhammer, Gunther; Herzig, Peter; Wolf, Walter

2011-09-01

Results from first-principles investigations of the energetical, structural, electronic, and vibrational properties of model structures probing the metal-rich region of the lanthanum-hydrogen system, i.e., the region of the solid solution of hydrogen in lanthanum, are presented. We have studied the site preference and the ordering tendency of hydrogen atoms interstitially bonded in close-packed lanthanum. Spatially separated hydrogen atoms have turned out to exhibit an energetical preference for the occupation of octahedral interstitial sites at low temperature. Indications for a reversal of the site preference in favor of the occupation of tetrahedral interstitial sites at elevated temperature have been found. Linearmore » arrangements consisting of pairs of octahedrally and/or tetrahedrally coordinated hydrogen atoms collinearly bonded to a central lanthanum atom have turned out to be energetically favorable structure elements. Further stabilization is achieved if such hydrogen pairs are in turn linked together so that extended chains of La-H bonds are formed. Pair formation and chain linking counteract the energetical preference for octahedral coordination observed for separated hydrogen atoms.« less

Bis(2-{2-[2-(benzyl­carbamo­yl)phen­oxy]acetamido}­eth­yl)ammonium nitrate ethanol disolvate

PubMed Central

Liu, Jiaji; Tang, Xiaoliang; Lu, Zhengdan; Zhang, Guolin; Liu, Weisheng

2011-01-01

In the title compound, C36H40N5O6 +·NO3 −·2C2H5OH, the nitrate anion is disordered over the two orientations of equal occupancy while the solvent mol­ecule reveals large displacement parameters. The cation is formed by protonation of the N atom of a secondary amine in the middle of the flexible chain and the whole compound has crystallographically imposed C-2 symmetry with the crystallographic b axis. An O atom of the nitrate anion links the acidic H atoms of the cation via N—H⋯O hydrogen bonding. In addition, neighbouring cations are connected by inter­molecular N—H⋯O hydrogen bonds and π–π inter­actions between the benzamide groups of the cations [centroid–centroid distance = 4.000 (3) Å], forming a chain along [001]. The ethanol solvent mol­ecules are arranged on the side of the chain through O—H⋯O hydrogen bonds. PMID:21522705

Synthesis and Stability of Lanthanum Superhydrides

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

Geballe, Zachary M.; Liu, Hanyu; Mishra, Ajay K.

Recent theoretical calculations predict that megabar pressure stabilizes very hydrogen-rich simple compounds having new clathrate-like structures and remarkable electronic properties including room-temperature superconductivity. X-ray diffraction and optical studies demonstrate that superhydrides of lanthanum can be synthesized with La atoms in an fcc lattice at 170 GPa upon heating to about 1000 K. The results match the predicted cubic metallic phase of LaH10 having cages of thirty-two hydrogen atoms surrounding each La atom. Upon decompression, the fcc-based structure undergoes a rhombohedral distortion of the La sublattice. The superhydride phases consist of an atomic hydrogen sublattice with H-H distances of about 1.1more » Å, which are close to predictions for solid atomic metallic hydrogen at these pressures. With stability below 200 GPa, the superhydride is thus the closest analogue to solid atomic metallic hydrogen yet to be synthesized and characterized.« less

Interaction of scandium and titanium atoms with a carbon surface containing five- and seven-membered rings

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

Krasnov, P. O., E-mail: kpo1980@gmail.com; Eliseeva, N. S.; Kuzubov, A. A., E-mail: alex_xx@rambler.ru

2012-01-15

The use of carbon nanotubes coated by atoms of transition metals to store molecular hydrogen is associated with the problem of the aggregation of these atoms, which leads to the formation of metal clusters. The quantum-chemical simulation of cluster models of the carbon surface of a graphene type with scandium and titanium atoms has been performed. It has been shown that the presence of five- and seven-membered rings, in addition to six-membered rings, in these structures makes it possible to strongly suppress the processes of the migration of metal atoms over the surface, preventing their clustering.

Atomistic simulations of the effect of embedded hydrogen and helium on the tensile properties of monocrystalline and nanocrystalline tungsten

NASA Astrophysics Data System (ADS)

Chen, Zhe; Kecskes, Laszlo J.; Zhu, Kaigui; Wei, Qiuming

2016-12-01

Uniaxial tensile properties of monocrystalline tungsten (MC-W) and nanocrystalline tungsten (NC-W) with embedded hydrogen and helium atoms have been investigated using molecular dynamics (MD) simulations in the context of radiation damage evolution. Different strain rates have been imposed to investigate the strain rate sensitivity (SRS) of the samples. Results show that the plastic deformation processes of MC-W and NC-W are dominated by different mechanisms, namely dislocation-based for MC-W and grain boundary-based activities for NC-W, respectively. For MC-W, the SRS increases and a transition appears in the deformation mechanism with increasing embedded atom concentration. However, no obvious embedded atom concentration dependence of the SRS has been observed for NC-W. Instead, in the latter case, the embedded atoms facilitate GB sliding and intergranular fracture. Additionally, a strong strain enhanced He cluster growth has been observed. The corresponding underlying mechanisms are discussed.

An atomic and molecular fluid model for efficient edge-plasma transport simulations at high densities

NASA Astrophysics Data System (ADS)

Rognlien, Thomas; Rensink, Marvin

2016-10-01

Transport simulations for the edge plasma of tokamaks and other magnetic fusion devices requires the coupling of plasma and recycling or injected neutral gas. There are various neutral models used for this purpose, e.g., atomic fluid model, a Monte Carlo particle models, transition/escape probability methods, and semi-analytic models. While the Monte Carlo method is generally viewed as the most accurate, it is time consuming, which becomes even more demanding for device simulations of high densities and size typical of fusion power plants because the neutral collisional mean-free path becomes very small. Here we examine the behavior of an extended fluid neutral model for hydrogen that includes both atoms and molecules, which easily includes nonlinear neutral-neutral collision effects. In addition to the strong charge-exchange between hydrogen atoms and ions, elastic scattering is included among all species. Comparisons are made with the DEGAS 2 Monte Carlo code. Work performed for U.S. DoE by LLNL under Contract DE-AC52-07NA27344.

Atomic hydrogen in. gamma. -irradiated hydroxides of alkaline-earth elements

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

Spitsyn, V.I.; Yurik, T.K.; Barsova, L.I.

1982-04-01

Atomic hydrogen is an important intermediate product formed in the radiolysis of compounds containing X-H bonds. H atoms have been detected in irradiated matrices of H/sub 2/ and inert gases at 4/sup 0/K, in irradiated ice and frozen solutions of acids in irradiated salts and in other systems. Here results are presented from a study of the ESR spectra of H atoms generated in polycrystalline hydroxides of alkaline-earth elements that have been ..gamma..-irradiated at 77/sup 0/K, after preliminary treatment at various temperatures. For the first time stabilization of atomic hydrogen in ..gamma..-irradiated polycrystalline alkaline-earth element hydroxides has been detected. Dependingmore » on the degree of dehydroxylation, several types of hydrogen atoms may be stabilized in the hydroxides, these hydrogen atoms having different radiospectroscopic parameters. In the magnesium-calcium-strontium-barium hydroxide series, a regular decrease has been found in the hfi constants for H atoms with the cations in the immediate surroundings. A direct proportionality has been found between the parameters ..delta..A/A/sub 0/ and the polarizability of the cation.« less

Measurements of atomic splittings in atomic hydrogen and the proton charge radius

NASA Astrophysics Data System (ADS)

Hessels, E. A.

2016-09-01

The proton charge radius can be determined from precise measurements of atomic hydrogen spectroscopy. A review of the relevant measurements will be given, including an update on our measurement of the n=2 Lamb shift. The values obtained from hydrogen will be compared to those obtained from muonic hydrogen and from electron-proton elastic scattering measurements. This work is funded by NSERC, CRC and CFI.

AutoSite: an automated approach for pseudo-ligands prediction—from ligand-binding sites identification to predicting key ligand atoms

PubMed Central

Ravindranath, Pradeep Anand; Sanner, Michel F.

2016-01-01

Motivation: The identification of ligand-binding sites from a protein structure facilitates computational drug design and optimization, and protein function assignment. We introduce AutoSite: an efficient software tool for identifying ligand-binding sites and predicting pseudo ligand corresponding to each binding site identified. Binding sites are reported as clusters of 3D points called fills in which every point is labelled as hydrophobic or as hydrogen bond donor or acceptor. From these fills AutoSite derives feature points: a set of putative positions of hydrophobic-, and hydrogen-bond forming ligand atoms. Results: We show that AutoSite identifies ligand-binding sites with higher accuracy than other leading methods, and produces fills that better matches the ligand shape and properties, than the fills obtained with a software program with similar capabilities, AutoLigand. In addition, we demonstrate that for the Astex Diverse Set, the feature points identify 79% of hydrophobic ligand atoms, and 81% and 62% of the hydrogen acceptor and donor hydrogen ligand atoms interacting with the receptor, and predict 81.2% of water molecules mediating interactions between ligand and receptor. Finally, we illustrate potential uses of the predicted feature points in the context of lead optimization in drug discovery projects. Availability and Implementation: http://adfr.scripps.edu/AutoDockFR/autosite.html Contact: sanner@scripps.edu Supplementary information: Supplementary data are available at Bioinformatics online. PMID:27354702

Synthetic NPA diagnostic for energetic particles in JET plasmas

NASA Astrophysics Data System (ADS)

Varje, J.; Sirén, P.; Weisen, H.; Kurki-Suonio, T.; Äkäslompolo, S.; contributors, JET

2017-11-01

Neutral particle analysis (NPA) is one of the few methods for diagnosing fast ions inside a plasma by measuring neutral atom fluxes emitted due to charge exchange reactions. The JET tokamak features an NPA diagnostic which measures neutral atom fluxes and energy spectra simultaneously for hydrogen, deuterium and tritium species. A synthetic NPA diagnostic has been developed and used to interpret these measurements to diagnose energetic particles in JET plasmas with neutral beam injection (NBI) heating. The synthetic NPA diagnostic performs a Monte Carlo calculation of the neutral atom fluxes in a realistic geometry. The 4D fast ion distributions, representing NBI ions, were simulated using the Monte Carlo orbit-following code ASCOT. Neutral atom density profiles were calculated using the FRANTIC neutral code in the JINTRAC modelling suite. Additionally, for rapid analysis, a scan of neutral profiles was precalculated with FRANTIC for a range of typical plasma parameters. These were taken from the JETPEAK database, which includes a comprehensive set of data from the flat-top phases of nearly all discharges in recent JET campaigns. The synthetic diagnostic was applied to various JET plasmas in the recent hydrogen campaign where different hydrogen/deuterium mixtures and NBI configurations were used. The simulated neutral fluxes from the fast ion distributions were found to agree with the measured fluxes, reproducing the slowing-down profiles for different beam isotopes and energies and quantitatively estimating the fraction of hydrogen and deuterium fast ions.

Quantum study of Eley-Rideal reaction and collision induced desorption of hydrogen atoms on a graphite surface. II. H-physisorbed case.

PubMed

Martinazzo, Rocco; Tantardini, Gian Franco

2006-03-28

Following previous investigation of collision induced (CI) processes involving hydrogen atoms chemisorbed on graphite [R. Martinazzo and G. F. Tantardini, J. Chem. Phys. 124, 124702 (2006)], the case in which the target hydrogen atom is initially physisorbed on the surface is considered here. Several adsorbate-substrate initial states of the target H atom in the physisorption well are considered, and CI processes are studied for projectile energies up to 1 eV. Results show that (i) Eley-Rideal cross sections at low collision energies may be larger than those found in the H-chemisorbed case but they rapidly decrease as the collision energy increases; (ii) product hydrogen molecules are vibrationally very excited; (iii) collision induced desorption cross sections rapidly increase, reaching saturation values greater than 10 A2; (iv) trapping of the incident atoms is found to be as efficient as the Eley-Rideal reaction at low energies and remains sizable (3-4 A2) at high energies. The latter adsorbate-induced trapping results mainly in formation of metastable hot hydrogen atoms, i.e., atoms with an excess energy channeled in the motion parallel to the surface. These atoms might contribute in explaining hydrogen formation on graphite.

Site-specific binding of a water molecule to the sulfa drugs sulfamethoxazole and sulfisoxazole: a laser-desorption isomer-specific UV and IR study.

PubMed

Uhlemann, Thomas; Seidel, Sebastian; Müller, Christian W

2018-03-07

To determine the preferred water molecule binding sites of the polybasic sulfa drugs sulfamethoxazole (SMX) and sulfisoxazole (SIX), we have studied their monomers and monohydrated complexes through laser-desorption conformer-specific UV and IR spectroscopy. Both the SMX and SIX monomer adopt a single conformer in the molecular beam. On the basis of their conformer-specific IR spectra in the NH stretch region, these conformers were assigned to the SMX and SIX global minimum structures, both exhibiting a staggered sulfonamide group and an intramolecular C-HO[double bond, length as m-dash]S hydrogen bond. The SMX-H 2 O and SIX-H 2 O complexes each adopt a single isomer in the molecular beam. Their isomeric structures were determined based on their isomer-specific IR spectra in the NH/OH stretch region. Quantum Theory of Atoms in Molecules analysis of the calculated electron densities revealed that in the SMX-H 2 O complex the water molecule donates an O-HN hydrogen bond to the heterocycle nitrogen atom and accepts an N-HO hydrogen bond from the sulfonamide NH group. In the SIX-H 2 O complex, however, the water molecule does not bind to the heterocycle but instead donates an O-HO[double bond, length as m-dash]S hydrogen bond to the sulfonamide group and accepts an N-HO hydrogen bond from the sulfonamide NH group. Both water complexes are additionally stabilized by a C ph -HOH 2 hydrogen bond. Interacting Quantum Atoms analysis suggests that all intermolecular hydrogen bonds are dominated by the short-range exchange-correlation contribution.

Porphyrins and their synthesis from dipyrromethanes and aldehydes

DOEpatents

Wijesekera, Tilak; Lyons, James E.; Ellis, Jr., Paul E.

1998-01-01

The invention comprises new compositions of matter, which are iron, manganese, cobalt or ruthenium complexes of porphyrins having hydrogen, haloalkyl or haloaryl groups in meso positions, two of the opposed meso atoms or groups being hydrogen or haloaryl, and two of the opposed meso atoms or groups being hydrogen or haloalkyl, but not all four of the meso atoms or groups being hydrogen. The invention also comprises new compositions of matter in which all four of the meso positions are substituted with haloalkyl groups and the beta positions are substituted with halogen atoms. A new method of synthesizing porphyrinogens is also provided.

Porphyrins and their synthesis from dipyrromethanes and aldehydes

DOEpatents

Wijesekera, T.; Lyons, J.E.; Ellis, P.E. Jr.

1998-06-02

The invention comprises new compositions of matter, which are iron, manganese, cobalt or ruthenium complexes of porphyrins having hydrogen, haloalkyl or haloaryl groups in meso positions, two of the opposed meso atoms or groups being hydrogen or haloaryl, and two of the opposed meso atoms or groups being hydrogen or haloalkyl, but not all four of the meso atoms or groups being hydrogen. The invention also comprises new compositions of matter in which all four of the meso positions are substituted with haloalkyl groups and the beta positions are substituted with halogen atoms. A new method of synthesizing porphyrinogens is also provided.

Atomic emission lines in the near ultraviolet; hydrogen through krypton, section 1

NASA Technical Reports Server (NTRS)

Kelly, R. L.

1979-01-01

A compilation of spectra from the first 36 elements was prepared from published literature available through October 1977. In most cases, only those lines which were actually observed in emission or absorption are listed. The wavelengths included range from 2000 Angstroms to 3200 Angstroms with some additional lines up to 3500 Angstroms. Only lines of stripped atoms are reported; no molecular bands are included.

Atomic emission lines in the near ultraviolet; hydrogen through krypton, section 2

NASA Technical Reports Server (NTRS)

Kelly, R. L.

1979-01-01

A compilation of spectra from the first 36 elements was prepared from published literature available through October 1977. In most cases, only those lines which were actually observed in emission or absorption are listed. The wavelengths included range from 2000 Angstroms to 3200 Angstroms with some additional lines up to 3500 Angstroms. Only lines of stripped atoms are reported; no molecular bands are included.

Restructuring and Hydrogen Evolution on Pt Nanoparticle† †Electronic supplementary information (ESI) available: Discussions on the structures of Pt clusters and the stability of the subsurface H atoms in Pt cluster, TS structure of H–H coupling on {111} facets of Pt44H80, XYZ coordinate of Pt44 and Pt44H80. Movie of structure evolution at Pt44H50 See DOI: 10.1039/c4sc02806f Click here for additional data file. Click here for additional data file.

PubMed Central

Wei, Guang-Feng

2015-01-01

The restructuring of nanoparticles at the in situ condition is a common but complex phenomenon in nanoscience. Here, we present the first systematic survey on the structure dynamics and its catalytic consequence for hydrogen evolution reaction (HER) on Pt nanoparticles, as represented by a magic number Pt44 octahedron (∼1 nm size). Using a first principles calculation based global structure search method, we stepwise follow the significant nanoparticle restructuring under HER conditions as driven by thermodynamics to expose {100} facets, and reveal the consequent large activity enhancement due to the marked increase of the concentration of the active site, being identified to be apex atoms. The enhanced kinetics is thus a “byproduct” of the thermodynamical restructuring. Based on the results, the best Pt catalyst for HER is predicted to be ultrasmall Pt particles without core atoms, a size below ∼20 atoms. PMID:29560237

Interactions of atomic hydrogen with amorphous SiO2

NASA Astrophysics Data System (ADS)

Yue, Yunliang; Wang, Jianwei; Zhang, Yuqi; Song, Yu; Zuo, Xu

2018-03-01

Dozens of models are investigated by the first-principles calculations to simulate the interactions of an atomic hydrogen with a defect-free random network of amorphous SiO2 (a-SiO2) and oxygen vacancies. A wide variety of stable configurations are discovered due to the disorder of a-SiO2, and their structures, charges, magnetic moments, spin densities, and density of states are calculated. The atomic hydrogen interacts with the defect-free a-SiO2 in positively or negatively charged state, and produces the structures absent in crystalline SiO2. It passivates the neutral oxygen vacancies and generates two neutral hydrogenated E‧ centers with different Si dangling bond projections. Electron spin resonance parameters, including Fermi contacts, and g-tensors, are calculated for these centers. The atomic hydrogen interacts with the positive oxygen vacancies in dimer configuration, and generate four different positive hydrogenated defects, two of which are puckered like the Eγ‧ centers. This research helps to understand the interactions between an atomic hydrogen, and defect-free a-SiO2 and oxygen vacancies, which may generate the hydrogen-complexed defects that play a key role in the degeneration of silicon/silica-based microelectronic devices.

The Halogen Bond in the Design of Functional Supramolecular Materials: Recent Advances

PubMed Central

2013-01-01

Halogen bonding is an emerging noncovalent interaction for constructing supramolecular assemblies. Though similar to the more familiar hydrogen bonding, four primary differences between these two interactions make halogen bonding a unique tool for molecular recognition and the design of functional materials. First, halogen bonds tend to be much more directional than (single) hydrogen bonds. Second, the interaction strength scales with the polarizability of the bond-donor atom, a feature that researchers can tune through single-atom mutation. In addition, halogen bonds are hydrophobic whereas hydrogen bonds are hydrophilic. Lastly, the size of the bond-donor atom (halogen) is significantly larger than hydrogen. As a result, halogen bonding provides supramolecular chemists with design tools that cannot be easily met with other types of noncovalent interactions and opens up unprecedented possibilities in the design of smart functional materials. This Account highlights the recent advances in the design of halogen-bond-based functional materials. Each of the unique features of halogen bonding, directionality, tunable interaction strength, hydrophobicity, and large donor atom size, makes a difference. Taking advantage of the hydrophobicity, researchers have designed small-size ion transporters. The large halogen atom size provided a platform for constructing all-organic light-emitting crystals that efficiently generate triplet electrons and have a high phosphorescence quantum yield. The tunable interaction strengths provide tools for understanding light-induced macroscopic motions in photoresponsive azobenzene-containing polymers, and the directionality renders halogen bonding useful in the design on functional supramolecular liquid crystals and gel-phase materials. Although halogen bond based functional materials design is still in its infancy, we foresee a bright future for this field. We expect that materials designed based on halogen bonding could lead to applications in biomimetics, optics/photonics, functional surfaces, and photoswitchable supramolecules. PMID:23805801

Atmospheric Mining in the Outer Solar System: Outer Planet Orbital Transfer and Lander Analyses

NASA Technical Reports Server (NTRS)

Palaszewski, Bryan

2016-01-01

High energy propellants for human lunar missions are analyzed, focusing on very advanced ozone and atomic hydrogen. One of the most advanced launch vehicle propulsion systems, such as the Space Shuttle Main Engine (SSME), used hydrogen and oxygen and had a delivered specific impulse of 453 seconds. In the early days of the space program, other propellants (or so called metapropellants) were suggested, including atomic hydrogen and liquid ozone. Theoretical and experimental studies of atomic hydrogen and ozone were conducted beginning in the late 1940s. This propellant research may have provided screenwriters with the idea of an atomic hydrogen-ozone rocket engine in the 1950 movie, Rocketship X-M. This paper presents analyses showing that an atomic hydrogen-ozone rocket engine could produce a specific impulse over a wide range of specific impulse values reaching as high as 1,600 seconds. A series of single stage and multistage rocket vehicle analyses were conducted to find the minimum specific impulse needed to conduct high energy round trip lunar missions.

Propulsion Estimates for High Energy Lunar Missions Using Future Propellants

NASA Technical Reports Server (NTRS)

Palaszewski, Bryan A.; Bennett, Gary L.

2016-01-01

High energy propellants for human lunar missions are analyzed, focusing on very advanced ozone and atomic hydrogen. One of the most advanced launch vehicle propulsion systems, such as the Space Shuttle Main Engine (SSME), used hydrogen and oxygen and had a delivered specific impulse of 453 seconds. In the early days of the space program, other propellants (or so called metapropellants) were suggested, including atomic hydrogen and liquid ozone. Theoretical and experimental studies of atomic hydrogen and ozone were conducted beginning in the late 1940s. This propellant research may have provided screenwriters with the idea of an atomic hydrogen-ozone rocket engine in the 1950 movie, Rocketship X-M. This paper presents analyses showing that an atomic hydrogen-ozone rocket engine could produce a specific impulse over a wide range of specific impulse values reaching as high as 1,600 s. A series of single stage and multistage rocket vehicle analyses were conducted to find the minimum specific impulse needed to conduct high energy round trip lunar missions.

Measurements of the Activation Energies for Atomic Hydrogen Diffusion on Pure Solid CO

NASA Astrophysics Data System (ADS)

Kimura, Y.; Tsuge, M.; Pirronello, V.; Kouchi, A.; Watanabe, N.

2018-05-01

The diffusion of hydrogen atoms on dust grains is a key process in the formation of interstellar H2 and some hydrogenated molecules such as formaldehyde and methanol. We investigate the adsorption and diffusion of H atoms on pure solid CO as an analog of dust surfaces observed toward some cold interstellar regions. Using a combination of photostimulated desorption and resonance-enhanced multiphoton ionization methods to detect H atoms directly, the relative adsorption probabilities and diffusion coefficients of the H atoms are measured on pure solid CO at 8, 12, and 15 K. There is little difference between the diffusion coefficients of the hydrogen and deuterium atoms, indicating that the diffusion is limited by thermal hopping. The activation energies controlling the H-atom diffusion depend on the surface temperature, and values of 22, 30, and ∼37 meV were obtained for 8, 12, and 15 K, respectively.

Radiation and Thermal Transformations of Hydrogen Defects in Li6F and LiF:OH

NASA Astrophysics Data System (ADS)

Akhvlediani, Z. G.; Akhvlediani, I. G.

2010-11-01

Hydrogen and tritium defects formed in LiF under the action of neutron radiation under different conditions have been studied. It is shown that U-centers are registered in LiF:OH without additional heating of the sample after irradiation. The behavior of H0 and T0 atoms in Li6 F irradiated at 20 K was studied, and the places of their stabilization were established.

Chemical Reactions and Properties of Organosilicon Compounds Related to New Materials.

DTIC Science & Technology

1985-10-31

out. The compound behaves like an olefin in some reactions, for in- stance addition of hydrogen halides or chlorine: C1 2 HCI Mes 2 SiCl-SiClMes2...polymers have been synthesized which contain some silicon atoms bonded to hydrogen . These become crosslinked when mixed with substances containing several...and highly efficient catalysts, very small amounts are required in this process. Moreover, photocatalysis using polysilanes produces polymers with

Lithium-decorated oxidized graphyne for hydrogen storage by first principles study

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

Yan, Zeyu; Wang, Lang; Cheng, Julong

2014-11-07

The geometric stability and hydrogen storage capacity of Li decorated oxidized γ-graphyne are studied based on the first-principles calculations. It is found that oxygen atoms trend to bond with acetylenic carbons and form C=O double bonds on both sides of graphyne. The binding energy of single Li atom on oxidized graphyne is 3.29 eV, owning to the strong interaction between Li atom and O atom. Meanwhile, the dispersion of Li is stable even under a relatively high density. One attached Li atom can at least adsorb six hydrogen molecules around. Benefitting from the porous structure of graphyne and the high attachedmore » Li density, a maximum hydrogen storage density 12.03 wt. % is achieved with four Li atoms in graphyne cell. The corresponding average binding energy is 0.24 eV/H{sub 2}, which is suitable for reversible storage. These results indicate that Li decorated graphyne can serve as a promising hydrogen storage material.« less

The long-range non-additive three-body dispersion interactions for the rare gases, alkali, and alkaline-earth atoms

NASA Astrophysics Data System (ADS)

Tang, Li-Yan; Yan, Zong-Chao; Shi, Ting-Yun; Babb, James F.; Mitroy, J.

2012-03-01

The long-range non-additive three-body dispersion interaction coefficients Z111, Z112, Z113, and Z122 are computed for many atomic combinations using standard expressions. The atoms considered include hydrogen, the rare gases, the alkali atoms (up to Rb), and the alkaline-earth atoms (up to Sr). The term Z111 arising from three mutual dipole interactions is known as the Axilrod-Teller-Muto coefficient or the DDD (dipole-dipole-dipole) coefficient. Similarly, the terms Z112, Z113, and Z122 arise from the mutual combinations of dipole (1), quadrupole (2), and octupole (3) interactions between atoms and they are sometimes known, respectively, as dipole-dipole-quadrupole, dipole-dipole-octupole, and dipole-quadrupole-quadrupole coefficients. Results for the four Z coefficients are given for the homonuclear trimers, for the trimers involving two like-rare-gas atoms, and for the trimers with all combinations of the H, He, and Li atoms. An exhaustive compilation of all coefficients between all possible atomic combinations is presented as supplementary data.

Neutron Nucleic Acid Crystallography.

PubMed

Chatake, Toshiyuki

2016-01-01

The hydration shells surrounding nucleic acids and hydrogen-bonding networks involving water molecules and nucleic acids are essential interactions for the structural stability and function of nucleic acids. Water molecules in the hydration shells influence various conformations of DNA and RNA by specific hydrogen-bonding networks, which often contribute to the chemical reactivity and molecular recognition of nucleic acids. However, X-ray crystallography could not provide a complete description of structural information with respect to hydrogen bonds. Indeed, X-ray crystallography is a powerful tool for determining the locations of water molecules, i.e., the location of the oxygen atom of H2O; however, it is very difficult to determine the orientation of the water molecules, i.e., the orientation of the two hydrogen atoms of H2O, because X-ray scattering from the hydrogen atom is very small.Neutron crystallography is a specialized tool for determining the positions of hydrogen atoms. Neutrons are not diffracted by electrons, but are diffracted by atomic nuclei; accordingly, neutron scattering lengths of hydrogen and its isotopes are comparable to those of non-hydrogen atoms. Therefore, neutron crystallography can determine both of the locations and orientations of water molecules. This chapter describes the current status of neutron nucleic acid crystallographic research as well as the basic principles of neutron diffraction experiments performed on nucleic acid crystals: materials, crystallization, diffraction experiments, and structure determination.

Single-Atom Catalysts of Precious Metals for Electrochemical Reactions.

PubMed

Kim, Jiwhan; Kim, Hee-Eun; Lee, Hyunjoo

2018-01-10

Single-atom catalysts (SACs), in which metal atoms are dispersed on the support without forming nanoparticles, have been used for various heterogeneous reactions and most recently for electrochemical reactions. In this Minireview, recent examples of single-atom electrocatalysts used for the oxygen reduction reaction (ORR), hydrogen oxidation reaction (HOR), hydrogen evolution reaction (HER), formic acid oxidation reaction (FAOR), and methanol oxidation reaction (MOR) are introduced. Many density functional theory (DFT) simulations have predicted that SACs may be effective for CO 2 reduction to methane or methanol production while suppressing H 2 evolution, and those cases are introduced here as well. Single atoms, mainly Pt single atoms, have been deposited on TiN or TiC nanoparticles, defective graphene nanosheets, N-doped covalent triazine frameworks, graphitic carbon nitride, S-doped zeolite-templated carbon, and Sb-doped SnO 2 surfaces. Scanning transmission electron microscopy, extended X-ray absorption fine structure measurement, and in situ infrared spectroscopy have been used to detect the single-atom structure and confirm the absence of nanoparticles. SACs have shown high mass activity, minimizing the use of precious metal, and unique selectivity distinct from nanoparticle catalysts owing to the absence of ensemble sites. Additional features that SACs should possess for effective electrochemical applications were also suggested. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Quantitative analysis of hydrogen in SiO{sub 2}/SiN/SiO{sub 2} stacks using atom probe tomography

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

Kunimune, Yorinobu, E-mail: yorinobu.kunimune.vz@renesas.com; Shimada, Yasuhiro; Sakurai, Yusuke

2016-04-15

We have demonstrated that it is possible to reproducibly quantify hydrogen concentration in the SiN layer of a SiO{sub 2}/SiN/SiO{sub 2} (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 actualmore » 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.« less

Stability of surface and subsurface hydrogen on and in Au/Ni near-surface alloys

DOE PAGES

Celik, Fuat E.; Mavrikakis, Manos

2015-01-12

Periodic, self-consistent DFT-GGA (PW91) calculations were used to study the interaction of hydrogen atoms with the (111) surfaces of substitutional near-surface alloys (NSAs) of Au and Ni with different surface layer compositions and different arrangements of Au atoms in the surface layer. The effect of hydrogen adsorption on the surface and in the first and second subsurface layers of the NSAs was studied. Increasing the Au content in the surface layer weakens hydrogen binding on the surface, but strengthens subsurface binding, suggesting that the distribution of surface and subsurface hydrogen will be different than that on pure Ni(111). While themore » metal composition of the surface layer has an effect on the binding energy of hydrogen on NSA surfaces, the local composition of the binding site has a stronger effect. For example, fcc hollow sites consisting of three Ni atoms bind H nearly as strongly as on Ni(111), and fcc sites consisting of three Au atoms bind H nearly as weakly as on Au(111). Sites with one or two Au atoms show intermediate binding energies. The preference of hydrogen for three-fold Ni hollow sites alters the relative stabilities of different surface metal atom arrangements, and may provide a driving force for adsorbate-induced surface rearrangement.« less

Stability of Surface and Subsurface Hydrogen on and in Au/Ni Near-Surface Alloys

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

Celik, Fuat E.; Mavrikakis, Manos

2015-10-01

Periodic, self-consistent DFT-GGA (PW91) calculations were used to study the interaction of hydrogen atoms with the (111) surfaces of substitutional near-surface alloys (NSAs) of Au and Ni with different surface layer compositions and different arrangements of Au atoms in the surface layer. The effect of hydrogen adsorption on the surface and in the first and second subsurface layers of the NSAs was studied. Increasing the Au content in the surface layer weakens hydrogen binding on the surface, but strengthens subsurface binding, suggesting that the distribution of surface and subsurface hydrogen will be different than that on pure Ni(111). While themore » metal composition of the surface layer has an effect on the binding energy of hydrogen on NSA surfaces, the local composition of the binding site has a stronger effect. For example, fcc hollow sites consisting of three Ni atoms bind H nearly as strongly as on Ni(111), and fcc sites consisting of three Au atoms bind H nearly as weakly as on Au(111). Sites with one or two Au atoms show intermediate binding energies. The preference of hydrogen for three-fold Ni hollow sites alters the relative stabilities of different surface metal atom arrangements, and may provide a driving force for adsorbate-induced surface rearrangement.« less

Stability of surface and subsurface hydrogen on and in Au/Ni near-surface alloys

NASA Astrophysics Data System (ADS)

Celik, Fuat E.; Mavrikakis, Manos

2015-10-01

Periodic, self-consistent DFT-GGA (PW91) calculations were used to study the interaction of hydrogen atoms with the (111) surfaces of substitutional near-surface alloys (NSAs) of Au and Ni with different surface layer compositions and different arrangements of Au atoms in the surface layer. The effect of hydrogen adsorption on the surface and in the first and second subsurface layers of the NSAs was studied. Increasing the Au content in the surface layer weakens hydrogen binding on the surface, but strengthens subsurface binding, suggesting that the distribution of surface and subsurface hydrogen will be different than that on pure Ni(111). While the metal composition of the surface layer has an effect on the binding energy of hydrogen on NSA surfaces, the local composition of the binding site has a stronger effect. For example, fcc hollow sites consisting of three Ni atoms bind H nearly as strongly as on Ni(111), and fcc sites consisting of three Au atoms bind H nearly as weakly as on Au(111). Sites with one or two Au atoms show intermediate binding energies. The preference of hydrogen for three-fold Ni hollow sites alters the relative stabilities of different surface metal atom arrangements, and may provide a driving force for adsorbate-induced surface rearrangement.

Hydrogen-Bonding Network and OH Stretch Vibration of Cellulose: Comparison of Computational Modeling with Polarized IR and SFG Spectra.

PubMed

Lee, Christopher M; Kubicki, James D; Fan, Bingxin; Zhong, Linghao; Jarvis, Michael C; Kim, Seong H

2015-12-10

Hydrogen bonds play critical roles in noncovalent directional interactions determining the crystal structure of cellulose. Although diffraction studies accurately determined the coordinates of carbon and oxygen atoms in crystalline cellulose, the structural information on hydrogen atoms involved in hydrogen-bonding is still elusive. This could be complemented by vibrational spectroscopy; but the assignment of the OH stretch peaks has been controversial. In this study, we performed calculations using density functional theory with dispersion corrections (DFT-D2) for the cellulose Iβ crystal lattices with the experimentally determined carbon and oxygen coordinates. DFT-D2 calculations revealed that the OH stretch vibrations of cellulose are highly coupled and delocalized through intra- and interchain hydrogen bonds involving all OH groups in the crystal. Additionally, molecular dynamics (MD) simulations of a single cellulose microfibril showed that the conformations of OH groups exposed at the microfibril surface are not well-defined. Comparison of the computation results with the experimentally determined IR dichroism of uniaxially aligned cellulose microfibrils and the peak positions of various cellulose crystals allowed unambiguous identification of OH stretch modes observed in the vibrational spectra of cellulose.

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

PubMed

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

2009-02-01

Density functional theory (DFT) calculations were carried out to study the inner hydrogen atom transfer in low symmetrical metal-free tetrapyrrole analogues ranging from tetraazaporphyrin H(2)TAP (A(0)B(0)C(0)D(0)) to naphthalocyanine H(2)Nc (A(2)B(2)C(2)D(2)) via phthalocyanine H(2)Pc (A(1)B(1)C(1)D(1)). All the transition paths of sixteen different compounds (A(0)B(0)C(0)D(0)-A(2)B(2)C(2)D(2) and A(0)B(0)C(m)D(n), m

Atomic-scale investigation of point defects and hydrogen-solute atmospheres on the edge dislocation mobility in alpha iron

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

Bhatia, M. A.; Solanki, K. N., E-mail: kiran.solanki@asu.edu; Groh, S.

2014-08-14

In this study, we present atomistic mechanisms of 1/2 [111](11{sup ¯}0) edge dislocation interactions with point defects (hydrogen and vacancies) and hydrogen solute atmospheres in body centered cubic (bcc) iron. In metals such as iron, increases in hydrogen concentration can increase dislocation mobility and/or cleavage-type decohesion. Here, we first investigate the dislocation mobility in the presence of various point defects, i.e., change in the frictional stress as the edge dislocation interacts with (a) vacancy, (b) substitutional hydrogen, (c) one substitutional and one interstitial hydrogen, (d) interstitial hydrogen, (e) vacancy and interstitial hydrogen, and (f) two interstitial hydrogen. Second, we examinemore » the role of a hydrogen-solute atmosphere on the rate of local dislocation velocity. The edge dislocation simulation with a vacancy in the compression side of the dislocation and an interstitial hydrogen atom at the tension side exhibit the strongest mechanical response, suggesting a higher potential barrier and hence, the higher frictional stress (i.e., ∼83% higher than the pure iron Peierls stress). In the case of a dislocation interacting with a vacancy on the compressive side, the vacancy binds with the edge dislocation, resulting in an increase in the friction stress of about 28% when compared with the Peierls stress of an edge dislocation in pure iron. Furthermore, as the applied strain increases, the vacancy migrates through a dislocation transportation mechanism by attaining a velocity of the same order as the dislocation velocity. For the case of the edge dislocation interacting with interstitial hydrogen on the tension side, the hydrogen atom jumps through one layer perpendicular to the glide plane during the pinning-unpinning process. Finally, our simulation of dislocation interactions with hydrogen show first an increase in the local dislocation velocity followed by a pinning of the dislocation core in the atmosphere, resulting in resistance to dislocation motion as the dislocation moves though the hydrogen-solute atmospheres. With this systematic, atomistic study of the edge dislocation with various point defects, we show significant increase in obstacle strengths in addition to an increase in the local dislocation velocity during interaction with solute atmospheres. The results have implications for constitutive development and modeling of the hydrogen effect on dislocation mobility and deformation in metals.« less

Copernicus observations of interstellar absorption at Lyman alpha

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

Bohlin, R C

1975-09-01

Column densities N/sub H/ of atomic hydrogen have been derived for 40 OB stars from spectral scans at L$alpha$ obtained by the Copernicus (OAO-3) satellite. The stars are all between 60 and 1100 pc away with a range of mean densities n/sub H/ of 0.01 to 2.5 atoms cm $sup -3$. For 27 stars without significant amounts of molecular hydrogen, the mean ratio of gas to color excess is =3.6times10$sup 21$ atoms cm$sup -2$ mag$sup -1$, and the mean density is =0.12 atoms cm$sup -3$. For 10 stars where the molecular hydrogen is at least 5 percent of the totalmore » hydrogen, is 5.4times10$sup 21$ atoms cm $sup -2$ mag$sup -1$ and is 0.7 atoms cm$sup -3$. In this limited set of data, the ratio of gas to color excess in clouds varies from 1 to 3 times the mean outside of clouds. The presence of molecular hydrogen correlates with E (B-V), but the best tracer for H$sub 2$ is atomic hydrogen. The mean density of the gas for all 40 stars is much smaller than the mean of 0.7 atoms cm$sup -3$ obtained from 21-cm observations, because the brightest stars with less than average amounts of matter in the line of sight were selected for observation. (AIP)« less

Compact hydrogenator

NASA Technical Reports Server (NTRS)

Simmonds, P. G. (Inventor)

1974-01-01

The development and characteristics of a hydrogenating apparatus are described. The device consists of a reaction chamber which is selectively permeable to atomic hydrogen and catalytically active to a hydrogenating reaction. In one device, hydrogen is pumped out of the reaction chamber while the reactant remains inside to remove molecular hydrogen so that more atomic hydrogen can pass through the walls. In another device, the reactant is pumped through the reaction chamber, and the hydrogen is removed from the material leaving the chamber. The reactant is then cycled through the chamber.

Infrared spectroscopy of matrix-isolated neutral polycyclic aromatic nitrogen heterocycles: The acridine series

NASA Astrophysics Data System (ADS)

Mattioda, A. L.; Bauschlicher, C. W.; Ricca, A.; Bregman, J.; Hudgins, D. M.; Allamandola, L. J.

2017-06-01

The matrix-isolated, mid-infrared spectra of seven acridine-based polycyclic aromatic nitrogen heterocycles (PANHs) have been measured and compared to their non-nitrogen containing parent molecule. The acridine species investigated include acridine, benz[a]acridine, benz[c]acridine, dibenz[a,j]acridine, dibenz[c,h]acridine, dibenz[a,h]acridine and dibenz[a,c]acridine. The previously reported results for 1 and 2-azabenz[a]anthracenes are included for comparison. The experimentally determined band frequencies and intensities are compared with their B3LYP/6-31G(d) values. The overall agreement between experimental and theoretical values is good and in line with our previous investigations. Shifts, typically to the blue, are noted for the C-H out-of-plane (CHoop) motions upon insertion of a nitrogen atom. The formation of a bay region upon addition of additional benzene rings to the anthracene/acridine structure splits the solo hydrogen motions into a bay region solo and an external solo hydrogen, with the bay region solo hydrogen coupling to the quartet hydrogen motions and the external solo hydrogen coupling with the duo hydrogen motions resulting in an extreme decrease in intensity for the CHoop solo hydrogen band when the external hydrogen is replaced by a nitrogen atom. The C-C and C-H in-plane region of this acridine series exhibits the characteristic two fold increase in intensity, noted previously for PANHs. The strong ≈1400 cm-1 band, which was identified in the previous PANH study, is noted in several molecular species as well as another strong PANH feature between 1480 and 1515 cm-1 for several molecules. The presence of these strong bands appear to be primarily responsible for the two-fold increase in the C-H in-plane region's (1100-1600 cm-1) intensity. The C-H stretching region can be characterized by contributions from the solo (bay or external), duo and quartet hydrogens, similar to what was observed in the dibenzopolyacene compounds.

Reactions of solvated electrons initiated by sodium atom ionization at the vacuum-liquid interface.

PubMed

Alexander, William A; Wiens, Justin P; Minton, Timothy K; Nathanson, Gilbert M

2012-03-02

Solvated electrons are powerful reagents in the liquid phase that break chemical bonds and thereby create additional reactive species, including hydrogen atoms. We explored the distinct chemistry that ensues when electrons are liberated near the liquid surface rather than within the bulk. Specifically, we detected the products resulting from exposure of liquid glycerol to a beam of sodium atoms. The Na atoms ionized in the surface region, generating electrons that reacted with deuterated glycerol, C(3)D(5)(OD)(3), to produce D atoms, D(2), D(2)O, and glycerol fragments. Surprisingly, 43 ± 4% of the D atoms traversed the interfacial region and desorbed into vacuum before attacking C-D bonds to produce D(2).

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.

Absolute rate constant for the reaction of atomic chlorine with hydrogen peroxide vapor over the temperature range 265-400 K

NASA Technical Reports Server (NTRS)

Michael, J. V.; Whytock, D. A.; Lee, J. H.; Payne, W. A.; Stief, L. J.

1977-01-01

Rate constants for the reaction of atomic chlorine with hydrogen peroxide were measured from 265-400 K using the flash photolysis-resonance fluorescence technique. Analytical techniques were developed to measure H2O2 under reaction conditions. Due to ambiguity in the interpretation of the analytical results, the data combine to give two equally acceptable representations of the temperature dependence. The results are compared to previous work at 298 K and are theoretically discussed in terms of the mechanism of the reaction. Additional experiments on the H + H2O2 reaction at 298 and 359 K are compared with earlier results from this laboratory and give a slightly revised bimolecular rate constant.

On the driving force of PAH production

NASA Technical Reports Server (NTRS)

Frenklach, Michael

1989-01-01

The kinetic factors affecting the production of polycyclic aromatic hydrocarbons (PAH) in high-temperature pyrolysis and combustion environments are analyzed. A lumped kinetic model representing polymerization-type growth by one irreversible step and two reversible steps is considered. It is shown that at high temperatures, PAH growth is controlled by the superequilibrium of hydrogen atoms; at low temperatures and low H2 concentrations, the PAH growth rate is proportional to the rate of the H-abstraction of a hydrogen atom from aromatic molecules; while at low temperatures and high H2 concentrations, it is controlled by the thermodynamics of the H-abstraction and the kinetics of acetylene addition to aromatic radicals. The presence of oxygen mainly affects the small-molecule reactions during the induction period.

Molecular Modeling of an Electrophilic Addition Reaction with "Unexpected" Regiochemistry

ERIC Educational Resources Information Center

Best, Katherine T.; Li, Diana; Helms, Eric D.

2017-01-01

The electrophilic addition of a hydrohalic acid (HX) to an alkene is often one of the first reactions learned in second-year undergraduate organic chemistry classes. During the ensuing discussion of the mechanism, it is shown that this reaction follows Markovnikov's rule, which states that the hydrogen atom will attach to the carbon with fewer…

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

PubMed

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

2017-03-09

Hydrogen atom abstraction from allylic C-H bonds by molecular oxygen plays a very important role in determining the reactivity of fuel molecules having allylic hydrogen atoms. Rate constants for hydrogen atom abstraction by molecular oxygen from molecules with allylic sites have been calculated. A series of molecules with primary, secondary, tertiary, and super secondary allylic hydrogen atoms of alkene, furan, and alkylbenzene families are taken into consideration. Those molecules include propene, 2-butene, isobutene, 2-methylfuran, and toluene containing the primary allylic hydrogen atom; 1-butene, 1-pentene, 2-ethylfuran, ethylbenzene, and n-propylbenzene containing the secondary allylic hydrogen atom; 3-methyl-1-butene, 2-isopropylfuran, and isopropylbenzene containing tertiary allylic hydrogen atom; and 1-4-pentadiene containing super allylic secondary hydrogen atoms. The M06-2X/6-311++G(d,p) level of theory was used to optimize the geometries of all of the reactants, transition states, products and also the hinder rotation treatments for lower frequency modes. The G4 level of theory was used to calculate the electronic single point energies for those species to determine the 0 K barriers to reaction. Conventional transition state theory with Eckart tunnelling corrections was used to calculate the rate constants. The comparison between our calculated rate constants with the available experimental results from the literature shows good agreement for the reactions of propene and isobutene with molecular oxygen. The rate constant for toluene with O 2 is about an order magnitude slower than that experimentally derived from a comprehensive model proposed by Oehlschlaeger and coauthors. The results clearly indicate the need for a more detailed investigation of the combustion kinetics of toluene oxidation and its key pyrolysis and oxidation intermediates. Despite this, our computed barriers and rate constants retain an important internal consistency. Rate constants calculated in this work have also been used in predicting the reactivity of the target fuels of 1-butene, 2-butene, isobutene, 2-methylfuran, 2,5-dimethylfuran, and toluene, and the results show that the ignition delay times for those fuels have been increased by a factor of 1.5-3. This work provides a first systematic study of one of the key initiation reaction for compounds containing allylic hydrogen atoms.

Method of improving field emission characteristics of diamond thin films

DOEpatents

Krauss, A.R.; Gruen, D.M.

1999-05-11

A method of preparing diamond thin films with improved field emission properties is disclosed. The method includes preparing a diamond thin film on a substrate, such as Mo, W, Si and Ni. An atmosphere of hydrogen (molecular or atomic) can be provided above the already deposited film to form absorbed hydrogen to reduce the work function and enhance field emission properties of the diamond film. In addition, hydrogen can be absorbed on intergranular surfaces to enhance electrical conductivity of the diamond film. The treated diamond film can be part of a microtip array in a flat panel display. 3 figs.

Method of improving field emission characteristics of diamond thin films

DOEpatents

Krauss, Alan R.; Gruen, Dieter M.

1999-01-01

A method of preparing diamond thin films with improved field emission properties. The method includes preparing a diamond thin film on a substrate, such as Mo, W, Si and Ni. An atmosphere of hydrogen (molecular or atomic) can be provided above the already deposited film to form absorbed hydrogen to reduce the work function and enhance field emission properties of the diamond film. In addition, hydrogen can be absorbed on intergranular surfaces to enhance electrical conductivity of the diamond film. The treated diamond film can be part of a microtip array in a flat panel display.

Comet Kohoutek - Ultraviolet images and spectrograms

NASA Technical Reports Server (NTRS)

Opal, C. B.; Carruthers, G. R.; Prinz, D. K.; Meier, R. R.

1974-01-01

Emissions of atomic oxygen (1304 A), atomic carbon (1657 A), and atomic hydrogen (1216 A) from Comet Kohoutek were observed with ultraviolet cameras carried on a sounding rocket on Jan. 8, 1974. Analysis of the Lyman alpha halo at 1216 A gave an atomic hydrogen production rate of 4.5 x 10 to the 29th atoms per second.

Pt Single Atoms Embedded in the Surface of Ni Nanocrystals as Highly Active Catalysts for Selective Hydrogenation of Nitro Compounds.

PubMed

Peng, Yuhan; Geng, Zhigang; Zhao, Songtao; Wang, Liangbing; Li, Hongliang; Wang, Xu; Zheng, Xusheng; Zhu, Junfa; Li, Zhenyu; Si, Rui; Zeng, Jie

2018-06-13

Single-atom catalysts exhibit high selectivity in hydrogenation due to their isolated active sites, which ensure uniform adsorption configurations of substrate molecules. Compared with the achievement in catalytic selectivity, there is still a long way to go in exploiting the catalytic activity of single-atom catalysts. Herein, we developed highly active and selective catalysts in selective hydrogenation by embedding Pt single atoms in the surface of Ni nanocrystals (denoted as Pt 1 /Ni nanocrystals). During the hydrogenation of 3-nitrostyrene, the TOF numbers based on surface Pt atoms of Pt 1 /Ni nanocrystals reached ∼1800 h -1 under 3 atm of H 2 at 40 °C, much higher than that of Pt single atoms supported on active carbon, TiO 2 , SiO 2 , and ZSM-5. Mechanistic studies reveal that the remarkable activity of Pt 1 /Ni nanocrystals derived from sufficient hydrogen supply because of spontaneous dissociation of H 2 on both Pt and Ni atoms as well as facile diffusion of H atoms on Pt 1 /Ni nanocrystals. Moreover, the ensemble composed of the Pt single atom and nearby Ni atoms in Pt 1 /Ni nanocrystals leads to the adsorption configuration of 3-nitrostyrene favorable for the activation of nitro groups, accounting for the high selectivity for 3-vinylaniline.

Formation of H a - hydrogen centers upon additive coloration of alkaline-earth fluoride crystals

NASA Astrophysics Data System (ADS)

Radzhabov, E. A.; Egranov, A. V.; Shendrik, R. Yu.

2017-06-01

The mechanism of coloration of alkaline-earth fluoride crystals CaF2, SrF2, and BaF2 in calcium vapors in an autoclave with a cold zone is studied. It was found that the pressure in the autoclave upon constant evacuation by a vacuum pump within the temperature range of 500-800°C increases due to evaporation of metal calcium. In addition to the optical-absorption bands of color centers in the additively colored undoped crystals or to the bands of divalent ions in the crystals doped with rare-earth Sm, Yb, and Tm elements, there appear intense bands in the vacuum ultraviolet region at 7.7, 7.0, and 6.025 eV in CaF2, SrF2, and BaF2, respectively. These bands belong to the Ha - hydrogen centers. The formation of hydrogen centers is also confirmed by the appearance of the EPR signal of interstitial hydrogen atoms after X-ray irradiation of the additively colored crystals. Grinding of the outer edges of the colored crystals leads to a decrease in the hydrogen absorption-band intensity with depth to complete disappearance. The rate of hydrogen penetration inside the crystal is lower than the corresponding rate of color centers (anion vacancies) by a factor of tens. The visible color density of the outer regions of the hydrogen-containing crystals is several times lower than that of the inner region due to the competition between the color centers and hydrogen centers.

Correlation of reaction sites during the chlorine extraction by hydrogen atom from Cl /Si(100)-2×1

NASA Astrophysics Data System (ADS)

Hsieh, Ming-Feng; Chung, Jen-Yang; Lin, Deng-Sung; Tsay, Shiow-Fon

2007-07-01

The Cl abstraction by gas-phase H atoms from a Cl-terminated Si(100) surface was investigated by scanning tunneling microscopy (STM), high-resolution core level photoemission spectroscopy, and computer simulation. The core level measurements indicate that some additional reactions occur besides the removal of Cl. The STM images show that the Cl-extracted sites disperse randomly in the initial phase of the reaction, but form small clusters as more Cl is removed, indicating a correlation between Cl-extracted sites. These results suggest that the hot-atom process may occur during the atom-adatom collision.

Characterization of an Atomic Hydrogen Source for Charge Exchange Experiments

NASA Technical Reports Server (NTRS)

Leutenegger, M. A.; Beierdorfer, P.; Betancourt-Martinez, G. L.; Brown, G. V.; Hell, N; Kelley, R. L.; Kilbourne, C. A.; Magee, E. W.; Porter, F. S.

2016-01-01

We characterized the dissociation fraction of a thermal dissociation atomic hydrogen source byinjecting the mixed atomic and molecular output of the source into an electron beam ion trapcontaining highly charged ions and recording the x-ray spectrum generated by charge exchangeusing a high-resolution x-ray calorimeter spectrometer. We exploit the fact that the charge exchangestate-selective capture cross sections are very different for atomic and molecular hydrogen incidenton the same ions, enabling a clear spectroscopic diagnostic of the neutral species.

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.

Mechanistic aspects of hydrogen abstraction for phenolic antioxidants. Electronic structure and topological electron density analysis.

PubMed

Singh, Nakul; O'Malley, Patrick J; Popelier, Paul L A

2005-02-21

Density functional calculations using the B3LYP functional are used to provide insight into the hydrogen abstraction mechanism of phenolic antioxidants. The energy profiles for 13 ortho, meta, para and di-methyl substituted phenols with hydroperoxyl radical have been determined. An excellent correlation between the enthalpy (DeltaH) and activation energy (DeltaEa) was found, obeying the Evans-Polanyi rule. The effects of hydrogen bonding on DeltaEa are also discussed. Electron donating groups at the ortho and para positions are able to lower the activation energy for hydrogen abstraction. The highly electron withdrawing fluoro substituent increases the activation energies relative to phenol at the meta position but not at the para position. The electron density is studied using the atoms in molecules (AIM) approach. Atomic and bond properties are extracted to describe the hydrogen atom abstraction mechanism. It is found that on going from reactants to transition state, the hydrogen atom experiences a loss in volume, electronic population and dipole moment. These features suggest that the phenol hydroperoxyl reactions proceed according to a proton coupled electron transfer (PCET) as opposed to a hydrogen atom transfer (HAT) mechanism.

(E)-1-(4-Chloro­benzyl­idene)thio­semi­carbazide

PubMed Central

Saeed, Aamer; Mahmood, Shams-ul; Bolte, Michael; Rauf, Abdul; Subhan, Mohammad

2011-01-01

In the crystal of the title compound, C8H8ClN3S, mol­ecules are connected by N—H⋯S hydrogen bonds into strips parallel to the (112) planes and running along [10]. One of the amino H atoms is not involved in a classical hydrogen bond. In addition, there is a rather short inter­molecular Cl⋯S distance of 3.3814 (5) Å. PMID:21522401

Boron-Based Hydrogen Storage: Ternary Borides and Beyond

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

Vajo, John J.

DOE continues to seek reversible solid-state hydrogen materials with hydrogen densities of ≥11 wt% and ≥80 g/L that can deliver hydrogen and be recharged at moderate temperatures (≤100 °C) and pressures (≤100 bar) enabling incorporation into hydrogen storage systems suitable for transportation applications. Boron-based hydrogen storage materials have the potential to meet the density requirements given boron’s low atomic weight, high chemical valance, and versatile chemistry. However, the rates of hydrogen exchange in boron-based compounds are thus far much too slow for practical applications. Although contributing to the high hydrogen densities, the high valance of boron also leads to slowmore » rates of hydrogen exchange due to extensive boron-boron atom rearrangements during hydrogen cycling. This rearrangement often leads to multiple solid phases occurring over hydrogen release and recharge cycles. These phases must nucleate and react with each other across solid-solid phase boundaries leading to energy barriers that slow the rates of hydrogen exchange. This project sought to overcome the slow rates of hydrogen exchange in boron-based hydrogen storage materials by minimizing the number of solid phases and the boron atom rearrangement over a hydrogen release and recharge cycle. Two novel approaches were explored: 1) developing matched pairs of ternary borides and mixed-metal borohydrides that could exchange hydrogen with only one hydrogenated phase (the mixed-metal borohydride) and only one dehydrogenated phase (the ternary boride); and 2) developing boranes that could release hydrogen by being lithiated using lithium hydride with no boron-boron atom rearrangement.« less

Carbon-tuned bonding method significantly enhanced the hydrogen storage of BN-Li complexes.

PubMed

Deng, Qing-ming; Zhao, Lina; Luo, You-hua; Zhang, Meng; Zhao, Li-xia; Zhao, Yuliang

2011-11-01

Through first-principles calculations, we found doping carbon atoms onto BN monolayers (BNC) could significantly strengthen the Li bond on this material. Unlike the weak bond strength between Li atoms and the pristine BN layer, it is observed that Li atoms are strongly hybridized and donate their electrons to the doped substrate, which is responsible for the enhanced binding energy. Li adsorbed on the BNC layer can serve as a high-capacity hydrogen storage medium, without forming clusters, which can be recycled at room temperature. Eight polarized H(2) molecules are attached to two Li atoms with an optimal binding energy of 0.16-0.28 eV/H(2), which results from the electrostatic interaction of the polarized charge of hydrogen molecules with the electric field induced by positive Li atoms. This practical carbon-tuned BN-Li complex can work as a very high-capacity hydrogen storage medium with a gravimetric density of hydrogen of 12.2 wt%, which is much higher than the gravimetric goal of 5.5 wt % hydrogen set by the U.S. Department of Energy for 2015.

Thermodynamics of the clusterization process of cis isomers of unsaturated fatty acids at the air/water interface.

PubMed

Vysotsky, Yu B; Belyaeva, E A; Fainerman, V B; Vollhardt, D; Aksenenko, E V; Miller, R

2009-04-02

In the framework of the semiempirical PM3 method, the thermodynamic parameters of cis isomers of unsaturated carboxylic acids at the air/water interface are studied. The model systems used are unsaturated cis fatty acid of the composition Delta = 12-15 and omega = 6-11, where Delta and omega refer to the number of carbon atoms between the functional group and double bond, and that between the double bond and methyl group, respectively. For dimers, trimers, and tetramers of the four acid series, the thermodynamic parameters of clusterization are calculated. It is shown that the position of the double bond does not significantly affect the values of thermodynamic parameters of formation and clusterization of carboxylic acids for equal chain lengths (n = Delta + omega). The calculated results show that for cis unsaturated fatty acid with odd Delta values the spontaneous clusterization threshold corresponds to n = 17-18 carbon atoms in the alkyl chain, while for monounsaturated acids with even Delta values this threshold corresponds to n = 18-19 carbon atoms in the alkyl chain. These differences in the clusterization threshold between the acids with even and odd Delta values are attributed to the formation of additional intermolecular hydrogen bonds between the ketonic oxygen atom of one monomer and the hydrogen atom linked to the alpha-carbon atom of the second monomer for the acids with odd Delta values or between the hydroxyl oxygen atom of one monomer and hydrogen atom linked to the alpha-carbon atom of the second monomer for the acids with even Delta values. The results obtained in the study agree satisfactorily with our experimental data for cis unsaturated nervonic (Delta15, omega9) and erucic acids (Delta13, omega9), and published data for some fatty acids, namely cis-16-heptadecenoic (Delta16, omega1), cis-9-hexadecenoic (Delta7, omega9), cis-11-eicosenoic (Delta11, omega9) and cis-9-octadecenoic acid (Delta9, omega9).

Unraveling the formation of HCPH(X2A') molecules in extraterrestrial environments: crossed molecular beam study of the reaction of carbon atoms, C(3Pj), with phosphine, PH3(X1A1).

PubMed

Guo, Y; Gu, X; Zhang, F; Sun, B J; Tsai, M F; Chang, A H H; Kaiser, R I

2007-05-03

The reaction between ground state carbon atoms, C(3P(j)), and phosphine, PH3(X(1)A1), was investigated at two collision energies of 21.1 and 42.5 kJ mol(-1) using the crossed molecular beam technique. The chemical dynamics extracted from the time-of-flight spectra and laboratory angular distributions combined with ab initio calculations propose that the reaction proceeds on the triplet surface via an addition of atomic carbon to the phosphorus atom. This leads to a triplet CPH3 complex. A successive hydrogen shift forms an HCPH2 intermediate. The latter was found to decompose through atomic hydrogen emission leading to the cis/trans-HCPH(X(2)A') reaction products. The identification of cis/trans-HCPH(X(2)A') molecules under single collision conditions presents a potential pathway to form the very first carbon-phosphorus bond in extraterrestrial environments like molecular clouds and circumstellar envelopes, and even in the postplume chemistry of the collision of comet Shoemaker-Levy 9 with Jupiter.

Study on glass-forming ability and hydrogen storage properties of amorphous Mg{sub 60}Ni{sub 30}La{sub 10−x}Co{sub x} (x = 0, 4) alloys

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

Lv, Peng; Wang, Zhong-min, E-mail: zmwang@guet.edu.cn; Zhang, Huai-gang

2013-12-15

Mg{sub 60}Ni{sub 30}La{sub 10−x}Co{sub x} (x = 0, 4) amorphous alloys were prepared by rapid solidification, using a melt-spinning technique. X-ray diffraction and differential scanning calorimetry analysis were employed to measure their microstructure, thermal stability and glass-forming ability, and hydrogen storage properties were studied by means of PCTPro2000. Based on differential scanning calorimetry results, their glass-forming ability and thermal stability were investigated by Kissinger method, Lasocka curves and atomic cluster model, respectively. The results indicate that glass-forming ability, thermal properties and hydrogen storage properties in the Mg-rich corner of Mg–Ni–La–Co system alloys were enhanced by Co substitution for La. Itmore » can be found that the smaller activation energy (ΔΕ) and frequency factor (υ{sub 0}), the bigger value of B (glass transition point in Lasocka curves), and higher glass-forming ability of Mg–Ni–La–Co alloys would be followed. In addition, atomic structure parameter (λ), deduced from atomic cluster model is valuable in the design of Mg–Ni–La–Co system alloys with good glass-forming ability. With an increase of Co content from 0 to 4, the hydrogen desorption capacity within 4000 s rises from 2.25 to 2.85 wt.% at 573 K. - Highlights: • Amorphous Mg{sub 60}Ni{sub 30}La{sub 10−x}Co{sub x} (x = 0 and 4) alloys were produced by melt spinning. • The GFA and hydrogen storage properties were enhanced by Co substitution for La. • With an increase of Co content, the hydrogen desorption capacity rises at 573 K.« less

Quantized impedance dealing with the damping behavior of the one-dimensional oscillator

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

Zhu, Jinghao; Zhang, Jing; Li, Yuan

2015-11-15

A quantized impedance is proposed to theoretically establish the relationship between the atomic eigenfrequency and the intrinsic frequency of the one-dimensional oscillator in this paper. The classical oscillator is modified by the idea that the electron transition is treated as a charge-discharge process of a suggested capacitor with the capacitive energy equal to the energy level difference of the jumping electron. The quantized capacitance of the impedance interacting with the jumping electron can lead the resonant frequency of the oscillator to the same as the atomic eigenfrequency. The quantized resistance reflects that the damping coefficient of the oscillator is themore » mean collision frequency of the transition electron. In addition, the first and third order electric susceptibilities based on the oscillator are accordingly quantized. Our simulation of the hydrogen atom emission spectrum based on the proposed method agrees well with the experimental one. Our results exhibits that the one-dimensional oscillator with the quantized impedance may become useful in the estimations of the refractive index and one- or multi-photon absorption coefficients of some nonmagnetic media composed of hydrogen-like atoms.« less

Quantized impedance dealing with the damping behavior of the one-dimensional oscillator

NASA Astrophysics Data System (ADS)

Zhu, Jinghao; Zhang, Jing; Li, Yuan; Zhang, Yong; Fang, Zhengji; Zhao, Peide; Li, Erping

2015-11-01

A quantized impedance is proposed to theoretically establish the relationship between the atomic eigenfrequency and the intrinsic frequency of the one-dimensional oscillator in this paper. The classical oscillator is modified by the idea that the electron transition is treated as a charge-discharge process of a suggested capacitor with the capacitive energy equal to the energy level difference of the jumping electron. The quantized capacitance of the impedance interacting with the jumping electron can lead the resonant frequency of the oscillator to the same as the atomic eigenfrequency. The quantized resistance reflects that the damping coefficient of the oscillator is the mean collision frequency of the transition electron. In addition, the first and third order electric susceptibilities based on the oscillator are accordingly quantized. Our simulation of the hydrogen atom emission spectrum based on the proposed method agrees well with the experimental one. Our results exhibits that the one-dimensional oscillator with the quantized impedance may become useful in the estimations of the refractive index and one- or multi-photon absorption coefficients of some nonmagnetic media composed of hydrogen-like atoms.

Tracing the Fuel for Forming Stars

NASA Astrophysics Data System (ADS)

Kohler, Susanna

2017-11-01

Huge reservoirs of cold hydrogen gas the raw fuel for star formation lurk in galaxies throughout the universe. A new study examines whether these reservoirs have always been similar, or whether those in distant galaxies are very different from those in local galaxies today.Left: Optical SLOAN images of the five HIGHz galaxies in this study. Right: ALMA images of the molecular gas in these galaxies. Both images are 30 wide. [Adapted from Cortese et al. 2017]Molecular or Atomic?The formation of stars is a crucial process that determines how galaxies are built and evolve over time. Weve observed that star formation takes place in cold clouds of molecular gas, and that star-formation rates increase in galaxies with a larger surface density of molecular hydrogen so we know that molecular hydrogen feeds the star-forming process.But not all cold gas in the interstellar medium of galaxies exists in molecular form. In the local universe, only around 30% of cold gas is found in molecular form (H2) and able to directly feed star formation; the rest is atomic hydrogen (H I). But is this true of galaxies earlier in the universe as well?Studying Distant GalaxiesCosmological simulations have predicted that earlier in our universes history, the ratio of molecular to atomic hydrogen could be larger i.e., more cold hydrogen may be in a form ready to fuel star formation but this prediction is difficult to test observationally. Currently, radio telescopes are not able to measure the atomic hydrogen in very distant galaxies, such as those at the peak of star formation in the universe, 10 billion years ago.Recently, however, we have measured atomic hydrogen in closer galaxies: those at a redshift of about z 0.20.4, a few billion years ago. One recent study of seven galaxies at this distance, usinga sample from a survey known as COOL BUDHIES, showed that the hydrogen reservoirs of these galaxies are dominated by molecular hydrogen, unlike in the local universe. If this is true of most galaxies at this distance, it would suggest that gas reservoirs have drastically changed in the short time between then and now.But a team of scientists from the International Centre for Radio Astronomy Research in Australia, led by Luca Cortese, has now challenged this conclusion.Top: molecular vs. atomic hydrogen gas in galaxies between z = 0 and z = 1.5. Bottom: the evolution of the molecular-to-atomic mass ratio with redshift. [Adapted from Cortese et al. 2017]Adding to the SampleCortese and collaborators combined observations from the Atacama Large Millimeter/submillimeter Array (ALMA) and Arecibo to estimate the ratio of molecular to atomic hydrogen in five HIGHz-survey massive star-forming galaxies at a redshift of z 0.2. They then combine these results with those of the COOL BUDHIES survey; they argue that, since the two surveys use different selection criteria, the combination of the two samples provides a fairer view of the overall population of star-forming galaxies at z 0.2.Intriguingly, the HIGHz galaxies do not show the molecular-gas dominance that the COOL BUDHIES galaxies do. Cortese and collaborators demonstrate that the addition of the HIGHz galaxies to the sample reveals that the gas reservoirs of star-forming disks 3 billion years ago are, in fact, still the same as what we see today, suggesting that star formation in galaxies at z 0.2 is likely fueled in much the same way as it is today.As telescope capabilities increase, we may be able to explore whether this continues to hold true for more distant galaxies. In the meantime, increasing our sample size within the range that we can observe will help us to further explore how galaxies have formed stars over time.CitationLuca Cortese et al 2017 ApJL 848 L7. doi:10.3847/2041-8213/aa8cc3

Deuterium enrichment by selective photo-induced dissociation of an organic carbonyl compound

DOEpatents

Marling, John B.

1981-01-01

A method for producing a deuterium enriched material by photoinduced dissociation which uses as the working material a gas phase photolytically dissociable organic carbonyl compound containing at least one hydrogen atom bonded to an atom which is adjacent to a carbonyl group and consisting of molecules wherein said hydrogen atom is present as deuterium and molecules wherein said hydrogen atom is present as another isotope of hydrogen. The organic carbonyl compound is subjected to intense infrared radiation at a preselected wavelength to selectively excite and thereby induce dissociation of the deuterium containing species to yield a deuterium enriched stable molecular product. Undissociated carbonyl compound, depleted in deuterium, is preferably redeuterated for reuse.

Method for oxidizing alkanes using novel porphyrins synthesized from dipyrromethanes and aldehydes

DOEpatents

Wijesekera, Tilak; Lyons, James E.; Ellis, Jr., Paul E.

1999-01-01

The invention comprises a method for the oxidation of alkanes to alcohols and for decomposition of hydroperoxides to alcohols utilizing new compositions of matter, which are metal complexes of porphyrins. Preferred complexes have hydrogen, haloalkyl or haloaryl groups in meso positions, two of the opposed meso atoms or groups being hydrogen or haloaryl, and two of the opposed meso atoms or groups being hydrogen or haloalkyl, but not all four of the meso atoms or groups being hydrogen. Other preferred complexes are ones in which all four of the meso positions are substituted with haloalkyl groups and the beta positions are substituted with halogen atoms. A new method of synthesizing porphyrinogens is also disclosed.

Method for hydroperoxide decomposition using novel porphyrins synthesized from dipyrromethanes and aldehydes

DOEpatents

Wijesekera, T.; Lyons, J.E.; Ellis, P.E. Jr.

1998-03-03

The invention comprises a method for the oxidation of alkanes to alcohols and for decomposition of hydroperoxides to alcohols utilizing new compositions of matter, which are metal complexes of porphyrins. Preferred complexes have hydrogen, haloalkyl or haloaryl groups in meso positions, two of the opposed meso atoms or groups being hydrogen or haloaryl, and two of the opposed meso atoms or groups being hydrogen or haloalkyl, but not all four of the meso atoms or groups being hydrogen. Other preferred complexes are ones in which all four of the meso positions are substituted with haloalkyl groups and the beta positions are substituted with halogen atoms. A new method of synthesizing porphyrinogens is also disclosed.

Method for hydroperoxide decomposition using novel porphyrins synthesized from dipyrromethanes and aldehydes

DOEpatents

Wijesekera, Tilak; Lyons, James E.; Ellis, Jr., Paul E.

1998-01-01

The invention comprises a method for the oxidation of alkanes to alcohols and for decomposition of hydroperoxides to alcohols utilizing new compositions of matter, which are metal complexes of porphyrins. Preferred complexes have hydrogen, haloalkyl or haloaryl groups in meso positions, two of the opposed meso atoms or groups being hydrogen or haloaryl, and two of the opposed meso atoms or groups being hydrogen or haloalkyl, but not all four of the meso atoms or groups being hydrogen. Other preferred complexes are ones in which all four of the meso positions are substituted with haloalkyl groups and the beta positions are substituted with halogen atoms. A new method of synthesizing porphyrinogens is also disclosed.

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.

Atomic and molecular hydrogen in the circumstellar envelopes of late-type stars

NASA Technical Reports Server (NTRS)

Glassgold, A. E.; Huggins, P. J.

1983-01-01

The distribution of atomic and molecular hydrogen in the expanding circumstellar envelopes of cool evolved stars is discussed. The main concern is to evaluate the effects of photodestruction of H2 by galactic UV radiation, including shielding of the radiation by H2 itself and by dust in the envelope. One of the most important parameters is the H/H2 ratio which is frozen out in the upper atmosphere of the star. For stars with photospheric temperatures greater than about 2500 K, atmospheric models suggest that the outflowing hydrogen is mainly atomic, whereas cooler stars should be substantially molecular. In the latter case, photodissociation of H2 and heavy molecules contribute to the atomic hydrogen content of the outer envelope. The presented estimates indicate that atomic hydrogen is almost at the limit of detection in the C-rich star IRC + 10216, and may be detectable in warmer stars. Failure to detect it would have important implications for the general understanding of circumstellar envelopes.

On the Lamb shift in neutral muonic helium

NASA Astrophysics Data System (ADS)

Amusia, Miron; Karshenboim, Savely; Ivanov, Vladimir

2015-05-01

The neutral muonic helium is an exotic atomic system consisting of an electron, muon and a nucleus. We consider it as a hydrogen-like atom with a compound nucleus that is also hydrogen-like system. There are a number of corrections to the Bohr energy levels, which all can be treated as contributions of generic hydrogen-like theory. While the form of those contributions is the same for all hydrogen-like atoms, their relative numerical importance differs from an atom to an atom. Here, the leading contribution to the electronic Lamb shift in the neutral muonic helium is found in a close analytic form together with the most important corrections. We believe that the Lamb shift in the neutral muonic hydrogen is measurable, at least through a measurement of the electronic 1 s - 2 s transition. We present a theoretical prediction for the 1 s - 2 s transitions with the uncertainty of 2 ppm (4 GHz), as well as for the 2 s - 2 p Lamb shift with the uncertainty of 0.6 GHz.

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.

Inelastic fingerprints of hydrogen contamination in atomic gold wire systems

NASA Astrophysics Data System (ADS)

Frederiksen, Thomas; Paulsson, Magnus; Brandbyge, Mads

2007-03-01

We present series of first-principles calculations for both pure and hydrogen contaminated gold wire systems in order to investigate how such impurities can be detected. We show how a single H atom or a single H2 molecule in an atomic gold wire will affect forces and Au-Au atom distances under elongation. We further determine the corresponding evolution of the low-bias conductance as well as the inelastic contributions from vibrations. Our results indicate that the conductance of gold wires is only slightly reduced from the conductance quantum G0 = 2e2/h by the presence of a single hydrogen impurity, hence making it difficult to use the conductance itself to distinguish between various configurations. On the other hand, our calculations of the inelastic signals predict significant differences between pure and hydrogen contaminated wires, and, importantly, between atomic and molecular forms of the impurity. A detailed characterization of gold wires with a hydrogen impurity should therefore be possible from the strain dependence of the inelastic signals in the conductance.

STRUCTURE OF POTASSIUM HYDROGEN MALEATE BY NEUTRON DIFFRACTION

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

Peterson, S.W.; Levy, H.A.

1958-10-01

The preliminary results of a neutron diffraction study are presented which confirm the existence in potassium hydrogen maleate of a short, strong, hydrogen bond and show the ion to be at least statistically symmetrical. The hydrogen is strongly linked to both neighboring oxygen atoms, and there is an existing mode of correlated motion of considerable amplitude in which the oxygen atoms are displaced but hydrogen is not. (J.R.D.)

Spectroscopic study of uracil, 1-methyluracil and 1-methyl-4-thiouracil: Hydrogen bond interactions in crystals and ab-initio molecular dynamics

NASA Astrophysics Data System (ADS)

Brela, Mateusz Z.; Boczar, Marek; Malec, Leszek M.; Wójcik, Marek J.; Nakajima, Takahito

2018-05-01

Hydrogen bond networks in uracil, 1-methyluracil and 1-methyl-4-thiouracil were studied by ab initio molecular dynamics as well as analysis of the orbital interactions. The power spectra calculated by ab initio molecular dynamics for atoms involved in hydrogen bonds were analyzed. We calculated spectra by using anharmonic approximation based on the autocorrelation function of the atom positions obtained from the Born-Oppenheimer simulations. Our results show the differences between hydrogen bond networks in uracil and its methylated derivatives. The studied methylated derivatives, 1-methyluracil as well as 1-methyl-4-thiouracil, form dimeric structures in the crystal phase, while uracil does not form that kind of structures. The presence of sulfur atom instead oxygen atom reflects weakness of the hydrogen bonds that build dimers.

Trapping of hydrogen atoms in X-irradiated salts at room temperature and the decay kinetics

NASA Technical Reports Server (NTRS)

May, C. E.; Philipp, W. H.; Marsik, S. J.

1974-01-01

The salts (hypophosphites, formates, a phosphite, a phosphate, and an oxalate) were X-irradiated, whereby hydrogen formed chemically by a radiolytic process becomes trapped in the solid. By room temperature vacuum extraction, the kinetics for the evolution of this trapped hydrogen was studied mass spectrometrically. All salts except two exhibited second-order kinetics. The two exceptions (NaH2PO2(H2O) and K2HPO4) showed first-order kinetics. Based on experimental results, the escape of hydrogen involves three steps: the diffusion of hydrogen atoms from the bulk to the surface, association of these atoms on the surface (rate controlling step for second-order hydrogen evolution), and the desorption of molecular hydrogen from the surface. The hydrogen does not escape if the irradiated salt is stored in air, apparently because adsorbed air molecules occupy surface sites required in the escape mechanism.

Characterization of an atomic hydrogen source for charge exchange experiments

DOE PAGES

Leutenegger, M. A.; Beiersdorfer, P.; Betancourt-Martinez, G. L.; ...

2016-07-02

Here, we characterized the dissociation fraction of a thermal dissociation atomic hydrogen source by injecting the mixed atomic and molecular output of the source into an electron beam ion trap containing highly charged ions and recording the x-ray spectrum generated by charge exchange using a high-resolution x-ray calorimeter spectrometer. We exploit the fact that the charge exchange state-selective capture cross sections are very different for atomic and molecular hydrogen incident on the same ions, enabling a clear spectroscopic diagnostic of the neutral species.

Low-temperature Condensation of Carbon

NASA Astrophysics Data System (ADS)

Krasnokutski, S. A.; Goulart, M.; Gordon, E. B.; Ritsch, A.; Jäger, C.; Rastogi, M.; Salvenmoser, W.; Henning, Th.; Scheier, P.

2017-10-01

Two different types of experiments were performed. In the first experiment, we studied the low-temperature condensation of vaporized graphite inside bulk liquid helium, while in the second experiment, we studied the condensation of single carbon atoms together with H2, H2O, and CO molecules inside helium nanodroplets. The condensation of vaporized graphite leads to the formation of partially graphitized carbon, which indicates high temperatures, supposedly higher than 1000°C, during condensation. Possible underlying processes responsible for the instant rise in temperature during condensation are discussed. This suggests that such processes cause the presence of partially graphitized carbon dust formed by low-temperature condensation in the diffuse interstellar medium. Alternatively, in the denser regions of the ISM, the condensation of carbon atoms together with the most abundant interstellar molecules (H2, H2O, and CO), leads to the formation of complex organic molecules (COMs) and finally organic polymers. Water molecules were found not to be involved directly in the reaction network leading to the formation of COMs. It was proposed that COMs are formed via the addition of carbon atoms to H2 and CO molecules ({{C}}+{{{H}}}2\\to {HCH},{HCH}+{CO}\\to {{OCCH}}2). Due to the involvement of molecular hydrogen, the formation of COMs by carbon addition reactions should be more efficient at high extinctions compared with the previously proposed reaction scheme with atomic hydrogen.

H(D) → D(H) + Cu(111) collision system: Molecular dynamics study of surface temperature effects

PubMed Central

Vurdu, Can D.; Güvenç, Ziya B.

2011-01-01

All the channels of the reaction dynamics of gas-phase H (or D) atoms with D (or H) atoms adsorbed onto a Cu(111) surface have been studied by quasiclassical constant energy molecular dynamics simulations. The surface is flexible and is prepared at different temperature values, such as 30 K, 94 K, and 160 K. The adsorbates were distributed randomly on the surface to create 0.18 ML, 0.28 ML, and 0.50 ML of coverages. The multi-layer slab is mimicked by a many-body embedded-atom potential energy function. The slab atoms can move according to the exerted external forces. Treating the slab atoms non-rigid has an important effect on the dynamics of the projectile atom and adsorbates. Significant energy transfer from the projectile atom to the surface lattice atoms takes place especially during the first impact that modifies significantly the details of the dynamics of the collisions. Effects of the different temperatures of the slab are investigated in this study. Interaction between the surface atoms and the adsorbates is modeled by a modified London–Eyring–Polanyi–Sato (LEPS) function. The LEPS parameters are determined by using the total energy values which were calculated by a density functional theory and a generalized gradient approximation for an exchange-correlation energy for many different orientations, and locations of one- and two-hydrogen atoms on the Cu(111) surface. The rms value of the fitting procedure is about 0.16 eV. Many different channels of the processes on the surface have been examined, such as inelastic reflection of the incident hydrogen, subsurface penetration of the incident projectile and adsorbates, sticking of the incident atom on the surface. In addition, hot-atom and Eley-Rideal direct processes are investigated. The hot-atom process is found to be more significant than the Eley-Rideal process. Furthermore, the rate of subsurface penetration is larger than the sticking rate on the surface. In addition, these results are compared and analyzed as a function of the surface temperatures. PMID:21528959

H(D) → D(H) + Cu(111) collision system: molecular dynamics study of surface temperature effects.

PubMed

Vurdu, Can D; Güvenç, Ziya B

2011-04-28

All the channels of the reaction dynamics of gas-phase H (or D) atoms with D (or H) atoms adsorbed onto a Cu(111) surface have been studied by quasiclassical constant energy molecular dynamics simulations. The surface is flexible and is prepared at different temperature values, such as 30 K, 94 K, and 160 K. The adsorbates were distributed randomly on the surface to create 0.18 ML, 0.28 ML, and 0.50 ML of coverages. The multi-layer slab is mimicked by a many-body embedded-atom potential energy function. The slab atoms can move according to the exerted external forces. Treating the slab atoms non-rigid has an important effect on the dynamics of the projectile atom and adsorbates. Significant energy transfer from the projectile atom to the surface lattice atoms takes place especially during the first impact that modifies significantly the details of the dynamics of the collisions. Effects of the different temperatures of the slab are investigated in this study. Interaction between the surface atoms and the adsorbates is modeled by a modified London-Eyring-Polanyi-Sato (LEPS) function. The LEPS parameters are determined by using the total energy values which were calculated by a density functional theory and a generalized gradient approximation for an exchange-correlation energy for many different orientations, and locations of one- and two-hydrogen atoms on the Cu(111) surface. The rms value of the fitting procedure is about 0.16 eV. Many different channels of the processes on the surface have been examined, such as inelastic reflection of the incident hydrogen, subsurface penetration of the incident projectile and adsorbates, sticking of the incident atom on the surface. In addition, hot-atom and Eley-Rideal direct processes are investigated. The hot-atom process is found to be more significant than the Eley-Rideal process. Furthermore, the rate of subsurface penetration is larger than the sticking rate on the surface. In addition, these results are compared and analyzed as a function of the surface temperatures.

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

PubMed

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

2017-10-19

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

Free Radical Metabolism of Methyleugenol and Related Compounds

PubMed Central

2015-01-01

Methyleugenol, the methyl ether of eugenol, both of which are flavorant constituents of spices, has been listed by the National Toxicology Program’s Report on Carcinogens as reasonably anticipated to be a human carcinogen. This finding is based on the observation of increased incidence of malignant tumors at multiple tissue sites in experimental animals of different species. By contrast, eugenol is not listed. In this study, we show that both methyleugenol and eugenol readily undergo peroxidative metabolism in vitro to form free radicals with large hyperfine interactions of the methylene allylic hydrogen atoms. These large hyperfine splittings indicate large electron densities adjacent to those hydrogen atoms. Methyleugenol undergoes autoxidation such that the commercial product contains 10–30 mg/L hydroperoxide and is capable of activating peroxidases without the presence of added hydrogen peroxide. Additionally, the hydroperoxide is not a good substrate for catalase, which demonstrates that these antioxidant defenses will not be effective in protecting against methyleugenol exposure. PMID:24564854

Database of non-canonical base pairs found in known RNA structures

NASA Technical Reports Server (NTRS)

Nagaswamy, U.; Voss, N.; Zhang, Z.; Fox, G. E.

2000-01-01

Atomic resolution RNA structures are being published at an increasing rate. It is common to find a modest number of non-canonical base pairs in these structures in addition to the usual Watson-Crick pairs. This database summarizes the occurrence of these rare base pairs in accordance with standard nomenclature. The database, http://prion.bchs.uh.edu/, contains information such as sequence context, sugar pucker conformation, anti / syn base conformations, chemical shift, p K (a)values, melting temperature and free energy. Of the 29 anticipated pairs with two or more hydrogen bonds, 20 have been encountered to date. In addition, four unexpected pairs with two hydrogen bonds have been reported bringing the total to 24. Single hydrogen bond versions of five of the expected geometries have been encountered among the single hydrogen bond interactions. In addition, 18 different types of base triplets have been encountered, each of which involves three to six hydrogen bonds. The vast majority of the rare base pairs are antiparallel with the bases in the anti configuration relative to the ribose. The most common are the GU wobble, the Sheared GA pair, the Reverse Hoogsteen pair and the GA imino pair.

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.

Infrared absorption of trans-1-chloromethylallyl and trans-1-methylallyl radicals produced in photochemical reactions of trans-1,3-butadiene and Cl2 in solid para-hydrogen.

PubMed

Bahou, Mohammed; Wu, Jen-Yu; Tanaka, Keiichi; Lee, Yuan-Pern

2012-08-28

The reactions of chlorine and hydrogen atoms with trans-1,3-butadiene in solid para-hydrogen (p-H(2)) were investigated with infrared (IR) absorption spectra. When a p-H(2) matrix containing Cl(2) and trans-1,3-butadiene was irradiated with ultraviolet light at 365 nm, intense lines at 650.3, 809.0, 962.2, 1240.6 cm(-1), and several weaker ones due to the trans-1-chloromethylallyl radical, ●(CH(2)CHCH)CH(2)Cl, appeared. Observed wavenumbers and relative intensities agree with the anharmonic vibrational wavenumbers and IR intensities predicted with the B3PW91/6-311++g(2d, 2p) method. That the Cl atom adds primarily to the terminal carbon atom of trans-1,3-butadiene is in agreement with the path of minimum energy predicted theoretically, but in contrast to the reaction of Cl + propene in solid p-H(2) [J. Amicangelo and Y.-P. Lee, J. Phys. Chem. Lett. 1, 2956 (2010)] in which the addition of Cl to the central C atom is favored, likely through steric effects in a p-H(2) matrix. A second set of lines, intense at 781.6, 957.9, 1433.6, 2968.8, 3023.5, 3107.3 cm(-1), were observed when the UV-irradiated Cl(2)/trans-1,3-butadiene/p-H(2) matrix was further irradiated with IR light from a SiC source. These lines are assigned to the trans-1-methylallyl radical, ●(CH(2)CHCH)CH(3), produced from reaction of 1,3-butadiene with a H atom resulted from the reaction of Cl atoms with solid p-H(2) exposed to IR radiation.

Precision spectroscopy of the 2S-4P transition in atomic hydrogen

NASA Astrophysics Data System (ADS)

Maisenbacher, Lothar; Beyer, Axel; Matveev, Arthur; Grinin, Alexey; Pohl, Randolf; Khabarova, Ksenia; Kolachevsky, Nikolai; Hänsch, Theodor W.; Udem, Thomas

2017-04-01

Precision measurements of atomic hydrogen have long been successfully used to extract fundamental constants and to test bound-state QED. However, both these applications are limited by measurements of hydrogen lines other than the very precisely known 1S-2S transition. Moreover, the proton r.m.s.charge radius rp extracted from electronic hydrogen measurements currently disagrees by 4 σ with the much more precise value extracted from muonic hydrogen spectroscopy. We have measured the 2S-4P transition in atomic hydrogen using a cryogenic beam of hydrogen atoms optically excited to the initial 2S state. The first order Doppler shift of the one-photon 2S-4P transition is suppressed by actively stabilized counter-propagating laser beams and time-of-flight resolved detection. Quantum interference between excitation paths can lead to significant line distortions in our system. We use an experimentally verified, simple line shape model to take these distortions into account. With this, we can extract a new value for rp and the Rydberg constant R∞ with comparable accuracy as the combined previous H world data.

A theoretical perspective of the nature of hydrogen-bond types - the atoms in molecules approach

NASA Astrophysics Data System (ADS)

Vijaya Pandiyan, B.; Kolandaivel, P.; Deepa, P.

2014-06-01

Hydrogen bonds and their strength were analysed based on their X-H proton-donor bond properties and the parameters of the H-Y distance (Y proton acceptor). Strong, moderate and weak interactions in hydrogen-bond types were verified through the proton affinities of bases (PA), deprotanation enthalpies of acids (DPE) and the chemical shift (σ). The aromaticity and anti-aromaticity were analysed by means of the NICS (0) (nucleus-independent chemical shift), NICS (1) and ΔNICS (0), ΔNICS (1) of hydrogen-bonded molecules. The strength of a hydrogen bond depends on the capacity of hydrogen atom engrossing into the electronegative acceptor atom. The correlation between the above parameters and their relations were discussed through curve fitting. Bader's theory of atoms in molecules has been applied to estimate the occurrence of hydrogen bonds through eight criteria reported by Popelier et al. The lengths and potential energy shifts have been found to have a strong negative linear correlation, whereas the lengths and Laplacian shifts have a strong positive linear correlation. This study illustrates the common factors responsible for strong, moderate and weak interactions in hydrogen-bond types.

Influence of surface oxides on hydrogen-sensitive Pd:GaN Schottky diodes

NASA Astrophysics Data System (ADS)

Weidemann, O.; Hermann, M.; Steinhoff, G.; Wingbrant, H.; Lloyd Spetz, A.; Stutzmann, M.; Eickhoff, M.

2003-07-01

The hydrogen response of Pd:GaN Schottky diodes, prepared by in situ and ex situ deposition of catalytic Pd Schottky contacts on Si-doped GaN layers is compared. Ex situ fabricated devices show a sensitivity towards molecular hydrogen, which is about 50 times higher than for in situ deposited diodes. From the analysis of these results, we conclude that adsorption sites for atomic hydrogen in Pd:GaN sensors are provided by an oxidic intermediate layer. In addition, in situ deposited Pd Schottky contacts reveal lower barrier heights and drastically higher reverse currents. We suggest that the passivation of the GaN surface before ex situ deposition of Pd also results in quenching of leakage paths caused by structural defects.

Reaction of H rad with H 2O 2 as observed by optical absorption of perhydroxyl radicals or aliphatic alcohol radicals and of rad OH with H 2O 2. A pulse radiolysis study

NASA Astrophysics Data System (ADS)

Alam, M. S.; Kelm, M.; Rao, B. S. M.; Janata, E.

2004-12-01

Two new procedures were employed for studying the reaction of hydrogen atoms with hydrogen peroxide. The absorption in the UV-range was observed either for an acidic aqueous solution containing only hydrogen peroxide or for a similar solution but also containing an aliphatic alcohol. From the increase in absorption of various alcohol radicals, a rate constant of 3.5×10 7 dm 3 mol -1 s -1 was determined. In addition, the rate constant for the reaction of hydroxyl radicals with hydrogen peroxide was determined to be 3.0×10 7 dm 3 mol -1 s -1.

Interaction of ammonia with semiconducting oxide surfaces

NASA Astrophysics Data System (ADS)

Nigam, Sandeep; Sahoo, Suman Kalyan; Majumder, Chiranjib

2018-04-01

Using density functional theory (DFT) we have investigated the adsorption of NH3 molecule on the rutile SnO2(110) and mixed Sn0.5Ti0.5O2(110) surfaces. NH3 molecule gets absorbed on the 5-coordinated Sn atom (Sn5c) of the surface in tilted mode having an additional hydrogen bond with nearby surface bridged oxygen (Obr) atom. After adsorption, 3a1 molecular orbital of ammonia undergo significant dispersal as it donates its electron to surface atoms. The adsorption energy is found to be 1.4-1.6eV. Inclusion of Ti atoms in the SnO2 lattice leads to decrease in the adsorption energy value.

Crystal structure of poly[{μ-N,N′-bis[(pyridin-4-yl)meth­yl]oxalamide}-μ-oxalato-cobalt(II)

PubMed Central

Zou, Hengye; Qi, Yanjuan

2014-01-01

In the polymeric title compound, [Co(C2O4)(C14H14N4O2)]n, the CoII atom is six-coordinated by two N atoms from symmetry-related bis­[(pyridin-4-yl)meth­yl]oxalamide (BPMO) ligands and four O atoms from two centrosymmetric oxalate anions in a distorted octa­hedral coordination geometry. The CoII atoms are linked by the oxalate anions into a chain running parallel to [100]. The chains are linked by the BPMO ligands into a three-dimensional architecture. In addition, N—H⋯O hydrogen bonds stabilize the crystal packing. PMID:25309173

Porphyrins

DOEpatents

Wijesekera, T.; Lyons, J.E.; Ellis, P.E. Jr.

1996-11-05

The invention comprises new compositions of matter, which are iron, manganese, cobalt or ruthenium complexes of porphyrins having hydrogen, haloalkyl or haloaryl groups in meso positions, two of the opposed meso atoms or groups being hydrogen or haloaryl, and two of the opposed meso atoms or groups being hydrogen or haloalkyl, but not all four of the meso atoms or groups being hydrogen. The invention also comprises new compositions of matter in which all four of the meso positions are substituted with haloalkyl groups and the beta positions are substituted with halogen atoms. A new method of synthesizing porphyrinogens is also provided. The novel compositions and others made according to the process of the invention are useful as hydrocarbon conversion catalysts; for example, for the oxidation of alkanes and the decomposition of hydroperoxides.

Porphyrins

DOEpatents

Wijesekera, Tilak; Lyons, James E.; Ellis, Jr., Paul E.

1996-01-01

The invention comprises new compositions of matter, which are iron, manganese, cobalt or ruthenium complexes of porphyrins having hydrogen, haloalkyl or haloaryl groups in meso positions, two of the opposed meso atoms or groups being hydrogen or haloaryl, and two of the opposed meso atoms or groups being hydrogen or haloalkyl, but not all four of the meso atoms or groups being hydrogen. The invention also comprises new compositions of matter in which all four of the meso positions are substituted with haloalkyl groups and the beta positions are substituted with halogen atoms. A new method of synthesizing porphyrinogens is also provided. The novel compositions and others made according to the process of the invention are useful as hydrocarbon conversion catalysts; for example, for the oxidation of alkanes and the decomposition of hydroperoxides.

Ab initio molecular dynamics simulation study of successive hydrogenation reactions of carbon monoxide producing methanol

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

Pham, Thi Nu; Ono, Shota; Ohno, Kaoru, E-mail: ohno@ynu.ac.jp

Doing ab initio molecular dynamics simulations, we demonstrate a possibility of hydrogenation of carbon monoxide producing methanol step by step. At first, the hydrogen atom reacts with the carbon monoxide molecule at the excited state forming the formyl radical. Formaldehyde was formed after adding one more hydrogen atom to the system. Finally, absorption of two hydrogen atoms to formaldehyde produces methanol molecule. This study is performed by using the all-electron mixed basis approach based on the time dependent density functional theory within the adiabatic local density approximation for an electronic ground-state configuration and the one-shot GW approximation for an electronicmore » excited state configuration.« less

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.

Spectroscopic study of uracil, 1-methyluracil and 1-methyl-4-thiouracil: Hydrogen bond interactions in crystals and ab-initio molecular dynamics.

PubMed

Brela, Mateusz Z; Boczar, Marek; Malec, Leszek M; Wójcik, Marek J; Nakajima, Takahito

2018-05-15

Hydrogen bond networks in uracil, 1-methyluracil and 1-methyl-4-thiouracil were studied by ab initio molecular dynamics as well as analysis of the orbital interactions. The power spectra calculated by ab initio molecular dynamics for atoms involved in hydrogen bonds were analyzed. We calculated spectra by using anharmonic approximation based on the autocorrelation function of the atom positions obtained from the Born-Oppenheimer simulations. Our results show the differences between hydrogen bond networks in uracil and its methylated derivatives. The studied methylated derivatives, 1-methyluracil as well as 1-methyl-4-thiouracil, form dimeric structures in the crystal phase, while uracil does not form that kind of structures. The presence of sulfur atom instead oxygen atom reflects weakness of the hydrogen bonds that build dimers. Copyright © 2018 Elsevier B.V. All rights reserved.

Measurements of the structure of an ionizing shock wave in a hydrogen-helium mixture

NASA Technical Reports Server (NTRS)

Leibowitz, L. P.

1972-01-01

Shock structure during ionization of a hydrogen-helium mixture was studied using hydrogen line and continuum emission measurements. A reaction scheme is proposed which includes hydrogen dissociation and a two-step excitation-ionization mechanism for hydrogen ionization by atom-atom and atom-electron collisions. Agreement was achieved between numerical calculations and measurements of emission intensity as a function of time for shock velocities from 13 to 20 km/sec in a 0.208 H2 - 0.792 He mixture. The electron temperature was found to be significantly different from the heavy particle temperature during much of the ionization process. Similar time histories for H beta and continuum emission indicate upper level populations of hydrogen in equilibrium with the electron concentration during the relaxation process.

Measurements of the structure of an ionizing shock wave in a hydrogen-helium mixture.

NASA Technical Reports Server (NTRS)

Leibowitz, L. P.

1973-01-01

Shock structure during ionization of a hydrogen-helium mixture has been followed using hydrogen line and continuum emission measurements. A reaction scheme is proposed which includes hydrogen dissociation and a two-step excitation-ionization mechanism for hydrogen ionization by atom-atom and atom-electron collisions. Agreement has been achieved between numerical calculations and measurements of emission intensity as a function of time for shock velocities from 13 to 20 km/sec in a 0.208 H2-0.792 He mixture. The electron temperature was found to be significantly different from the heavy particle temperature during much of the ionization process. Similar time histories for H beta and continuum emission indicate upper level populations of hydrogen in equilibrium with the electron concentration during the relaxation process.

2-Amino-5-chloro-pyrimidin-1-ium hydrogen maleate.

PubMed

Fun, Hoong-Kun; Hemamalini, Madhukar; Rajakannan, Venkatachalam

2012-01-01

In the title salt, C(4)H(5)ClN(3) (+)·C(4)H(3)O(4) (-), the 2-amino-5-chloro-pyrimidinium cation is protonated at one of its pyrimidine N atoms. In the roughly planar (r.m.s. deviation = 0.026 Å) hydrogen malate anion, an intra-molecular O-H⋯O hydrogen bond generates an S(7) ring. In the crystal, the protonated N atom and the 2-amino group of the cation are hydrogen bonded to the carboxyl-ate O atoms of the anion via a pair of N-H⋯O hydrogen bonds, forming an R(2) (2)(8) ring motif. The ion pairs are connected via further N-H⋯O hydrogen bonds and a short C-H⋯O inter-action, forming layers lying parallel to the bc plane.

Fully methylated, atomically flat (111) silicon surface

NASA Astrophysics Data System (ADS)

Fidélis, A.; Ozanam, F.; Chazalviel, J.-N.

2000-01-01

The atomically flat hydrogenated (111) silicon surface has been methylated by anodization in a Grignard reagent and the surface obtained characterized by infrared spectroscopy. 100% substitution of the hydrogen atoms by methyl groups is observed. The resulting surface exhibits preserved ordering and superior chemical stability.

Selective hydrogenation of 1,3-butadiene on platinum–copper alloys at the single-atom limit

DOE PAGES

Lucci, Felicia R.; Liu, Jilei; Marcinkowski, Matthew D.; ...

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.more » 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.« less

Hydrogen atoms in protein structures: high-resolution X-ray diffraction structure of the DFPase

PubMed Central

2013-01-01

Background Hydrogen atoms represent about half of the total number of atoms in proteins and are often involved in substrate recognition and catalysis. Unfortunately, X-ray protein crystallography at usual resolution fails to access directly their positioning, mainly because light atoms display weak contributions to diffraction. However, sub-Ångstrom diffraction data, careful modeling and a proper refinement strategy can allow the positioning of a significant part of hydrogen atoms. Results A comprehensive study on the X-ray structure of the diisopropyl-fluorophosphatase (DFPase) was performed, and the hydrogen atoms were modeled, including those of solvent molecules. This model was compared to the available neutron structure of DFPase, and differences in the protein and the active site solvation were noticed. Conclusions A further examination of the DFPase X-ray structure provides substantial evidence about the presence of an activated water molecule that may constitute an interesting piece of information as regard to the enzymatic hydrolysis mechanism. PMID:23915572

Shaped Ceria Nanocrystals Catalyze Efficient and Selective Para-Hydrogen-Enhanced Polarization.

PubMed

Zhao, Evan W; Zheng, Haibin; Zhou, Ronghui; Hagelin-Weaver, Helena E; Bowers, Clifford R

2015-11-23

Intense para-hydrogen-enhanced NMR signals are observed in the hydrogenation of propene and propyne over ceria nanocubes, nano-octahedra, and nanorods. The well-defined ceria shapes, synthesized by a hydrothermal method, expose different crystalline facets with various oxygen vacancy densities, which are known to play a role in hydrogenation and oxidation catalysis. While the catalytic activity of the hydrogenation of propene over ceria is strongly facet-dependent, the pairwise selectivity is low (2.4% at 375 °C), which is consistent with stepwise H atom transfer, and it is the same for all three nanocrystal shapes. Selective semi-hydrogenation of propyne over ceria nanocubes yields hyperpolarized propene with a similar pairwise selectivity of (2.7% at 300 °C), indicating product formation predominantly by a non-pairwise addition. Ceria is also shown to be an efficient pairwise replacement catalyst for propene. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

First-principles study of hydrogen-bonded molecular conductor κ -H3(Cat-EDT-TTF/ST)2

NASA Astrophysics Data System (ADS)

Tsumuraya, Takao; Seo, Hitoshi; Kato, Reizo; Miyazaki, Tsuyoshi

2015-07-01

We theoretically study hydrogen-bonded molecular conductors synthesized recently, κ -H3(Cat-EDT-TTF) 2 and its diselena analog, κ -H3(Cat-EDT-ST) 2, by first-principles density functional theory calculations. In these crystals, two H(Cat-EDT-TTF/ST) units share a hydrogen atom with a short O-H-O hydrogen bond. The calculated band structure near the Fermi level shows a quasi-two-dimensional character with a rather large interlayer dispersion due to the absence of insulating layers, in contrast with conventional molecular conductors. We discuss effective low-energy models based on H(Cat-EDT-TTF/ST) units and its dimers, respectively, where the microscopic character of the orbitals composing them are analyzed. Furthermore, we find a stable structure which is different from the experimentally determined structure, where the shared hydrogen atom becomes localized to one of the oxygen atoms, in which charge disproportionation between the two types of H(Cat-EDT-TTF) units is associated. The calculated potential energy surface for the H atom is very shallow near the minimum points; therefore the probability of the H atom can be delocalized between the two O atoms.

Effect of alcohol addition on shock-initiated formation of soot from benzene

NASA Technical Reports Server (NTRS)

Frenklach, Michael; Yuan, Tony

1988-01-01

Soot formation in benzene-methanol and benzene-ethanol argon-diluted mixtures was studied behind reflected shock waves by monitoring the attenuation of an He-Ne laser beam. The experiments were performed at temperatures 1580-2250 K, pressures 2.0-3.0 bar, and total carbon atom concentrations (2.0-2.7) x 10 to the 17th atoms/cu cm. The results obtained indicate that the addition of alcohol suppresses the formation of soot from benzene at all temperatures, and that the reduction in soot yields is increased with the amount of alcohol added. The analysis of the results indicates that the suppression effect is probably due to the oxidation of soot and soot precursors by OH and the removal of hydrogen atoms by alcohol and water molecules.

Properties of Surface-Modification Layer Generated by Atomic Hydrogen Annealing on Poly(ethylene naphthalate) Substrate

NASA Astrophysics Data System (ADS)

Heya, Akira; Matsuo, Naoto

2008-01-01

The surface of a poly(ethylene naphthalate) (PEN) substrate was modified by atomic hydrogen annealing (AHA). In this method, a PEN substrate was exposed to atomic hydrogen generated by cracking hydrogen molecules on heated tungsten wire. The properties of the surface-modification layer by AHA were evaluated by spectroscopic ellipsometry. It is found that the thickness of the modified layer was 5 nm and that the modification layer has a low refractive index compared with the PEN substrate. The modification layer relates to the reduction reaction of the PEN substrate by AHA.

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

Brady, Michael P.; Ievlev, Anton V.; Fayek, Mostafa

Hydrogen gas is formed when Mg corrodes in water; however, the manner and extent to which the hydrogen may also enter the Mg metal is poorly understood. Such knowledge is critical as stress corrosion cracking (SCC)/embrittlement phenomena limit many otherwise promising structural and functional uses of Mg. Here, we report via D 2O/D isotopic tracer and H 2O exposures with characterization by secondary ion mass spectrometry, inelastic neutron scattering vibrational spectrometry, electron microscopy, and atom probe tomography techniques direct evidence that hydrogen rapidly penetrated tens of micrometers into Mg metal after only 4 h of exposure to water at roommore » temperature. Further, technologically important microalloying additions of <1 wt % Zr and Nd used to improve the manufacturability and mechanical properties of Mg significantly increased the extent of hydrogen ingress, whereas Al additions in the 2–3 wt % range did not. Segregation of hydrogen species was observed at regions of high Mg/Zr/Nd nanoprecipitate density and at Mg(Zr) metastable solid solution microstructural features. We also report evidence that this ingressed hydrogen was unexpectedly present in the alloy as nanoconfined, molecular H 2. These new insights provide a basis for strategies to design Mg alloys to resist SCC in aqueous environments as well as potentially impact functional uses such as hydrogen storage where increased hydrogen uptake is desired.« less

Crystal structure of tetra­aqua­bis­(pyrimidin-1-ium-4,6-diolato-κO 4)manganese(II)

PubMed Central

Shennara, Khaled A.

2017-01-01

The MnII ion in the structure of the mononuclear title compound, [Mn(C4H3N2O2)2(H2O)4], is situated on an inversion center and is coordinated by two O atoms from two deprotonated 4,6-di­hydroxy­pyrimidine ligands and by four O atoms from water mol­ecules giving rise to a slightly distorted octa­hedral coordination sphere. The complex includes an intra­molecular hydrogen bond between an aqua ligand and the non-protonated N ring atom. The extended structure is stabilized by inter­molecular hydrogen bonds between aqua ligands, by hydrogen bonds between N and O atoms of the ligands of adjacent mol­ecules, and by hydrogen bonds between aqua ligands and the non-coordinating O atom of an adjacent mol­ecule. PMID:28435734

Gas-phase Reactivity of meta-Benzyne Analogs Toward Small Oligonucleotides of Differing Lengths

NASA Astrophysics Data System (ADS)

Widjaja, Fanny; Max, Joann P.; Jin, Zhicheng; Nash, John J.; Kenttämaa, Hilkka I.

2017-07-01

The gas-phase reactivity of two aromatic carbon-centered σ,σ-biradicals ( meta-benzyne analogs) and a related monoradical towards small oligonucleotides of differing lengths was investigated in a Fourier-transform ion cyclotron resonance (FT-ICR) mass spectrometer coupled with laser-induced acoustic desorption (LIAD). The mono- and biradicals were positively charged to allow for manipulation in the mass spectrometer. The oligonucleotides were evaporated into the gas phase as intact neutral molecules by using LIAD. One of the biradicals was found to be unreactive. The reactive biradical reacts with dinucleoside phosphates and trinucleoside diphosphates mainly by addition to a nucleobase moiety followed by cleavage of the glycosidic bond, leading to a nucleobase radical (e.g., base-H) abstraction. In some instances, after the initial cleavage, the unquenched radical site of the biradical abstracts a hydrogen atom from the neutral fragment, which results in a net nucleobase abstraction. In sharp contrast, the related monoradical mainly undergoes facile hydrogen atom abstraction from the sugar moiety. As the size of the oligonucleotides increases, the rate of hydrogen atom abstraction from the sugar moiety by the monoradical was found to increase due to the presence of more hydrogen atom donor sites, and it is the only reaction observed for tetranucleoside triphosphates. Hence, the monoradical only attacks sugar moieties in these substrates. The biradical also shows significant attack at the sugar moiety for tetranucleoside triphosphates. This drastic change in reactivity indicates that the size of the oligonucleotides plays a key role in the outcome of these reactions. This finding is attributed to more compact conformations in the gas phase for the tetranucleoside triphosphates than for the smaller oligonucleotides, which result from stronger stabilizing interactions between the nucleobases.

Quantitative structure-activity relationship for the oxidation of aromatic organic contaminants in water by TAML/H2O2.

PubMed

Su, Hanrui; Yu, Chunyang; Zhou, Yongfeng; Gong, Lidong; Li, Qilin; Alvarez, Pedro J J; Long, Mingce

2018-05-02

Tetra-amido macrocyclic ligand (TAML) activator is a functional analog of peroxidase enzymes, which activates hydrogen peroxide (H 2 O 2 ) to form high valence iron-oxo complexes that selectively degrade persistent aromatic organic contaminants (ACs) in water. Here, we develop quantitative structure-activity relationship (QSAR) models based on measured pseudo first-order kinetic rate coefficients (k obs ) of 29 ACs (e.g., phenols and pharmaceuticals) oxidized by TAML/H 2 O 2 at neutral and basic pH values to gain mechanistic insight on the selectivity and pH dependence of TAML/H 2 O 2 systems. These QSAR models infer that electron donating ability (E HOMO ) is the most important AC characteristic for TAML/H 2 O 2 oxidation, pointing to a rate-limiting single-electron transfer (SET) mechanism. Oxidation rates at pH 7 also depend on AC reactive indices such as f min - and qH + , which respectively represent propensity for electrophilic attack and the most positive net atomic charge on hydrogen atoms. At pH 10, TAML/H 2 O 2 is more reactive towards ACs with a lower hydrogen to carbon atoms ratio (#H:C), suggesting the significance of hydrogen atom abstraction. In addition, lnk obs of 14 monosubstituted phenols is negatively correlated with Hammett constants (σ) and exhibits similar sensitivity to substituent effects as horseradish peroxidase. Although accurately predicting degradation rates of specific ACs in complex wastewater matrices could be difficult, these QSAR models are statistically robust and help predict both relative degradability and reaction mechanism for TAML/H 2 O 2 -based treatment processes. Copyright © 2018 Elsevier Ltd. All rights reserved.

Loss of benzene to generate an enolate anion by a site-specific double-hydrogen transfer during CID fragmentation of o-alkyl ethers of ortho-hydroxybenzoic acids.

PubMed

Attygalle, Athula B; Bialecki, Jason B; Nishshanka, Upul; Weisbecker, Carl S; Ruzicka, Josef

2008-09-01

Collision-induced dissociation of anions derived from ortho-alkyloxybenzoic acids provides a facile way of producing gaseous enolate anions. The alkyloxyphenyl anion produced after an initial loss of CO(2) undergoes elimination of a benzene molecule by a double-hydrogen transfer mechanism, unique to the ortho isomer, to form an enolate anion. Deuterium labeling studies confirmed that the two hydrogen atoms transferred in the benzene loss originate from positions 1 and 2 of the alkyl chain. An initial transfer of a hydrogen atom from the C-1 position forms a phenyl anion and a carbonyl compound, both of which remain closely associated as an ion/neutral complex. The complex breaks either directly to give the phenyl anion by eliminating the neutral carbonyl compound, or to form an enolate anion by transferring a hydrogen atom from the C-2 position and eliminating a benzene molecule in the process. The pronounced primary kinetic isotope effect observed when a deuterium atom is transferred from the C-1 position, compared to the weak effect seen for the transfer from the C-2 position, indicates that the first transfer is the rate determining step. Quantum mechanical calculations showed that the neutral loss of benzene is a thermodynamically favorable process. Under the conditions used, only the spectra from ortho isomers showed peaks at m/z 77 for the phenyl anion and m/z 93 for the phenoxyl anion, in addition to that for the ortho-specific enolate anion. Under high collision energy, the ortho isomers also produce a peak at m/z 137 for an alkene loss. The spectra of meta and para compounds show a peak at m/z 92 for the distonic anion produced by the homolysis of the O-C bond. Moreover, a small peak at m/z 136 for a distonic anion originating from an alkyl radical loss allows the differentiation of para compounds from meta isomers.

Nitrated metalloporphyrins as catalysts for alkane oxidation

DOEpatents

Ellis, Jr., Paul E.; Lyons, James E.

1992-01-01

Alkanes are oxidized by contact with oxygen-containing gas in the presence as catalyst of a metalloporphyrin in which hydrogen atoms in the porphyrin ring have been replaced with one or more nitro groups. Hydrogen atoms in the porphyrin ring may also be substituted with halogen atoms.

Cyano- and polycyanometalloporphyrins as catalysts for alkane oxidation

DOEpatents

Ellis, Jr., Paul E.; Lyons, James E.

1992-01-01

Alkanes are oxidized by contact with oxygen-containing gas in the presence as catalyst of a metalloporphyrin in which hydrogen atoms in the porphyrin ring have been substituted with one or more cyano groups. Hydrogen atoms in the porphyrin ring may also be substituted with halogen atoms.

Inelastic Transitions in Slow Collisions of Anti-Hydrogen with Hydrogen Atoms

NASA Astrophysics Data System (ADS)

Harrison, Robert; Krstic, Predrag

2007-06-01

We calculate excited adiabatic states and nonadiabatic coupling matrix elements of a quasimolecular system containing hydrogen and anti-hydrogen atoms, for a range of internuclear distances from 0.2 to 20 Bohrs. High accuracy is achieved by exact diagonalization of the molecular Hamiltionian in a large Gaussian basis. Nonadiabatic dynamics was calculated by solving MOCC equations. Positronium states are included in the consideration.

Sc-Decorated Porous Graphene for High-Capacity Hydrogen Storage: First-Principles Calculations.

PubMed

Chen, Yuhong; Wang, Jing; Yuan, Lihua; Zhang, Meiling; Zhang, Cairong

2017-08-02

The generalized gradient approximation (GGA) function based on density functional theory is adopted to investigate the optimized geometrical structure, electron structure and hydrogen storage performance of Sc modified porous graphene (PG). It is found that the carbon ring center is the most stable adsorbed position for a single Sc atom on PG, and the maximum number of adsorbed H₂ molecules is four with the average adsorption energy of -0.429 eV/H₂. By adding a second Sc atom on the other side of the system, the hydrogen storage capacity of the system can be improved effectively. Two Sc atoms located on opposite sides of the PG carbon ring center hole is the most suitable hydrogen storage structure, and the hydrogen storage capacity reach a maximum 9.09 wt % at the average adsorption energy of -0.296 eV/H₂. The adsorption of H₂ molecules in the PG system is mainly attributed to orbital hybridization among H, Sc, and C atoms, and Coulomb attraction between negatively charged H₂ molecules and positively charged Sc atoms.

Sc-Decorated Porous Graphene for High-Capacity Hydrogen Storage: First-Principles Calculations

PubMed Central

Chen, Yuhong; Wang, Jing; Yuan, Lihua; Zhang, Meiling

2017-01-01

The generalized gradient approximation (GGA) function based on density functional theory is adopted to investigate the optimized geometrical structure, electron structure and hydrogen storage performance of Sc modified porous graphene (PG). It is found that the carbon ring center is the most stable adsorbed position for a single Sc atom on PG, and the maximum number of adsorbed H2 molecules is four with the average adsorption energy of −0.429 eV/H2. By adding a second Sc atom on the other side of the system, the hydrogen storage capacity of the system can be improved effectively. Two Sc atoms located on opposite sides of the PG carbon ring center hole is the most suitable hydrogen storage structure, and the hydrogen storage capacity reach a maximum 9.09 wt % at the average adsorption energy of −0.296 eV/H2. The adsorption of H2 molecules in the PG system is mainly attributed to orbital hybridization among H, Sc, and C atoms, and Coulomb attraction between negatively charged H2 molecules and positively charged Sc atoms. PMID:28767084

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

PubMed

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

2015-09-28

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

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

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

Bahar, M. K., E-mail: mussiv58@gmail.com

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 andmore » 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.« less

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

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

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

2015-09-28

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

A Comprehensive Study of Hydrogen Adsorbing to Amorphous Water ice: Defining Adsorption in Classical Molecular Dynamics

NASA Astrophysics Data System (ADS)

Dupuy, John L.; Lewis, Steven P.; Stancil, P. C.

2016-11-01

Gas-grain and gas-phase reactions dominate the formation of molecules in the interstellar medium (ISM). Gas-grain reactions require a substrate (e.g., a dust or ice grain) on which the reaction is able to occur. The formation of molecular hydrogen (H2) in the ISM is the prototypical example of a gas-grain reaction. In these reactions, an atom of hydrogen will strike a surface, stick to it, and diffuse across it. When it encounters another adsorbed hydrogen atom, the two can react to form molecular hydrogen and then be ejected from the surface by the energy released in the reaction. We perform in-depth classical molecular dynamics simulations of hydrogen atoms interacting with an amorphous water-ice surface. This study focuses on the first step in the formation process; the sticking of the hydrogen atom to the substrate. We find that careful attention must be paid in dealing with the ambiguities in defining a sticking event. The technical definition of a sticking event will affect the computed sticking probabilities and coefficients. Here, using our new definition of a sticking event, we report sticking probabilities and sticking coefficients for nine different incident kinetic energies of hydrogen atoms [5-400 K] across seven different temperatures of dust grains [10-70 K]. We find that probabilities and coefficients vary both as a function of grain temperature and incident kinetic energy over the range of 0.99-0.22.

Stark effect on an excited hydrogen atom

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

Barratt, C.

1983-07-01

The method of degenerate perturbation theory is used to study the dipolar nature of an excited hydrogen atom in an external electric field. The dependence of the atoms perturbed energy levels on the principal and magnetic quantum numbers, n and m, is investigated, along with the perturbed wave functions.

Preliminary results for a measurement of the n=2 Lamb shift in atomic hydrogen

NASA Astrophysics Data System (ADS)

Bezginov, N.; Valdez, T.; Vutha, A. C.; Kato, K.; Skinner, T. D. G.; Hessels, E. A.

2017-04-01

We perform a measurement of the Lamb shift in atomic hydrogen (n = 2 S1/2 F = 0 to P1/2 F = 1). A beam of protons moving at 0.01 c undergoes charge exchange with hydrogen gas to produce atomic hydrogen in the metastable 2S state. The atoms travel through two microwave regions where we utilize the novel technique of frequency offset separated oscillatory fields (FOSOF). The surviving 2S population is observed using a Lyman-alpha detector. The outcome of this experiment will lead to a measurement of the proton radius, contributing to the resolution of the proton radius puzzle. We present preliminary experimental results, along with systematic studies. This research is funded by NSERC, CRC, CFI and NIST.

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.

Determination of atomic hydrogen in non-thermal hydrogen plasmas by means of molecular beam threshold ionization mass spectrometry.

PubMed

Wang, Wei-Guo; Xu, Yong; Yang, Xue-Feng; Wang, Wen-Chun; Zhu, Ai-Min

2005-01-01

Atomic hydrogen plays important roles in chemical vapor deposition of functional materials, plasma etching and new approaches to chemical synthesis of hydrogen-containing compounds. The present work reports experimental determinations of atomic hydrogen near the grounded electrode in medium-pressure dielectric barrier discharge hydrogen plasmas by means of molecular beam threshold ionization mass spectrometry (MB-TIMS). At certain discharge conditions (a.c. frequency of 24 kHz, 28 kV of peak-to-peak voltage), the measured hydrogen dissociation fraction is decreased from approximately 0.83% to approximately 0.14% as the hydrogen pressure increases from 2.0 to 14.0 Torr. A simulation method for extraction of the approximate electron beam energy distribution function in the mass spectrometer ionizer and a semi-quantitative approach to calibrate the mass discrimination effect caused by the supersonic beam formation and the mass spectrometer measurement are reported. Copyright 2005 John Wiley & Sons, Ltd.

Causes of High-temperature Superconductivity in the Hydrogen Sulfide Electron-phonon System

NASA Astrophysics Data System (ADS)

Degtyarenko, N. N.; Mazur, E. A.

The electron and phonon spectra, as well as the density of electron and phonon states of the stable orthorhombic structure of hydrogen sulfide (SH2) at pressures 100-180 GPa have been calculated. It is found that the set of parallel planes of hydrogen atoms is formed at pressure ∼175 GPa as a result of structural changes in the unit cell of the crystal under pressure. There should be complete concentration of hydrogen atoms in these planes. As a result the electron properties of the system acquire a quasi-two-dimensional character. The features of in phase and antiphase oscillations of hydrogen atoms in these planes leading to two narrow high-energy peaks in the phonon density of states are investigated.

Reasons for high-temperature superconductivity in the electron-phonon system of hydrogen sulfide

NASA Astrophysics Data System (ADS)

Degtyarenko, N. N.; Mazur, E. A.

2015-08-01

We have calculated the electron and phonon spectra, as well as the densities of the electron and phonon states, of the stable orthorhombic structure of hydrogen sulfide SH2 in the pressure interval 100-180 GPa. It is found that at a pressure of 175 GPa, a set of parallel planes of hydrogen atoms is formed due to a structural modification of the unit cell under pressure with complete accumulation of all hydrogen atoms in these planes. As a result, the electronic properties of the system become quasi-two-dimensional. We have also analyzed the collective synphase and antiphase vibrations of hydrogen atoms in these planes, leading to the occurrence of two high-energy peaks in the phonon density of states.

Infrared spectroscopy of matrix-isolated neutral polycyclic aromatic nitrogen heterocycles: The acridine series.

PubMed

Mattioda, A L; Bauschlicher, C W; Ricca, A; Bregman, J; Hudgins, D M; Allamandola, L J

2017-06-15

The matrix-isolated, mid-infrared spectra of seven acridine-based polycyclic aromatic nitrogen heterocycles (PANHs) have been measured and compared to their non-nitrogen containing parent molecule. The acridine species investigated include acridine, benz[a]acridine, benz[c]acridine, dibenz[a,j]acridine, dibenz[c,h]acridine, dibenz[a,h]acridine and dibenz[a,c]acridine. The previously reported results for 1 and 2-azabenz[a]anthracenes are included for comparison. The experimentally determined band frequencies and intensities are compared with their B3LYP/6-31G(d) values. The overall agreement between experimental and theoretical values is good and in line with our previous investigations. Shifts, typically to the blue, are noted for the C-H out-of-plane (CH oop ) motions upon insertion of a nitrogen atom. The formation of a bay region upon addition of additional benzene rings to the anthracene/acridine structure splits the solo hydrogen motions into a bay region solo and an external solo hydrogen, with the bay region solo hydrogen coupling to the quartet hydrogen motions and the external solo hydrogen coupling with the duo hydrogen motions resulting in an extreme decrease in intensity for the CH oop solo hydrogen band when the external hydrogen is replaced by a nitrogen atom. The C-C and C-H in-plane region of this acridine series exhibits the characteristic two fold increase in intensity, noted previously for PANHs. The strong ≈1400cm -1 band, which was identified in the previous PANH study, is noted in several molecular species as well as another strong PANH feature between 1480 and 1515cm -1 for several molecules. The presence of these strong bands appear to be primarily responsible for the two-fold increase in the C-H in-plane region's (1100-1600cm -1 ) intensity. The C-H stretching region can be characterized by contributions from the solo (bay or external), duo and quartet hydrogens, similar to what was observed in the dibenzopolyacene compounds. Published by Elsevier B.V.

Derived properties from the dipole and generalized oscillator strength distributions of an endohedral confined hydrogen atom

NASA Astrophysics Data System (ADS)

Martínez-Flores, C.; Cabrera-Trujillo, R.

2018-03-01

We report the electronic properties of a hydrogen atom confined by a fullerene molecule by obtaining the eigenvalues and eigenfunctions of the time-independent Schrödinger equation by means of a finite-differences approach. The hydrogen atom confinement by a C60 fullerene cavity is accounted for by two model potentials: a square-well and a Woods-Saxon. The Woods-Saxon potential is implemented to study the role of a smooth cavity on the hydrogen atom generalized oscillator strength distribution. Both models characterize the cavity by an inner radius R 0, thickness Δ, and well depth V 0. We use two different values for R 0 and Δ, found in the literature, that characterize H@C60 to analyze the role of the fullerene cage size and width. The electronic properties of the confined hydrogen atom are reported as a function of the well depth V 0, emulating different electronic configurations of the endohedral cavity. We report results for the hyper-fine splitting, nuclear magnetic screening, dipole oscillator strength, the static and dynamic polarizability, mean excitation energy, photo-ionization, and stopping cross section for the confined hydrogen atom. We find that there is a critical potential well depth value around V 0 = 0.7 a.u. for the first set of parameters and around V 0 = 0.9 a.u. for the second set of parameters, which produce a drastic change in the electronic properties of the endohedral hydrogen system. These values correspond to the first avoided crossing on the energy levels. Furthermore, a clear discrepancy is found between the square-well and Woods-Saxon model potential results on the hydrogen atom generalized oscillator strength due to the square-well discontinuity. These differences are reflected in the stopping cross section for protons colliding with H@C60.

Quantitative characterization of new supramolecular synthons involving fluorine atoms in the crystal structures of di- and tetrafluorinated benzamides.

PubMed

Mondal, Pradip Kumar; Yadav, Hare Ram; Choudhury, Angshuman Roy; Chopra, Deepak

2017-10-01

Strong hydrogen bonds play a significant role in crystal packing. In particular, the involvement of interactions involving fluorine in controlling the crystal packing requires appropriate attention, especially in the presence of other strong hydrogen bonds. In the present study, a detailed quantitative assessment has been performed of the nature, energetics and topological properties derived from the electron density in model compounds based on fluorinated benzamides (a total of 46 fluorine-substituted benzamides containing multiple fluorine atoms) in the solid state. The primary motivation in the design of such molecules is to enhance the acidity of the interacting H atoms in the presence of an increasing number of F atoms on the molecular scaffold, resulting in increased propensity towards the formation of intermolecular interactions involving organic fluorine. This exercise has resulted in the identification of new and frequently occurring supramolecular synthons involving F atoms in the packing of molecules in the solid state. The energetics associated with short and directional intermolecular Csp 2 -H...F-Csp 2 interactions with significantly high electrostatic contributions is noteworthy, and the topological analysis reveals the bonding character of these ubiquitous interactions in crystal packing in addition to the presence of Csp 2 -F...F-Csp 2 contacts.

Thermal decomposition of silane to form hydrogenated amorphous Si

DOEpatents

Strongin, M.; Ghosh, A.K.; Wiesmann, H.J.; Rock, E.B.; Lutz, H.A. III

Hydrogenated amorphous silicon is produced by thermally decomposing silane (SiH/sub 4/) or other gases comprising H and Si, at elevated temperatures of about 1700 to 2300/sup 0/C, in a vacuum of about 10/sup -8/ to 10/sup -4/ torr. A gaseous mixture is formed of atomic hydrogen and atomic silicon. The gaseous mixture is deposited onto a substrate to form hydrogenated amorphous silicon.

Surface Engineering of a Supported PdAg Catalyst for Hydrogenation of CO2 to Formic Acid: Elucidating the Active Pd Atoms in Alloy Nanoparticles.

PubMed

Mori, Kohsuke; Sano, Taiki; Kobayashi, Hisayoshi; Yamashita, Hiromi

2018-06-22

The hydrogenation of carbon dioxide (CO 2 ) to formic acid (FA; HCOOH), a renewable hydrogen storage material, is a promising means of realizing an economical CO 2 -mediated hydrogen energy cycle. The development of reliable heter-ogeneous catalysts is an urgent yet challenging task associated with such systems, although precise catalytic site design protocols are still lacking. In the present study, we demonstrate that PdAg alloy nanoparticles (NPs) supported on TiO 2 promote the efficient selective hydrogenation of CO 2 to give FA even under mild reaction conditions (2.0 MPa, 100 °C). Specimens made using surface engineering with atomic precision reveal a strong correlation between increased cata-lytic activity and decreased electron density of active Pd atoms resulting from a synergistic effect of alloying with Ag atoms. The isolated and electronically promoted surface-exposed Pd atoms in Pd@Ag alloy NPs exhibit a maximum turnover number of 14,839 based on the quantity of surface Pd atoms, which represents a more than ten-fold increase compared to the activity of monometallic Pd/TiO 2 . Kinetic and density functional theory (DFT) calculations show that the attack on the C atom in HCO 3 - by a dissociated H atom over an active Pd site is the rate-determining step during this reaction, and this step is boosted by PdAg alloy NPs having a low Pd/Ag ratio.

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.

The hydrogen atom in D = 3 - 2ɛ dimensions

NASA Astrophysics Data System (ADS)

Adkins, Gregory S.

2018-06-01

The nonrelativistic hydrogen atom in D = 3 - 2 ɛ dimensions is the reference system for perturbative schemes used in dimensionally regularized nonrelativistic effective field theories to describe hydrogen-like atoms. Solutions to the D-dimensional Schrödinger-Coulomb equation are given in the form of a double power series. Energies and normalization integrals are obtained numerically and also perturbatively in terms of ɛ. The utility of the series expansion is demonstrated by the calculation of the divergent expectation value <(V‧)2 >.

Rapid Diffusion and Nanosegregation of Hydrogen in Magnesium Alloys from Exposure to Water.

PubMed

Brady, Michael P; Ievlev, Anton V; Fayek, Mostafa; Leonard, Donovan N; Frith, Matthew G; Meyer, Harry M; Ramirez-Cuesta, Anibal J; Daemen, Luke L; Cheng, Yongqiang; Guo, Wei; Poplawsky, Jonathan D; Ovchinnikova, Olga S; Thomson, Jeffrey; Anovitz, Lawrence M; Rother, Gernot; Shin, Dongwon; Song, Guang-Ling; Davis, Bruce

2017-11-01

Hydrogen gas is formed when Mg corrodes in water; however, the manner and extent to which the hydrogen may also enter the Mg metal is poorly understood. Such knowledge is critical as stress corrosion cracking (SCC)/embrittlement phenomena limit many otherwise promising structural and functional uses of Mg. Here, we report via D 2 O/D isotopic tracer and H 2 O exposures with characterization by secondary ion mass spectrometry, inelastic neutron scattering vibrational spectrometry, electron microscopy, and atom probe tomography techniques direct evidence that hydrogen rapidly penetrated tens of micrometers into Mg metal after only 4 h of exposure to water at room temperature. Further, technologically important microalloying additions of <1 wt % Zr and Nd used to improve the manufacturability and mechanical properties of Mg significantly increased the extent of hydrogen ingress, whereas Al additions in the 2-3 wt % range did not. Segregation of hydrogen species was observed at regions of high Mg/Zr/Nd nanoprecipitate density and at Mg(Zr) metastable solid solution microstructural features. We also report evidence that this ingressed hydrogen was unexpectedly present in the alloy as nanoconfined, molecular H 2 . These new insights provide a basis for strategies to design Mg alloys to resist SCC in aqueous environments as well as potentially impact functional uses such as hydrogen storage where increased hydrogen uptake is desired.

Rapid Diffusion and Nanosegregation of Hydrogen in Magnesium Alloys from Exposure to Water

DOE PAGES

Brady, Michael P.; Ievlev, Anton V.; Fayek, Mostafa; ...

2017-10-10

Hydrogen gas is formed when Mg corrodes in water; however, the manner and extent to which the hydrogen may also enter the Mg metal is poorly understood. Such knowledge is critical as stress corrosion cracking (SCC)/embrittlement phenomena limit many otherwise promising structural and functional uses of Mg. Here, we report via D 2O/D isotopic tracer and H 2O exposures with characterization by secondary ion mass spectrometry, inelastic neutron scattering vibrational spectrometry, electron microscopy, and atom probe tomography techniques direct evidence that hydrogen rapidly penetrated tens of micrometers into Mg metal after only 4 h of exposure to water at roommore » temperature. Further, technologically important microalloying additions of <1 wt % Zr and Nd used to improve the manufacturability and mechanical properties of Mg significantly increased the extent of hydrogen ingress, whereas Al additions in the 2–3 wt % range did not. Segregation of hydrogen species was observed at regions of high Mg/Zr/Nd nanoprecipitate density and at Mg(Zr) metastable solid solution microstructural features. We also report evidence that this ingressed hydrogen was unexpectedly present in the alloy as nanoconfined, molecular H 2. These new insights provide a basis for strategies to design Mg alloys to resist SCC in aqueous environments as well as potentially impact functional uses such as hydrogen storage where increased hydrogen uptake is desired.« less

Microstructure and high-temperature tribological properties of Si-doped hydrogenated diamond-like carbon films

NASA Astrophysics Data System (ADS)

Zhang, Teng Fei; Wan, Zhi Xin; Ding, Ji Cheng; Zhang, Shihong; Wang, Qi Min; Kim, Kwang Ho

2018-03-01

Si-doped DLC films have attracted great attention for use in tribological applications. However, their high-temperature tribological properties remain less investigated, especially in harsh oxidative working conditions. In this study, Si-doped hydrogenated DLC films with various Si content were synthesized and the effects of the addition of Si on the microstructural, mechanical and high-temperature tribological properties of the films were investigated. The results indicate that Si doping leads to an obvious increase in the sp3/sp2 ratio of DLC films, likely due to the silicon atoms preferentially substitute the sp2-hybridized carbon atoms and augment the number of sp3 sites. With Si doping, the mechanical properties, including hardness and adhesion strength, were improved, while the residual stress of the DLC films was reduced. The addition of Si leads to higher thermal and mechanical stability of DLC films because the Si atoms inhibit the graphitization of the films at an elevated temperature. Better high-temperature tribological properties of the Si-DLC films under oxidative conditions were observed, which can be attributed to the enhanced thermal stability and formation of a Si-containing lubricant layer on the surfaces of the wear tracks. The nano-wear resistance of the DLC films was also improved by Si doping.

Characterization of Ar/N2/H2 middle-pressure RF discharge and application of the afterglow region for nitridation of GaAs

NASA Astrophysics Data System (ADS)

Raud, J.; Jõgi, I.; Matisen, L.; Navrátil, Z.; Talviste, R.; Trunec, D.; Aarik, J.

2017-12-01

This work characterizes the production and destruction of nitrogen and hydrogen atoms in RF capacitively coupled middle-pressure discharge in argon/nitrogen/hydrogen mixtures. Input power, electron concentration, electric field strength and mean electron energy were determined on the basis of electrical measurements. Gas temperature and concentration of Ar atoms in 1s states were determined from spectral measurements. On the basis of experimentally determined plasma characteristics, main production and loss mechanisms of H and N atoms were discussed. The plasma produced radicals were applied for the nitridation and oxide reduction of gallium arsenide in the afterglow region of discharge. After plasma treatment the GaAs samples were analyzed using x-ray photoelectron spectroscopy (XPS) technique. Successful nitridation of GaAs sample was obtained in the case of Ar/5% N2 discharge. In this gas mixture the N atoms were generated via dissociative recombination of N2+ created by charge transfer from Ar+. The treatment in Ar/5% N2/1% H2 mixture resulted in the reduction of oxide signals in the XPS spectra. Negligible formation of GaN in the latter mixture was connected with reduced concentration of N atoms, which was, in turn, due to less efficient mechanism of N atom production (electron impact dissociation of N2 molecules) and additional loss channel in reaction with H2.

Hydrogen-bonding Interactions between Apigenin and Ethanol/Water: A Theoretical Study

NASA Astrophysics Data System (ADS)

Zheng, Yan-Zhen; Zhou, Yu; Liang, Qin; Chen, Da-Fu; Guo, Rui; Lai, Rong-Cai

2016-10-01

In this work, hydrogen-bonding interactions between apigenin and water/ethanol were investigated from a theoretical perspective using quantum chemical calculations. Two conformations of apigenin molecule were considered in this work. The following results were found. (1) For apigenin monomer, the molecular structure is non-planar, and all of the hydrogen and oxygen atoms can be hydrogen-bonding sites. (2) Eight and seven optimized geometries are obtained for apigenin (I)-H2O/CH3CH2OH and apigenin (II)-H2O/CH3CH2OH complexes, respectively. In apigenin, excluding the aromatic hydrogen atoms in the phenyl substituent, all other hydrogen atoms and the oxygen atoms form hydrogen-bonds with H2O and CH3CH2OH. (3) In apigenin-H2O/CH3CH2OH complexes, the electron density and the E(2) in the related localized anti-bonding orbital are increased upon hydrogen-bond formation. These are the cause of the elongation and red-shift of the X-H bond. The sum of the charge change transfers from the hydrogen-bond acceptor to donor. The stronger interaction makes the charge change more intense than in the less stable structures. (4) Most of the hydrogen-bonds in the complexes are electrostatic in nature. However, the C4-O5···H, C9-O4···H and C13-O2···H hydrogen-bonds have some degree of covalent character. Furthermore, the hydroxyl groups of the apigenin molecule are the preferred hydrogen-bonding sites.

Surface Treatment of Plastic Substrates using Atomic Hydrogen Generated on Heated Tungsten Wire at Low Temperatures

NASA Astrophysics Data System (ADS)

Heya, Akira; Matsuo, Naoto

2007-06-01

The surface properties of a plastic substrate were changed by a novel surface treatment called atomic hydrogen annealing (AHA). In this method, a plastic substrate was exposed to atomic hydrogen generated by cracking hydrogen molecules on heated tungsten wire. For the substrate, surface roughness was increased and halogen elements (F and Cl) were selectively etched by AHA. AHA was useful for pretreatment before film deposition on a plastic substrate because the changes in surface state relate to adhesion improvement. It is concluded that this method is a promising technique for preparing high-performance plastic substrates at low temperatures.

Hydrogen bonding between hydrides of the upper-right part of the periodic table

NASA Astrophysics Data System (ADS)

Simončič, Matjaž; Urbic, Tomaz

2018-05-01

One of the most important electrostatic interactions between molecules is most definitely the hydrogen bond. Understanding the basis of this interaction may offer us the insight needed to understand its effect on the macroscopic scale. Hydrogen bonding is for example the reason for anomalous properties in compounds like water and naturally life as we know it. The strength of the bond depends on numerous factors, among them the electronegativity of participating atoms. In this work we calculated the strength of hydrogen bonds between hydrides of the upper-right part of the periodic table (C, N, O, F, P, S, Cl, As, Se, Br) using quantum-chemical methods. The aim was to determine what influences the strength of strong and weak hydrogen bonds in simple hydrides. Various relationships were checked. A relation between the strength of the bond and the electronegativity of the participating atoms was found. We also observed a correlation between the strength of hydrogen bonds and the inter-atomic distances, along with the dependence on the charge transfer on the atom of the donor. We also report characteristic geometries of different dimers.

Studies of EUV contamination mitigation

NASA Astrophysics Data System (ADS)

Graham, Samual, Jr.; Malinowski, Michael E.; Steinhaus, Chip; Grunow, Philip A.; Klebanoff, Leonard E.

2002-07-01

Carbon contamination removal was investigated using remote RF-O2, RF-H2, and atomic hydrogen experiments. Samples consisted of silicon wafers coated with 100 Angstrom sputtered carbon, as well as bare Si-capped Mo/Si optics. Samples were exposed to atomic hydrogen or RF plasma discharges at 100 W, 200 W, and 300 W. Carbon removal rate, optic oxidation rate, at-wavelength (13.4 nm) peak reflectance, and optic surface roughness were characterized. Data show that RF- O2 removes carbon at a rate approximately 6 times faster RF- H2 for a given discharge power. However, both cleaning techniques induce Mo/Si optic degradation through the loss of reflectivity associated with surface oxide growth for RF-O2 and an unknown mechanism with hydrogen cleaning. Atomic hydrogen cleaning shows carbon removal rates sufficient for use as an in-situ cleaning strategy for EUVoptics with less risk of optic degradation from overexposures than RF-discharge cleaning. While hydrogen cleaning (RF and atomic) of EUV optics has proven effective in carbon removal, attempts to dissociate hydrogen in co-exposures with EUV radiation have resulted in no detectable removal of carbon contamination.

Measurement of the Lamb shift in the hydrogen atom (n = 2)

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

Sokolov, Y.L.; Yakovlev, V.P.

1982-07-01

A principle is proposed for the observation of the stationary interference pattern of two phase-shifted components of the 2p (or 2s) state of the hydrogen atom (Yu. L. Sokolov, Sov. Phys. JETP 36, 243 (1973)); (Proc. 6-th Internat. Conf. on Atomic Phys., Riga, 1978, p. 207). An atomic interferometer, a device analogous in principle to a two-channel optical (such as Michelson's) interferometer, is used to measure the frequency of the (2s/sub 1/2/, F = 0)--(2p/sub 1/2/, F = 0) transition in the hydrogen atom, which is found to equal 909.9014 +- 0.0019 MHz. The corresponding Lamb shift is delta(H, nmore » = 2) = 1057.8594 +- 0.0019 MHz.« less

Modeling inelastic phonon scattering in atomic- and molecular-wire junctions

NASA Astrophysics Data System (ADS)

Paulsson, Magnus; Frederiksen, Thomas; Brandbyge, Mads

2005-11-01

Computationally inexpensive approximations describing electron-phonon scattering in molecular-scale conductors are derived from the nonequilibrium Green’s function method. The accuracy is demonstrated with a first-principles calculation on an atomic gold wire. Quantitative agreement between the full nonequilibrium Green’s function calculation and the newly derived expressions is obtained while simplifying the computational burden by several orders of magnitude. In addition, analytical models provide intuitive understanding of the conductance including nonequilibrium heating and provide a convenient way of parameterizing the physics. This is exemplified by fitting the expressions to the experimentally observed conductances through both an atomic gold wire and a hydrogen molecule.

Hydrogen-Antihydrogen Collisions at Cold Temperatures

NASA Astrophysics Data System (ADS)

Zygelman, Bernard

2001-05-01

With the CERN anti-proton de-accelerator now on line, it is anticipated that antihydrogen ( \\overline H) atoms will be created, cooled, and stored in large numbers (M. H. Holzscheitner and M. Charlton, Rep. Prog. Phys. 62),1 (1999). It has recently been proposed that the introduction of cold, spin-polarized, hydrogen atoms into a gas of trapped anti-hydrogen could allow the sympathetic cooling of the anti-hydrogen into the sub-Kelvin regime (P. Froelich, S. Jonsell, A.Saenz, B. Zygelman, and A. Dalgarno, Phys. Rev. Lett. 84), 4577 (2000). In this talk we will present the results of calculations that estimate the rate of elastic scattering of H with \\overline H, and compare that to the rate in which the fragmentation reaction, H + \\overline H arrow p \\overline p + e^+ e^- occurs and limits the utility of sympathetic cooling. Unlike the ground state of the H2 system, the H \\overline H system possesses a non-vanishing electric dipole moment (B. Zygelman, A. Saenz, P. Froelich, S. Jonsell and A. Dalgarno, Phys. Rev. A, in Press (2001).) that allows for the additional inelastic reaction H + \\overline H arrow H\\overline H^* + h ν , where H \\overline H^* is a quasi-bound state of the hydrogen-antihydrogen complex. The rate for radiative association into quasi-bound states of the H \\overline H^* complex will be presented and we will explore the viability for the spectroscopic study of this novel four-body matter-antimatter system. Collaborators in this study include, A. Dalgarno, P. Froelich, A. Saenz and S. Jonsell. I wish to thank the Institute for Theoretical Atomic and Molecular Physics (ITAMP) for their hospitality and support during sabbatical leave where part of this work was done. Partial support was provided by NSF grants to the Smithsonian Institution and Harvard University for ITAMP.

Nanoscopic morphological changes in yeast cell surfaces caused by oxidative stress: an atomic force microscopic study.

PubMed

Canetta, Elisabetta; Walker, Graeme M; Adya, Ashok K

2009-06-01

Nanoscopic changes in the cell surface morphology of the yeasts Saccharomyces cerevisiae (strain NCYC 1681) and Schizosaccharomyces pombe (strain DVPB 1354), due to their exposure to varying concentrations of hydrogen peroxide (oxidative stress), were investigated using an atomic force microscope (AFM). Increasing hydrogen peroxide concentration led to a decrease in cell viabilities and mean cell volumes, and an increase in the surface roughness of the yeasts. In addition, AFM studies revealed that oxidative stress caused cell compression in both S. cerevisiae and Schiz. pombe cells and an increase in the number of aged yeasts. These results confirmed the importance and usefulness of AFM in investigating the morphology of stressed microbial cells at the nanoscale. The results also provided novel information on the relative oxidative stress tolerance of S. cerevisiae and Schiz. pombe.

A theoretical study on the mechanism and dynamics of reactions (CF3)2CHOCH2F/(CF3)2CHOCHF2 with OH radical

NASA Astrophysics Data System (ADS)

Wang, Chunzhang; Wen, Jinmiao; He, Hongqing; Wang, Li

2014-11-01

The information related with the mechanism of reactions (CF3)2CHOCH2F + OH (R1) and (CF3)2CHOCHF2 + OH (R2) was explored theoretically at the BMC-CCSD//BMK/6-311 + G(d,p) level. Based on the optimised structures, energies, and other information, the rate constants were evaluated by the canonical variational transition-state theory with small curvature tunneling contributions in a temperature range of 220-2000 K. For each reaction, there are both hydrogen-abstraction and displacement channels. In addition, more than one hydrogen atom can be abstracted. The relationship between hydrogen abstraction and displacement, between different hydrogen-abstraction channels, and between reactions R1 and R2 are elucidated.

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.

THE DYNAMICS OF HYDROGEN ATOM ABSTRACTION FROM POLYATOMIC MOLECULES.

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

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,more » 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.« less

Nitrogen diffusion in hafnia and the impact of nitridation on oxygen and hydrogen diffusion: A first-principles study

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

Sathiyanarayanan, Rajesh, E-mail: rajessat@in.ibm.com, E-mail: rajesh.sathiyanarayanan@gmail.com; Pandey, R. K.; Murali, K. V. R. M.

2015-01-21

Using first-principles simulations, we have computed incorporation energies and diffusion barriers of ammonia, the nitrogen molecule and atomic nitrogen in monoclinic hafnia (m-HfO{sub 2}). Our calculations show that ammonia is likely to dissociate into an NH{sub 2} molecular unit, whereas the nitrogen molecule remains as a molecule either in the interstitial space or at an oxygen lattice site. The lowest energy pathway for the diffusion of atomic nitrogen interstitials consists of the hopping of the nitrogen interstitial between neighboring three-coordinated lattice oxygen atoms that share a single Hf atom, and the barrier for such hops is determined by a switchingmore » mechanism. The substitutional nitrogen atom shows a preference for diffusion through the doubly positive oxygen vacancy-mediated mechanism. Furthermore, we have investigated the impact of nitrogen atoms on the diffusion barriers of oxygen and hydrogen interstitials in m-HfO{sub 2}. Our results show that nitrogen incorporation has a significant impact on the barriers for oxygen and hydrogen diffusion: nitrogen atoms attract oxygen and hydrogen interstitials diffusing in the vicinity, thereby slowing down (reducing) their diffusion (diffusion length)« less

Polymethoxyflavones: Novel β-Secretase (BACE1) Inhibitors from Citrus Peels.

PubMed

Youn, Kumju; Yu, Yoonjin; Lee, Jinhyuk; Jeong, Woo-Sik; Ho, Chi-Tang; Jun, Mira

2017-09-04

Beta-site amyloid precursor protein (APP) cleaving enzyme1 (BACE1) catalyzes the rate-limiting step of amyloid-β protein (Aβ) generation, and is considered as a prime target for Alzheimer's disease (AD). In search of a candidate for AD prevention, our efforts exploring the natural BACE1 inhibitor have led to the finding of nobiletin, tangeretin, and sinensetin-representative compounds of polymethoxyflavones (PMFs). Tangeretin exhibited the strongest BACE1 inhibition (IC 50 , 4.9 × 10 -5 M), followed by nobiletin and sinensetin with IC 50 values of 5.9 × 10 -5 M and 6.3 × 10 -5 M, respectively. In addition, all compounds reacted in a non-competitive manner with the substrate. Docking analysis results for complexes with BACE1 indicated that SER10 and THR232 residues of BACE1 hydrogen bonded with two oxygen atoms of tangeretin, while three additional BACE1 residues (ALA157, VAL336 and THR232) interacted with three oxygen atoms of nobiletin. Furthermore, sinensetin formed four hydrogen bonds through nitrogen atoms of TYR71, LYS75, and TRP76, and an oxygen atom of TYR198. Furthermore, the lowest-energy conformations of the most proposed complexes of sinensetin, nobiletin, and tangeretin with BACE1 were -7.2, -7.0, and -6.8 kcal/mol, respectively. Taken together, our results suggest that these polymethoxyflavones (PMFs) might be considered as promising BACE1 inhibitory agents that could lower Aβ production in AD.

Polymethoxyflavones: Novel β-Secretase (BACE1) Inhibitors from Citrus Peels

PubMed Central

Youn, Kumju; Yu, Yoonjin; Lee, Jinhyuk; Jeong, Woo-Sik; Ho, Chi-Tang; Jun, Mira

2017-01-01

Beta-site amyloid precursor protein (APP) cleaving enzyme1 (BACE1) catalyzes the rate-limiting step of amyloid-β protein (Aβ) generation, and is considered as a prime target for Alzheimer’s disease (AD). In search of a candidate for AD prevention, our efforts exploring the natural BACE1 inhibitor have led to the finding of nobiletin, tangeretin, and sinensetin—representative compounds of polymethoxyflavones (PMFs). Tangeretin exhibited the strongest BACE1 inhibition (IC50, 4.9 × 10−5 M), followed by nobiletin and sinensetin with IC50 values of 5.9 × 10−5 M and 6.3 × 10−5 M, respectively. In addition, all compounds reacted in a non-competitive manner with the substrate. Docking analysis results for complexes with BACE1 indicated that SER10 and THR232 residues of BACE1 hydrogen bonded with two oxygen atoms of tangeretin, while three additional BACE1 residues (ALA157, VAL336 and THR232) interacted with three oxygen atoms of nobiletin. Furthermore, sinensetin formed four hydrogen bonds through nitrogen atoms of TYR71, LYS75, and TRP76, and an oxygen atom of TYR198. Furthermore, the lowest-energy conformations of the most proposed complexes of sinensetin, nobiletin, and tangeretin with BACE1 were −7.2, −7.0, and −6.8 kcal/mol, respectively. Taken together, our results suggest that these polymethoxyflavones (PMFs) might be considered as promising BACE1 inhibitory agents that could lower Aβ production in AD. PMID:28869548

Paradoxical roles of hydrogen in electrochemical performance of graphene: High rate capacity and atomistic origins

DOE PAGES

Ye, Jianchao C.; Ong, Mitchell T.; Heo, Tae Wook; ...

2015-11-05

Atomic hydrogen exists ubiquitously in graphene materials made by chemical methods. Yet determining the effect of hydrogen on the electrochemical performance of graphene remains a significant challenge. Here we report the experimental observations of high rate capacity in hydrogen-treated 3-dimensional (3D) graphene nanofoam electrodes for lithium ion batteries. Structural and electronic characterization suggests that defect sites and hydrogen play synergistic roles in disrupting sp 2 graphene to facilitate fast lithium transport and reversible surface binding, as evidenced by the fast charge-transfer kinetics and increased capacitive contribution in hydrogen-treated 3D graphene. In concert with experiments, multiscale calculations reveal that defect complexesmore » in graphene are prerequisite for low-temperature hydrogenation, and that the hydrogenation of defective or functionalized sites at strained domain boundaries plays a beneficial role in improving rate capacity by opening gaps to facilitate easier Li penetration. Additional reversible capacity is provided by enhanced lithium binding near hydrogen-terminated edge sites. Furthermore, these findings provide qualitative insights in helping the design of graphene-based materials for high-power electrodes.« less

Universal roles of hydrogen in electrochemical performance of graphene: high rate capacity and atomistic origins

PubMed Central

Ye, Jianchao; Ong, Mitchell T.; Heo, Tae Wook; Campbell, Patrick G.; Worsley, Marcus A.; Liu, Yuanyue; Shin, Swanee J.; Charnvanichborikarn, Supakit; Matthews, Manyalibo J.; Bagge-Hansen, Michael; Lee, Jonathan R.I.; Wood, Brandon C.; Wang, Y. Morris

2015-01-01

Atomic hydrogen exists ubiquitously in graphene materials made by chemical methods. Yet determining the effect of hydrogen on the electrochemical performance of graphene remains a significant challenge. Here we report the experimental observations of high rate capacity in hydrogen-treated 3-dimensional (3D) graphene nanofoam electrodes for lithium ion batteries. Structural and electronic characterization suggests that defect sites and hydrogen play synergistic roles in disrupting sp2 graphene to facilitate fast lithium transport and reversible surface binding, as evidenced by the fast charge-transfer kinetics and increased capacitive contribution in hydrogen-treated 3D graphene. In concert with experiments, multiscale calculations reveal that defect complexes in graphene are prerequisite for low-temperature hydrogenation, and that the hydrogenation of defective or functionalized sites at strained domain boundaries plays a beneficial role in improving rate capacity by opening gaps to facilitate easier Li penetration. Additional reversible capacity is provided by enhanced lithium binding near hydrogen-terminated edge sites. These findings provide qualitative insights in helping the design of graphene-based materials for high-power electrodes. PMID:26536830

Quantum Monte Carlo study of the phase diagram of solid molecular hydrogen at extreme pressures

PubMed Central

Drummond, N. D.; Monserrat, Bartomeu; Lloyd-Williams, Jonathan H.; Ríos, P. López; Pickard, Chris J.; Needs, R. J.

2015-01-01

Establishing the phase diagram of hydrogen is a major challenge for experimental and theoretical physics. Experiment alone cannot establish the atomic structure of solid hydrogen at high pressure, because hydrogen scatters X-rays only weakly. Instead, our understanding of the atomic structure is largely based on density functional theory (DFT). By comparing Raman spectra for low-energy structures found in DFT searches with experimental spectra, candidate atomic structures have been identified for each experimentally observed phase. Unfortunately, DFT predicts a metallic structure to be energetically favoured at a broad range of pressures up to 400 GPa, where it is known experimentally that hydrogen is non-metallic. Here we show that more advanced theoretical methods (diffusion quantum Monte Carlo calculations) find the metallic structure to be uncompetitive, and predict a phase diagram in reasonable agreement with experiment. This greatly strengthens the claim that the candidate atomic structures accurately model the experimentally observed phases. PMID:26215251

Concentration of atomic hydrogen in a dielectric barrier discharge measured by two-photon absorption fluorescence

NASA Astrophysics Data System (ADS)

Dvořák, P.; Talába, M.; Obrusník, A.; Kratzer, J.; Dědina, J.

2017-08-01

Two-photon absorption laser-induced fluorescence (TALIF) was utilized for measuring the concentration of atomic hydrogen in a volume dielectric barrier discharge (DBD) ignited in mixtures of Ar, H2 and O2 at atmospheric pressure. The method was calibrated by TALIF of krypton diluted in argon at atmospheric pressure, proving that three-body collisions had a negligible effect on quenching of excited krypton atoms. The diagnostic study was complemented with a 3D numerical model of the gas flow and a zero-dimensional model of the chemistry in order to better understand the reaction kinetics and identify the key pathways leading to the production and destruction of atomic hydrogen. It was determined that the density of atomic hydrogen in Ar-H2 mixtures was in the order of 1021 m-3 and decreased when oxygen was added into the gas mixture. Spatially resolved measurements and simulations revealed a sharply bordered region with low atomic hydrogen concentration when oxygen was added to the gas mixture. At substoichiometric oxygen/hydrogen ratios, this H-poor region is confined to an area close to the gas inlet and it is shown that the size of this region is not only influenced by the chemistry but also by the gas flow patterns. Experimentally, it was observed that a decrease in H2 concentration in the feeding Ar-H2 mixture led to an increase in H production in the DBD.

The quantization of the atom in three acts

NASA Astrophysics Data System (ADS)

Ridgen, J. S.

2001-01-01

The challenge that faced physicists soon after the discovery of the quantum in 1900 was to determine the structure of the atom. Success came through the application of quantum ideas to this challenge. The focus of these efforts was the hydrogen atom. Three very different approaches led to the successful explanation of the Balmer series of hydrogen and, in the process, the foundation for atomic and molecular physics was established.

Palladium-Catalyzed Atom-Transfer Radical Cyclization at Remote Unactivated C(sp3 )-H Sites: Hydrogen-Atom Transfer of Hybrid Vinyl Palladium Radical Intermediates.

PubMed

Ratushnyy, Maxim; Parasram, Marvin; Wang, Yang; Gevorgyan, Vladimir

2018-03-01

A novel mild, visible-light-induced palladium-catalyzed hydrogen atom translocation/atom-transfer radical cyclization (HAT/ATRC) cascade has been developed. This protocol involves a 1,5-HAT process of previously unknown hybrid vinyl palladium radical intermediates, thus leading to iodomethyl carbo- and heterocyclic structures. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

NMR investigation of substituent effects on strength the intramolecular hydrogen bonding interaction in X-phenylhydrazones switches: A theoretical study

NASA Astrophysics Data System (ADS)

Gholipour, Alireza; Sadat Neyband, Razeih; Farhadi, Saeed

2017-05-01

We proved by computational NMR data the effect of electron-withdrawing and donating substituents on sbnd H⋯Nsbnd and sbnd H⋯Osbnd intramolecular hydrogen bond of the E and Z isomers in X-phenylhydrazones switches. These interactions were analyzed in detail in terms of the energetic and geometrical parameters properties. In addition, atoms in molecules (AIM) and natural bond orbital (NBO) were also employed to characterize the interactions and to examine the strengthening of the interactions. Computational results indicate an enhanced hydrogen bond for all substituted related to an unsubstituted case. There are good relationships between the NMR, AIM, NBO, energy data and Hammett constants.

Higher order Stark effect and transition probabilities on hyperfine structure components of hydrogen like atoms

NASA Astrophysics Data System (ADS)

Pal'Chikov, V. G.

2000-08-01

A quantum-electrodynamical (QED) perturbation theory is developed for hydrogen and hydrogen-like atomic systems with interaction between bound electrons and radiative field being treated as the perturbation. The dependence of the perturbed energy of levels on hyperfine structure (hfs) effects and on the higher-order Stark effect is investigated. Numerical results have been obtained for the transition probability between the hfs components of hydrogen-like bismuth.

Elementary defects in graphane

NASA Astrophysics Data System (ADS)

Podlivaev, A. I.; Openov, L. A.

2017-07-01

The main zero-dimensional defects in graphane, a completely hydrogenated single-layer graphene, having the chair-type conformation have been numerically simulated. The hydrogen and carbon-hydrogen vacancies, Stone-Wales defect, and "transmutation defect" resulting from the simultaneous hoppings of two hydrogen atoms between the neighboring carbon atoms have been considered. The energies of formations of these defects have been calculated and their effect on the electronic structure, phonon spectra, and Young modulus has been studied.

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.

Direct observation of individual hydrogen atoms at trapping sites in a ferritic steel

NASA Astrophysics Data System (ADS)

Chen, Y.-S.; Haley, D.; Gerstl, S. S. A.; London, A. J.; Sweeney, F.; Wepf, R. A.; Rainforth, W. M.; Bagot, P. A. J.; Moody, M. P.

2017-03-01

The design of atomic-scale microstructural traps to limit the diffusion of hydrogen is one key strategy in the development of hydrogen-embrittlement-resistant materials. In the case of bearing steels, an effective trapping mechanism may be the incorporation of finely dispersed V-Mo-Nb carbides in a ferrite matrix. First, we charged a ferritic steel with deuterium by means of electrolytic loading to achieve a high hydrogen concentration. We then immobilized it in the microstructure with a cryogenic transfer protocol before atom probe tomography (APT) analysis. Using APT, we show trapping of hydrogen within the core of these carbides with quantitative composition profiles. Furthermore, with this method the experiment can be feasibly replicated in any APT-equipped laboratory by using a simple cold chain.

Enhanced hydrogen storage on Li-doped defective graphene with B substitution: A DFT study

NASA Astrophysics Data System (ADS)

Zhou, Yanan; Chu, Wei; Jing, Fangli; Zheng, Jian; Sun, Wenjing; Xue, Ying

2017-07-01

The characteristics of hydrogen adsorption on Li-doped defective graphene systems were investigated using density functional theory (DFT) calculations. Four types of defective structures were selected. Li atoms were well dispersed on the defective graphene without clustering, evidenced by the binding energy value between Li and defective graphene than that of Li-Lix. Additionally, as the amount of adsorbed H2 molecules increase, the H2 molecules show tilting configuration toward the Li adatom. This is beneficial for more hydrogen adsorption under the electrostatic interaction. On these four stable structures, there were up to three polarized H2 molecules adsorbed on per Li adatom, with the average hydrogen adsorption energy in the range of approximately 0.2-0.4 eV. These results provide new focus on the nature of Li-doped defective graphene with sometimes B substitution medium, which could be considered as a promising candidate for hydrogen storage.

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

Vörös, Márton; Brawand, Nicholas P.; Galli, Giulia

Lead chalcogenide (PbX) nanoparticles are promising materials for solar energy conversion. However, the presence of trap states in their electronic gap limits their usability, and developing a universal strategy to remove trap states is a persistent challenge. Using calculations based on density functional theory, we show that hydrogen acts as an amphoteric impurity on PbX nanoparticle surfaces; hydrogen atoms may passivate defects arising from ligand imbalance or off-stoichiometric surface terminations irrespective of whether they originate from cation or anion excess. In addition, we show, using constrained density functional theory calculations, that hydrogen treatment of defective nanoparticles is also beneficial formore » charge transport in films. We also find that hydrogen adsorption on stoichiometric nanoparticles leads to electronic doping, preferentially n-type. Lastly, our findings suggest that postsynthesis hydrogen treatment of lead chalcogenide nanoparticle films is a viable approach to reduce electronic trap states or to dope well-passivated films.« less

Reactions of gas phase H atoms with ethylene, acetylene and ethane adsorbed on Ni( 1 1 1 )

NASA Astrophysics Data System (ADS)

Bürgi, T.; Trautman, T. R.; Gostein, M.; Lahr, D. L.; Haug, K. L.; Ceyer, S. T.

2002-03-01

The products of the reaction of the most energetic form of hydrogen, gas phase H atoms, with ethylene, acetylene and ethane adsorbed on a Ni(1 1 1) surface at 60 K are probed. Adsorbed ethylidyne (CCH 3) is identified by high resolution electron energy loss spectroscopy to be the major product (30% yield) in all three cases. Adsorbed acetylene is a minor product (3% yield) and arises as a consequence of a dynamic equilibrium between CCH 3 and C 2H 2 in the presence of gas phase H atoms. The observation of the same product for the reaction of H atoms with all three hydrocarbons implies that CCH 3 is the most stable C 2 species in the presence of coadsorbed hydrogen. The rates of CCH 3 production are measured as a function of the time of exposure of H atoms to each hydrocarbon. A simple kinetic model treating each reaction as a pseudo-first order reaction in the hydrocarbon coverage is fit to these data. A mechanism for the formation of CCH 3 via a CHCH 2 intermediate common to all three reactants is proposed to describe this model. The observed instability of the CH 2CH 3 species relative to C 2H 4 plays a role in the formulation of this mechanism as does the observed stability of CHCH 2 species in the presence of coadsorbed hydrogen. The CH 2CH 3 and the CHCH 2 species are produced by the translational activation of ethane and the dissociative ionization of ethane and ethylene, respectively. In addition, the binding energy and the vibrational spectrum of ethane adsorbed on Ni(1 1 1) are determined and exceptionally high resolution vibrational spectra of adsorbed ethylene and acetylene are presented.

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

2016-02-23

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 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.

Comparative structural and electronic studies of hydrogen interaction with isolated versus ordered silicon nanoribbons grown on Ag(110)

NASA Astrophysics Data System (ADS)

Dávila, M. E.; Marele, A.; De Padova, P.; Montero, I.; Hennies, F.; Pietzsch, A.; Shariati, M. N.; Gómez-Rodríguez, J. M.; Le Lay, G.

2012-09-01

We have investigated the geometry and electronic structure of two different types of self-aligned silicon nanoribbons (SiNRs), forming either isolated SiNRs or a self-assembled 5 × 2/5 × 4 grating on an Ag(110) substrate, by scanning tunnelling microscopy and high resolution x-ray photoelectron spectroscopy. At room temperature we further adsorb on these SiNRs either atomic or molecular hydrogen. The hydrogen absorption process and hydrogenation mechanism are similar for isolated or 5 × 2/5 × 4 ordered SiNRs and are not site selective; the main difference arises from the fact that the isolated SiNRs are more easily attacked and destroyed faster. In fact, atomic hydrogen strongly interacts with any Si atoms, modifying their structural and electronic properties, while molecular hydrogen has first to dissociate. Hydrogen finally etches the Si nanoribbons and their complete removal from the Ag(110) surface could eventually be expected.

Effect of Doping on Hydrogen Evolution Reaction of Vanadium Disulfide Monolayer.

PubMed

Qu, Yuanju; Pan, Hui; Kwok, Chi Tat; Wang, Zisheng

2015-12-01

As cheap and abundant materials, transitional metal dichalcogenide monolayers have attracted increasing interests for their application as catalysts in hydrogen production. In this work, the hydrogen evolution reduction of doped vanadium disulfide monolayers is investigated based on first-principles calculations. We find that the doping elements and concentration affect strongly the catalytic ability of the monolayer. We show that Ti-doping can efficiently reduce the Gibbs free energy of hydrogen adsorption in a wide range of hydrogen coverage. The catalytic ability of the monolayer at high hydrogen coverage can be improved by low Ti-density doping, while that at low hydrogen coverage is enhanced by moderate Ti-density doping. We further show that it is much easier to substitute the Ti atom to the V atom in the vanadium disulfide (VS2) monolayer than other transitional metal atoms considered here due to its lowest and negative formation energy. It is expected that the Ti-doped VS2 monolayer may be applicable in water electrolysis with improved efficiency.

Deciphering the "chemical" nature of the exotic isotopes of hydrogen by the MC-QTAIM analysis: the positively charged muon and the muonic helium as new members of the periodic table.

PubMed

Goli, Mohammad; Shahbazian, Shant

2014-04-14

This report is a primarily survey on the chemical nature of some exotic species containing the positively charged muon and the muonic helium, i.e., the negatively charged muon plus helium nucleus, as exotic isotopes of hydrogen, using the newly developed multi-component quantum theory of atoms in molecules (MC-QTAIM) analysis, employing ab initio non-Born-Oppenhiemer wavefunctions. Accordingly, the "atoms in molecules" analysis performed on various asymmetric exotic isotopomers of the hydrogen molecule, recently detected experimentally [Science, 2011, 331, 448], demonstrates that both the exotic isotopes are capable of forming atoms in molecules and retaining the identity of hydrogen atoms. Various derived properties of atomic basins containing the muonic helium cast no doubt that apart from its short life time, it is a heavier isotope of hydrogen while the properties of basins containing the positively charged muon are more remote from those of the orthodox hydrogen basins, capable of appreciable donation of electrons as well as large charge polarization. However, with some tolerance, they may also be categorized as hydrogen basins though with a smaller electronegativity. All in all, the present study also clearly demonstrates that the MC-QTAIM analysis is an efficient approach to decipher the chemical nature of species containing exotic constituents, which are difficult to elucidate by experimental and/or alternative theoretical schemes.

The Feasibility of Formation and Kinetics of NMR Signal Amplification by Reversible Exchange (SABRE) at High Magnetic Field (9.4 T)

PubMed Central

2015-01-01

1H NMR signal amplification by reversible exchange (SABRE) was observed for pyridine and pyridine-d5 at 9.4 T, a field that is orders of magnitude higher than what is typically utilized to achieve the conventional low-field SABRE effect. In addition to emissive peaks for the hydrogen spins at the ortho positions of the pyridine substrate (both free and bound to the metal center), absorptive signals are observed from hyperpolarized orthohydrogen and Ir-complex dihydride. Real-time kinetics studies show that the polarization build-up rates for these three species are in close agreement with their respective 1H T1 relaxation rates at 9.4 T. The results suggest that the mechanism of the substrate polarization involves cross-relaxation with hyperpolarized species in a manner similar to the spin-polarization induced nuclear Overhauser effect. Experiments utilizing pyridine-d5 as the substrate exhibited larger enhancements as well as partial H/D exchange for the hydrogen atom in the ortho position of pyridine and concomitant formation of HD molecules. While the mechanism of polarization enhancement does not explicitly require chemical exchange of hydrogen atoms of parahydrogen and the substrate, the partial chemical modification of the substrate via hydrogen exchange means that SABRE under these conditions cannot rigorously be referred to as a non-hydrogenative parahydrogen induced polarization process. PMID:24528143

The feasibility of formation and kinetics of NMR signal amplification by reversible exchange (SABRE) at high magnetic field (9.4 T).

PubMed

Barskiy, Danila A; Kovtunov, Kirill V; Koptyug, Igor V; He, Ping; Groome, Kirsten A; Best, Quinn A; Shi, Fan; Goodson, Boyd M; Shchepin, Roman V; Coffey, Aaron M; Waddell, Kevin W; Chekmenev, Eduard Y

2014-03-05

(1)H NMR signal amplification by reversible exchange (SABRE) was observed for pyridine and pyridine-d5 at 9.4 T, a field that is orders of magnitude higher than what is typically utilized to achieve the conventional low-field SABRE effect. In addition to emissive peaks for the hydrogen spins at the ortho positions of the pyridine substrate (both free and bound to the metal center), absorptive signals are observed from hyperpolarized orthohydrogen and Ir-complex dihydride. Real-time kinetics studies show that the polarization build-up rates for these three species are in close agreement with their respective (1)H T1 relaxation rates at 9.4 T. The results suggest that the mechanism of the substrate polarization involves cross-relaxation with hyperpolarized species in a manner similar to the spin-polarization induced nuclear Overhauser effect. Experiments utilizing pyridine-d5 as the substrate exhibited larger enhancements as well as partial H/D exchange for the hydrogen atom in the ortho position of pyridine and concomitant formation of HD molecules. While the mechanism of polarization enhancement does not explicitly require chemical exchange of hydrogen atoms of parahydrogen and the substrate, the partial chemical modification of the substrate via hydrogen exchange means that SABRE under these conditions cannot rigorously be referred to as a non-hydrogenative parahydrogen induced polarization process.

Tensile properties of ADI material in water and gaseous environments

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

Rajnovic, Dragan, E-mail: draganr@uns.ac.rs; Balos, Sebastian; Sidjanin, Leposava

2015-03-15

Austempered ductile iron (ADI) is an advanced type of heat treated ductile iron, having comparable mechanical properties as forged steels. However, it was found that in contact with water the mechanical properties of austempered ductile irons decrease, especially their ductility. Despite considerable scientific attention, the cause of this phenomenon remains unclear. Some authors suggested that hydrogen or small atom chemisorption causes the weakening of the surface atomic bonds. To get additional reliable data of that phenomenon, in this paper, two different types of austempered ductile irons were tensile tested in various environments, such as: argon, helium, hydrogen gas and water.more » It was found that only the hydrogen gas and water gave a statistically significant decrease in mechanical properties, i.e. cause embrittlement. Furthermore, the fracture surface analysis revealed that the morphology of the embrittled zone near the specimen surface shares similarities to the fatigue micro-containing striation-like lines, which indicates that the morphology of the brittle zone may be caused by cyclic local-chemisorption, micro-embrittlement and local-fracture. - Highlights: • In contact with water and other liquids the ADI suddenly exhibits embrittlement. • The embrittlement is more pronounced in water than in the gaseous hydrogen. • The hydrogen chemisorption into ADI surface causes the formation of a brittle zone. • The ADI austempered at lower temperatures (300 °C) is more resistant to embrittlement.« less

The low photo-inactivation rate of bacteria in human plasma II. Inhibition of methylene blue bleaching in plasma and effective bacterial destruction by the addition of dilute acetic acid to human plasma.

PubMed

Chen, Jie; Cesario, Thomas C; Li, Runze; Er, Ali O; Rentzepis, Peter M

2015-10-01

Methylene blue (MB) and other photo-sensitizer molecules have been recognized as effective means for the inactivation of bacteria and other pathogens owing to their ability to photo-generate reactive oxygen species (ROS) including singlet oxygen. These reactive species react with the membrane of the bacteria causing their destruction. However, the efficiency of MB to destroy bacteria in plasma is very low because the MB 660 nm absorption band, that is responsible for the ROS generation, is bleached. The bleaching of MB, in plasma, is caused by the attachment of a hydrogen atom to the central ring nitrogen of MB, which destroys the ring conjugation and forms Leuco-MB which does not absorb in the 600 nm region. In this paper we show that addition of dilute acetic acid, ∼10(-4) M, to human plasma, prevents H-atom attachment to MB, allowing MB to absorb at 660 nm, generates singlet oxygen and thus inactivates bacteria. The mechanism proposed, for preventing MB bleaching in plasma, is based on the oxidation of cysteine to cystine, by reaction with added dilute acetic acid, thus eliminating the availability of the thiol hydrogen atom which attaches to the MB nitrogen. It is expected that the addition of acetic acid to plasma will be effective in the sterilization of plasma and killing of bacteria in wounds and burns.

Hydrogen molecules and hydrogen-related defects in crystalline silicon

NASA Astrophysics Data System (ADS)

Fukata, N.; Sasaki, S.; Murakami, K.; Ishioka, K.; Nakamura, K. G.; Kitajima, M.; Fujimura, S.; Kikuchi, J.; Haneda, H.

1997-09-01

We have found that hydrogen exists in molecular form in crystalline silicon treated with hydrogen atoms in the downstream of a hydrogen plasma. The vibrational Raman line of hydrogen molecules is observed at 4158 cm-1 for silicon samples hydrogenated between 180 and 500 °C. The assignment of the Raman line is confirmed by its isotope shift to 2990 cm-1 for silicon treated with deuterium atoms. The Raman intensity has a maximum for hydrogenation at 400 °C. The vibrational Raman line of the hydrogen molecules is broad and asymmetric. It consists of at least two components, possibly arising from hydrogen molecules in different occupation sites in crystalline silicon. The rotational Raman line of hydrogen molecules is observed at 590 cm-1. The Raman band of Si-H stretching is observed for hydrogenation temperatures between 100 and 500 °C and the intensity has a maximum for hydrogenation at 250 °C.

Neutron protein crystallography: A complementary tool for locating hydrogens in proteins.

PubMed

O'Dell, William B; Bodenheimer, Annette M; Meilleur, Flora

2016-07-15

Neutron protein crystallography is a powerful tool for investigating protein chemistry because it directly locates hydrogen atom positions in a protein structure. The visibility of hydrogen and deuterium atoms arises from the strong interaction of neutrons with the nuclei of these isotopes. Positions can be unambiguously assigned from diffraction at resolutions typical of protein crystals. Neutrons have the additional benefit to structural biology of not inducing radiation damage in protein crystals. The same crystal could be measured multiple times for parametric studies. Here, we review the basic principles of neutron protein crystallography. The information that can be gained from a neutron structure is presented in balance with practical considerations. Methods to produce isotopically-substituted proteins and to grow large crystals are provided in the context of neutron structures reported in the literature. Available instruments for data collection and software for data processing and structure refinement are described along with technique-specific strategies including joint X-ray/neutron structure refinement. Examples are given to illustrate, ultimately, the unique scientific value of neutron protein crystal structures. Copyright © 2015 Elsevier Inc. All rights reserved.

Passivating the sulfur vacancy in monolayer MoS2

NASA Astrophysics Data System (ADS)

Lu, Haichang; Kummel, Andrew; Robertson, John

2018-06-01

Various methods to passivate the sulfur vacancy in 2D MoS2 are modeled using density functional theory (DFT) to understand the passivation mechanism at an atomic scale. First, the organic super acid, bis(trifluoromethane)sulfonimide (TFSI) is a strong protonating agent, and it is experimentally found to greatly increase the photoluminescence efficiency. DFT simulations find that the effectiveness of passivation depends critically on the charge state and number of hydrogens donated by TFSI since this determines the symmetry of the defect complex. A symmetrical complex is formed by three hydrogen atoms bonding to the defect in a -1 charge state, and this gives no bandgap states and a Fermi level in the midgap. However, a charge state of +1 gives a lower symmetry complex with one state in the gap. One or two hydrogens also give complexes with gap states. Second, passivation by O2 can provide partial passivation by forming a bridge bond across the S vacancy, but it leaves a defect state in the lower bandgap. On the other hand, substitutional additions do not shift the vacancy states out of the gap.

Atom Probe Analysis of Ex Situ Gas-Charged Stable Hydrides.

PubMed

Haley, Daniel; Bagot, Paul A J; Moody, Michael P

2017-04-01

In this work, we report on the atom probe tomography analysis of two metallic hydrides formed by pressurized charging using an ex situ hydrogen charging cell, in the pressure range of 200-500 kPa (2-5 bar). Specifically we report on the deuterium charging of Pd/Rh and V systems. Using this ex situ system, we demonstrate the successful loading and subsequent atom probe analysis of deuterium within a Pd/Rh alloy, and demonstrate that deuterium is likely present within the oxide-metal interface of a native oxide formed on vanadium. Through these experiments, we demonstrate the feasibility of ex situ hydrogen analysis for hydrides via atom probe tomography, and thus a practical route to three-dimensional imaging of hydrogen in hydrides at the atomic scale.

Crystal and molecular structure of N-(4-nitrophenyl)-β-alanine—Its vibrational spectra and theoretical calculations

NASA Astrophysics Data System (ADS)

Marchewka, M. K.; Drozd, M.; Janczak, J.

2011-08-01

The N-(4-nitrophenyl)-β-alanine in crystalline form directly by the addition of 4-nitroaniline to the acrylic acid in aqueous solution has been obtained. The title β-alanine derivative crystallizes in the P2 1/ c space group of monoclinic system with four molecules per unit cell. The X-ray geometry of β-alanine derivative molecule has been compared with those obtained by molecular orbital calculations corresponding to the gas phase. In the crystal the molecules related by an inversion center interact via symmetrically equivalent O-H⋯O hydrogen bonds with O⋯O distance of 2.656(2) Å forming a dimeric structure. The dimers of β-alanine derivative weakly interact via N-H⋯O hydrogen bonds between the H atom of β-amine groups and one of O atom of nitro groups. The room temperature powder vibrational (infrared and Raman) measurements are in accordance with the X-ray analysis. In aqueous solution of 4-nitroaniline and acrylic acid, the double C dbnd C bond of vinyl group of acrylic acid breaks as result of 4-nitroaniline addition.

Electronic and optical properties of hydrogenated silicon carbide nanosheets: A DFT study

NASA Astrophysics Data System (ADS)

Delavari, Najmeh; Jafari, Mahmoud

2018-07-01

Density-functional theory has been applied to investigate the effect of hydrogen adsorption on silicon carbide (SiC) nanosheets, considering six, different configurations for adsorption process. The chair-like configuration is found to be the most stable because of the adsorption of hydrogen atoms by silicon and carbon atoms on the opposite sides. The pure and hydrogenated SiC monolayers are also found to be sp2- and sp3-hybridized, respectively. The binding energy of the hydrogen atoms in the chair-like structure is calculated about -3.845 eV, implying the system to be much more stable than the same study based on graphene, though with nearly the same electronic properties, strongly proposing the SiC monolayer to be a promising material for next generation hydrogen storage. Optical properties presented in terms of the real and the imaginary parts of the dielectric function also demonstrate a decrease in the dielectric constant and the static refractive index due to hydrogen adsorption with the Plasmon frequency of the chair-like, hydrogenated monolayer, occurring at higher energies compared to that of the pure one.

Ethylene hydrogenation catalysis on Pt(111) single-crystal surfaces studied by using mass spectrometry and in situ infrared absorption spectroscopy

NASA Astrophysics Data System (ADS)

Tillekaratne, Aashani; Simonovis, Juan Pablo; Zaera, Francisco

2016-10-01

The catalytic hydrogenation of ethylene promoted by a Pt(111) single crystal was studied by using a ultrahigh-vacuum surface-science instrument equipped with a so-called high-pressure cell. Kinetic data were acquired continuously during the catalytic conversion of atmospheric-pressure mixtures of ethylene and hydrogen by using mass spectrometry while simultaneously characterizing the surface species in operando mode by reflection-absorption infrared spectroscopy (RAIRS). Many observations reported in previous studies of this system were corroborated, including the presence of adsorbed alkylidyne intermediates during the reaction and the zero-order dependence of the rate of hydrogenation on the pressure of ethylene. In addition, the high quality of the kinetic data, which could be recorded continuously versus time and processed to calculate time-dependent turnover frequencies (TOFs), afforded a more detailed analysis of the mechanism. Specifically, deuterium labeling could be used to estimate the extent of isotope scrambling reached with mixed-isotope-substituted reactants (C2H4 + D2 and C2D4 + H2). Perhaps the most important new observation from this work is that, although extensive H-D exchange takes place on ethylene before being fully converted to ethane, the average stoichiometry of the final product retains the expected stoichiometry of the gas mixture, that is, four regular hydrogen atoms and two deuteriums per ethane molecule in the case of the experiments with C2H4 + D2. This means that no hydrogen atoms are removed from the surface via their inter-recombination to produce X2 (X = H or D). It is concluded that, under catalytic conditions, hydrogen surface recombination is much slower than ethylene hydrogenation and H-D exchange.

Hydrogen as an atomic beam standard

NASA Technical Reports Server (NTRS)

Peters, H. E.

1972-01-01

After a preliminary discussion of feasibility, new experimental work with a hydrogen beam is described. A space focused magnetic resonance technique with separated oscillatory fields is used with a monochromatic beam of cold hydrogen atoms which are selected from a higher temperature source. The first resonance curves and other experimental results are presented. These results are interpreted from the point of view of accuracy potential and frequency stability, and are compared with hydrogen maser and cesium beam capabilities.

The Rydberg constant and proton size from atomic hydrogen

NASA Astrophysics Data System (ADS)

Beyer, Axel; Maisenbacher, Lothar; Matveev, Arthur; Pohl, Randolf; Khabarova, Ksenia; Grinin, Alexey; Lamour, Tobias; Yost, Dylan C.; Hänsch, Theodor W.; Kolachevsky, Nikolai; Udem, Thomas

2017-10-01

At the core of the “proton radius puzzle” is a four-standard deviation discrepancy between the proton root-mean-square charge radii (rp) determined from the regular hydrogen (H) and the muonic hydrogen (µp) atoms. Using a cryogenic beam of H atoms, we measured the 2S-4P transition frequency in H, yielding the values of the Rydberg constant R∞ = 10973731.568076(96) per meterand rp = 0.8335(95) femtometer. Our rp value is 3.3 combined standard deviations smaller than the previous H world data, but in good agreement with the µp value. We motivate an asymmetric fit function, which eliminates line shifts from quantum interference of neighboring atomic resonances.

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

Conceptual Launch Vehicles Using Metallic Hydrogen Propellant

NASA Astrophysics Data System (ADS)

Cole, John W.; Silvera, Isaac F.; Foote, John P.

2008-01-01

Solid molecular hydrogen is predicted to transform into an atomic solid with metallic properties under pressures >4.5 Mbar. Atomic metallic hydrogen is predicted to be metastable, limited by some critical temperature and pressure, and to store very large amounts of energy. Experiments may soon determine the critical temperature, critical pressure, and specific energy availability. It is useful to consider the feasibility of using metastable atomic hydrogen as a rocket propellant. If one assumes that metallic hydrogen is stable at usable temperatures and pressures, and that it can be affordably produced, handled, and stored, then it may be a useful rocket propellant. Assuming further that the available specific energy can be determined from the recombination of the atoms into molecules (216 MJ/kg), then conceptual engines and launch vehicle concepts can be developed. Under these assumptions, metallic hydrogen would be a revolutionary new rocket fuel with a theoretical specific impulse of 1700 s at a chamber pressure of 100 atm. A practical problem that arises is that rocket chamber temperatures may be too high for the use of this pure fuel. This paper examines an engine concept that uses liquid hydrogen or water as a diluent coolant for the metallic hydrogen to reduce the chamber temperature to usable values. Several launch vehicles are then conceptually developed. Results indicate that if metallic hydrogen is experimentally found to have the properties assumed in this analysis, then there are significant benefits. These benefits become more attractive as the chamber temperatures increase.

Electron-impact ionization of atomic hydrogen at incident electron energies of 15.6, 17.6, 25, and 40 eV

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

Childers, J. G.; James, K. E.; Hughes, M.

2003-09-01

Absolute doubly differential cross sections for the electron-impact ionization of atomic hydrogen have been measured from near threshold to intermediate energies. The measurements are calibrated to the well-established, accurate differential cross section for electron-impact excitation of the atomic hydrogen transition H(1{sup 2}S{yields}2{sup 2}S+2{sup 2}P). In these experiments background secondary electrons are suppressed by moving the atomic hydrogen target source to and from the collision region. Measurements cover the incident electron energy range of 14.6-40 eV, for scattering angles of 10 degree sign -120 degree sign and are found to be in very good agreement with the results of the mostmore » advanced theoretical models--the convergent close-coupling model and the exterior complex scaling model.« less

Interaction of intense laser pulses with hydrogen atomic clusters

NASA Astrophysics Data System (ADS)

Du, Hong-Chuan; Wang, Hui-Qiao; Liu, Zuo-Ye; Sun, Shao-Hua; Li, Lu; Ma, Ling-Ling; Hu, Bi-Tao

2010-03-01

The interaction between intense femtosecond laser pulses and hydrogen atomic clusters is studied by a simplified Coulomb explosion model. The dependences of average proton kinetic energy on cluster size, pulse duration, laser intensity and wavelength are studied respectively. The calculated results indicate that the irradiation of a femtosecond laser of longer wavelength on hydrogen atomic clusters may be a simple, economical way to produce highly kinetic hydrogen ions. The phenomenon suggests that the irradiation of femtosecond laser of longer wavelength on deuterium atomic clusters may be easier than that of shorter wavelength to drive nuclear fusion reactions. The product of the laser intensity and the squared laser wavelength needed to make proton energy saturated as a function of the squared cluster radius is also investigated. The proton energy distribution calculated is also shown and compared with the experimental data. Our results are in agreement with the experimental results fairly well.

An ab initio cluster study of the chemisorption of atomic cesium and hydrogen on reconstructed surfaces of gallium rich gallium arsenide

NASA Astrophysics Data System (ADS)

Schailey, Ronald

1999-11-01

Chemisorption properties of cesium and hydrogen atoms on the Ga-rich GaAs (100) (2 x 1), (2 x 2), and β(4 x 2) surfaces are investigated using ab initio self-consistent restricted open shell Hartree-Fock (ROHF) total energy calculations with Hay- Wadt effective core potentials. The effects of electron correlation have been included using many-body perturbation theory through second order, with the exception of β(4 x 2) symmetry due to computational limitations. The semiconductor surface is modeled by finite sized hydrogen saturated clusters. The effects of surface relaxation and reconstruction have been investigated in detail. Results are given for the energetics of chemisorption, charge population analysis, HOMO-LUMO gaps, and consequent possibilities of metallization for atomic cesium adsorption. For the chemisorption of atomic hydrogen, the experimentally verified mechanism of surface dimer bond breaking is investigated in detail.

Electron- and photon-stimulated desorption of atomic hydrogen from radiation-modified alkali halide surfaces

NASA Astrophysics Data System (ADS)

Hudson, L. T.; Tolk, N. H.; Bao, C.; Nordlander, P.; Russell, D. P.; Xu, J.

2000-10-01

The desorption yields of excited hydrogen atoms from the surfaces of KCl, KBr, NaCl, NaF, and LiF have been measured as a function of incident photon and electron energy and flux, time of irradiation, dosing pressure of H2 and sample temperature. As these surfaces are exposed to H2 gas during electron or photon bombardment, the fluorescence from excited hydrogen atoms ejected from the surface is monitored. The desorption yields are found to be contingent upon surface damage induced by the incident particle radiation, leading to dissociative adsorption at surface sites containing an excess of alkali metal. A desorption mechanism is presented in which incident electrons or photons induce a valence excitation to a neutral, antibonding state of the surface alkali hydride molecule complex, leading to the desorption of hydrogen atoms possessing several eV of kinetic energy.

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…

Auroral zone effects on hydrogen geocorona structure and variability

NASA Technical Reports Server (NTRS)

Moore, T. E.; Biddle, A. P.; Waite, J. H., Jr.; Killeen, T. L.

1985-01-01

The effect of diurnal and magnetospheric modulations on the structure of the hydrogen geocorona is analyzed on the basis of recent observations. Particular attention is given to the enhancement of neutral escape by plasma effects, including the recently observed phenomenon of low-altitude ion acceleration. It is found that, while significant fluxes of neutral H should be produced by transverse ion acceleration in the auroral zone, the process is probably insufficient to account for the observed polar depletion of hydrogen atoms. Analysis of recent exospheric temperature measurements from the Dynamics Explorer-2 satellite suggest that neutral heating in and near the high latitude cusp may be the major contributor to depleted atomic hydrogen densities at high latitudes. Altitude profiles of the production rates for escaping neutral hydrogen atoms during periods of maximum, minimum, and typical solar activity are provided.

Highly hydrogen-sensitive thermal desorption spectroscopy system for quantitative analysis of low hydrogen concentration (˜1 × 1016 atoms/cm3) in thin-film samples

NASA Astrophysics Data System (ADS)

Hanna, Taku; Hiramatsu, Hidenori; Sakaguchi, Isao; Hosono, Hideo

2017-05-01

We developed a highly hydrogen-sensitive thermal desorption spectroscopy (HHS-TDS) system to detect and quantitatively analyze low hydrogen concentrations in thin films. The system was connected to an in situ sample-transfer chamber system, manipulators, and an rf magnetron sputtering thin-film deposition chamber under an ultra-high-vacuum (UHV) atmosphere of ˜10-8 Pa. The following key requirements were proposed in developing the HHS-TDS: (i) a low hydrogen residual partial pressure, (ii) a low hydrogen exhaust velocity, and (iii) minimization of hydrogen thermal desorption except from the bulk region of the thin films. To satisfy these requirements, appropriate materials and components were selected, and the system was constructed to extract the maximum performance from each component. Consequently, ˜2000 times higher sensitivity to hydrogen than that of a commercially available UHV-TDS system was achieved using H+-implanted Si samples. Quantitative analysis of an amorphous oxide semiconductor InGaZnO4 thin film (1 cm × 1 cm × 1 μm thickness, hydrogen concentration of 4.5 × 1017 atoms/cm3) was demonstrated using the HHS-TDS system. This concentration level cannot be detected using UHV-TDS or secondary ion mass spectroscopy (SIMS) systems. The hydrogen detection limit of the HHS-TDS system was estimated to be ˜1 × 1016 atoms/cm3, which implies ˜2 orders of magnitude higher sensitivity than that of SIMS and resonance nuclear reaction systems (˜1018 atoms/cm3).

Analytic model of a multi-electron atom

NASA Astrophysics Data System (ADS)

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

2017-12-01

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

Excited-state hydrogen atom abstraction initiates the photochemistry of β-2′-deoxycytidine† †Electronic supplementary information (ESI) available: Including relevant preliminary results as well as illustrations and geometrical parameters of selected structures. See DOI: 10.1039/c4sc03761h Click here for additional data file.

PubMed Central

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

2015-01-01

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

Platinum single-atom and cluster catalysis of the hydrogen evolution reaction

NASA Astrophysics Data System (ADS)

Cheng, Niancai; Stambula, Samantha; Wang, Da; Banis, Mohammad Norouzi; Liu, Jian; Riese, Adam; Xiao, Biwei; Li, Ruying; Sham, Tsun-Kong; Liu, Li-Min; Botton, Gianluigi A.; Sun, Xueliang

2016-11-01

Platinum-based catalysts have been considered the most effective electrocatalysts for the hydrogen evolution reaction in water splitting. However, platinum utilization in these electrocatalysts is extremely low, as the active sites are only located on the surface of the catalyst particles. Downsizing catalyst nanoparticles to single atoms is highly desirable to maximize their efficiency by utilizing nearly all platinum atoms. Here we report on a practical synthesis method to produce isolated single platinum atoms and clusters using the atomic layer deposition technique. The single platinum atom catalysts are investigated for the hydrogen evolution reaction, where they exhibit significantly enhanced catalytic activity (up to 37 times) and high stability in comparison with the state-of-the-art commercial platinum/carbon catalysts. The X-ray absorption fine structure and density functional theory analyses indicate that the partially unoccupied density of states of the platinum atoms' 5d orbitals on the nitrogen-doped graphene are responsible for the excellent performance.

Platinum single-atom and cluster catalysis of the hydrogen evolution reaction

PubMed Central

Cheng, Niancai; Stambula, Samantha; Wang, Da; Banis, Mohammad Norouzi; Liu, Jian; Riese, Adam; Xiao, Biwei; Li, Ruying; Sham, Tsun-Kong; Liu, Li-Min; Botton, Gianluigi A.; Sun, Xueliang

2016-01-01

Platinum-based catalysts have been considered the most effective electrocatalysts for the hydrogen evolution reaction in water splitting. However, platinum utilization in these electrocatalysts is extremely low, as the active sites are only located on the surface of the catalyst particles. Downsizing catalyst nanoparticles to single atoms is highly desirable to maximize their efficiency by utilizing nearly all platinum atoms. Here we report on a practical synthesis method to produce isolated single platinum atoms and clusters using the atomic layer deposition technique. The single platinum atom catalysts are investigated for the hydrogen evolution reaction, where they exhibit significantly enhanced catalytic activity (up to 37 times) and high stability in comparison with the state-of-the-art commercial platinum/carbon catalysts. The X-ray absorption fine structure and density functional theory analyses indicate that the partially unoccupied density of states of the platinum atoms' 5d orbitals on the nitrogen-doped graphene are responsible for the excellent performance. PMID:27901129

Probing the accuracy and precision of Hirshfeld atom refinement with HARt interfaced with Olex2.

PubMed

Fugel, Malte; Jayatilaka, Dylan; Hupf, Emanuel; Overgaard, Jacob; Hathwar, Venkatesha R; Macchi, Piero; Turner, Michael J; Howard, Judith A K; Dolomanov, Oleg V; Puschmann, Horst; Iversen, Bo B; Bürgi, Hans-Beat; Grabowsky, Simon

2018-01-01

Hirshfeld atom refinement (HAR) is a novel X-ray structure refinement technique that employs aspherical atomic scattering factors obtained from stockholder partitioning of a theoretically determined tailor-made static electron density. HAR overcomes many of the known limitations of independent atom modelling (IAM), such as too short element-hydrogen distances, r ( X -H), or too large atomic displacement parameters (ADPs). This study probes the accuracy and precision of anisotropic hydrogen and non-hydrogen ADPs and of r ( X -H) values obtained from HAR. These quantities are compared and found to agree with those obtained from (i) accurate neutron diffraction data measured at the same temperatures as the X-ray data and (ii) multipole modelling (MM), an established alternative method for interpreting X-ray diffraction data with the help of aspherical atomic scattering factors. Results are presented for three chemically different systems: the aromatic hydro-carbon rubrene (orthorhombic 5,6,11,12-tetra-phenyl-tetracene), a co-crystal of zwitterionic betaine, imidazolium cations and picrate anions (BIPa), and the salt potassium hydrogen oxalate (KHOx). The non-hydrogen HAR-ADPs are as accurate and precise as the MM-ADPs. Both show excellent agreement with the neutron-based values and are superior to IAM-ADPs. The anisotropic hydrogen HAR-ADPs show a somewhat larger deviation from neutron-based values than the hydrogen SHADE-ADPs used in MM. Element-hydrogen bond lengths from HAR are in excellent agreement with those obtained from neutron diffraction experiments, although they are somewhat less precise. The residual density contour maps after HAR show fewer features than those after MM. Calculating the static electron density with the def2-TZVP basis set instead of the simpler def2-SVP one does not improve the refinement results significantly. All HARs were performed within the recently introduced HARt option implemented in the Olex2 program. They are easily launched inside its graphical user interface following a conventional IAM.

Probing the accuracy and precision of Hirshfeld atom refinement with HARt interfaced with Olex2

PubMed Central

Fugel, Malte; Hathwar, Venkatesha R.; Turner, Michael J.; Howard, Judith A. K.

2018-01-01

Hirshfeld atom refinement (HAR) is a novel X-ray structure refinement technique that employs aspherical atomic scattering factors obtained from stockholder partitioning of a theoretically determined tailor-made static electron density. HAR overcomes many of the known limitations of independent atom modelling (IAM), such as too short element–hydrogen distances, r(X—H), or too large atomic displacement parameters (ADPs). This study probes the accuracy and precision of anisotropic hydrogen and non-hydrogen ADPs and of r(X—H) values obtained from HAR. These quantities are compared and found to agree with those obtained from (i) accurate neutron diffraction data measured at the same temperatures as the X-ray data and (ii) multipole modelling (MM), an established alternative method for interpreting X-ray diffraction data with the help of aspherical atomic scattering factors. Results are presented for three chemically different systems: the aromatic hydro­carbon rubrene (orthorhombic 5,6,11,12-tetra­phenyl­tetracene), a co-crystal of zwitterionic betaine, imidazolium cations and picrate anions (BIPa), and the salt potassium hydrogen oxalate (KHOx). The non-hydrogen HAR-ADPs are as accurate and precise as the MM-ADPs. Both show excellent agreement with the neutron-based values and are superior to IAM-ADPs. The anisotropic hydrogen HAR-ADPs show a somewhat larger deviation from neutron-based values than the hydrogen SHADE-ADPs used in MM. Element–hydrogen bond lengths from HAR are in excellent agreement with those obtained from neutron diffraction experiments, although they are somewhat less precise. The residual density contour maps after HAR show fewer features than those after MM. Calculating the static electron density with the def2-TZVP basis set instead of the simpler def2-SVP one does not improve the refinement results significantly. All HARs were performed within the recently introduced HARt option implemented in the Olex2 program. They are easily launched inside its graphical user interface following a conventional IAM. PMID:29354269

Hydrogen treatment as a detergent of electronic trap states in lead chalcogenide nanoparticles

DOE PAGES

Vörös, Márton; Brawand, Nicholas P.; Galli, Giulia

2016-11-15

Lead chalcogenide (PbX) nanoparticles are promising materials for solar energy conversion. However, the presence of trap states in their electronic gap limits their usability, and developing a universal strategy to remove trap states is a persistent challenge. Using calculations based on density functional theory, we show that hydrogen acts as an amphoteric impurity on PbX nanoparticle surfaces; hydrogen atoms may passivate defects arising from ligand imbalance or off-stoichiometric surface terminations irrespective of whether they originate from cation or anion excess. In addition, we show, using constrained density functional theory calculations, that hydrogen treatment of defective nanoparticles is also beneficial formore » charge transport in films. We also find that hydrogen adsorption on stoichiometric nanoparticles leads to electronic doping, preferentially n-type. Lastly, our findings suggest that postsynthesis hydrogen treatment of lead chalcogenide nanoparticle films is a viable approach to reduce electronic trap states or to dope well-passivated films.« less

Formation of the low-resistivity compound Cu{sub 3}Ge by low-temperature treatment in an atomic hydrogen flux

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

Erofeev, E. V., E-mail: erofeev@micran.ru; Kazimirov, A. I.; Fedin, I. V.

The systematic features of the formation of the low-resistivity compound Cu{sub 3}Ge by low-temperature treatment of a Cu/Ge two-layer system in an atomic hydrogen flux are studied. The Cu/Ge two-layer system is deposited onto an i-GaAs substrate. Treatment of the Cu/Ge/i-GaAs system, in which the layer thicknesses are, correspondingly, 122 and 78 nm, in atomic hydrogen with a flux density of 10{sup 15} at cm{sup 2} s{sup –1} for 2.5–10 min at room temperature induces the interdiffusion of Cu and Ge, with the formation of a polycrystalline film containing the stoichiometric Cu{sub 3}Ge phase. The film consists of vertically orientedmore » grains 100–150 nm in size and exhibits a minimum resistivity of 4.5 µΩ cm. Variations in the time of treatment of the Cu/Ge/i-GaAs samples in atomic hydrogen affect the Cu and Ge depth distribution, the phase composition of the films, and their resistivity. Experimental observation of the synthesis of the Cu{sub 3}Ge compound at room temperature suggests that treatment in atomic hydrogen has a stimulating effect on both the diffusion of Cu and Ge and the chemical reaction of Cu{sub 3}Ge-compound formation. These processes can be activated by the energy released upon the recombination of hydrogen atoms adsorbed at the surface of the Cu/Ge/i-GaAs sample.« less

Effect of Boron Microalloying Element on Susceptibility to Hydrogen Embrittlement in High Strength Mooring Chain Steel

NASA Astrophysics Data System (ADS)

Li, H.; Cheng, X. Y.; Shen, H. P.; Su, L. C.; Zhang, S. Y.

The susceptibility to hydrogen embrittlement in high strength mooring chain steel with different boron content (0, 0.003 %, 0.008 %) were investigated by electrochemical hydrogen charging technique and tensile test. The results revealed that appropriate boron content can effectively depress hydrogen induced embrittlement. Precharged with a low current density, this effect seemed to be unobvious. It gradually became clearly with the increasing current density. The increase of resistance to the hydrogen embrittlement for 3B and 8B after adding appropriate boron was attributed to three facts. The first was that the segregation of boron atoms along grain boundaries reduced the grain boundary segregation of phosphorus, which prohibited hydrogen concentration at the grain boundaries, depressing the possibility of the intergranular fracture due to H. The second was that the segregation of boron increased intergranular cohesion, enhanced grain boundary strength, and refined the final microstructure. The third was that the addition of boron changed the state of hydrogen traps, leading to the small amount of diffusible hydrogen. That is to say, hydrogen transferred to these defects by dislocations was accordingly decreased, which led to the low sensitive of hydrogen induced cracking.

Candidate chemical systems for air cooled solar powered, absorption air conditioner design. Part I. Organic absorbent systems

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

Biermann, W. J.

1978-01-01

All the available experimental evidence suggests that the optimum ''organic'' absorbent/refrigerant combination would be a methane derivative with a single hydrogen atom with chlorine and fluorine atoms in the other sites, as refrigerant. This would be hydrogen bonded to an absorbent molecule containing the group =NC/sup -/O, with the substituent groups being such that no steric hindrance took place. Cycle analyses showed that the ratio of internal heat transfer to cooling would be large, probably impractically so in view of the high coefficient of performance needed for solar driven cooling and the additional handicap of heat rejection to the atmosphere.more » A more promising approach would be to reduce the internal heat transfer per unit of space cooling by selecting a refrigerant with a high latent heat of vaporization and selecting an absorbent with suitable properties.« less

Correlated high-resolution x-ray diffraction photoluminescence and atom probe tomography analysis of continuous and discontinuous In xGa 1-xN quantum wells

DOE PAGES

Ren, Xiaochen; Riley, James R.; Koleske, Daniel; ...

2015-07-14

In this study, atom probe tomography (APT) is used to characterize the influence of hydrogen dosing duringGaN barrier growth on the indium distribution of In xGa 1-xN quantum wells, and correlatedmicro-photoluminescence is used to measure changes in the emission spectrum and efficiency. We found that relative to the control growth, hydrogen dosing leads to a 50% increase in emission intensity arising from discontinuous quantum wells that are narrower, of lower indium content, and with more abrupt interfaces. Additionally, simulations of carrier distributions based on APT composition profiles indicate that the greater carrier confinement leads to an increased radiative recombination rate.more » Furthermore, APT analysis of quantum well profiles enables refinement of x-ray diffractionanalysis for more accurate nondestructive measurements of composition.« less

Deexcitation Dynamics of Superhydrogenated Polycyclic Aromatic Hydrocarbon Cations after Soft-x-Ray Absorption

NASA Astrophysics Data System (ADS)

Reitsma, G.; Boschman, L.; Deuzeman, M. J.; González-Magaña, O.; Hoekstra, S.; Cazaux, S.; Hoekstra, R.; Schlathölter, T.

2014-08-01

We have investigated the response of superhydrogenated gas-phase coronene cations upon soft x-ray absorption. Carbon (1s)⟶π⋆ transitions were resonantly excited at hν =285 eV. The resulting core hole is then filled in an Auger decay process, with the excess energy being released in the form of an Auger electron. Predominantly highly excited dications are thus formed, which cool down by hydrogen emission. In superhydrogenated systems, the additional H atoms act as a buffer, quenching loss of native H atoms and molecular fragmentation. Dissociation and transition state energies for several H loss channels were computed by means of density functional theory. Using these energies as input into an Arrhenius-type cascade model, very good agreement with the experimental data is found. The results have important implications for the survival of polyaromatic hydrocarbons in the interstellar medium and reflect key aspects of graphene hydrogenation.

N-(2-Allyl-4-chloro-2H-indazol-5-yl)-4-meth­oxy­benzene­sulfonamide hemi­hydrate

PubMed Central

Chicha, Hakima; Kouakou, Assoman; Rakib, El Mostapha; Saadi, Mohamed; El Ammari, Lahcen

2013-01-01

The fused five- and six-membered rings in the title compound, C17H16ClN3O3S·0.5H2O, are practically coplanar, with the maximum deviation from the mean plane being 0.057 (3) Å for the C atom bound to the exocyclic N atom. The indazole system makes a dihedral angle of 66.18 (12)° with the plane through the benzene ring, and it is nearly perpendicular to the allyl group, as indicated by the N—N—C—C torsion angle of 79.2 (3)°. In the crystal, the water mol­ecule, lying on a twofold axis, forms O—H⋯N and accepts N—H⋯O hydrogen bonds. Additional C—H⋯O hydrogen bonds contribute to the formation of a chain along the b-axis direction. PMID:24109418

N-(2-Allyl-4-chloro-2H-indazol-5-yl)-4-meth-oxy-benzene-sulfonamide hemi-hydrate.

PubMed

Chicha, Hakima; Kouakou, Assoman; Rakib, El Mostapha; Saadi, Mohamed; El Ammari, Lahcen

2013-01-01

The fused five- and six-membered rings in the title compound, C17H16ClN3O3S·0.5H2O, are practically coplanar, with the maximum deviation from the mean plane being 0.057 (3) Å for the C atom bound to the exocyclic N atom. The indazole system makes a dihedral angle of 66.18 (12)° with the plane through the benzene ring, and it is nearly perpendicular to the allyl group, as indicated by the N-N-C-C torsion angle of 79.2 (3)°. In the crystal, the water mol-ecule, lying on a twofold axis, forms O-H⋯N and accepts N-H⋯O hydrogen bonds. Additional C-H⋯O hydrogen bonds contribute to the formation of a chain along the b-axis direction.

Molecular modeling and multispectroscopic studies of the interaction of mesalamine with bovine serum albumin

NASA Astrophysics Data System (ADS)

Shahabadi, Nahid; Fili, Soraya Moradi

2014-01-01

The interaction of mesalamine (5-aminosalicylic acid (5-ASA)) with bovine serum albumin (BSA) was investigated by fluorescence quenching, absorption spectroscopy, circular dichroism (CD) techniques, and molecular docking. Thermodynamic parameters (ΔH < 0 and ΔS 0) indicated that the hydrogen bond and electrostatic forces played the major role in the binding of 5-ASA to BSA. The results of CD and UV-vis spectroscopy showed that the binding of this drug to BSA induces some conformational changes in BSA. Displacement experiments predicted that the binding of 5-ASA to BSA is located within domain III, Sudlows site 2, that these observations were substantiated by molecular docking studies. In addition, the docking result shows that the 5-ASA in its anionic form mainly interacts with Gln-416 residue through one hydrogen bond between H atom of 5-ASA anion and the adjacent O atom of the hydroxyl group of Gln-416.

Thermal decomposition of silane to form hydrogenated amorphous Si film

DOEpatents

Strongin, Myron; Ghosh, Arup K.; Wiesmann, Harold J.; Rock, Edward B.; Lutz, III, Harry A.

1980-01-01

This invention relates to hydrogenated amorphous silicon produced by thermally decomposing silano (SiH.sub.4) or other gases comprising H and Si, at elevated temperatures of about 1700.degree.-2300.degree. C., and preferably in a vacuum of about 10.sup.-8 to 10.sup.-4 torr, to form a gaseous mixture of atomic hydrogen and atomic silicon, and depositing said gaseous mixture onto a substrate outside said source of thermal decomposition to form hydrogenated amorphous silicon.

Reaction kinetics of hydrogen atom abstraction from isopentanol by the H atom and HO2˙ radical.

PubMed

Parab, Prajakta Rajaram; Heufer, K Alexander; Fernandes, Ravi Xavier

2018-04-25

Isopentanol is a potential next-generation biofuel for future applications to Homogeneous Charge Compression Ignition (HCCI) engine concepts. To provide insights into the combustion behavior of isopentanol, especially to its auto-ignition behavior which is linked both to efficiency and pollutant formation in real combustion systems, detailed quantum chemical studies for crucial reactions are desired. H-Abstraction reaction rates from fuel molecules are key initiation steps for chain branching required for auto-ignition. In this study, rate constants are determined for the hydrogen atom abstraction reactions from isopentanol by the H atom and HO2˙ radical by implementing the CBS-QB3 composite method. For the treatment of the internal rotors, a Pitzer-Gwinn-like approximation is applied. On comparing the computed reaction energies, the highest exothermicity (ΔE = -46 kJ mol-1) is depicted for Hα abstraction by the H atom whereas the lowest endothermicity (ΔE = 29 kJ mol-1) is shown for the abstraction of Hα by the HO2˙ radical. The formation of hydrogen bonding is found to affect the kinetics of the H atom abstraction reactions by the HO2˙ radical. Further above 750 K, the calculated high pressure limit rate constants indicate that the total contribution from delta carbon sites (Cδ) is predominant for hydrogen atom abstraction by the H atom and HO2˙ radical.

Studies for the Loss of Atomic and Molecular Species from Io

NASA Technical Reports Server (NTRS)

Smyth, William H.

1998-01-01

Continued effort is reported to improve the emission rates of various emission lines for atomic oxygen and sulfur. Atomic hydrogen has been included as a new species in the neutral cloud model. The pertinent lifetime processes for hydrogen in the plasma torus and the relevant excitation processes for H Lyman-alpha emission in Io's atmosphere are discussed.

Atomic Layer Epitaxy of Aluminum Nitride: Unraveling the Connection between Hydrogen Plasma and Carbon Contamination.

PubMed

Erwin, Steven C; Lyons, John L

2018-06-13

Atomistic control over the growth of semiconductor thin films, such as aluminum nitride, is a long-sought goal in materials physics. One promising approach is plasma-assisted atomic layer epitaxy, in which separate reactant precursors are employed to grow the cation and anion layers in alternating deposition steps. The use of a plasma during the growth-most often a hydrogen plasma-is now routine and generally considered critical, but the precise role of the plasma is not well-understood. We propose a theoretical atomistic model and elucidate its consequences using analytical rate equations, density functional theory, and kinetic Monte Carlo statistical simulations. We show that using a plasma has two important consequences, one beneficial and one detrimental. The plasma produces atomic hydrogen in the gas phase, which is important for removing methyl radicals left over from the aluminum precursor molecules. However, atomic hydrogen also leads to atomic carbon on the surface and, moreover, opens a channel for trapping these carbon atoms as impurities in the subsurface region, where they remain as unwanted contaminants. Understanding this dual role leads us to propose a solution for the carbon contamination problem which leaves the main benefit of the plasma largely unaffected.

Origin of the periodic structure in the conductance curve of gold nanojunctions in hydrogen environment

NASA Astrophysics Data System (ADS)

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

2016-03-01

The evolution of the atomic structure and the vibrational and electronic transport properties of gold atomic junctions incorporating molecular and atomic hydrogen upon elongation have been investigated with the nonequilibrium Green's function formalism combined with density functional theory. Our calculations show that for the case of gold junctions doped with a single H2 molecule the low-bias conductance drops rapidly with the electrodes' separation, while it remains almost constant if a single H atom replaces the molecule. In contrast, when one considers two H atoms adsorbed on a gold monatomic chain forming an Au-H-Au-H-Au double-bridge structure, the low-bias conductance increases first and then shows a plateau upon stretching the junction, in perfect agreement with experiments on gold nanocontacts in hydrogen environment. Furthermore, also the distribution of the calculated vibrational energies of the two H atoms is consistent with the experimental result in the low-conductance region, demonstrating clear evidence that hydrogen molecules can dissociate on stretched gold monatomic chains. These findings are helpful to improve our understanding of the structure-property relation of gold nanocontacts and also provide a new prospect for gold nanowires being used as chemical sensors and catalysts.

Influence of Fluorine Atoms and Aromatic Rings on the Acidity of Ethanol

NASA Astrophysics Data System (ADS)

Ramírez, Ramsés E.; García-Martínez, Cirilo; Méndez, Francisco

2009-09-01

Absolute gas-phase acidities ΔacidG0(OH) and ΔacidG0(CH) were calculated at the B3LYP and MP2 levels using six different standard basis sets for the OH and CH heterolytic bond cleavage of ethanol and twelve derivatives of the type CH3-nFnCHXrOH, where n ranges from zero to three and represents the number of fluorine atoms and r represents hydrogen and the type of aromatic ring, namely: X0 = hydrogen, X1 = phenyl, X2 = 1-naphthyl, and X3 = 9-anthryl. The similarity between calculated and experimental ΔacidG0(OH) values for ethanol (1a), 2-fluoroethanol (1b), 2,2-difluoroethanol (1c), 2,2,2-trifluoroethanol (1d), and 1-phenylethanol (2a) was used to validate the right theoretical method for this study. Substituent partial contributions to hydroxyl-, methylene-, and methine-hydrogen acidities were evaluated by linear combination. Good parameter fittings of the primary and secondary alcohols were obtained and interpreted as additive contribution of the substituent effects. The nonlinear contributions were identified. Calculations prove that fluoroalcohols exhibit C-H acidity, which is usually lower than O-H acidity. In principle, the inversion of this acidity order is possible by the introduction of a large aromatic ring instead to increase the number of fluorine atoms.

Variation of the water production rate of comet C/2013 X1 (PanSTARRS) from SOHO/SWAN observations throughout its apparition

NASA Astrophysics Data System (ADS)

Combi, Michael R.; Makinen, Terhi; Bertaux, Jean-Loup; Quémerais, Eric; Ferron, Stephane

2016-10-01

The all-sky hydrogen Lyman-alpha camera, SWAN (Solar Wind ANisotropies), on the SOlar and Heliospheric Observatory (SOHO) satellite makes observations of the hydrogen coma of comets. Most water vapor produced by comets is ultimately photodissociated into two H atoms (in addition to one O atom) producing a huge atomic hydrogen coma that is routinely observed in the daily full-sky SWAN images in comets of sufficient brightness. Water production rates are calculated using our time-resolved model (Mäkinen & Combi, 2005, Icarus 177, 217), typically yielding about 1 observation every 2 days on the average over an apparition. Here we describe the analysis of observations of bright comet C/2013 X1 (PanSTARRS) observed during 2016. C/2013 X1 reached a perihelion distance of 1.314278 AU on 20.72 April 2016. Its brightening toward the end of June 2016 is influenced by a somewhat close geocentric distance of 0.64 AU. A status update on the entire SOHO/SWAN archive of water production rates in comets will also be given. Support from grants NNX15AJ81G from the NASA Solar System Observations Planetary Astronomy Program and NNX13AQ66G from the NASA Planetary Mission Data Analysis Program are gratefully acknowledged, as is support from CNRS, CNES, and the Finnish Meteorological Institute (FMI).

Nitrilotris(methylenephosphonato)potassium K[μ{sup 6}-NH(CH{sub 2}PO{sub 3}){sub 3}H{sub 4}]: Synthesis, structure, and the nature of the K–O chemical bond

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

Somov, N. V., E-mail: somov@phys.unn.ru; Chausov, F. F., E-mail: xps@ftiudm.ru; Zakirova, R. M., E-mail: ftt@udsu.ru

2016-07-15

The crystal structure of nitrilotris(methylenephosphonato)potassium K[μ{sup 6}-NH(CH{sub 2}PO{sub 3}){sub 3}H{sub 4}]—a three-dimensional coordination polymer—was determined. The potassium atom is coordinated by seven oxygen atoms belonging to the six nearest ligand molecules, resulting in distorted monocapped octahedral coordination geometry. The complex contains the four-membered chelate ring K–O–P–O. The K–O chemical bond is predominantly ionic. Meanwhile, the bonds of the potassium atom with some oxygen atoms have a noticeable covalent component. In addition to coordination bonds, the molecules in the crystal packing are linked by hydrogen bonds.

Combinatorial Search for High-Activity Hydrogen Catalysts Based on Transition-Metal-Embedded Graphitic Carbons

DOE PAGES

Choi, Woon Ih; Wood, Brandon C.; Schwegler, Eric; ...

2015-09-22

Transition metal (TM) atoms in porphyrin–like complexes play important roles in many protein and enzymetic systems, where crystal–field effects are used to modify d–orbital levels. Inspired by the tunable electronic structure of these motifs, a high–throughput computational search for synthetic hydrogen catalysts is performed based on a similar motif of TM atoms embedded into the lattice of graphene. Based on an initial list of 300 possible embedding geometries, binders, and host atoms, descriptors for stability and catalytic activity are applied to extract ten promising candidates for hydrogen evolution, two of which are expected to exhibit high activity for hydrogen oxidation.more » In several instances, the active TM atoms are earth–abundant elements that show no activity in the bulk phase, highlighting the importance of the coordination environment in tuning the d–orbitals. In conclusion, it is found that the most active candidates involve a hitherto unreported surface reaction pathway that involves a Kubas–complex intermediate, which significantly lowers the kinetic barrier associated with hydrogen dissociation and association.« less

Repulsive tip tilting as the dominant mechanism for hydrogen bond-like features in atomic force microscopy imaging

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

Lee, Alex J.; Sakai, Yuki; Kim, Minjung

2016-05-09

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 frommore » repulsive tip tilting induced by neighboring electron-rich atoms.« less

Functionalized graphene-Pt composites for fuel cells and photoelectrochemical cells

DOEpatents

Diankov, Georgi; An, Jihwan; Park, Joonsuk; Goldhaber, David J. K.; Prinz, Friedrich B.

2017-08-29

A method of growing crystals on two-dimensional layered material is provided that includes reversibly hydrogenating a two-dimensional layered material, using a controlled radio-frequency hydrogen plasma, depositing Pt atoms on the reversibly hydrogenated two-dimensional layered material, using Atomic Layer Deposition (ALD), where the reversibly hydrogenated two-dimensional layered material promotes loss of methyl groups in an ALD Pt precursor, and forming Pt-O on the reversibly hydrogenated two-dimensional layered material, using combustion by O.sub.2, where the Pt-O is used for subsequent Pt half-cycles of the ALD process, where growth of Pt crystals occurs.

Influence of Hydrogen on Atomized Titanium Powders Sintering

NASA Astrophysics Data System (ADS)

Senkevich, K. S.

2018-07-01

The aim of this work is to study the effect of hydrogen reversible alloying (thermohydrogen processing, THP) on low-temperature sintering of atomized titanium powders. It is stated that alloying with 0.2 to 0.8 wt pct of hydrogen beneficially affects titanium powders sintering. The effect is caused by phase transformations occurring upon hydrogen saturation of powders and dehydrogenation, which substantially intensifies sintering at temperatures from 800 °C to 900 °C. The role of certain THP stages (sintering in hydrogenated state and upon dehydrogenation) on formation of sintered contacts in porous materials is shown.

Hydrogen-bond coordination in organic crystal structures: statistics, predictions and applications.

PubMed

Galek, Peter T A; Chisholm, James A; Pidcock, Elna; Wood, Peter A

2014-02-01

Statistical models to predict the number of hydrogen bonds that might be formed by any donor or acceptor atom in a crystal structure have been derived using organic structures in the Cambridge Structural Database. This hydrogen-bond coordination behaviour has been uniquely defined for more than 70 unique atom types, and has led to the development of a methodology to construct hypothetical hydrogen-bond arrangements. Comparing the constructed hydrogen-bond arrangements with known crystal structures shows promise in the assessment of structural stability, and some initial examples of industrially relevant polymorphs, co-crystals and hydrates are described.

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.

Influence of Hydrogen on Atomized Titanium Powders Sintering

NASA Astrophysics Data System (ADS)

Senkevich, K. S.

2018-05-01

The aim of this work is to study the effect of hydrogen reversible alloying (thermohydrogen processing, THP) on low-temperature sintering of atomized titanium powders. It is stated that alloying with 0.2 to 0.8 wt pct of hydrogen beneficially affects titanium powders sintering. The effect is caused by phase transformations occurring upon hydrogen saturation of powders and dehydrogenation, which substantially intensifies sintering at temperatures from 800 °C to 900 °C. The role of certain THP stages (sintering in hydrogenated state and upon dehydrogenation) on formation of sintered contacts in porous materials is shown.

Collision cascades enhanced hydrogen redistribution in cobalt implanted hydrogenated diamond-like carbon films

NASA Astrophysics Data System (ADS)

Gupta, P.; Becker, H.-W.; Williams, G. V. M.; Hübner, R.; Heinig, K.-H.; Markwitz, A.

2017-03-01

Hydrogenated diamond-like carbon films produced by C3H6 deposition at 5 kV and implanted at room temperature with 30 keV Co atoms to 12 at.% show not only a bimodal distribution of Co atoms but also a massive redistribution of hydrogen in the films. Resonant nuclear reaction analysis was used to measure the hydrogen depth profiles (15N-method). Depletion of hydrogen near the surface was measured to be as low as 7 at.% followed by hydrogen accumulation from 27 to 35 at.%. A model is proposed considering the thermal energy deposited by collision cascade for thermal insulators. In this model, sufficient energy is provided for dissociated hydrogen to diffuse out of the sample from the surface and diffuse into the sample towards the interface which is however limited by the range of the incoming Co ions. At a hydrogen concentration of ∼35 at.%, the concentration gradient of the mobile unbounded hydrogen atoms is neutralised effectively stopping diffusion towards the interface. The results point towards new routes of controlling the composition and distribution of elements at the nanoscale within a base matrix without using any heat treatment methods. Exploring these opportunities can lead to a new horizon of materials and device engineering needed for enabling advanced technologies and applications.

Neutral atom analyzers for diagnosing hot plasmas: A review of research at the ioffe physicotechnical institute

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

Kislyakov, A. I.; Petrov, M. P.

2009-07-15

Research on neutral particle diagnostics of thermonuclear plasmas that has been carried out in recent years at the Ioffe Physicotechnical Institute of the Russian Academy of Sciences (St. Petersburg, Russia) is reviewed. Work on the creation and improvement of neutral atom analyzers was done in two directions: for potential applications (in particular, on the International Thermonuclear Experimental Reactor, which is now under construction at Cadarache in France) and for investigation of the ion plasma component in various devices (in particular, in the largest tokamaks, such as JET, TFTR, and JT-60). Neutral atom analyzers are the main tool for studying themore » behavior of hydrogen ions and isotopes in magnetic confinement systems. They make it possible to determine energy spectra, to perform the isotope analysis of atom fluxes from the plasma, to measure the absolute intensity of the fluxes, and to record how these parameters vary with time. A comparative description of the analyzers developed in recent years at the Ioffe Institute is given. These are ACORD-12/24 analyzers for recording 0.2-100-keV hydrogen and deuterium atoms with a tunable range of simultaneously measured energies, CNPA compact analyzers for a fixed energy gain in the ranges 80-1000 eV and 0.8-100 keV, an ISEP analyzer for simultaneously recording the atoms of all the three hydrogen isotopes (H, D, and T) in the energy range 5-700 keV, and GEMMA analyzers for recording atom fluxes of hydrogen and helium isotopes in the range 0.1-4 MeV. The scintillating detectors of the ISEP and GEMMA analyzers have a lowered sensitivity to neutrons and thus can operate without additional shielding in neutron fields of up to 10{sup 9} n/(cm{sup 2} s). These two types of analyzers, intended to operate under deuterium-tritium plasma conditions, are prototypes of atom analyzers created at the Ioffe Institute for use in the International Thermonuclear Experimental Reactor. With these analyzers, a number of new results have been obtained in recent years in various devices. Some results are presented from investigation of ions in the Globus-M spherical tokamak, the W7-AS stellarator, and the JET tokamak by means of the analyzers developed at the Ioffe Institute. Challenges and opportunities for applying these diagnostics in the International Thermonuclear Experimental Reactor project are discussed.« less

DFT STUDY OF HYDROGEN STORAGE ON Li- AND Na-DOPED C59B HETEROFULLERENE

NASA Astrophysics Data System (ADS)

Zahedi, Ehsan; Mozaffari, Majid

2014-05-01

Effect of light alkali metal (Li and Na) decorated on the C59B heterofullerene for hydrogen storage is considered using DFT-MPW1PW91 method. Results show that Li and Na atoms strongly prefer to adsorb on top of five-member and six-member ring where a carbon atom is replaced by a boron atom. Significant charge transfer from the alkali metal to the C59B compensates for the electron deficiency of C59B and makes the latter aromatic in nature. Corrected binding energies of hydrogen molecule on the alkali-doped C59B using counterpoise method, structural properties and NBO analysis indicate that first hydrogen molecule is adsorbed physically and does not support minimal conditions of DOE requirement. Finally, positive values of binding energies for the adsorption of a second hydrogen molecule show that alkali doped C59B are capable of storing a maximum of one hydrogen molecule.

Analytical transition-matrix treatment of electric multipole polarizabilities of hydrogen-like atoms

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

Kharchenko, V.F., E-mail: vkharchenko@bitp.kiev.ua

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 determinemore » 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.« less

On the thermal stability of graphone

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

Podlivaev, A. I.; Openov, L. A., E-mail: LAOpenov@mephi.ru

2011-07-15

Molecular dynamics simulation is used to study thermally activated migration of hydrogen atoms in graphone, a magnetic semiconductor formed of a graphene monolayer with one side covered with hydrogen. The temperature dependence of the characteristic time of disordering of graphone via hopping of hydrogen atoms to neighboring carbon atoms is established directly. The activation energy of this process is determined at E{sub a} = (0.05 {+-} 0.01) eV. The small value of E{sub a} is indicative of the extremely low thermal stability of graphone. The low stability presents a serious handicap for practical use of the material in nanoelectronics.

Hyperspherical Symmetry of Hydrogenic Orbitals and Recoupling Coefficients among Alternative Bases

NASA Astrophysics Data System (ADS)

Aquilanti, Vincenzo; Cavalli, Simonetta; Coletti, Cecilia

1998-04-01

Fock's representation of momentum space hydrogenic orbitals in terms of harmonics on the hypersphere S3 of a four-dimensional space is extended to classify alternative bases. These orbitals are of interest for Sturmian expansions of use in atomic and molecular structure calculations and for the description of atoms in fields. Because of the correspondence between the S3 manifold and the SU\\(2\\) group, new sum rules are established which are of relevance for the connection, not only among hydrogen atom orbitals in different bases, but also among the usual vector coupling coefficients and rotation matrix elements.

Effect of Ge atoms on crystal structure and optoelectronic properties of hydrogenated Si-Ge films

NASA Astrophysics Data System (ADS)

Li, Tianwei; Zhang, Jianjun; Ma, Ying; Yu, Yunwu; Zhao, Ying

2017-07-01

Optoelectronic and structural properties of hydrogenated microcrystalline silicon-germanium (μc-Si1-xGex:H) alloys prepared by radio-frequency plasma-enhanced chemical vapor deposition (RF-PECVD) were investigated. When the Ge atoms were predominantly incorporated in amorphous matrix, the dark and photo-conductivity decreased due to the reduced crystalline volume fraction of the Si atoms (XSi-Si) and the increased Ge dangling bond density. The photosensitivity decreased monotonously with Ge incorporation under higher hydrogen dilution condition, which was attributed to the increase in both crystallization of Ge and the defect density.

Structure and Dynamics of Hydroxyl-Functionalized Protic Ammonium Carboxylate Ionic Liquids.

PubMed

Thummuru, Dhileep Nagi Reddy; Mallik, Bhabani S

2017-10-26

We performed classical molecular dynamics simulations to investigate the structure and dynamics of protic ionic liquids, 2-hydroxy ethylammonium acetate, ethylammonium hydroxyacetate, and 2-hydroxyethylammonium hydroxyacetate at ambient conditions. Structural properties such as density, radial distribution functions, spatial distribution functions, and structure factors have been calculated. Dynamic properties such as mean square displacements, as well as residence and hydrogen bond dynamics have also been calculated. Hydrogen bond lifetimes and residence times change with the addition of hydroxyl groups. We observe that when a hydroxyl group is present on the cation, dynamics become very slow and it forms a strong hydrogen bond with carboxylate oxygen atoms of the anion. The hydroxyl functionalized ILs show more dynamic diversity than structurally similar ILs.

Constraints on Vesta's elemental composition: Fast neutron measurements by Dawn's gamma ray and neutron detector

PubMed Central

Lawrence, David J; Peplowski, Patrick N; Prettyman, Thomas H; Feldman, William C; Bazell, David; Mittlefehldt, David W; Reedy, Robert C; Yamashita, Naoyuki

2013-01-01

Surface composition information from Vesta is reported using fast neutron data collected by the gamma ray and neutron detector on the Dawn spacecraft. After correcting for variations due to hydrogen, fast neutrons show a compositional dynamic range and spatial variability that is consistent with variations in average atomic mass from howardite, eucrite, and diogenite (HED) meteorites. These data provide additional compositional evidence that Vesta is the parent body to HED meteorites. A subset of fast neutron data having lower statistical precision show spatial variations that are consistent with a 400 ppm variability in hydrogen concentrations across Vesta and supports the idea that Vesta's hydrogen is due to long-term delivery of carbonaceous chondrite material. PMID:26074718

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

DOE PAGES

Cho, Eun Seon; Ruminski, Anne M.; Aloni, Shaul; ...

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 H 2 per litre inmore » 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. 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

Hydrogen absorption-desorption properties of U 2Ti

NASA Astrophysics Data System (ADS)

Takuya, Yamamoto; Satoru, Tanaka; Michio, Yamawaki

1990-02-01

Hydrogen absorption-desorption properties of U 2Ti intermetallic compound was examined over the temperature range of 298 to 973 K and at hydrogen pressures below 10 5 Pa. It absorbs hydrogen up to 7.6 atoms per F.U. (formula unit) by two step reactions and hence each desorption isotherm is separated into two plateau regions. In the first plateau, a newly-found ternary hydride is formed, where the hydrogen concentration, cH, reaches 2.4 H atoms/F.U. In the second plateau, UH 3 is formed and cH reaches 7.6 H atoms/F.U. The specimen is disintegrated into fine powder in the second plateau, while in the first plateau the ternary hydride which was identified to be UTi 2H x, ( x = 4.8 to 6.2) showed high durability against powdering. It is predicted that UTi 2 can be suitable material for tritium storage.

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.

Homologation process making higher alcohols

DOEpatents

Leung, Tak W.; Dombek, Bernard D.

1990-01-01

A liquid phase process for the manufacture of C.sub.2+ alkanols by the reaction of hydrogen with carbon monoxide in the presence of a catalyst containing ruthenium, cobalt, a halide-containing compound, and an aromatic compound substituted in adjacent ring positions by nitrogen atoms. The process embraces the use of rhodium as an additive to the catalyst system.

Surface characterization of hydrogen charged and uncharged alpha-2 and gamma titanium aluminide alloys using AES and REELS

NASA Technical Reports Server (NTRS)

Shanabarger, M. R.

1990-01-01

The surfaces of selected uncharged and hydrogen charged alpha-2 and gamma titanium aluminide alloys with Nb additions were characterized by Auger electron (AES) and reflected electron energy loss (REELS) spectroscopy. The alloy surfaces were cleaned before analysis at room temperature by ion sputtering. The low energy (500 eV) ion sputtering process preferentially sputtered the surface concentration. The surface concentrations were determined by comparing AES data from the alloys with corresponding data from elemental references. No differences were observed in the Ti or Nb Auger spectra for the uncharged and hydrogen charged alloys, even though the alpha-2 alloy had 33.4 atomic percent dissolved hydrogen. Also, no differences were observed in the AES spectra when hydrogen was adsorbed from the gas phase. Bulk plasmon energy shifts were observed in all alloys. The energy shifts were induced either by dissolved hydrogen (alpha-2 alloy) or hydrogen adsorbed from the gas phase (alpha-2 and gamma alloys). The adsorption induced plasmon energy shifts were greatest for the gamma alloy and cp-Ti metal.

Enhanced etching of tin-doped indium oxide due to surface modification by hydrogen ion injection

NASA Astrophysics Data System (ADS)

Li, Hu; Karahashi, Kazuhiro; Friederich, Pascal; Fink, Karin; Fukasawa, Masanaga; Hirata, Akiko; Nagahata, Kazunori; Tatsumi, Tetsuya; Wenzel, Wolfgang; Hamaguchi, Satoshi

2018-06-01

It is known that the etching yield (i.e., sputtering yield) of tin-doped indium oxide (ITO) by hydrocarbon ions (CH x +) is higher than its corresponding physical sputtering yield [H. Li et al., J. Vac. Sci. Technol. A 33, 060606 (2015)]. In this study, the effects of hydrogen in the incident hydrocarbon ion beam on the etching yield of ITO have been examined experimentally and theoretically with the use of a mass-selected ion beam system and by first-principles quantum mechanical (QM) simulation. As in the case of ZnO [H. Li et al., J. Vac. Sci. Technol. A 35, 05C303 (2017)], mass-selected ion beam experiments have shown that the physical sputtering yield of ITO by chemically inert Ne ions increases after a pretreatment of the ITO film by energetic hydrogen ion injection. First-principles QM simulation of the interaction of In2O3 with hydrogen atoms shows that hydrogen atoms embedded in In2O3 readily form hydroxyl (OH) groups and weaken or break In–O bonds around the hydrogen atoms, making the In2O3 film less resistant to physical sputtering. This is consistent with experimental observation of the enhanced etching yields of ITO by CH x + ions, considering the fact that hydrogen atoms of the incident CH x + ions are embedded into ITO during the etching process.

Hydrogen adsorption site on the Ni?110?-p(1 × 2)-H surface from time-of-flight scattering and recoiling spectrometry (TOF-SARS)

NASA Astrophysics Data System (ADS)

Bu, H.; Roux, C. D.; Rabalais, J. W.

The adsorption site of hydrogen on the Ni{110}-p(1 × 2)-H surface resulting from saturation exposure to H 2 at ˜ 310-350 K has been investigated by time-of-flight scattering and recoiling spectrometry (TOF-SARS). The recoiled neutral plus ion hydrogen atom flux resulting from 2-5 keV Ar + or Ne + pulsed ion beams incident on the surface was monitored as a function of crystal azimuthal angle and beam incidence angle. From classical trajectory calculations and shadowing and blocking analyses, it is concluded that hydrogen atoms are localized at the pseudo-three-fold sites on the (1 × 2) missing-row (MR) reconstructed Ni{110} surface; the (1 × 2) MR reconstruction is induced by hydrogen adsorption shown elsewhere [Surf. Sci. 259 (1991) 253]. Only the pseudo-three-fold site is consistent with all of the experimental data. The coordinates of the hydrogen adsorption site with respect to the nickel lattice were determined. The lateral distance of hydrogen from the 1st-layer Ni <1 overline10> rows is 1.56 ± 0.12 Å and the vertical distance above the substrate is 0.21 ± 0.12 Å, providing NiH bond lengths of 2.0 Å to the two-layer Ni atoms and 1.5 Å to the 2nd-layer Ni atom.

The Potential Role Played by the Fullerene-Like Structures of Interstellar Carbon Dust in the Formation of Molecular Hydrogen in Space

NASA Astrophysics Data System (ADS)

Cataldo, Franco; Iglesias-Groth, Susana

After a general introduction to the problem of formation of molecular hydrogen from atomic hydrogen in the interstellar medium and in the dense molecular clouds in particular, and after the explanation of the key role played by the surfaces on this process, it is proposed that the most suitable carbon surface for the formation of molecular hydrogen (from the radiative association process of atomic hydrogen) can be represented by carbon black rather than by graphite. Furthermore, it is proposed that the fullerene-like structures present in the carbon black graphene sheets are the reaction sites where molecular hydrogen may be formed.

Deposition of device quality low H content, amorphous silicon films

DOEpatents

Mahan, A.H.; Carapella, J.C.; Gallagher, A.C.

1995-03-14

A high quality, low hydrogen content, hydrogenated amorphous silicon (a-Si:H) film is deposited by passing a stream of silane gas (SiH{sub 4}) over a high temperature, 2,000 C, tungsten (W) filament in the proximity of a high temperature, 400 C, substrate within a low pressure, 8 mTorr, deposition chamber. The silane gas is decomposed into atomic hydrogen and silicon, which in turn collides preferably not more than 20--30 times before being deposited on the hot substrate. The hydrogenated amorphous silicon films thus produced have only about one atomic percent hydrogen, yet have device quality electrical, chemical, and structural properties, despite this lowered hydrogen content. 7 figs.

Deposition of device quality low H content, amorphous silicon films

DOEpatents

Mahan, Archie H.; Carapella, Jeffrey C.; Gallagher, Alan C.

1995-01-01

A high quality, low hydrogen content, hydrogenated amorphous silicon (a-Si:H) film is deposited by passing a stream of silane gas (SiH.sub.4) over a high temperature, 2000.degree. C., tungsten (W) filament in the proximity of a high temperature, 400.degree. C., substrate within a low pressure, 8 mTorr, deposition chamber. The silane gas is decomposed into atomic hydrogen and silicon, which in turn collides preferably not more than 20-30 times before being deposited on the hot substrate. The hydrogenated amorphous silicon films thus produced have only about one atomic percent hydrogen, yet have device quality electrical, chemical, and structural properties, despite this lowered hydrogen content.

Direct observation and control of hydrogen-bond dynamics using low-temperature scanning tunneling microscopy

NASA Astrophysics Data System (ADS)

Kumagai, Takashi

2015-08-01

Hydrogen(H)-bond dynamics are involved in many elementary processes in chemistry and biology. Because of its fundamental importance, a variety of experimental and theoretical approaches have been employed to study the dynamics in gas, liquid, solid phases, and their interfaces. This review describes the recent progress of direct observation and control of H-bond dynamics in several model systems on a metal surface by using low-temperature scanning tunneling microscopy (STM). General aspects of H-bond dynamics and the experimental methods are briefly described in chapter 1 and 2. In the subsequent four chapters, I present direct observation of an H-bond exchange reaction within a single water dimer (chapter 3), a symmetric H bond (chapter 4) and H-atom relay reactions (chapter 5) within water-hydroxyl complexes, and an intramolecular H-atom transfer reaction (tautomerization) within a single porphycene molecule (chapter 6). These results provide novel microscopic insights into H-bond dynamics at the single-molecule level, and highlight significant impact on the process from quantum effects, namely tunneling and zero-point vibration, resulting from the small mass of H atom. Additionally, local environmental effect on H-bond dynamics is also examined by using atom/molecule manipulation with the STM.

Lamb shift and fine structure at n =2 in a hydrogenlike muonic atom with the nuclear spin I =0

NASA Astrophysics Data System (ADS)

Korzinin, Evgeny Yu.; Shelyuto, Valery A.; Ivanov, Vladimir G.; Karshenboim, Savely G.

2018-01-01

The paper is devoted to the Lamb shift and fine structure in a hydrogenlike muonic atom with a spinless nucleus up to the order α5m with all the recoil corrections included. Enhanced contributions of a higher order are also considered. We present the results on the pure QED contribution and on the finite-nuclear-size contribution, proportional to RN2, with the higher-order corrections included. We also consider the consistency of the pure QED theory and the evaluation of the nuclear-structure effects. Most of the QED theory is the same as the theory for the case of the nuclear spin 1/2. Additional nuclear-spin-dependent terms are considered in detail. The issue of the difference for the theories with a spinor nucleus and a scalar one is discussed for the recoil contributions in the order (Zα ) 4m ,α (Zα ) 4m , and (Zα ) 5m . The numerical results are presented for the muonic atoms with two lightest scalar nuclei, helium-4 and beryllium-10. We compare the theory of those muonic atoms with theory for the muonic hydrogen. Some higher-order finite-nuclear-size corrections for the Lamb shift in muonic hydrogen are revisited.

2-Amino­pyrimidin-1-ium 4-methyl­benzene­sulfonate

PubMed Central

Tabatabaee, Masoumeh; Noozari, Najmeh

2011-01-01

In the crystal structure of the title compound, C4H6N3 +·C7H7O3S−, inter­molecular N—H⋯O hydrogen bonds link the cations and anions into chains along [100]. Additional stabilization is provided by weak C—H⋯O hydrogen bonds. An inter­molecular π–π stacking inter­action with a centroid–centroid distance of 3.6957 (7) Å is also observed. The H atoms of the methyl group were refined as disordered over two sets of sites with equal occupancies PMID:21754830

Spectroscopic properties of vitamin E models in solution

NASA Astrophysics Data System (ADS)

Oliveira, L. B. A.; Colherinhas, G.; Fonseca, T. L.; Castro, M. A.

2015-05-01

We investigate the first absorption band and the 13C and 17O magnetic shieldings of vitamin E models in chloroform and in water using the S-MC/QM methodology in combination with the TD-DFT and GIAO approaches. The results show that the solvent effects on these spectroscopic properties are small but a proper description of the solvent shift for 17O magnetic shielding of the hydroxyl group in water requires the use of explicit solute-solvent hydrogen bonds. In addition, the effect of the replacement of hydrogen atoms by methyl groups in the vitamin E models only affects magnetic shieldings.

Surface loss probability of atomic hydrogen for different electrode cover materials investigated in H₂-Ar low-pressure plasmas

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

Sode, M., E-mail: maik.sode@ipp.mpg.de; Schwarz-Selinger, T.; Jacob, W.

2014-07-07

In an inductively coupled H₂-Ar plasma at a total pressure of 1.5 Pa, the influence of the electrode cover material on selected line intensities of H, H₂, and Ar are determined by optical emission spectroscopy and actinometry for the electrode cover materials stainless steel, copper, tungsten, Macor{sup ®}, and aluminum. Hydrogen dissociation degrees for the considered conditions are determined experimentally from the measured emission intensity ratios. The surface loss probability β{sub H} of atomic hydrogen is correlated with the measured line intensities, and β{sub H} values are determined for the considered materials. Without the knowledge of the atomic hydrogen temperature,more » β{sub H} cannot be determined exactly. However, ratios of β{sub H} values for different surface materials are in first order approximation independent of the atomic hydrogen temperature. Our results show that β{sub H} of copper is equal to the value of stainless steel, β{sub H} of Macor{sup ®} and tungsten is about 2 times smaller and β{sub H} of aluminum about 5 times smaller compared with stainless steel. The latter ratio is in reasonable agreement with literature. The influence of the atomic hydrogen temperature T{sub H} on the absolute value is thoroughly discussed. For our assumption of T{sub H}=600 K, we determine a β{sub H} for stainless steel of 0.39±0.13.« less

Communication: Hydrogen bonding interactions in water-alcohol mixtures from X-ray absorption spectroscopy

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

Lam, Royce K.; Smith, Jacob W.; Saykally, Richard J., E-mail: saykally@berkeley.edu

While methanol and ethanol are macroscopically miscible with water, their mixtures exhibit negative excess entropies of mixing. Despite considerable effort in both experiment and theory, there remains significant disagreement regarding the origin of this effect. Different models for the liquid mixture structure have been proposed to address this behavior, including the enhancement of the water hydrogen bonding network around the alcohol hydrophobic groups and microscopic immiscibility or clustering. We have investigated mixtures of methanol, ethanol, and isopropanol with water by liquid microjet X-ray absorption spectroscopy on the oxygen K-edge, an atom-specific probe providing details of both inter- and intra-molecular structure.more » The measured spectra evidence a significant enhancement of hydrogen bonding originating from the methanol and ethanol hydroxyl groups upon the addition of water. These additional hydrogen bonding interactions would strengthen the liquid-liquid interactions, resulting in additional ordering in the liquid structures and leading to a reduction in entropy and a negative enthalpy of mixing, consistent with existing thermodynamic data. In contrast, the spectra of the isopropanol-water mixtures exhibit an increase in the number of broken alcohol hydrogen bonds for mixtures containing up to 0.5 water mole fraction, an observation consistent with existing enthalpy of mixing data, suggesting that the measured negative excess entropy is a result of clustering or micro-immiscibility.« less

Computer Animation of a Chemical Reaction.

ERIC Educational Resources Information Center

Eaker, Charles W.; Jacobs, Edwin L.

1982-01-01

Taking a prototype chemical reaction (molecular hydrogen plus hydrogen atom), constructs an accurate semiempirical, generalized diatomics-in-molecules potential energy surface, calculates motions of these atoms on this surface using REACTS trajectory program, and presents results as moving picture on a microcomputer graphics system. Provides…

Hydrogen Embrittlement

NASA Technical Reports Server (NTRS)

Woods, Stephen; Lee, Jonathan A.

2016-01-01

Hydrogen embrittlement (HE) is a process resulting in a decrease in the fracture toughness or ductility of a metal due to the presence of atomic hydrogen. In addition to pure hydrogen gas as a direct source for the absorption of atomic hydrogen, the damaging effect can manifest itself from other hydrogen-containing gas species such as hydrogen sulfide (H2S), hydrogen chloride (HCl), and hydrogen bromide (HBr) environments. It has been known that H2S environment may result in a much more severe condition of embrittlement than pure hydrogen gas (H2) for certain types of alloys at similar conditions of stress and gas pressure. The reduction of fracture loads can occur at levels well below the yield strength of the material. Hydrogen embrittlement is usually manifest in terms of singular sharp cracks, in contrast to the extensive branching observed for stress corrosion cracking. The initial crack openings and the local deformation associated with crack propagation may be so small that they are difficult to detect except in special nondestructive examinations. Cracks due to HE can grow rapidly with little macroscopic evidence of mechanical deformation in materials that are normally quite ductile. This Technical Memorandum presents a comprehensive review of experimental data for the effects of gaseous Hydrogen Environment Embrittlement (HEE) for several types of metallic materials. Common material screening methods are used to rate the hydrogen degradation of mechanical properties that occur while the material is under an applied stress and exposed to gaseous hydrogen as compared to air or helium, under slow strain rates (SSR) testing. Due to the simplicity and accelerated nature of these tests, the results expressed in terms of HEE index are not intended to necessarily represent true hydrogen service environment for long-term exposure, but rather to provide a practical approach for material screening, which is a useful concept to qualitatively evaluate the severity of hydrogen embrittlement. The effects of hydrogen gas on mechanical properties such as tensile strength, ductility, fracture, low and high cycle fatigue, crack growth rate, and creep rupture are analyzed with respect to the general trends established from the HEE index values. It is observed that the severity of HE effects is also influenced by environmental factors such as pressure, temperature, and hydrogen gas purity. The severity of HE effects is also influenced by material factors such as surface finish, heat treatment, and product forms, compositions, grain direction, and crystal orientations.

Aggregation Number in Water/n-Hexanol Molecular Clusters Formed in Cyclohexane at Different Water/n-Hexanol/Cyclohexane Compositions Calculated by Titration 1H NMR.

PubMed

Flores, Mario E; Shibue, Toshimichi; Sugimura, Natsuhiko; Nishide, Hiroyuki; Moreno-Villoslada, Ignacio

2017-11-09

Upon titration of n-hexanol/cyclohexane mixtures of different molar compositions with water, water/n-hexanol clusters are formed in cyclohexane. Here, we develop a new method to estimate the water and n-hexanol aggregation numbers in the clusters that combines integration analysis in one-dimensional 1 H NMR spectra, diffusion coefficients calculated by diffusion-ordered NMR spectroscopy, and further application of the Stokes-Einstein equation to calculate the hydrodynamic volume of the clusters. Aggregation numbers of 5-15 molecules of n-hexanol per cluster in the absence of water were observed in the whole range of n-hexanol/cyclohexane molar fractions studied. After saturation with water, aggregation numbers of 6-13 n-hexanol and 0.5-5 water molecules per cluster were found. O-H and O-O atom distances related to hydrogen bonds between donor/acceptor molecules were theoretically calculated using density functional theory. The results show that at low n-hexanol molar fractions, where a robust hydrogen-bond network is held between n-hexanol molecules, addition of water makes the intermolecular O-O atom distance shorter, reinforcing molecular association in the clusters, whereas at high n-hexanol molar fractions, where dipole-dipole interactions dominate, addition of water makes the intermolecular O-O atom distance longer, weakening the cluster structure. This correlates with experimental NMR results, which show an increase in the size and aggregation number in the clusters upon addition of water at low n-hexanol molar fractions, and a decrease of these magnitudes at high n-hexanol molar fractions. In addition, water produces an increase in the proton exchange rate between donor/acceptor molecules at all n-hexanol molar fractions.

An Electron Density Source-Function Study of DNA Base Pairs in Their Neutral and Ionized Ground States†.

PubMed

Gatti, Carlo; Macetti, Giovanni; Boyd, Russell J; Matta, Chérif F

2018-07-05

The source function (SF) decomposes the electron density at any point into contributions from all other points in the molecule, complex, or crystal. The SF "illuminates" those regions in a molecule that most contribute to the electron density at a point of reference. When this point of reference is the bond critical point (BCP), a commonly used surrogate of chemical bonding, then the SF analysis at an atomic resolution within the framework of Bader's Quantum Theory of Atoms in Molecules returns the contribution of each atom in the system to the electron density at that BCP. The SF is used to locate the important regions that control the hydrogen bonds in both Watson-Crick (WC) DNA dimers (adenine:thymine (AT) and guanine:cytosine (GC)) which are studied in their neutral and their singly ionized (radical cationic and anionic) ground states. The atomic contributions to the electron density at the BCPs of the hydrogen bonds in the two dimers are found to be delocalized to various extents. Surprisingly, gaining or loosing an electron has similar net effects on some hydrogen bonds concealing subtle compensations traced to atomic sources contributions. Coarser levels of resolutions (groups, rings, and/or monomers-in-dimers) reveal that distant groups and rings often have non-negligible effects especially on the weaker hydrogen bonds such as the third weak CH⋅⋅⋅O hydrogen bond in AT. Interestingly, neither the purine nor the pyrimidine in the neutral or ionized forms dominate any given hydrogen bond despite that the former has more atoms that can act as source or sink for the density at its BCP. © 2018 Wiley Periodicals, Inc. © 2018 Wiley Periodicals, Inc.

Atomic Forces for Geometry-Dependent Point Multipole and Gaussian Multipole Models

PubMed Central

Elking, Dennis M.; Perera, Lalith; Duke, Robert; Darden, Thomas; Pedersen, Lee G.

2010-01-01

In standard treatments of atomic multipole models, interaction energies, total molecular forces, and total molecular torques are given for multipolar interactions between rigid molecules. However, if the molecules are assumed to be flexible, two additional multipolar atomic forces arise due to 1) the transfer of torque between neighboring atoms, and 2) the dependence of multipole moment on internal geometry (bond lengths, bond angles, etc.) for geometry-dependent multipole models. In the current study, atomic force expressions for geometry-dependent multipoles are presented for use in simulations of flexible molecules. The atomic forces are derived by first proposing a new general expression for Wigner function derivatives ∂Dlm′m/∂Ω. The force equations can be applied to electrostatic models based on atomic point multipoles or Gaussian multipole charge density. Hydrogen bonded dimers are used to test the inter-molecular electrostatic energies and atomic forces calculated by geometry-dependent multipoles fit to the ab initio electrostatic potential (ESP). The electrostatic energies and forces are compared to their reference ab initio values. It is shown that both static and geometry-dependent multipole models are able to reproduce total molecular forces and torques with respect to ab initio, while geometry-dependent multipoles are needed to reproduce ab initio atomic forces. The expressions for atomic force can be used in simulations of flexible molecules with atomic multipoles. In addition, the results presented in this work should lead to further development of next generation force fields composed of geometry-dependent multipole models. PMID:20839297

Hot hydrogen and oxygen atoms in the upper atmospheres of Venus and Mars

NASA Astrophysics Data System (ADS)

Nagy, A. F.; Kim, J.; Cravens, T. E.

1990-04-01

Optical observations of hot atoms in the atmospheres of Venus and Mars are briefly reviewed. A summary of hot hydrogen and oxygen production and loss processes is given. Results of some recent model calculations as well as a number of new results of the hot hydrogen and oxygen populations are presented and their implication in terms of solar wind interaction processes is discussed.

The First Stars in the Universe and Cosmic Reionization

NASA Astrophysics Data System (ADS)

Barkana, Rennan

2006-08-01

The earliest generation of stars, far from being a mere novelty, transformed the universe from darkness to light. The first atoms to form after the Big Bang filled the universe with atomic hydrogen and a few light elements. As gravity pulled gas clouds together, the first stars ignited and their radiation turned the surrounding atoms into ions. By looking at gas between us and distant galaxies, we know that this ionization eventually pervaded all space, so that few hydrogen atoms remain today between galaxies. Knowing exactly when and how it did so is a primary goal of cosmologists, because this would tell us when the early stars formed and in what kinds of galaxies. Although this ionization is beginning to be understood by using theoretical models and computer simulations, a new generation of telescopes is being built that will map atomic hydrogen throughout the universe.

Periodic density functional theory study of ethylene hydrogenation over Co3O4 (1 1 1) surface: The critical role of oxygen vacancies

NASA Astrophysics Data System (ADS)

Lu, Jinhui; Song, JiaJia; Niu, Hongling; Pan, Lun; Zhang, Xiangwen; Wang, Li; Zou, Ji-Jun

2016-05-01

Recently, metal oxides are attracting increasing interests as hydrogenation catalyst. Herein we studied the hydrogenation of ethylene on perfect and oxygen defective Co3O4 (1 1 1) using periodic density functional theory. The energetics and pathways of ethylene hydrogenation to ethane were determined. We have demonstrated that (i) H2 dissociation on Co3O4 is a complicated two-step process through a heterolytic cleavage, followed by the migration of H atom and finally yields the homolytic product on both perfect and oxygen defective Co3O4 (1 1 1) surfaces easily. (ii) After introducing the surface oxygen vacancy, the stepwise hydrogenation of ethylene by atomic hydrogen is much easier than that on perfect surface due to the weaker bond strength of OH group. The strength of Osbnd H bond is a crucial factor for the hydrogenation reaction which involves the breakage of Osbnd H bond. The formation of oxygen vacancy increases the electronic charges at the adjacent surface O, which reduces its capability of further gaining electrons from adsorbed atomic hydrogen and then weakens the strength of Osbnd H bond. These results emphasize the importance of the oxygen vacancies for hydrogenation on metal oxides.

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

Tsuo, Y.S.; Smith, E.B.; Deb, S.K.

A Kaufman ion beam source was used to implant hydrogen atoms into glow-discharge-deposited amorphous silicon materials in which the hydrogen content had been driven out by heating. We found that the hydrogen atoms introduced by this low-energy (less than 700 eV) ion implantation method bonded predominantly as SiH. An air mass one, photo-to-dark-conductivity ratio as high as 5.6 x 10/sup 5/ has been obtained with hydrogen-implanted materials. No light-induced reduction of the photo- and dark conductivities has been observed in these materials after 20 h of AMl illumnination.

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.

Development of an Mg-Based Alloy with a Hydrogen-Storage Capacity over 6 wt% by Adding Graphene

NASA Astrophysics Data System (ADS)

Choi, Eunho; Kwak, Young Jun; Song, Myoung Youp

2018-06-01

Graphene (multilayer graphene) was chosen as an additive to improve the hydrogen uptake and release properties of magnesium (Mg). Five weight percent of graphene was added to pre-milled Mg by milling in hydrogen (reaction-involving milling). The hydrogen uptake and release properties of the graphene-added Mg were investigated. The activation of Mg-5graphene, which was prepared by adding 5 wt% graphene to Mg pre-milled for 24 h, was completed after the second cycle (cycle number, CN = 2). Mg-5graphene had a high effective hydrogen-storage capacity (the quantity of hydrogen absorbed for 60 min) of 6.21 wt% at CN = 3 at 593 K in 12 bar H2. At CN = 1, Mg-5graphene released 0.46 wt% hydrogen for 10 min and 4.99 wt% hydrogen for 60 min. Milling in hydrogen is believed to create defects (leading to facilitation of nucleation), produce cracks and clean surfaces (leading to increase in reactivity), and decrease particle size (leading to diminution of diffusion distances or increasing the flux of diffusing hydrogen atoms). The added graphene is believed to have helped the sample have higher hydrogen uptake and release rates, weakly but partly, by dispersing heat rapidly.

Direct atomic-scale imaging of hydrogen and oxygen interstitials in pure niobium using atom-probe tomography and aberration-corrected scanning transmission electron microscopy.

PubMed

Kim, Yoon-Jun; Tao, Runzhe; Klie, Robert F; Seidman, David N

2013-01-22

Imaging the three-dimensional atomic-scale structure of complex interfaces has been the goal of many recent studies, due to its importance to technologically relevant areas. Combining atom-probe tomography and aberration-corrected scanning transmission electron microscopy (STEM), we present an atomic-scale study of ultrathin (~5 nm) native oxide layers on niobium (Nb) and the formation of ordered niobium hydride phases near the oxide/Nb interface. Nb, an elemental type-II superconductor with the highest critical temperature (T(c) = 9.2 K), is the preferred material for superconducting radio frequency (SRF) cavities in next-generation particle accelerators. Nb exhibits high solubilities for oxygen and hydrogen, especially within the RF-field penetration depth, which is believed to result in SRF quality factor losses. STEM imaging and electron energy-loss spectroscopy followed by ultraviolet laser-assisted local-electrode atom-probe tomography on the same needle-like sample reveals the NbO(2), Nb(2)O(5), NbO, Nb stacking sequence; annular bright-field imaging is used to visualize directly hydrogen atoms in bulk β-NbH.

Hydrogen maser oscillation at 10 K

NASA Technical Reports Server (NTRS)

Crampton, S. B.; Jones, K. M.; Souza, S. P.

1984-01-01

A low temperature atomic hydrogen maser was developed using frozen atomic neon as the storage surface. The maser has been operated in the pulsed mode at temperatures from 6 K to 11 K and as a self-excited oscillator from 9 K to 10.5 K.

Effects of the molecule-electrode interface on the low-bias conductance of Cu-H2-Cu single-molecule junctions.

PubMed

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

2016-07-28

The atomic structure and electronic transport properties of a single hydrogen molecule connected to both symmetric and asymmetric Cu electrodes are investigated by using the non-equilibrium Green's function formalism combined with the density functional theory. Our calculations show that in symmetric Cu-H2-Cu junctions, the low-bias conductance drops rapidly upon stretching, while asymmetric ones present a low-bias conductance spanning the 0.2-0.3 G0 interval for a wide range of electrode separations. This is in good agreement with experiments on Cu atomic contacts in a hydrogen environment. Furthermore, the distribution of the calculated vibrational energies of the two hydrogen atoms in the asymmetric Cu-H2-Cu junction is also consistent with experiments. These findings provide clear evidence for the formation of asymmetric Cu-H2-Cu molecular junctions in breaking Cu atomic contacts in the presence of hydrogen and are also helpful for the design of molecular devices with Cu electrodes.

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

Gabriel, O.; Harskamp, W. E. N. van; Schram, D. C.

The cascaded arc is a plasma source providing high fluxes of excited and reactive species such as ions, radicals and rovibrationally excited molecules. The plasma is produced under pressures of some kPa in a direct current arc with electrical powers up to 10 kW. The plasma leaves the arc channel through a nozzle and expands with supersonic velocity into a vacuum-chamber kept by pumps at low pressures. We investigated the case of a pure hydrogen plasma jet with and without an applied axial magnetic field that confines ions and electrons in the jet. Highly excited molecules and atoms were detectedmore » by means of laser-induced fluorescence and optical emission spectroscopy. In case of an applied magnetic field the atomic state distribution of hydrogen atoms shows an overpopulation between the electronic states p = 5, 4 and 3. The influence of the highly excited hydrogen molecules on H{sup -} ion formation and a possible mechanism involving this negative ion and producing atomic hydrogen in state p = 3 will be discussed.« less

Reaction of atomic hydrogen with formic acid.

PubMed

Cao, Qian; Berski, Slawomir; Latajka, Zdzislaw; Räsänen, Markku; Khriachtchev, Leonid

2014-04-07

We study the reaction of atomic hydrogen with formic acid and characterize the radical products using IR spectroscopy in a Kr matrix and quantum chemical calculations. The reaction first leads to the formation of an intermediate radical trans-H2COOH, which converts to the more stable radical trans-cis-HC(OH)2via hydrogen atom tunneling on a timescale of hours at 4.3 K. These open-shell species are observed for the first time as well as a reaction between atomic hydrogen and formic acid. The structural assignment is aided by extensive deuteration experiments and ab initio calculations at the UMP2 and UCCSD(T) levels of theory. The simplest geminal diol radical trans-cis-HC(OH)2 identified in the present work as the final product of the reaction should be very reactive, and further reaction channels are of particular interest. These reactions and species may constitute new channels for the initiation and propagation of more complex organic species in the interstellar clouds.

Structural and magnetic properties of FeHx (x=0.25; 0.50; 0.75)

NASA Astrophysics Data System (ADS)

Mikhaylushkin, A. S.; Skorodumova, N. V.; Ahuja, R.; Johansson, B.

2006-05-01

The structural and magnetic properties of the FeHx (x=0.25; 0.50; 0.75) compounds have been studied using the projector augmented wave (PAW) method within the generalized gradient approximation (GGA). We compare the hcp, dhcp and fcc structures and find that for the considered concentrations of hydrogen the hcp structure is most stable in a wide pressure range. The magnetic behavior of iron is crucially influenced by hydrogen. In particular, the local moment on a Fe atom depends on the number of hydrogen atoms in the atom surroundings. Iron atoms, which are crystallographically equivalent in their original structures (hcp, fcc) but have different number of hydrogen neighbors, are shown to have different local magnetic moments. This finding suggests that the experimental observations of two magnetic moments in iron hydride can be explained by nonstoichiometry of the hydride and might not be a direct evidence for the presence of the dhcp phase.

Kinetics of Hydrogen Abstraction and Addition Reactions of 3-Hexene by ȮH Radicals.

PubMed

Yang, Feiyu; Deng, Fuquan; Pan, Youshun; Zhang, Yingjia; Tang, Chenglong; Huang, Zuohua

2017-03-09

Rate coefficients of H atom abstraction and H atom addition reactions of 3-hexene by the hydroxyl radicals were determined using both conventional transition-state theory and canonical variational transition-state theory, with the potential energy surface (PES) evaluated at the CCSD(T)/CBS//BHandHLYP/6-311G(d,p) level and quantum mechanical effect corrected by the compounded methods including one-dimensional Wigner method, multidimensional zero-curvature tunneling method, and small-curvature tunneling method. Results reveal that accounting for approximate 70% of the overall H atom abstractions occur in the allylic site via both direct and indirect channels. The indirect channel containing two van der Waals prereactive complexes exhibits two times larger rate coefficient relative to the direct one. The OH addition reaction also contains two van der Waals complexes, and its submerged barrier results in a negative temperature coefficient behavior at low temperatures. In contrast, The OH addition pathway dominates only at temperatures below 450 K whereas the H atom abstraction reactions dominate overwhelmingly at temperature over 1000 K. All of the rate coefficients calculated with an uncertainty of a factor of 5 were fitted in a quasi-Arrhenius formula. Analyses on the PES, minimum reaction path and activation free Gibbs energy were also performed in this study.

Hirshfeld atom refinement.

PubMed

Capelli, Silvia C; Bürgi, Hans-Beat; Dittrich, Birger; Grabowsky, Simon; Jayatilaka, Dylan

2014-09-01

Hirshfeld atom refinement (HAR) is a method which determines structural parameters from single-crystal X-ray diffraction data by using an aspherical atom partitioning of tailor-made ab initio quantum mechanical molecular electron densities without any further approximation. Here the original HAR method is extended by implementing an iterative procedure of successive cycles of electron density calculations, Hirshfeld atom scattering factor calculations and structural least-squares refinements, repeated until convergence. The importance of this iterative procedure is illustrated via the example of crystalline ammonia. The new HAR method is then applied to X-ray diffraction data of the dipeptide Gly-l-Ala measured at 12, 50, 100, 150, 220 and 295 K, using Hartree-Fock and BLYP density functional theory electron densities and three different basis sets. All positions and anisotropic displacement parameters (ADPs) are freely refined without constraints or restraints - even those for hydrogen atoms. The results are systematically compared with those from neutron diffraction experiments at the temperatures 12, 50, 150 and 295 K. Although non-hydrogen-atom ADPs differ by up to three combined standard uncertainties (csu's), all other structural parameters agree within less than 2 csu's. Using our best calculations (BLYP/cc-pVTZ, recommended for organic molecules), the accuracy of determining bond lengths involving hydrogen atoms from HAR is better than 0.009 Å for temperatures of 150 K or below; for hydrogen-atom ADPs it is better than 0.006 Å(2) as judged from the mean absolute X-ray minus neutron differences. These results are among the best ever obtained. Remarkably, the precision of determining bond lengths and ADPs for the hydrogen atoms from the HAR procedure is comparable with that from the neutron measurements - an outcome which is obtained with a routinely achievable resolution of the X-ray data of 0.65 Å.

Hirshfeld atom refinement

PubMed Central

Capelli, Silvia C.; Bürgi, Hans-Beat; Dittrich, Birger; Grabowsky, Simon; Jayatilaka, Dylan

2014-01-01

Hirshfeld atom refinement (HAR) is a method which determines structural parameters from single-crystal X-ray diffraction data by using an aspherical atom partitioning of tailor-made ab initio quantum mechanical molecular electron densities without any further approximation. Here the original HAR method is extended by implementing an iterative procedure of successive cycles of electron density calculations, Hirshfeld atom scattering factor calculations and structural least-squares refinements, repeated until convergence. The importance of this iterative procedure is illustrated via the example of crystalline ammonia. The new HAR method is then applied to X-ray diffraction data of the dipeptide Gly–l-Ala measured at 12, 50, 100, 150, 220 and 295 K, using Hartree–Fock and BLYP density functional theory electron densities and three different basis sets. All positions and anisotropic displacement parameters (ADPs) are freely refined without constraints or restraints – even those for hydrogen atoms. The results are systematically compared with those from neutron diffraction experiments at the temperatures 12, 50, 150 and 295 K. Although non-hydrogen-atom ADPs differ by up to three combined standard uncertainties (csu’s), all other structural parameters agree within less than 2 csu’s. Using our best calculations (BLYP/cc-pVTZ, recommended for organic molecules), the accuracy of determining bond lengths involving hydrogen atoms from HAR is better than 0.009 Å for temperatures of 150 K or below; for hydrogen-atom ADPs it is better than 0.006 Å2 as judged from the mean absolute X-ray minus neutron differences. These results are among the best ever obtained. Remarkably, the precision of determining bond lengths and ADPs for the hydrogen atoms from the HAR procedure is comparable with that from the neutron measurements – an outcome which is obtained with a routinely achievable resolution of the X-ray data of 0.65 Å. PMID:25295177

Hydrogen storage capacity on Ti-decorated porous graphene: First-principles investigation

NASA Astrophysics Data System (ADS)

Yuan, Lihua; Kang, Long; Chen, Yuhong; Wang, Daobin; Gong, Jijun; Wang, Chunni; Zhang, Meiling; Wu, Xiaojuan

2018-03-01

Hydrogen storage capacity on Titanium (Ti) decorated porous graphene (PG) has been investigated using density functional theory simulations with generalized gradient approximation method. The possible adsorption sites of Ti atom on PG and electronic properties of Ti-PG system are also discussed.The results show a Ti atom prefers to strongly adsorb on the center site above the C hexagon with the binding energy of 3.65 eV, and the polarization and the hybridization mechanisms both contribute to the Ti atom adsorption on PG. To avoid a tendency of clustering among Ti atoms, the single side of the PG unit cell should only contain one Ti atom. For the single side of PG, four H2 molecules can be adsorbed around Ti atom, and the adsorption mechanism of H2 molecules come from not only the polarization mechanism between Ti and H atoms but also the orbital hybridization among Ti atom, H2 molecules and C atoms. For the case of double sides of PG, eight H2 molecules can be adsorbed on Ti-decorated PG unit cell with the average adsorption energy of -0.457 eV, and the gravimetric hydrogen storage capacity is 6.11 wt.%. Furthermore, ab inito molecular-dynaics simulation result shows that six H2 molecules can be adsorbed on double sides of unit cell of Ti-PG system and the configuration of Ti-PG is very stable at 300 K and without external pressure, which indicates Ti-decorated PG could be considered as a potential hydrogen storage medium at ambient conditions.

Atom-bond electronegativity equalization method fused into molecular mechanics. I. A seven-site fluctuating charge and flexible body water potential function for water clusters.

PubMed

Yang, Zhong-Zhi; Wu, Yang; Zhao, Dong-Xia

2004-02-08

Recently, experimental and theoretical studies on the water system are very active and noticeable. A transferable intermolecular potential seven points approach including fluctuation charges and flexible body (ABEEM-7P) based on a combination of the atom-bond electronegativity equalization and molecular mechanics (ABEEM/MM), and its application to small water clusters are explored and tested in this paper. The consistent combination of ABEEM and molecular mechanics (MM) is to take the ABEEM charges of atoms, bonds, and lone-pair electrons into the intermolecular electrostatic interaction term in molecular mechanics. To examine the charge transfer we have used two models coming from the charge constraint types: one is a charge neutrality constraint on whole water system and the other is on each water molecule. Compared with previous water force fields, the ABEEM-7P model has two characters: (1) the ABEEM-7P model not only presents the electrostatic interaction of atoms, bonds and lone-pair electrons and their changing in respond to different ambient environment but also introduces "the hydrogen bond interaction region" in which a new parameter k(lp,H)(R(lp,H)) is used to describe the electrostatic interaction of the lone-pair electron and the hydrogen atom which can form the hydrogen bond; (2) nonrigid but flexible water body permitting the vibration of the bond length and angle is allowed due to the combination of ABEEM and molecular mechanics, and for van der Waals interaction the ABEEM-7P model takes an all atom-atom interaction, i.e., oxygen-oxygen, hydrogen-hydrogen, oxygen-hydrogen interaction into account. The ABEEM-7P model based on ABEEM/MM gives quite accurate predictions for gas-phase state properties of the small water clusters (H(2)O)(n) (n=2-6), such as optimized geometries, monomer dipole moments, vibrational frequencies, and cluster interaction energies. Due to its explicit description of charges and the hydrogen bond, the ABEEM-7P model will be applied to discuss properties of liquid water, ice, aqueous solutions, and biological systems.

Hydrogen storage in N- and B-doped graphene decorated by small platinum clusters: A computational study

NASA Astrophysics Data System (ADS)

Chen, I.-Nan; Wu, Shiuan-Yau; Chen, Hsin-Tsung

2018-05-01

In this work, we perform density functional theory (DFT) calculations to investigate the hydrogen adsorption on Pt4 cluster supported on pristine, B-, and N-doped graphene sheets. It is found that the doping B or N atom in the graphene could enhance the interaction between the Pt4 cluster and the supporting substrate. The first H2 molecule is found to be dissociative chemisorption on the three substrates. Further, dissociative and molecular adsorption of multiple H2 molecules are co-adsorbed on the three substrates. In addition, the interaction between Pt4(H2)x and the substrate is illustrated for the stability of Pt4(H2)x on the substrate. AIMD simulation is also performed to verify the stability and hydrogen storage. Accordingly, the B-graphene is predicted to be the most potential materials for hydrogen storage among these three materials.

Nuclear spin polarized H and D by means of spin-exchange optical pumping

NASA Astrophysics Data System (ADS)

Stenger, Jörn; Grosshauser, Carsten; Kilian, Wolfgang; Nagengast, Wolfgang; Ranzenberger, Bernd; Rith, Klaus; Schmidt, Frank

1998-01-01

Optically pumped spin-exchange sources for polarized hydrogen and deuterium atoms have been demonstrated to yield high atomic flow and high electron spin polarization. For maximum nuclear polarization the source has to be operated in spin temperature equilibrium, which has already been demonstrated for hydrogen. In spin temperature equilibrium the nuclear spin polarization PI equals the electron spin polarization PS for hydrogen and is even larger than PS for deuterium. We discuss the general properties of spin temperature equilibrium for a sample of deuterium atoms. One result are the equations PI=4PS/(3+PS2) and Pzz=PSṡPI, where Pzz is the nuclear tensor polarization. Furthermore we demonstrate that the deuterium atoms from our source are in spin temperature equilibrium within the experimental accuracy.

Rocket and spacecraft studies of ultraviolet emissions from astrophysical targets

NASA Technical Reports Server (NTRS)

Fastie, W. G.; Moos, H. W.; Feldman, P. D.; Henry, R. C.

1975-01-01

Rocket and spacecraft far-UV spectral measurements of several astrophysical targets are reviewed. These include observations of Ly-alpha emissions from Arcturus, Apollo-17 far-UV spectrometry of eta UMa and five other stars, Apollo-17 observations of the lunar atmosphere and the diffuse UV background, and far-UV spectral studies of Venus, Jupiter, and Comet Kohoutek. The Arcturus observations indicated a chromosphere with neutral atomic-hydrogen and atomic-oxygen emissions as well as a very weak atomic-carbon line. The planetary studies revealed O I and C I emissions in the Venusian spectrum as well as large Ly-alpha emissions and possible molecular-hydrogen emissions in that of Jupiter. The lunar observations demonstrated that solar protons do not produce an atomic-hydrogen atmosphere on the moon.

Calculating Relativistic Transition Matrix Elements for Hydrogenic Atoms Using Monte Carlo Methods

NASA Astrophysics Data System (ADS)

Alexander, Steven; Coldwell, R. L.

2015-03-01

The nonrelativistic transition matrix elements for hydrogen atoms can be computed exactly and these expressions are given in a number of classic textbooks. The relativistic counterparts of these equations can also be computed exactly but these expressions have been described in only a few places in the literature. In part, this is because the relativistic equations lack the elegant simplicity of the nonrelativistic equations. In this poster I will describe how variational Monte Carlo methods can be used to calculate the energy and properties of relativistic hydrogen atoms and how the wavefunctions for these systems can be used to calculate transition matrix elements.

Epi-cleaning of Ge/GeSn heterostructures

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

Di Gaspare, L.; Sabbagh, D.; De Seta, M.

2015-01-28

We demonstrate a very-low temperature cleaning technique based on atomic hydrogen irradiation for highly (1%) tensile strained Ge epilayers grown on metastable, partially strain relaxed GeSn buffer layers. Atomic hydrogen is obtained by catalytic cracking of hydrogen gas on a hot tungsten filament in an ultra-high vacuum chamber. X-ray photoemission spectroscopy, reflection high energy electron spectroscopy, atomic force microscopy, secondary ion mass spectroscopy, and micro-Raman showed that an O- and C-free Ge surface was achieved, while maintaining the same roughness and strain condition of the as-deposited sample and without any Sn segregation, at a process temperature in the 100–300 °C range.

Epi-cleaning of Ge/GeSn heterostructures

NASA Astrophysics Data System (ADS)

Di Gaspare, L.; Sabbagh, D.; De Seta, M.; Sodo, A.; Wirths, S.; Buca, D.; Zaumseil, P.; Schroeder, T.; Capellini, G.

2015-01-01

We demonstrate a very-low temperature cleaning technique based on atomic hydrogen irradiation for highly (1%) tensile strained Ge epilayers grown on metastable, partially strain relaxed GeSn buffer layers. Atomic hydrogen is obtained by catalytic cracking of hydrogen gas on a hot tungsten filament in an ultra-high vacuum chamber. X-ray photoemission spectroscopy, reflection high energy electron spectroscopy, atomic force microscopy, secondary ion mass spectroscopy, and micro-Raman showed that an O- and C-free Ge surface was achieved, while maintaining the same roughness and strain condition of the as-deposited sample and without any Sn segregation, at a process temperature in the 100-300 °C range.

N′-[(E)-3-Chloro-2-fluoro­benzyl­idene]-6-methyl­nicotinohydrazide monohydrate

PubMed Central

Fun, Hoong-Kun; Quah, Ching Kheng; Shyma, P. C.; Kalluraya, Balakrishna; Vidyashree, J. H. S.

2012-01-01

The title compound, C14H11ClFN3O·H2O, exists in an E conformation with respect to the N=C bond. The pyridine ring forms a dihedral angle of 5.00 (9)° with the benzene ring. In the crystal, the ketone O atom accepts one O—H⋯O and one C—H⋯O hydrogen bond, the water O atom accepts one N—H⋯O and two C—H⋯O hydrogen bonds and the pyridine N atom accepts one O—H⋯N hydrogen bond, forming layers parallel to the ab plane. PMID:22798798

Origins of hole traps in hydrogenated nanocrystalline and amorphous silicon revealed through machine learning

NASA Astrophysics Data System (ADS)

Mueller, Tim; Johlin, Eric; Grossman, Jeffrey C.

2014-03-01

Genetic programming is used to identify the structural features most strongly associated with hole traps in hydrogenated nanocrystalline silicon with very low crystalline volume fraction. The genetic programming algorithm reveals that hole traps are most strongly associated with local structures within the amorphous region in which a single hydrogen atom is bound to two silicon atoms (bridge bonds), near fivefold coordinated silicon (floating bonds), or where there is a particularly dense cluster of many silicon atoms. Based on these results, we propose a mechanism by which deep hole traps associated with bridge bonds may contribute to the Staebler-Wronski effect.

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

PubMed

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

2015-11-15

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

Protein dynamics as seen by (quasi) elastic neutron scattering.

PubMed

Magazù, S; Mezei, F; Falus, P; Farago, B; Mamontov, E; Russina, M; Migliardo, F

2017-01-01

Elastic and quasielastic neutron scattering studies proved to be efficient probes of the atomic mean square displacement (MSD), a fundamental parameter for the characterization of the motion of individual atoms in proteins and its evolution with temperature and compositional environment. We present a technical overview of the different types of experimental situations and the information quasi-elastic neutron scattering approaches can make available. In particular, MSD can crucially depend on the time scale over which the averaging (building of the "mean") takes place, being defined by the instrumental resolution. Due to their high neutron scattering cross section, hydrogen atoms can be particularly sensitively observed with little interference by the other atoms in the sample. A few examples, including new data, are presented for illustration. The incoherent character of neutron scattering on hydrogen atoms restricts the information obtained to the self-correlations in the motion of individual atoms, simplifying at the same time the data analysis. On the other hand, the (often overlooked) exploration of the averaging time dependent character of MSD is crucial for unambiguous interpretation and can provide a wealth of information on micro- and nanoscale atomic motion in proteins. By properly exploiting the broad range capabilities of (quasi)elastic neutron scattering techniques to deliver time dependent characterization of atomic displacements, they offer a sensitive, direct and simple to interpret approach to exploration of the functional activity of hydrogen atoms in proteins. Partial deuteration can add most valuable selectivity by groups of hydrogen atoms. "This article is part of a Special Issue entitled "Science for Life" Guest Editor: Dr. Austen Angell, Dr. Salvatore Magazù and Dr. Federica Migliardo". Copyright © 2016 Elsevier B.V. All rights reserved.

Large-scale atomistic simulations of helium-3 bubble growth in complex palladium alloys

DOE PAGES

Hale, Lucas M.; Zimmerman, Jonathan A.; Wong, Bryan M.

2016-05-18

Palladium is an attractive material for hydrogen and hydrogen-isotope storage applications due to its properties of large storage density and high diffusion of lattice hydrogen. When considering tritium storage, the material’s structural and mechanical integrity is threatened by both the embrittlement effect of hydrogen and the creation and evolution of additional crystal defects (e.g., dislocations, stacking faults) caused by the formation and growth of helium-3 bubbles. Using recently developed inter-atomic potentials for the palladium-silver-hydrogen system, we perform large-scale atomistic simulations to examine the defect-mediated mechanisms that govern helium bubble growth. Our simulations show the evolution of a distribution of materialmore » defects, and we compare the material behavior displayed with expectations from experiment and theory. In conclusion, we also present density functional theory calculations to characterize ideal tensile and shear strengths for these materials, which enable the understanding of how and why our developed potentials either meet or confound these expectations.« less

Fluoroalkenylphosphonates

NASA Astrophysics Data System (ADS)

Kadyrov, A. A.; Rokhlin, E. M.

1988-09-01

In this review we survey the methods for the preparation of derivatives of fluoroalkenylphosphonic acid and their reactions. The main methods for obtaining these compounds are based on the reactions of fluoroolefins with phosphites and also on the elimination of halogens, hydrogen halides and alkyl halides from fluoroalkylphosphonates or fluorine-containing phosphorus ylides. The chemical properties of fluoroalkenylphosphonates are due to the combined effect of the fluorine atoms and the phosphonate group. Their reactions with different reagents leads to modifications of the phosphonate group, addition to the C=C bond, replacement of the vinyl halogen atom, and cleavage of the C-P bond. The bibliography includes 96 references.

Optical properties of an indium doped CdSe nanocrystal: A density functional approach

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

Salini, K.; Mathew, Vincent, E-mail: vincent@cukerala.ac.in; Mathew, Thomas

2016-05-06

We have studied the electronic and optical properties of a CdSe nanocrystal doped with n-type impurity atom. First principle calculations of the CdSe nanocrystal based on the density functional theory (DFT), as implemented in the Vienna Ab Initio Simulation Package (VASP) was used in the calculations. We have introduced a single Indium impurity atom into CdSe nanocrystal with 1.3 nm diameter. Nanocrystal surface dangling bonds are passivated with hydrogen atom. The band-structure, density of states and absorption spectra of the doped and undopted nanocrystals were discussed. Inclusion of the n-type impurity atom introduces an additional electron in conduction band, and significantlymore » alters the electronic and optical properties of undoped CdSe nanocrystal. Indium doped CdSe nannocrystal have potential applications in optoelectronic devices.« less

Analysis of Data on the Cross Sections for Electron-Impact Ionization and Excitation of Electronic States of Atomic Hydrogen (Review)

NASA Astrophysics Data System (ADS)

Shakhatov, V. A.; Lebedev, Yu. A.

2018-01-01

A review is given of experimental and theoretical data on the cross sections for ionization, excitation, and deexcitation of atomic hydrogen. The set of the cross sections required to calculate the electron energy distribution function and find the level-to-level rate coefficients needed to solve balance equations for the densities of neutral and charged particles in hydrogen plasma is determined.

Preliminary neutron crystallographic analysis of selectively CH3-protonated, deuterated rubredoxin from Pyrococcus furiosus

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

Weiss, Kevin L; Meilleur, Flora; Blakeley, Matthew

2008-01-01

Neutron crystallography is used to locate hydrogen atoms in biological materials and can distinguish between negatively scattering hydrogen and positively scattering deuterium substituted positions in isomorphous neutron structures. Recently, Hauptman and Langs (2003) have shown that neutron diffraction data can be used to solve macromolecular structures by direct methods and that solution is aided by the presence of negatively scattering hydrogen atoms in the structure. Selective labeling protocols allow the design and production of H/D-labeled macromolecular structures in which the ratio of hydrogen to deuterium atoms can be precisely controlled. We have applied methyl-selective labeling protocols to introduce (1H-delta methyl)-leucinemore » and (1H-gamma methyl)-valine into deuterated rubredoxin from Pyrococcus furiosus (PfRd). Here we report on the production, crystallization, and preliminary neutron analysis of the selectively CH3-protonated, deuterated PfRd sample, which provided a high quality neutron data set extending to 1.75 resolution at the new LADI-III instrument at the Insititut Laue-Langevin. Preliminary analysis of neutron density maps allows unambiguous assignment of the positions of hydrogen atoms at the methyl groups of the valine and leucine residues in the otherwise deuterated rubredoxin structure.« less

Atomic Scale Analysis of the Enhanced Electro- and Photo-Catalytic Activity in High-Index Faceted Porous NiO Nanowires

NASA Astrophysics Data System (ADS)

Shen, Meng; Han, Ali; Wang, Xijun; Ro, Yun Goo; Kargar, Alireza; Lin, Yue; Guo, Hua; Du, Pingwu; Jiang, Jun; Zhang, Jingyu; Dayeh, Shadi A.; Xiang, Bin

2015-02-01

Catalysts play a significant role in clean renewable hydrogen fuel generation through water splitting reaction as the surface of most semiconductors proper for water splitting has poor performance for hydrogen gas evolution. The catalytic performance strongly depends on the atomic arrangement at the surface, which necessitates the correlation of the surface structure to the catalytic activity in well-controlled catalyst surfaces. Herein, we report a novel catalytic performance of simple-synthesized porous NiO nanowires (NWs) as catalyst/co-catalyst for the hydrogen evolution reaction (HER). The correlation of catalytic activity and atomic/surface structure is investigated by detailed high resolution transmission electron microscopy (HRTEM) exhibiting a strong dependence of NiO NW photo- and electrocatalytic HER performance on the density of exposed high-index-facet (HIF) atoms, which corroborates with theoretical calculations. Significantly, the optimized porous NiO NWs offer long-term electrocatalytic stability of over one day and 45 times higher photocatalytic hydrogen production compared to commercial NiO nanoparticles. Our results open new perspectives in the search for the development of structurally stable and chemically active semiconductor-based catalysts for cost-effective and efficient hydrogen fuel production at large scale.

Graphenes in the absence of metals as carbocatalysts for selective acetylene hydrogenation and alkene hydrogenation

NASA Astrophysics Data System (ADS)

Primo, Ana; Neatu, Florentina; Florea, Mihaela; Parvulescu, Vasile; Garcia, Hermenegildo

2014-10-01

Catalysis makes possible a chemical reaction by increasing the transformation rate. Hydrogenation of carbon-carbon multiple bonds is one of the most important examples of catalytic reactions. Currently, this type of reaction is carried out in petrochemistry at very large scale, using noble metals such as platinum and palladium or first row transition metals such as nickel. Catalysis is dominated by metals and in many cases by precious ones. Here we report that graphene (a single layer of one-atom-thick carbon atoms) can replace metals for hydrogenation of carbon-carbon multiple bonds. Besides alkene hydrogenation, we have shown that graphenes also exhibit high selectivity for the hydrogenation of acetylene in the presence of a large excess of ethylene.

Selective sp3 C-H alkylation via polarity-match-based cross-coupling.

PubMed

Le, Chip; Liang, Yufan; Evans, Ryan W; Li, Ximing; MacMillan, David W C

2017-07-06

The functionalization of carbon-hydrogen (C-H) bonds is one of the most attractive strategies for molecular construction in organic chemistry. The hydrogen atom is considered to be an ideal coupling handle, owing to its relative abundance in organic molecules and its availability for functionalization at almost any stage in a synthetic sequence. Although many C-H functionalization reactions involve C(sp 3 )-C(sp 2 ) coupling, there is a growing demand for C-H alkylation reactions, wherein sp 3 C-H bonds are replaced with sp 3 C-alkyl groups. Here we describe a polarity-match-based selective sp 3 C-H alkylation via the combination of photoredox, nickel and hydrogen-atom transfer catalysis. This methodology simultaneously uses three catalytic cycles to achieve hydridic C-H bond abstraction (enabled by polarity matching), alkyl halide oxidative addition, and reductive elimination to enable alkyl-alkyl fragment coupling. The sp 3 C-H alkylation is highly selective for the α-C-H of amines, ethers and sulphides, which are commonly found in pharmaceutically relevant architectures. This cross-coupling protocol should enable broad synthetic applications in de novo synthesis and late-stage functionalization chemistry.

Selective sp3 C–H alkylation via polarity-match-based cross-coupling

PubMed Central

Le, Chip; Liang, Yufan; Evans, Ryan W.; Li, Ximing; MacMillan, David W. C.

2017-01-01

The functionalization of carbon–hydrogen (C–H) bonds is one of the most attractive strategies for molecular construction in organic chemistry. The hydrogen atom is considered to be an ideal coupling handle, owing to its relative abundance in organic molecules and its availability for functionalization at almost any stage in a synthetic sequence1. Although many C–H functionalization reactions involve C(sp3)–C(sp2) coupling, there is a growing demand for C–H alkylation reactions, wherein sp3 C–H bonds are replaced with sp3 C–alkyl groups. Here we describe a polarity-match-based selective sp3 C–H alkylation via the combination of photoredox, nickel and hydrogen-atom transfer catalysis. This methodology simultaneously uses three catalytic cycles to achieve hydridic C–H bond abstraction (enabled by polarity matching), alkyl halide oxidative addition, and reductive elimination to enable alkyl–alkyl fragment coupling. The sp3 C–H alkylation is highly selective for the α-C–H of amines, ethers and sulphides, which are commonly found in pharmaceutically relevant architectures. This cross-coupling protocol should enable broad synthetic applications in de novo synthesis and late-stage functionalization chemistry. PMID:28636596

Selective sp3 C-H alkylation via polarity-match-based cross-coupling

NASA Astrophysics Data System (ADS)

Le, Chip; Liang, Yufan; Evans, Ryan W.; Li, Ximing; MacMillan, David W. C.

2017-07-01

The functionalization of carbon-hydrogen (C-H) bonds is one of the most attractive strategies for molecular construction in organic chemistry. The hydrogen atom is considered to be an ideal coupling handle, owing to its relative abundance in organic molecules and its availability for functionalization at almost any stage in a synthetic sequence. Although many C-H functionalization reactions involve C(sp3)-C(sp2) coupling, there is a growing demand for C-H alkylation reactions, wherein sp3 C-H bonds are replaced with sp3 C-alkyl groups. Here we describe a polarity-match-based selective sp3 C-H alkylation via the combination of photoredox, nickel and hydrogen-atom transfer catalysis. This methodology simultaneously uses three catalytic cycles to achieve hydridic C-H bond abstraction (enabled by polarity matching), alkyl halide oxidative addition, and reductive elimination to enable alkyl-alkyl fragment coupling. The sp3 C-H alkylation is highly selective for the α-C-H of amines, ethers and sulphides, which are commonly found in pharmaceutically relevant architectures. This cross-coupling protocol should enable broad synthetic applications in de novo synthesis and late-stage functionalization chemistry.

Validation of the role of bulk charging of hydrogen in the corrosion fatigue cracking of a low alloy steel

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

Griffiths, A.J.; Hutchings, R.B.; Turnbull, A.

1993-09-01

The enhanced corrosion fatigue crack growth rates of low alloy steels cathodically protected in marine environments results from absorbed hydrogen atoms. Hydrogen atoms are generated at the crack tip, crack walls and the external surface of the specimen (bulk charging). In previous work, Turnbull and Saenz de Santa Maria developed a model to predict the rate of generation of hydrogen atoms at the tips of fatigue cracks for steels cathodically polarized in marine environments. The main prediction from this work was that the external surface of the specimen can be the dominant source of hydrogen atoms at potentials more negativemore » than about [minus]900 mV (SCE), at a cyclic frequency of 0.1 Hz and a stress ratio of 0.5. The relative importance of bulk charging depends on the specific test conditions and is influenced by the applied potential, bulk chemistry, cyclic frequency, specimen thickness, temperature and use of coatings. Since laboratory test times are usually short in relation to the time required for hydrogen transport measured crack growth rates may be lower than those occurring in practice, for which there is sufficient time for full hydrogen charging. The purpose of this study is to verify experimentally the importance of bulk charging. Since the sensitivity of cracking to variations in hydrogen concentration will be material dependent a high strength steel was selected in this initial study because of its sensitivity to hydrogen. This will enable validation of the basic premise that bulk charging can be important, prior to more extensive studies using lower strength alloys.« less

Understanding the mechanism of DNA deactivation in ion therapy of cancer cells: hydrogen peroxide action*

NASA Astrophysics Data System (ADS)

Piatnytskyi, Dmytro V.; Zdorevskyi, Oleksiy O.; Perepelytsya, Sergiy M.; Volkov, Sergey N.

2015-11-01

Changes in the medium of biological cells under ion beam irradiation has been considered as a possible cause of cell function disruption in the living body. The interaction of hydrogen peroxide, a long-lived molecular product of water radiolysis, with active sites of DNA macromolecule was studied, and the formation of stable DNA-peroxide complexes was considered. The phosphate groups of the macromolecule backbone were picked out among the atomic groups of DNA double helix as a probable target for interaction with hydrogen peroxide molecules. Complexes consisting of combinations including: the DNA phosphate group, H2O2 and H2O molecules, and Na+ counterion, were considered. The counterions have been taken into consideration insofar as under the natural conditions they neutralise DNA sugar-phosphate backbone. The energy of the complexes have been determined by considering the electrostatic and the Van der Waals interactions within the framework of atom-atom potential functions. As a result, the stability of various configurations of molecular complexes was estimated. It was shown that DNA phosphate groups and counterions can form stable complexes with hydrogen peroxide molecules, which are as stable as the complexes with water molecules. It has been demonstrated that the formation of stable complexes of H2O2-Na+-PO4- may be detected experimentally by observing specific vibrations in the low-frequency Raman spectra. The interaction of H2O2 molecule with phosphate group of the double helix backbone can disrupt DNA biological function and induce the deactivation of the cell genetic apparatus. Thus, the production of hydrogen peroxide molecules in the nucleus of living cells can be considered as an additional mechanism by which high-energy ion beams destroy tumour cells during ion beam therapy. Contribution to the Topical Issue "COST Action Nano-IBCT: Nano-scale Processes Behind Ion-Beam Cancer Therapy", edited by Andrey Solov'yov, Nigel Mason, Gustavo García, Eugene Surdutovich.

Kinetics of self-decomposition and hydrogen atom transfer reactions of substituted phthalimide N-oxyl radicals in acetic acid.

PubMed

Cai, Yang; Koshino, Nobuyoshi; Saha, Basudeb; Espenson, James H

2005-01-07

Kinetic data have been obtained for three distinct types of reactions of phthalimide N-oxyl radicals (PINO(.)) and N-hydroxyphthalimide (NHPI) derivatives. The first is the self-decomposition of PINO(.) which was found to follow second-order kinetics. In the self-decomposition of 4-methyl-N-hydroxyphthalimide (4-Me-NHPI), H-atom abstraction competes with self-decomposition in the presence of excess 4-Me-NHPI. The second set of reactions studied is hydrogen atom transfer from NHPI to PINO(.), e.g., PINO(.) + 4-Me-NHPI <=> NHPI + 4-Me-PINO(.). The substantial KIE, k(H)/k(D) = 11 for both forward and reverse reactions, supports the assignment of H-atom transfer rather than stepwise electron-proton transfer. These data were correlated with the Marcus cross relation for hydrogen-atom transfer, and good agreement between the experimental and the calculated rate constants was obtained. The third reaction studied is hydrogen abstraction by PINO(.) from p-xylene and toluene. The reaction becomes regularly slower as the ring substituent on PINO(.) is more electron donating. Analysis by the Hammett equation gave rho = 1.1 and 1.8 for the reactions of PINO(.) with p-xylene and toluene, respectively.

First principles study of hydrogen adsorption on carbon nanowires.

NASA Astrophysics Data System (ADS)

Tapia, Alejandro; Aguilera, Luis; Murrieta, Gabriel; de Coss, Romeo

2007-03-01

Recently has been reported a new type of one-dimensional carbon structures. Carbon nanowires formed by a linear carbon-atom chain inside an armchair (5,5) carbon nanotube has been observed using high-resolution transmission electron microscopy. In the present work we have studied the changes in the electronic structure of a carbon nanowires and (5,5) single-walled carbon nanotubes (SWCN) when a hydrogen atom is adsorbed. We used the Density Functional Theory and the calculations where performed by the pseudopotentials LCAO method (SIESTA code) and the Generalized Gradient Approximation (GGA) for the exchange-correlation potential. We have analyzed the changes in the atomic structure, density of states (LDOS), and the local orbital population. We found charge transfer from the nanotube to the linear chain and the hydrogen atom, the electronic character of the chain and nanotube sub-systems in chain@SWCN is the same that in the corresponding isolated systems, chain or SWCN. But the hydrogen adsorption produced changes in the atomic estructure and the electronic properties. This research was supported by PRIORI-UADY under Grant No. FING-05-004 and Consejo Nacional de Ciencia y Tecnolog'ia (Conacyt) under Grants No. 43830-F and 49985-J.

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

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

Lee, June Key, E-mail: junekey@jnu.ac.kr, E-mail: hskim7@jbnu.ac.kr; Hyeon, Gil Yong; Tawfik, Wael Z.

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 ofmore » 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.« less

Energy-transfer processes in neon-hydrogen mixtures excited by electron beams

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

Morozov, A.; Kruecken, R.; Ulrich, A.

2005-12-15

Energy- and charge-transfer processes in neon-hydrogen mixtures (500-1400 hPa neon and 0.001-3 hPa hydrogen partial pressures) excited by a pulsed low-energy ({approx}10 keV) electron beam were investigated using time-resolved spectroscopy. Time spectra of the hydrogen Lyman-{alpha} line, neon excimer emission (second continuum), and neon atomic lines (3p-3s transitions) were recorded. The time-integrated intensity of the Lyman-{alpha} emission was measured for the same range of gas mixtures. It is shown that direct energy transfer from Ne{sub 2}* excimers and neon atoms in the four lowest excited states as well as recombination of H{sub 3}{sup +} ions are the main channels populatingmore » atomic hydrogen in the n=2 state. A rate constant of (4.2{+-}1.4)x10{sup -11} cm{sup 3} s{sup -1} was obtained for the charge transfer from Ne{sub 2}{sup +} ions to molecular hydrogen. A lower limit for the depopulation rate constant of Ne{sub 2}* excimers by molecular hydrogen (combination of energy transfer and ionization) was found to be 1.0x10{sup -10} cm{sup 3} s{sup -1}.« less

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.

Philip A. Parilla | NREL

Science.gov Websites

atomic layer deposition for applications. He also manages the majority of X-ray characterization equipment at NREL, specifically X-ray diffraction and X-ray fluorescence instrumentation. Additionally, he for EERE's Hydrogen Storage program. He is also an expert in X-ray diffraction and X-ray fluorescence

Calculated Properties of Fully Hydrogenated Single Layers of BN, BC2N, and Graphene: Graphane and Its BN-Containing Analogues

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

Averill, Frank; Morris, James R; Cooper, Valentino R

2009-01-01

Carbon is an attractive material for hydrogen adsorption, due to its light weight, variety of structures, and ability to both physisorb and chemisorb hydrogen. Recently, fully hydrogenated graphene layers ( graphane ) have been predicted to exist [J.O. Sofo et al., Phys. Rev. B 75, 15340 (2007)], and experimentally observed [D.C. Elias et al., Science 323, 610 (2009)]. In this work, we examine analogues of graphane, in particular BNH2 and BC2NH4. Unlike graphene, these materials have a band gap without hydrogenation. Our results indicate that the hydrogenation product of BN is metastable: the fully hydrogenated compound BNH2 is higher inmore » energy than hexagonal BN sheets plus H2 molecules, in sharp contrast with graphane. We find that BC2NH4 is energetically very close to hexagonal BC2N+2H2 molecules. Furthermore our examination of the relative binding strengths of rows of symmetry related hydrogen atoms on BC2NH4shows that this compound is marginally higher in energy than BC2NH2 plus an H2 molecule, with the hydrogen atoms in BC2NH2 absorbed on the carbon sites. These remaining hydrogen atoms are not as strongly bound as in graphane, indicating that the average hydrogen chemisorption energy is controllable by changing the carbon content in the B-C-N layer.« less

Another Unprecedented Wieland Mechanism Confirmed: Hydrogen Formation from Hydrogen Peroxide, Formaldehyde, and Sodium Hydroxide.

PubMed

Czochara, Robert; Litwinienko, Grzegorz; Korth, Hans-Gert; Ingold, Keith U

2018-03-26

In 1923, Wieland and Wingler reported that in the molecular hydrogen producing reaction of hydrogen peroxide with formaldehyde in basic solution, free hydrogen atoms (H . ) are not involved. They postulated that bis(hydroxymethyl)peroxide, HOCH 2 OOCH 2 OH, is the intermediate, which decomposes to yield H 2 and formate, proposing a mechanism that would nowadays be considered as a "concerted process". Since then, several other (conflicting) "mechanisms" have been suggested. Our NMR and Raman spectroscopic and kinetic studies, particularly the determination of the deuterium kinetic isotope effect (DKIE), now confirm that in this base-dependent reaction, both H atoms of H 2 derive from the CH 2 hydrogen atoms of formaldehyde, and not from the OH groups of HOCH 2 OOCH 2 OH or from water. Quantum-chemical CBS-QB3 and W1BD computations show that H 2 release proceeds through a concerted process, which is strongly accelerated by double deprotonation of HOCH 2 OOCH 2 OH, thereby ruling out a free radical pathway. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Al4H7− is a resilient building block for aluminum hydrogen cluster materials

PubMed Central

Roach, P. J.; Reber, A. C.; Woodward, W. H.; Khanna, S. N.; Castleman, A. W.

2007-01-01

The formation and oxygen etching of AlnHm− clusters are characterized in a flow reactor experiment with first-principles theoretical investigations to demonstrate the exceptional stability of Al4H7−. The origin of the preponderance of Al4H7− in the mass spectra of hydrogenated aluminum anions and its resistance to O2 etching are discussed. Al4H7− is shown to have the ability to bond with ionic partners to form stable hydrides through addition of an alkali atom [XAl4H7 (X = Li-Cs)]. An intuitive model that can predict the existence of stable hydrogenated cluster species is proposed. The potential synthetic utility of the superatom assemblies built on these units is addressed. PMID:17823245

Teaching Bohr Theory.

ERIC Educational Resources Information Center

Latimer, Colin J.

1983-01-01

Discusses some lesser known examples of atomic phenomena to illustrate to students that the old quantum theory in its simplest (Bohr) form is not an antiquity but can still make an important contribution to understanding such phenomena. Topics include hydrogenic/non-hydrogenic spectra and atoms in strong electric and magnetic fields. (Author/JN)

Hydrogen-impurity complexes in III V semiconductors

NASA Astrophysics Data System (ADS)

Ulrici, W.

2004-12-01

This review summarizes the presently available knowledge concerning hydrogen-impurity complexes in III-V compounds. The impurities form shallow acceptors on group III sites (Be, Zn, Cd) and on group V sites (C, Si, Ge) as well as shallow donors on group V sites (S, Se, Te) and on group III sites (Si, Sn). These complexes are mainly revealed by their hydrogen stretching modes. Therefore, nearly all information about their structure and dynamic properties is derived from vibrational spectroscopy. The complexes of shallow impurities with hydrogen have been most extensively investigated in GaAs, GaP and InP. This holds also for Mg-H in GaN. The complexes exhibit a different microscopic structure, which is discussed in detail. The isoelectronic impurity nitrogen, complexed with one hydrogen atom, is investigated in detail in GaAs and GaP. Those complexes can exist in different charge states. The experimental results such as vibrational frequencies, the microscopic structure and the activation energy for reorientation for many of these complexes are in very good agreement with results of ab initio calculations. Different types of oxygen-hydrogen complexes in GaAs and GaP are described, with one hydrogen atom or two hydrogen atoms bonded to oxygen. Three of these complexes in GaAs were found to be electrically active.

An experimental and theoretical study of a hydrogen-bonded complex: O-phenylenediamine with 2,6-pyridinedicarboxylic acid

NASA Astrophysics Data System (ADS)

Ghasemi, Khaled; Rezvani, Ali Reza; Habibi-Khorassani, Sayyed Mostafa; Shahraki, Mehdi; Shokrollahi, Ardeshir; Moghimi, Abolghasem; Tamandani, Halimeh Kord; Gavahi, Sara

2015-11-01

The hydrogen-bonded complex, [(OPDH)+(dipicH)-.H2O], between o-phenylenediamine (OPD) and 2,6-pyridinedicarboxylic acid (dipicH2) has been characterized in water by the 1H, 13C NMR and IR spectroscopies. The crystal structure showed that the edge to face C-H⋯π and C-O⋯π stacking interactions between the dipicH2 and OPD rings play an extra significant role in the formation of the hydrogen-bonded complex and supported the H-bonding interactions. The proton transfer also investigated theoretically in gas phase and thermodynamic parameters such as ΔH‡, ΔG‡, ΔS‡ were calculated for this process. Moreover, intramolecular hydrogen-bonding interaction has been recognized by calculating the electron density ρ(r) and Laplacian ∇2ρ(r) at the bond critical point (BCP) using Atoms-In-Molecule (AIM) method and also the interaction between electron acceptor (σ*) of OH with the lone pair of the nitrogen atom as an electron donor using Natural Bond Orbital (NBO) analysis. In addition, the protonation constants of dipicH2 and OPD and the equilibrium constants for the dipic-OPD (1:1) proton transfer system were obtained by the potentiometric pH titration method using the Hyperquad 2008 program. The stoichiometry of the proton transfer species in the solution confirmed the solid state result.

Proton-coupled electron transfer versus hydrogen atom transfer: generation of charge-localized diabatic states.

PubMed

Sirjoosingh, Andrew; Hammes-Schiffer, Sharon

2011-03-24

The distinction between proton-coupled electron transfer (PCET) and hydrogen atom transfer (HAT) mechanisms is important for the characterization of many chemical and biological processes. PCET and HAT mechanisms can be differentiated in terms of electronically nonadiabatic and adiabatic proton transfer, respectively. In this paper, quantitative diagnostics to evaluate the degree of electron-proton nonadiabaticity are presented. Moreover, the connection between the degree of electron-proton nonadiabaticity and the physical characteristics distinguishing PCET from HAT, namely, the extent of electronic charge redistribution, is clarified. In addition, a rigorous diabatization scheme for transforming the adiabatic electronic states into charge-localized diabatic states for PCET reactions is presented. These diabatic states are constructed to ensure that the first-order nonadiabatic couplings with respect to the one-dimensional transferring hydrogen coordinate vanish exactly. Application of these approaches to the phenoxyl-phenol and benzyl-toluene systems characterizes the former as PCET and the latter as HAT. The diabatic states generated for the phenoxyl-phenol system possess physically meaningful, localized electronic charge distributions that are relatively invariant along the hydrogen coordinate. These diabatic electronic states can be combined with the associated proton vibrational states to generate the reactant and product electron-proton vibronic states that form the basis of nonadiabatic PCET theories. Furthermore, these vibronic states and the corresponding vibronic couplings may be used to calculate rate constants and kinetic isotope effects of PCET reactions.

A Quasi-Laue Neutron Crystallographic Study of D-Xylose Isomerase

NASA Technical Reports Server (NTRS)

Meilleur, Flora; Snell, Edward H.; vanderWoerd, Mark; Judge, Russell A.; Myles, Dean A. A.

2006-01-01

Hydrogen atom location and hydrogen bonding interaction determination are often critical to explain enzymatic mechanism. Whilst it is difficult to determine the position of hydrogen atoms using X-ray crystallography even with subatomic (less than 1.0 Angstrom) resolution data available, neutron crystallography provides an experimental tool to directly localise hydrogeddeuteriwn atoms in biological macromolecules at resolution of 1.5-2.0 Angstroms. Linearisation and isomerisation of xylose at the active site of D-xylose isomerase rely upon a complex hydrogen transfer. Neutron quasi-Laue data were collected on Streptomyces rubiginosus D-xylose isomerase crystal using the LADI instrument at ILL with the objective to provide insight into the enzymatic mechanism (Myles et al. 1998). The neutron structure unambiguously reveals the protonation state of His 53 in the active site, identifying the model for the enzymatic pathway.

DFT investigations of the hydrogenation effect on silicene/graphene hybrids.

PubMed

Drissi, L B; Saidi, E H; Bousmina, M; Fassi-Fehri, O

2012-12-05

We report here a study on the effect of hydrogenation on a new one-atom thick material made of silicon and carbon atoms (silicene/graphene (SG) hybrid) within density functional theory. The structural, electronic and magnetic properties are investigated for non-, semi- and fully hydrogenated SG hybrids in a chair configuration and are compared with their parent materials. Calculations reveal that pure SG is a non-zero band gap semi-conductor with stable planar honeycomb structure. So mixing C and Si in an alternating manner gives another way to generate a finite band gap in one-atom thick materials. Fully hydrogenation makes the gap larger; however half chemical modification with H reduces the gap in favor of ferromagnetism order. The findings of this work open a wide spectrum of possibilities for designing SG-based nanodevices with controlled and tuned properties.

Operating characteristics of a hydrogen-argon plasma torch for supersonic combustion applications

NASA Technical Reports Server (NTRS)

Barbi, E.; Mahan, J. R.; O'Brien, W. F.; Wagner, T. C.

1989-01-01

The residence time of the combustible mixture in the combustion chamber of a scramjet engine is much less than the time normally required for complete combustion. Hydrogen and hydrocarbon fuels require an ignition source under conditions typically found in a scramjet combustor. Analytical studies indicate that the presence of hydrogen atoms should greatly reduce the ignition delay in this environment. Because hydrogen plasmas are prolific sources of hydrogen atoms, a low-power, uncooled hydrogen plasma torch has been built and tested to evaluate its potential as a possible flame holder for supersonic combustion. The torch was found to be unstable when operated on pure hydrogen; however, stable operation could be obtained by using argon as a body gas and mixing in the desired amount of hydrogen. The stability limits of the torch are delineated and its electrical and thermal behavior documented. An average torch thermal efficiency of around 88 percent is demonstrated.

Synthesis and crystal structure of new copper(II) metal complex: Noncovalent interactions and electrical conductance properties

NASA Astrophysics Data System (ADS)

Pathak, Sudipta; Chakraborty, Koushik; Ghosh, Surajit; Roy, Kunal; Jana, Barnali; Konar, Saugata

2018-01-01

[Cu(pydc)(apyz)(H2O)2] (1) (where pydcH2 = pyridine-2,6-dicarboxylic acid; apyz = 2- aminopyrazine) has been synthesized and characterized by elemental analysis, IR spectroscopy and single crystal X-ray diffraction techniques. Crystallographic analysis revealed that complex 1 has distorted octahedral geometry with pydcH2 coordinated as tridentate ligands to metal ion through two oxygen atoms of each carboxylate group, nitrogen atom of the pyridine ring and the auxiliary ligand pyrazine nitrogen atom form basal plane and apical positions are occupied by two oxygen atoms of water molecules. In addition, the coordination compounds are connected by a variety of non covalent interactions like OH … π, lone pair … π, π … π and hydrogen bonds. The evaluation of these noncovalent interactions is useful for rationalizing their influence in the crystal packing. In addition, electrical current measured at room temperature on thin film before and after annealed is in the order of 229 μA and 246 μA respectively with bias voltage 1 V.

Analytical chemical kinetic investigation of the effects of oxygen, hydrogen, and hydroxyl radicals on hydrogen-air combustion

NASA Technical Reports Server (NTRS)

Carson, G. T., Jr.

1974-01-01

Quantitative values were computed which show the effects of the presence of small amounts of oxygen, hydrogen, and hydroxyl radicals on the finite-rate chemical kinetics of premixed hydrogen-air mixtures undergoing isobaric autoignition and combustion. The free radicals were considered to be initially present in hydrogen-air mixtures at equivalence ratios of 0.2, 0.6, 1.0, and 1.2. Initial mixture temperatures were 1100 K, 1200 K, and 1500 K, and pressures were 0.5, 1.0, 2.0, and 4.0 atm. Of the radicals investigated, atomic oxygen was found to be the most effective for reducing induction time, defined as the time to 5 percent of the total combustion temperature rise. The reaction time, the time between 5 percent and 95 percent of the temperature rise, is not decreased by the presence of free radicals in the initial hydrogen-air mixture. Fuel additives which yield free radicals might be used to effect a compact supersonic combustor design for efficient operation in an otherwise reaction-limited combustion regime.

2-Hydroxybenzophenone as a Chemical Auxiliary for the Activation of Ketiminoesters for Highly Enantioselective Addition to Nitroalkenes under Bifunctional Catalysis.

PubMed

Guerrero-Corella, Andrea; Esteban, Francisco; Iniesta, Manuel; Martín-Somer, Ana; Parra, Mario; Díaz-Tendero, Sergio; Fraile, Alberto; Alemán, Jose

2018-05-04

An organocatalytic system is presented for the Michael addition of monoactivated glycine ketimine ylides with a bifunctional catalyst. The ketimine bears an ortho hydroxy group, which increases the acidity of the methylene hydrogen atoms and enhances the reactivity, thus allowing the synthesis of a large variety of α,γ-diamino acid derivatives with excellent stereoselectivity. © 2018 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

Influence of different amino substituents in position 1 and 4 on spectroscopic and acid base properties of 9,10-anthraquinone moiety

NASA Astrophysics Data System (ADS)

Wcisło, Anna; Niedziałkowski, Paweł; Wnuk, Elżbieta; Zarzeczańska, Dorota; Ossowski, Tadeusz

2013-05-01

A series of novel 1-amino and 1,4-diamino-9,10-anthraquinones, substituted with different alkyl groups, were synthesized as the result of alkylation with amino substituents. All the obtained aminoanthraquinone derivatives were characterized by NMR, IR spectroscopy and mass spectrometry. The spectroscopic properties of these compounds were determined by using UV-Vis spectroscopy in acetonitrile, and in the mixture of acetonitrile and methanol at different pH ranges. The effects of various substituents present in the newly developed anthraquinone derivatives and their ability to form hydrogen bonds between the carbonyl oxygen atom of anthraquinone moiety and nitrogen atom of N-H group in 1-aminoanthraquinone (1-AAQ) and 1,4-diaminoanthraquinone (1,4-DAAQ) were studied. Additionally, the effects of hydrogen bond formation between O-H group in hydroxyethylamino substituent and the carbonyl oxygen atom of anthraquinone were investigated. The spectroscopic behavior of the studied derivatives strongly depended on the solvent-solute interactions and the nature of solvent. The values of pKa for the new anthraquinones were determined by the combined potentiometric and spectrophotometric titration methods.

Axisymmetric Self-Consistent Model of the Solar Wind Interaction with the Lism: Basic Results and Possible Ways of Development

NASA Astrophysics Data System (ADS)

Baranov, V. B.; Malama, Yu. G.

1996-10-01

We analyze the main results of the axisymmetric self-consistent model of the solar wind (SW) and supersonic local interstellar medium (LISM) interaction proposed by Baranov and Malama (1993, hereafter BM93, 1995) for an interstellar flow assumed to be composed of protons, electrons and hydrogen atoms. Here, in addition to the resonant charge exchange we also take into account the photoionization and the ionization by electron impact. The characteristics of the plasma in the interface region and inside the heliosphere depend strongly on the ionization degree of the LISM. The distribution function of the H atoms which penetrate the solar system from the LISM is non-Maxwellian, which implies that a pure hydrodynamic description of their motion is not appropriate. The H atom number density is a non-monotonic function of the heliocentric distance and the existence of a “hydrogen wall” in the vicinity of the heliopause is important for the interpretation of solar Lyman-alpha scattering experiments. The influence of the interface plasma structure on the interstellar oxygen penetration into the solar system is also illustrated. Possible ways of development of the model are analyzed.

Influence of different amino substituents in position 1 and 4 on spectroscopic and acid base properties of 9,10-anthraquinone moiety.

PubMed

Wcisło, Anna; Niedziałkowski, Paweł; Wnuk, Elżbieta; Zarzeczańska, Dorota; Ossowski, Tadeusz

2013-05-01

A series of novel 1-amino and 1,4-diamino-9,10-anthraquinones, substituted with different alkyl groups, were synthesized as the result of alkylation with amino substituents. All the obtained aminoanthraquinone derivatives were characterized by NMR, IR spectroscopy and mass spectrometry. The spectroscopic properties of these compounds were determined by using UV-Vis spectroscopy in acetonitrile, and in the mixture of acetonitrile and methanol at different pH ranges. The effects of various substituents present in the newly developed anthraquinone derivatives and their ability to form hydrogen bonds between the carbonyl oxygen atom of anthraquinone moiety and nitrogen atom of N-H group in 1-aminoanthraquinone (1-AAQ) and 1,4-diaminoanthraquinone (1,4-DAAQ) were studied. Additionally, the effects of hydrogen bond formation between O-H group in hydroxyethylamino substituent and the carbonyl oxygen atom of anthraquinone were investigated. The spectroscopic behavior of the studied derivatives strongly depended on the solvent-solute interactions and the nature of solvent. The values of pKa for the new anthraquinones were determined by the combined potentiometric and spectrophotometric titration methods. Copyright © 2013 Elsevier B.V. All rights reserved.

Comparative evaluation of atom mapping algorithms for balanced metabolic reactions: application to Recon 3D

DOE PAGES

Preciat Gonzalez, German A.; El Assal, Lemmer R. P.; Noronha, Alberto; ...

2017-06-14

The mechanism of each chemical reaction in a metabolic network can be represented as a set of atom mappings, each of which relates an atom in a substrate metabolite to an atom of the same element in a product metabolite. Genome-scale metabolic network reconstructions typically represent biochemistry at the level of reaction stoichiometry. However, a more detailed representation at the underlying level of atom mappings opens the possibility for a broader range of biological, biomedical and biotechnological applications than with stoichiometry alone. Complete manual acquisition of atom mapping data for a genome-scale metabolic network is a laborious process. However, manymore » algorithms exist to predict atom mappings. How do their predictions compare to each other and to manually curated atom mappings? For more than four thousand metabolic reactions in the latest human metabolic reconstruction, Recon 3D, we compared the atom mappings predicted by six atom mapping algorithms. We also compared these predictions to those obtained by manual curation of atom mappings for over five hundred reactions distributed among all top level Enzyme Commission number classes. Five of the evaluated algorithms had similarly high prediction accuracy of over 91% when compared to manually curated atom mapped reactions. On average, the accuracy of the prediction was highest for reactions catalysed by oxidoreductases and lowest for reactions catalysed by ligases. In addition to prediction accuracy, the algorithms were evaluated on their accessibility, their advanced features, such as the ability to identify equivalent atoms, and their ability to map hydrogen atoms. In addition to prediction accuracy, we found that software accessibility and advanced features were fundamental to the selection of an atom mapping algorithm in practice.« less

Comparative evaluation of atom mapping algorithms for balanced metabolic reactions: application to Recon 3D

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

Preciat Gonzalez, German A.; El Assal, Lemmer R. P.; Noronha, Alberto

The mechanism of each chemical reaction in a metabolic network can be represented as a set of atom mappings, each of which relates an atom in a substrate metabolite to an atom of the same element in a product metabolite. Genome-scale metabolic network reconstructions typically represent biochemistry at the level of reaction stoichiometry. However, a more detailed representation at the underlying level of atom mappings opens the possibility for a broader range of biological, biomedical and biotechnological applications than with stoichiometry alone. Complete manual acquisition of atom mapping data for a genome-scale metabolic network is a laborious process. However, manymore » algorithms exist to predict atom mappings. How do their predictions compare to each other and to manually curated atom mappings? For more than four thousand metabolic reactions in the latest human metabolic reconstruction, Recon 3D, we compared the atom mappings predicted by six atom mapping algorithms. We also compared these predictions to those obtained by manual curation of atom mappings for over five hundred reactions distributed among all top level Enzyme Commission number classes. Five of the evaluated algorithms had similarly high prediction accuracy of over 91% when compared to manually curated atom mapped reactions. On average, the accuracy of the prediction was highest for reactions catalysed by oxidoreductases and lowest for reactions catalysed by ligases. In addition to prediction accuracy, the algorithms were evaluated on their accessibility, their advanced features, such as the ability to identify equivalent atoms, and their ability to map hydrogen atoms. In addition to prediction accuracy, we found that software accessibility and advanced features were fundamental to the selection of an atom mapping algorithm in practice.« less

Comparative evaluation of atom mapping algorithms for balanced metabolic reactions: application to Recon 3D.

PubMed

Preciat Gonzalez, German A; El Assal, Lemmer R P; Noronha, Alberto; Thiele, Ines; Haraldsdóttir, Hulda S; Fleming, Ronan M T

2017-06-14

The mechanism of each chemical reaction in a metabolic network can be represented as a set of atom mappings, each of which relates an atom in a substrate metabolite to an atom of the same element in a product metabolite. Genome-scale metabolic network reconstructions typically represent biochemistry at the level of reaction stoichiometry. However, a more detailed representation at the underlying level of atom mappings opens the possibility for a broader range of biological, biomedical and biotechnological applications than with stoichiometry alone. Complete manual acquisition of atom mapping data for a genome-scale metabolic network is a laborious process. However, many algorithms exist to predict atom mappings. How do their predictions compare to each other and to manually curated atom mappings? For more than four thousand metabolic reactions in the latest human metabolic reconstruction, Recon 3D, we compared the atom mappings predicted by six atom mapping algorithms. We also compared these predictions to those obtained by manual curation of atom mappings for over five hundred reactions distributed among all top level Enzyme Commission number classes. Five of the evaluated algorithms had similarly high prediction accuracy of over 91% when compared to manually curated atom mapped reactions. On average, the accuracy of the prediction was highest for reactions catalysed by oxidoreductases and lowest for reactions catalysed by ligases. In addition to prediction accuracy, the algorithms were evaluated on their accessibility, their advanced features, such as the ability to identify equivalent atoms, and their ability to map hydrogen atoms. In addition to prediction accuracy, we found that software accessibility and advanced features were fundamental to the selection of an atom mapping algorithm in practice.

Electron-stimulated reactions in layered CO/H2O films: Hydrogen atom diffusion and the sequential hydrogenation of CO to methanol

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

Petrik, Nikolay G.; Monckton, Rhiannon J.; Koehler, Sven

Low-energy (100 eV) electron-stimulated reactions in layered H2O/CO/H2O ices are investigated. For CO trapped within approximately 50 ML of the vacuum interface in the amorphous solid water (ASW) films, both oxidation and reduction reactions are observed. However for CO buried more deeply in the film, only the reduction of CO to methanol is observed. Experiments with layered films of H2O and D2O show that the hydrogen atoms participating in the reduction of the buried CO originate in region from ~10 – 40 ML below the surface of the ASW films and subsequently diffuse through the film. For deeply buried COmore » layers, the CO reduction reactions quickly increase with temperature above ~60 K. We present a simple chemical kinetic model that treats the diffusion of hydrogen atoms in the ASW and sequential hydrogenation of the CO to methanol that accounts for the observations.« less

Methyl group conformation and hydrogen bonds in proteins determined by neutron protein crystallography

NASA Astrophysics Data System (ADS)

Yamaguchi, Atsushi; Shibata, Kouji; Tanaka, Ichiro; Niimura, Nobuo

2009-02-01

Using 'Hydrogen and Hydration in Proteins Data Base' (HHDB) that catalogs all H atom positions in biological macromolecules and in hydration water molecules that have been determined thus far by neutron macromolecular crystallography, methyl group conformation and hydrogen bonds (H.B.) in proteins are explored. It is found that most of the methyl groups belong to the stable staggered conformation but 11% of them seemed to be close to the eclipsed conformation. And geometrical consideration has been done for H.B. involved in α-helices. 125 H.B. were identified as donors for acceptor C dbnd O in the main chain α-helix. For these H.B., it is found that co-linear H.B. were rare, that hydrogen atoms seen from acceptors C dbnd O can localize upon certain arrangements, that H.B. are not parallel to the helix axis but rather inclined to C-terminal direction, and that hydrogen atoms except water are located inside, not outside of cylinders which the backbones of α-helices form.

Diffusion and reactivity of ground-state nitrogen atoms N(4S) between 3 and 15 K: application to the hydrogen abstraction reaction from methane under non-energetic conditions

NASA Astrophysics Data System (ADS)

Nourry, Sendres; Krim, Lahouari

2015-07-01

We have characterized the CH4 + N(4S) reaction in solid phase, at very low temperature, under non-energetic conditions and where the CH4 and N reactants are in their ground states. A microwave-driven atomic source has been used to generate ground-state nitrogen atoms N(4S), and experiments have been carried out at temperatures as low as 3 K to reduce the mobility of the trapped species in solid phase and hence to freeze the first step of the CH4 + N reaction pathway. Leaving the formed solid sample in the dark for a while allows all trapped reactants to relax to the ground state, specifically radicals and excited species streaming from the plasma discharge. Such a method could be the only possibility of proving that the CH4 + N reaction occurs between CH4 and N reactants in their ground states without any additional energy to initiate the chemical process. The appearance of the CH3 reaction product, just by inducing the mobility of N atoms between 3 and 11 K, translates that a hydrogen abstraction reaction from methane, under non-energetic conditions, will start occurring at very low temperature. The formation of methyl radical, under these experimental conditions, is due to recombination processes N(4S)-N(4S) of ground-state nitrogen atoms without any contribution of cosmic ray particles or high-energy photons.

Crystal structure of bis-(μ-3-nitro-benzoato)-κ3O,O':O;κ3O:O,O'-bis-[bis-(3-cyano-pyridine-κN1)(3-nitro-benzoato-κ2O,O')cadmium].

PubMed

Hökelek, Tuncer; Akduran, Nurcan; Özen, Azer; Uğurlu, Güventürk; Necefoğlu, Hacali

2017-03-01

The asymmetric unit of the title compound, [Cd 2 (C 7 H 4 NO 4 ) 4 (C 6 H 4 N 2 ) 4 ], contains one Cd II atom, two 3-nitro-benzoate (NB) anions and two 3-cyano-pyridine (CPy) ligands. The two CPy ligands act as monodentate N(pyridine)-bonding ligands, while the two NB anions act as bidentate ligands through the carboxyl-ate O atoms. The centrosymmetric dinuclear complex is generated by application of inversion symmetry, whereby the Cd II atoms are bridged by the carboxyl-ate O atoms of two symmetry-related NB anions, thus completing the distorted N 2 O 5 penta-gonal-bipyramidal coordination sphere of each Cd II atom. The benzene and pyridine rings are oriented at dihedral angles of 10.02 (7) and 5.76 (9)°, respectively. In the crystal, C-H⋯N hydrogen bonds link the mol-ecules, enclosing R 2 2 (26) ring motifs, in which they are further linked via C-H⋯O hydrogen bonds, resulting in a three-dimensional network. In addition, π-π stacking inter-actions between parallel benzene rings and between parallel pyridine rings of adjacent mol-ecules [shortest centroid-to-centroid distances = 3.885 (1) and 3.712 (1) Å, respectively], as well as a weak C-H⋯π inter-action, may further stabilize the crystal structure.

Bandgap opening in hydrogenated germanene

NASA Astrophysics Data System (ADS)

Yao, Q.; Zhang, L.; Kabanov, N. S.; Rudenko, A. N.; Arjmand, T.; Rahimpour Soleimani, H.; Klavsyuk, A. L.; Zandvliet, H. J. W.

2018-04-01

We have studied the hydrogenation of germanene synthesized on Ge2Pt crystals using scanning tunneling microscopy and spectroscopy. The germanene honeycomb lattice is buckled and consists of two hexagonal sub-lattices that are slightly displaced with respect to each other. The hydrogen atoms adsorb exclusively on the Ge atoms of the upward buckled hexagonal sub-lattice. At a hydrogen exposure of about 100 L, the (1 × 1) buckled honeycomb structure of germanene converts to a (2 × 2) structure. Scanning tunneling spectra recorded on this (2 × 2) structure reveal the opening of a bandgap of about 0.2 eV. A fully (half) hydrogenated germanene surface is obtained after an exposure of about 9000 L hydrogen. The hydrogenated germanene, also referred to as germanane, has a sizeable bandgap of about 0.5 eV and is slightly n-type.

Fundamental Pathways for the Adsorption and Transport of Hydrogen on TiO2 Surfaces: Origin for Effective Sensing at about Room Temperature.

PubMed

Wang, Zhuo; Xia, Xiaohong; Guo, Meilan; Shao, Guosheng

2016-12-28

Effective detection of hydrogen at lowered temperature is highly desirable in promoting safety in using this abundant gas as a clean energy source. Through first-principle calculations in the framework of density functional theory, we find that the high-energy (002) surface for rutile TiO 2 is significantly more effective in adsorbing hydrogen atoms through dissociating hydrogen molecules. The pathways for the dissociation of hydrogen molecules and sequential migration of hydrogen atoms are identified through searching along various transitional states. Pathways of low potential barriers indicate promise for hydrogen sensing, even close to room temperature. This has been proven through sensors made of thin films of well-aligned rutile nanorods, wherein the high-energy (002) surface dictates the top surface of the active layer of the sensors.

Atomic Scale Structure of (001) Hydrogen-Induced Platelets in Germanium

NASA Astrophysics Data System (ADS)

David, Marie-Laure; Pizzagalli, Laurent; Pailloux, Fréderic; Barbot, Jean François

2009-04-01

An accurate characterization of the structure of hydrogen-induced platelets is a prerequisite for investigating both hydrogen aggregation and formation of larger defects. On the basis of quantitative high resolution transmission electron microscopy experiments combined with extensive first principles calculations, we present a model for the atomic structure of (001) hydrogen-induced platelets in germanium. It involves broken Ge-Ge bonds in the [001] direction that are dihydride passivated, vacancies, and trapped H2 molecules, showing that the species involved in platelet formation depend on the habit plane. This model explains all previous experimental observations.

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. Copyright © 2016 Elsevier Inc. All rights reserved.

a Study of Dilute Aluminum and Vanadium NMR in Alpha-Titanium and in Hydrogen Doped Alpha-Titanium

NASA Astrophysics Data System (ADS)

Chou, Lih-Hsin

Nuclear magnetic resonance was used to investigate Ti-1 at.% V, Ti-2 at.% V, Ti-1 at.% Al, Ti-2 at.% Al and in addition samples of these alloys containing 1 and 2 at.% H. Computer simulation of the absorption curves incorporates the effects of nuclear quadrupole and anisotropic shift interactions, dipolar broadening, and inhomogeneous Knight shift distribution. From the simulation work, experimental parameters such as electric field gradient (EFG), axial anisotropic Knight shift K(,ax), and isotropic Knight shift are obtained. In addition to shedding light on certain features of bonding of V and Al in Ti, this information is used to discuss the trapping of hydrogen in these systems. The resonance of a simple metal (Al) and transition metal (V) at low concentration in a transition metal (Ti) matrix are compared. The localized states of an Al impurity appear to differ radically from the host Ti atomic structure; V present as a dilute solute appears to join the Ti lattice smoothly. Very small isotropic and anisotropic Knight shifts were observed for ('27)Al in Ti. This implies an absence of an orbital contribution and a small value for the s conduction electron density at the local Fermi surface in the vicinity of Al in Ti. A sizeable isotropic and anisotropic Knight shift was observed for ('51)V in Ti. This is thought to be the result of a large orbital contribution. The substitutional vanadium retains much of the character of V, but experiences the symmetry of the Ti lattice. Four outer electrons of V may form nearest neighbor bonds similarly to those between Ti atoms in pure titanium. The one extra electron on the V may be more s-like in character. Measurement of the temperature dependence of K(,ax) and EFG values at V solute atoms in a Ti matrix show that both K(,ax) and EFG increase as temperature decreases. The local electric field gradient contribution from non-s-electrons q(,non -s-el) is about 2 to 5 times larger than the q(,ion) values in magnitude. Because the sign of the EFG is not determined, the validity of the so called "universal correlation" could not be tested. For hydrogen charged Ti-2V alloys, a line shape change was observed at both room and liquid nitrogen temperatures. Thermodynamic and kinetic arguments which include the presence of hydride, dissolved hydrogen, and trapped hydrogen (trapping enthalpy 0.05 eV or greater) are offered to explain the data. No change in the solute resonance line was detected for hydrogen charged Ti-1V, or for hydrogen charged Ti-1Al and Ti-2Al.

Adsorption, dissociation and diffusion of hydrogen on the ZrCo surface and subsurface: A comprehensive study using first principles approach

NASA Astrophysics Data System (ADS)

Chattaraj, D.; Kumar, Nandha; Ghosh, Prasenjit; Majumder, C.; Dash, Smruti

2017-11-01

With increasing demand for hydrogen economy driven world, the fundamental research of hydrogen-metal interactions has gained momentum. In this work we report a systematic theoretical study of the stability of different surfaces of intermetallic ZrCo that is a possible candidate as a getter bed for tritium. Our first principles ab initio thermodynamic calculations predict that amongst the (100), (110) and (111) surfaces, the stoichiometric (110) surface is the most stable one over a wide range of Co chemical potential. We have also studied adsorption, dissociation and diffusion of hydrogen on the (110) surface. On the basis of total energy, it is seen that adsorption of molecular hydrogen (H2) on the surface is much weaker than atomic hydrogen. The H2 decomposition on ZrCo surface can easily take place and the dissociation barrier is calculated to be 0.70 eV. The strength of binding of H atom on the surface is more or less independent of surface coverage till 1.0 ML of H. The thermodynamic stability of atomic H adsorbed on the surface, in subsurface and bulk decreases from surface to bulk to subsurface. Though the H atoms are mobile on the surface, their diffusion to the subsurface involves a barrier of about 0.79 eV.

(2E,5E)-2,5-Bis(4-hy-droxy-3-meth-oxy-benzyl-idene)cyclo-penta-none ethanol monosolvate.

PubMed

Da'i, Muhammad; Yanuar, Arry; Meiyanto, Edy; Jenie, Umar Anggara; Supardjan, Amir Margono

2013-04-01

In the title structure, C21H20O5·C2H5OH, the curcumine-type mol-ecule has a double E conformation for the two benzyl-idene double bonds [C=C = 1.342 (4) and 1.349 (4) Å] and is nearly planar with respect to the non-H atoms (r.m.s. deviation from planarity = 0.069 Å). The two phenolic OH groups form bifurcated hydrogen bonds with intra-molecular branches to adjacent meth-oxy O atoms and inter-molecular branches to either a neighbouring mol-ecule or an ethanol solvent mol-ecule. The ethanol O atom donates a hydrogen bond to the keto O atom. These hydrogen bonds link the constituents into layers parallel to (101) in the crystal structure.

catena-Poly[bis-(sulfamethoxazolium) [[trichloridocadmate(II)]-μ-chlorido] monohydrate].

PubMed

Subashini, Annamalai; Muthiah, Packianathan Thomas; Bocelli, Gabriele; Cantoni, Andrea

2007-12-21

In the title compound, {(C(10)H(12)N(3)O(3)S)(2)[CdCl(4)]·H(2)O}(n), the Cd(II) atom is five-coordinate with a distorted trigonal-bipyramidal geometry formed by chloride ions. The Cd atom and two of the Cl atoms lie on a mirror plane. The cation is protonated on the amino group N atom; it is not coordinated to cadmium, but is hydrogen bonded to the chlorido ligands. Each water mol-ecule bridges two chlorido ligands, generating ring motifs along the -Cd-Cl-Cd- chains. The isoxazole unit and the amide groups are linked through a pair of N-H⋯N hydrogen bonds. The crystal structure is stabilized by N-H⋯O, O-H⋯Cl, C-H⋯N, N-H⋯Cl and C-H⋯O hydrogen bonds.

catena-Poly[bis­(sulfamethoxazolium) [[trichloridocadmate(II)]-μ-chlorido] monohydrate

PubMed Central

Subashini, Annamalai; Muthiah, Packianathan Thomas; Bocelli, Gabriele; Cantoni, Andrea

2008-01-01

In the title compound, {(C10H12N3O3S)2[CdCl4]·H2O}n, the CdII atom is five-coordinate with a distorted trigonal–bipyramidal geometry formed by chloride ions. The Cd atom and two of the Cl atoms lie on a mirror plane. The cation is protonated on the amino group N atom; it is not coordinated to cadmium, but is hydrogen bonded to the chlorido ligands. Each water mol­ecule bridges two chlorido ligands, generating ring motifs along the –Cd—Cl—Cd– chains. The isoxazole unit and the amide groups are linked through a pair of N—H⋯N hydrogen bonds. The crystal structure is stabilized by N—H⋯O, O—H⋯Cl, C—H⋯N, N—H⋯Cl and C—H⋯O hydrogen bonds. PMID:21200590

Copernicus observations of interstellar absorption at Lyman alpha

NASA Technical Reports Server (NTRS)

Bohlin, R. C.

1975-01-01

Column densities NH of atomic hydrogen have been derived for 40 OB stars from spectral scans at Lyman alpha obtained by the Copernicus (OAO-3) satellite. The stars are all between 60 and 1100 pc away with a range of mean densities n sub H of 0.01 to 2.5 atoms cm-3. The gas to color-excess ratio in clouds varies from 1 to 3 times the mean outside of clouds. The presence of molecular hydrogen correlates with E(B-V), but the best tracer for H2 is atomic hydrogen. The mean density of the gas for all 40 stars is much smaller than the mean of 0.7 atoms cm-3 obtained from 21-cm observations, because the brightest stars with less than average amounts of matter in the line of sight were selected for observation.

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 information (ESI) available: Low-magnification optical images; Raman spectra of 0% and 5% H2 samples; AFM characterization; Schematic of the film before and after sulfurization annealing; Schematic illustrations of two typical Raman-active phonon modes (E12g, A1g); Raman (mapping) spectra for 40% and 80% H2 samples before and after sulfurization annealing; PL spectra. See DOI: 10.1039/c5nr00904a

Two photon absorption laser induced fluorescence measurements of neutral density in a helicon plasma

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

Galante, M. E.; Magee, R. M.; Scime, E. E.

2014-05-15

We have developed a new diagnostic based on two-photon absorption laser induced fluorescence (TALIF). We use a high intensity (5 MW/cm{sup 2}), narrow bandwidth (0.1 cm{sup −1}) laser to probe the ground state of neutral hydrogen, deuterium and krypton with spatial resolution better than 0.2 cm, a time resolution of 10 ns, and a measurement cadence of 20 Hz. Here, we describe proof-of-principle measurements in a helicon plasma source that demonstrate the TALIF diagnostic is capable of measuring neutral densities spanning four orders of magnitude; comparable to the edge neutral gradients predicted in the DIII-D tokamak pedestal. The measurements are performed in hydrogen and deuteriummore » plasmas and absolute calibration is accomplished through TALIF measurements in neutral krypton. The optical configuration employed is confocal, i.e., both light injection and collection are accomplished with a single lens through a single optical port in the vacuum vessel. The wavelength resolution of the diagnostic is sufficient to separate hydrogen and deuterium spectra and we present measurements from mixed hydrogen and deuterium plasmas that demonstrate isotopic abundance measurements are feasible. Time resolved measurements also allow us to explore the evolution of the neutral hydrogen density and temperature and effects of wall recycling. We find that the atomic neutral density grows rapidly at the initiation of the discharge, reaching the steady-state value within 1 ms. Additionally, we find that neutral hydrogen atoms are born with 0.08 eV temperatures, not 2 eV as is typically assumed.« less

Method of produce ultra-low friction carbon films

DOEpatents

Erdemir, Ali; Fenske, George R.; Eryilmaz, Osman Levent; Lee, Richard H.

2003-04-15

A method and article of manufacture of amorphous diamond-like carbon. The method involves providing a substrate in a chamber, providing a mixture of a carbon containing gas and hydrogen gas with the mixture adjusted such that the atomic molar ratio of carbon to hydrogen is less than 0.3, including all carbon atoms and all hydrogen atoms in the mixture. A plasma is formed of the mixture and the amorphous diamond-like carbon film is deposited on the substrate. To achieve optimum bonding an intervening bonding layer, such as Si or SiO.sub.2, can be formed from SiH.sub.4 with or without oxidation of the layer formed.

Low-energy electron scattering from atomic hydrogen. II. Elastic and inelastic scattering

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

James, K.E. Jr.; Childers, J.G.; Khakoo, M.A.

2004-02-01

We present measurements of differential cross sections for elastic electron scattering from atomic hydrogen at 20 eV and 40 eV incident electron energies and ratios of differential cross sections for electron-impact excitation of atomic hydrogen to the n=2, 3, and 4 levels at incident electron energies of 14.6 eV, 15.6 eV, 17.6 eV, 20 eV, 25 eV, and 40 eV with scattering angles ranging from 10 deg. to 130 deg. We compare our results to available experimental measurements and recent convergent close-coupling calculations. Our results resolve significant discrepancies that existed between theory and past experiments.

Unexpectedly high pressure for molecular dissociation in liquid hydrogen by electronic simulation.

PubMed

Mazzola, Guglielmo; Yunoki, Seiji; Sorella, Sandro

2014-03-19

The study of the high pressure phase diagram of hydrogen has continued with renewed effort for about one century as it remains a fundamental challenge for experimental and theoretical techniques. Here we employ an efficient molecular dynamics based on the quantum Monte Carlo method, which can describe accurately the electronic correlation and treat a large number of hydrogen atoms, allowing a realistic and reliable prediction of thermodynamic properties. We find that the molecular liquid phase is unexpectedly stable, and the transition towards a fully atomic liquid phase occurs at much higher pressure than previously believed. The old standing problem of low-temperature atomization is, therefore, still far from experimental reach.

Reduction of uranium hexafluoride to tetrafluoride by using the hydrogen atoms

NASA Astrophysics Data System (ADS)

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

2016-09-01

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

High-precision optical measurement of the 2S hyperfine interval in atomic hydrogen.

PubMed

Kolachevsky, N; Fischer, M; Karshenboim, S G; Hänsch, T W

2004-01-23

We have applied an optical method to the measurement of the 2S hyperfine interval in atomic hydrogen. The interval has been measured by means of two-photon spectroscopy of the 1S-2S transition on a hydrogen atomic beam shielded from external magnetic fields. The measured value of the 2S hyperfine interval is equal to 177 556 860(16) Hz and represents the most precise measurement of this interval to date. The theoretical evaluation of the specific combination of 1S and 2S hyperfine intervals D21 is in fair agreement (within 1.4 sigma) with the value for D21 deduced from our measurement.

Valley filters, accumulators, and switches induced in graphene quantum dots by lines of adsorbed hydrogen atoms

NASA Astrophysics Data System (ADS)

Azari, Mohammadhadi; Kirczenow, George

2018-06-01

We present electronic structure and quantum transport calculations that predict conducting channels induced in graphene quantum dots by lines of adsorbed hydrogen atoms to function as highly efficient, experimentally realizable valley filters, accumulators, and switches. The underlying physics is an interesting property of graphene Dirac point resonances (DPRs) that is revealed here, namely, that an electric current passing through a DPR-mediated conducting channel in a given direction is carried by electrons of only one of the two graphene valleys. Our predictions apply to lines of hydrogen atoms adsorbed on graphene quantum dots that are either free standing or supported on a hexagonal boron nitride substrate.

The relationship between the boron dipyrromethene (BODIPY) structure and the effectiveness of homogeneous and heterogeneous solar hydrogen-generating systems as well as DSSCs.

PubMed

Luo, Geng-Geng; Lu, Hui; Zhang, Xiao-Long; Dai, Jing-Cao; Wu, Ji-Huai; Wu, Jia-Jia

2015-04-21

A series of boron dipyrromethene (BODIPY) dyes (B1–B5) having H atoms at 2,6-positions or heavy-atom I at 2-/2,6-positions, and an ortho- or a para-COOH substituted phenyl moiety at the 8-position on the BODIPY core were synthesized and characterized. These organic dyes were applied for investigating the relationship between the BODIPY structure and the effectiveness of homogeneous and heterogeneous visible-light-driven hydrogen production as well as dye-sensitized solar cells (DSSCs). For the homogeneous photocatalytic hydrogen production systems with a cobaloxime catalyst, the efficiency of hydrogen production could be tuned by substituting with heavy atoms and varying carboxyl group orientations of BODIPYs. As a result, B5 containing two I atoms and an ortho-COOH anchoring group was the most active one (TONs = 197). The activity of hydrogen generation followed the order B5 > B3 > B2 > B1 = B4 = 0. An interesting “ortho-position effect” was observed in the present homogeneous systems, i.e., substitution groups were located at the ortho-position and higher hydrogen production activities were obtained. For the heterogeneous hydrogen production systems with a platinized TiO2 catalyst, the effectiveness of hydrogen evolution was highly influenced by the intersystem crossing efficiency, molar absorptivity and positions of the anchoring group of dyes. Thus, B3 having two core iodine atoms and a para-COOH group with TONs of 70 excelled other BODIPYs and the TONs of hydrogen generation showed the trend of B3 > B5 > B2 > B1 = B4 = 0. The results demonstrate that the present photocatalytic H2 production proceeds with higher efficiency and stability in the homogeneity than in the heterogeneity. In the case of DSSCs, the overall cell performance of BODIPY chromophores was highly dependent on both the absence or the presence of iodine atoms on the BODIPY core and –COOH anchoring positions. The B1–TiO2 system showed the best cell performance, because the most effective surface binding mode is allowed with this structure. This is also in contrast with the case of dye-sensitized solar H2 generation, in which B3 was the most efficient chromophore. The differences between dye-sensitized hydrogen-generating systems and DSSCs may be due to rates of electron transfer and the dye aggregation tendency.

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.

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.

Optimization of classical nonpolarizable force fields for OH(-) and H3O(+).

PubMed

Bonthuis, Douwe Jan; Mamatkulov, Shavkat I; Netz, Roland R

2016-03-14

We optimize force fields for H3O(+) and OH(-) that reproduce the experimental solvation free energies and the activities of H3O(+) Cl(-) and Na(+) OH(-) solutions up to concentrations of 1.5 mol/l. The force fields are optimized with respect to the partial charge on the hydrogen atoms and the Lennard-Jones parameters of the oxygen atoms. Remarkably, the partial charge on the hydrogen atom of the optimized H3O(+) force field is 0.8 ± 0.1|e|--significantly higher than the value typically used for nonpolarizable water models and H3O(+) force fields. In contrast, the optimal partial charge on the hydrogen atom of OH(-) turns out to be zero. Standard combination rules can be used for H3O(+) Cl(-) solutions, while for Na(+) OH(-) solutions, we need to significantly increase the effective anion-cation Lennard-Jones radius. While highlighting the importance of intramolecular electrostatics, our results show that it is possible to generate thermodynamically consistent force fields without using atomic polarizability.

Neutrino Photoproduction on the Electron of a Hydrogen-Like Atom

NASA Astrophysics Data System (ADS)

Skobelev, V. V.

2017-10-01

The process of interaction of a photon with the bound electron of a hydrogen-like atom with creation of a neutrino pair γ +{(Ze)}^{\\ast \\ast}\\to \\overline{νν}+{(Ze)}^{\\ast } is considered here for the first time. This process can take place with and without a change in the energy of the pair relative to the energy of the "initial" photon due to atomic transitions. It is shown that in the case when the system of atoms is located in an equilibrium radiation field with temperature T << m e this process can be neglected in comparison with spontaneous emission of the hydrogen-like atom {(Ze)}^{\\ast}\\to (Ze)+ν\\overline{ν} , despite the smaller power of the expansion parameter ( Zα) < < 1, α = e 2/ ℏc ≈ 1/137 in the expressions for the cross sections and probabilities. Calculations have been performed for the first time using the density matrix, introduced in the previous paper, of the electron in the field of the nucleus in the leading approximation in (Zα).

The formation of excited atoms during charge exchange between hydrogen ions and alkali atoms. Ph.D. Thesis

NASA Technical Reports Server (NTRS)

Nieman, R. A.

1971-01-01

The charge exchange cross sections for protons and various alkali atoms are calculated using the classical approximation of Gryzinski. It is assumed that the hydrogen atoms resulting from charge exchange exist in all possible excited states. Charge transfer collisions between protons and potassium as well as protons and sodium atoms are studied. The energy range investigated is between 4 and 30 keV. The theoretical calculations of the capture cross section and the cross section for the creation of metastable 2S hydrogen are compared to experimental values. Good quantitative agreement is found for the capture cross section but only qualitative agreement for the metastable cross section. Analysis of the Lyman alpha window in molecular oxygen suggests that measured values of the metastable cross section may be in error. Thick alkali target data are also presented. This allows the determination of the total electron loss cross section. Finally, some work was done with H2(+).

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

PubMed

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

2013-01-09

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

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…

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…

A classical treatment of the quadratic Zeeman effect in atomic hydrogen

NASA Astrophysics Data System (ADS)

Al-Laithy, M. A.; Farmer, C. M.; McDowell, M. R. C.

1985-03-01

A description of the non-relativistic classical motion of the electron of a hydrogen atom in the presence of a static magnetic field of arbitrary (non-relativistic) strength is given for arbitrary angular momentum. Applications are given to m = 0 and m = 3 at B = 26.877 kG.

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…

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…

Van der Waals forces in pNRQED

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

Shtabovenko, Vladyslav

2016-01-22

We report on the calculation of electromagnetic van der Waals forces [1] between two hydrogen atoms using non-relativistic effective field theories (EFTs) of QED for large and small momentum transfers with respect to the intrinsic energy scale of the hydrogen atom. Our results reproduce the well known London and Casimir-Polder forces.

Effects of the molecule-electrode interface on the low-bias conductance of Cu–H{sub 2}–Cu single-molecule junctions

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

Jiang, Zhuoling; Centre for Nanoscale Science and Technology, Academy for Advanced Interdisciplinary Studies, Peking University, Beijing 100871; Wang, Hao

The atomic structure and electronic transport properties of a single hydrogen molecule connected to both symmetric and asymmetric Cu electrodes are investigated by using the non-equilibrium Green’s function formalism combined with the density functional theory. Our calculations show that in symmetric Cu–H{sub 2}–Cu junctions, the low-bias conductance drops rapidly upon stretching, while asymmetric ones present a low-bias conductance spanning the 0.2–0.3 G{sub 0} interval for a wide range of electrode separations. This is in good agreement with experiments on Cu atomic contacts in a hydrogen environment. Furthermore, the distribution of the calculated vibrational energies of the two hydrogen atoms inmore » the asymmetric Cu–H{sub 2}–Cu junction is also consistent with experiments. These findings provide clear evidence for the formation of asymmetric Cu–H{sub 2}–Cu molecular junctions in breaking Cu atomic contacts in the presence of hydrogen and are also helpful for the design of molecular devices with Cu electrodes.« less

Intermetallic structures with atomic precision for selective hydrogenation of nitroarenes

DOE PAGES

Pei, Yuchen; Qi, Zhiyuan; Goh, Tian Wei; ...

2017-11-14

It is essential to bridge the structure-properties relationship of bimetallic catalysts for the rational design of heterogeneous catalysts. Different from random alloys, intermetallic compounds (IMCs) present atomically-ordered structures, which is advantageous for catalytic mechanism studies. Here, we used Pt-based intermetallic nanoparticles (iNPs), individually encapsulated in mesoporous silica shells, as catalysts for the hydrogenation of nitroarenes to functionalized anilines. With the capping-free nature and ordered atomic structure, PtSn iNPs show >99% selectivity to hydrogenate the nitro group of 3-nitrostyrene albeit with a lower activity, in contrast to Pt 3Sn iNPs and Pt NPs. The geometric structure of PtSn iNPs in eliminatingmore » Pt threefold sites hampers the adsorption/dissociation of molecular H 2 and leads to a non-Horiuti-Polanyi hydrogenation pathway, while Pt 3Sn and Pt surfaces are saturated by atomic H. Calculations using density functional theory (DFT) suggest a preferential adsorption of the nitro group on the intermetallic PtSn surface contributing to its high selectivity.« less

Atomic and molecular hydrogen gas temperatures in a low-pressure helicon plasma

NASA Astrophysics Data System (ADS)

Samuell, Cameron M.; Corr, Cormac S.

2015-08-01

Neutral gas temperatures in hydrogen plasmas are important for experimental and modelling efforts in fusion technology, plasma processing, and surface modification applications. To provide values relevant to these application areas, neutral gas temperatures were measured in a low pressure (< 10 mTorr) radiofrequency helicon discharge using spectroscopic techniques. The atomic and molecular species were not found to be in thermal equilibrium with the atomic temperature being mostly larger then the molecular temperature. In low power operation (< 1 kW), the molecular hydrogen temperature was observed to be linearly proportional to the pressure while the atomic hydrogen temperature was inversely proportional. Both temperatures were observed to rise linearly with input power. For high power operation (5-20 kW), the molecular temperature was found to rise with both power and pressure up to a maximum of approximately 1200 K. Spatially resolved measurements near a graphite target demonstrated localised cooling near the sample surface. The temporal evolution of the molecular gas temperature during a high power 1.1 ms plasma pulse was also investigated and found to vary considerably as a function of pressure.

Competing Intramolecular vs. Intermolecular Hydrogen Bonds in Solution

PubMed Central

Nagy, Peter I.

2014-01-01

A hydrogen bond for a local-minimum-energy structure can be identified according to the definition of the International Union of Pure and Applied Chemistry (IUPAC recommendation 2011) or by finding a special bond critical point on the density map of the structure in the framework of the atoms-in-molecules theory. Nonetheless, a given structural conformation may be simply favored by electrostatic interactions. The present review surveys the in-solution competition of the conformations with intramolecular vs. intermolecular hydrogen bonds for different types of small organic molecules. In their most stable gas-phase structure, an intramolecular hydrogen bond is possible. In a protic solution, the intramolecular hydrogen bond may disrupt in favor of two solute-solvent intermolecular hydrogen bonds. The balance of the increased internal energy and the stabilizing effect of the solute-solvent interactions regulates the new conformer composition in the liquid phase. The review additionally considers the solvent effects on the stability of simple dimeric systems as revealed from molecular dynamics simulations or on the basis of the calculated potential of mean force curves. Finally, studies of the solvent effects on the type of the intermolecular hydrogen bond (neutral or ionic) in acid-base complexes have been surveyed. PMID:25353178

Low temperature growth of heavy boron-doped hydrogenated Ge epilayers and its application in Ge/Si photodetectors

NASA Astrophysics Data System (ADS)

Kuo, Wei-Cheng; Lee, Ming Jay; Wu, Mount-Learn; Lee, Chien-Chieh; Tsao, I.-Yu; Chang, Jenq-Yang

2017-04-01

In this study, heavily boron-doped hydrogenated Ge epilayers are grown on Si substrates at a low growth temperature (220 °C). The quality of the boron-doped epilayers is dependent on the hydrogen flow rate. The optical emission spectroscopic, X-ray diffraction and Hall measurement results demonstrate that better quality boron-doped Ge epilayers can be obtained at low hydrogen flow rates (0 sccm). This reduction in quality is due to an excess of hydrogen in the source gas, which breaks one of the Ge-Ge bonds on the Ge surface, leading to the formation of unnecessary dangling bonds. The structure of the boron doped Ge epilayers is analyzed by transmission electron microscopy and atomic force microscopy. In addition, the performance, based on the I-V characteristics, of Ge/Si photodetectors fabricated with boron doped Ge epilayers produced under different hydrogen flow rates was examined. The photodetectors with boron doped Ge epilayers produced with a low hydrogen flow rate (0 sccm) exhibited a higher responsivity of 0.144 A/W and a lower dark current of 5.33 × 10-7 A at a reverse bias of 1 V.

Direct, enantioselective α-alkylation of aldehydes using simple olefins.

PubMed

Capacci, Andrew G; Malinowski, Justin T; McAlpine, Neil J; Kuhne, Jerome; MacMillan, David W C

2017-11-01

Although the α-alkylation of ketones has already been established, the analogous reaction using aldehyde substrates has proven surprisingly elusive. Despite the structural similarities between the two classes of compounds, the sensitivity and unique reactivity of the aldehyde functionality has typically required activated substrates or specialized additives. Here, we show that the synergistic merger of three catalytic processes-photoredox, enamine and hydrogen-atom transfer (HAT) catalysis-enables an enantioselective α-aldehyde alkylation reaction that employs simple olefins as coupling partners. Chiral imidazolidinones or prolinols, in combination with a thiophenol, iridium photoredox catalyst and visible light, have been successfully used in a triple catalytic process that is temporally sequenced to deliver a new hydrogen and electron-borrowing mechanism. This multicatalytic process enables both intra- and intermolecular aldehyde α-methylene coupling with olefins to construct both cyclic and acyclic products, respectively. With respect to atom and step-economy ideals, this stereoselective process allows the production of high-value molecules from feedstock chemicals in one step while consuming only photons.

DelPhi Web Server: A comprehensive online suite for electrostatic calculations of biological macromolecules and their complexes

PubMed Central

Sarkar, Subhra; Witham, Shawn; Zhang, Jie; Zhenirovskyy, Maxim; Rocchia, Walter; Alexov, Emil

2011-01-01

Here we report a web server, the DelPhi web server, which utilizes DelPhi program to calculate electrostatic energies and the corresponding electrostatic potential and ionic distributions, and dielectric map. The server provides extra services to fix structural defects, as missing atoms in the structural file and allows for generation of missing hydrogen atoms. The hydrogen placement and the corresponding DelPhi calculations can be done with user selected force field parameters being either Charmm22, Amber98 or OPLS. Upon completion of the calculations, the user is given option to download fixed and protonated structural file, together with the parameter and Delphi output files for further analysis. Utilizing Jmol viewer, the user can see the corresponding structural file, to manipulate it and to change the presentation. In addition, if the potential map is requested to be calculated, the potential can be mapped onto the molecule surface. The DelPhi web server is available from http://compbio.clemson.edu/delphi_webserver. PMID:24683424

A simple structural hydrazide-based gelator as a fluoride ion colorimetric sensor.

PubMed

Bai, Binglian; Ma, Jie; Wei, Jue; Song, Jianxi; Wang, Haitao; Li, Min

2014-06-07

A 4-nitrobenzohydrazide derivative, N-(3,4,5-octyloxybenzoyl)-N'-(4'-nitrobenzoyl)hydrazine (C8), was synthesized. It could form stable gels in some of the tested organic solvents. The wide-angle X-ray diffraction analysis showed that the xerogels exhibited a layered structure. SEM images revealed that the molecules self-assembled into fibrous aggregates in the xerogels. FT-IR studies confirmed that the intermolecular hydrogen bonding between C=O and N-H groups was the major driving force for the formation of self-assembling gel processes. The gel is utilized for a 'naked eye' detection of fluoride ions, through a reversible gel-sol transition, which is associated with a color change from colorless to red. An extended conjugated system formed through the phenyl group and a five-membered ring based on intramolecular hydrogen bonding between the oxygen atom near the deprotonation nitrogen atom and the other NH, which is responsible for the dramatic color change upon addition of fluoride ions.

Molecular modeling and multispectroscopic studies of the interaction of mesalamine with bovine serum albumin.

PubMed

Shahabadi, Nahid; Fili, Soraya Moradi

2014-01-24

The interaction of mesalamine (5-aminosalicylic acid (5-ASA)) with bovine serum albumin (BSA) was investigated by fluorescence quenching, absorption spectroscopy, circular dichroism (CD) techniques, and molecular docking. Thermodynamic parameters (ΔH<0 and ΔS 0) indicated that the hydrogen bond and electrostatic forces played the major role in the binding of 5-ASA to BSA. The results of CD and UV-vis spectroscopy showed that the binding of this drug to BSA induces some conformational changes in BSA. Displacement experiments predicted that the binding of 5-ASA to BSA is located within domain III, Sudlows site 2, that these observations were substantiated by molecular docking studies. In addition, the docking result shows that the 5-ASA in its anionic form mainly interacts with Gln-416 residue through one hydrogen bond between H atom of 5-ASA anion and the adjacent O atom of the hydroxyl group of Gln-416. Copyright © 2013 Elsevier B.V. All rights reserved.

Direct, enantioselective α-alkylation of aldehydes using simple olefins

PubMed Central

Capacci, Andrew G.; Malinowski, Justin T.; McAlpine, Neil J.; Kuhne, Jerome; MacMillan, David W. C.

2017-01-01

Although the α-alkylation of ketones has already been established, the analogous reaction using aldehyde substrates has proven surprisingly elusive. Despite the structural similarities between the two classes of compounds, the sensitivity and unique reactivity of the aldehyde functionality has typically required activated substrates or specialized additives. Here, we show that the synergistic merger of three catalytic processes—photoredox, enamine and hydrogen-atom transfer (HAT) catalysis—enables an enantioselective α-aldehyde alkylation reaction that employs simple olefins as coupling partners. Chiral imidazolidinones or prolinols, in combination with a thiophenol, iridium photoredox catalyst and visible light, have been successfully used in a triple catalytic process that is temporally sequenced to deliver a new hydrogen and electron-borrowing mechanism. This multicatalytic process enables both intra- and intermolecular aldehyde α-methylene coupling with olefins to construct both cyclic and acyclic products, respectively. With respect to atom and step-economy ideals, this stereoselective process allows the production of high-value molecules from feedstock chemicals in one step while consuming only photons. PMID:29064486

Direct, enantioselective α-alkylation of aldehydes using simple olefins

NASA Astrophysics Data System (ADS)

Capacci, Andrew G.; Malinowski, Justin T.; McAlpine, Neil J.; Kuhne, Jerome; MacMillan, David W. C.

2017-11-01

Although the α-alkylation of ketones has already been established, the analogous reaction using aldehyde substrates has proven surprisingly elusive. Despite the structural similarities between the two classes of compounds, the sensitivity and unique reactivity of the aldehyde functionality has typically required activated substrates or specialized additives. Here, we show that the synergistic merger of three catalytic processes—photoredox, enamine and hydrogen-atom transfer (HAT) catalysis—enables an enantioselective α-aldehyde alkylation reaction that employs simple olefins as coupling partners. Chiral imidazolidinones or prolinols, in combination with a thiophenol, iridium photoredox catalyst and visible light, have been successfully used in a triple catalytic process that is temporally sequenced to deliver a new hydrogen and electron-borrowing mechanism. This multicatalytic process enables both intra- and intermolecular aldehyde α-methylene coupling with olefins to construct both cyclic and acyclic products, respectively. With respect to atom and step-economy ideals, this stereoselective process allows the production of high-value molecules from feedstock chemicals in one step while consuming only photons.

Poly[[(μ2-acetato-κ3 O,O′:O′)aqua­bis­(μ3-isonicotinato-κ3 O:O′:N)samarium(III)silver(I)] perchlorate

PubMed Central

Zhu, Li-Cai; Zhu, Si-Ming

2011-01-01

The title compound, {[AgSm(C6H4NO2)2(CH3CO2)(H2O)]ClO4}n, is a three-dimensional heterobimetallic complex constructed from a repeating dimeric unit. Only half of the dimeric moiety is found in the asymmetric unit; the unit cell is completed by crystallographic inversion symmetry. The SmIII ion is eight-coordinated by four O atoms of four different isonicotinate ligands, three O atoms of two different acetate ligands, and one O atom of a water mol­ecule. The two-coordinate AgI ion is bonded to two N atoms of two different isonicotinate anions, thereby connecting the disamarium units. In addition, the isonicotinate ligands also act as bridging ligands, generating a three-dimensional network. The coordinated water mol­ecules link the carboxyl­ate group and acetate ligands by O—H⋯O hydrogen bonding. Another O—H⋯O hydrogen bond is observed in the crystal structure. The perchlorate ion is disordered over two sites with site-occupancy factors of 0.560 (11) and 0.440 (11), whereas the methyl group of the acetate ligand is disordered over two sites with site-occupancy factors of 0.53 (5) and 0.47 (5). PMID:22090841

Fisher information in confined hydrogen-like ions

NASA Astrophysics Data System (ADS)

Mukherjee, Neetik; Majumdar, Sangita; Roy, Amlan K.

2018-01-01

Fisher information (I) is investigated for confined hydrogen atom (CHA)-like systems in conjugate r and p spaces. A comparative study between CHA and free H atom (with respect to I) is pursued. A detailed systematic result of I with respect to variation of confinement radius rc is presented, with particular emphasis on non-zero- (l, m) states. In certain respect, inferences in CHA are significantly different from free counterpart, such as (i) dependence on n, l quantum numbers (ii) appearance of maxima in Ip plots for | m | ≠ 0 . The role of atomic number and atomic radius is discussed.

Radiation of partially ionized atomic hydrogen

NASA Technical Reports Server (NTRS)

Soon, W. H.; Kunc, J. A.

1990-01-01

A nonlinear collisional-radiative model for determination of production of electrons, positive and negative ions, excited atoms, and spectral and continuum line intensities in stationary partially ionized atomic hydrogen is presented. Transport of radiation is included by coupling the rate equations for production of the electrons, ions, and excited atoms with the radiation escape factors, which are not constant but depend on plasma conditions. It is found that the contribution of the negative ion emission to the total continuum emission can be important. Comparison of the calculated total continuum emission coefficient, including the negative ion emission, is in good agreement with experimental results.

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.

Surface Roughness of Various Diamond-Like Carbon Films

NASA Astrophysics Data System (ADS)

Liu, Dongping; Liu, Yanhong; Chen, Baoxiang

2006-11-01

Atomic force microscopy is used to estimate and compare the surface morphology of hydrogenated and hydrogen-free diamond-like carbon (DLC) films. The films were prepared by using DC magnetron sputtering of a graphite target, pulsed cathodic carbon arcs, electron cyclotron resonance (ECR), plasma source ion implantation and dielectric barrier discharge (DBD). The difference in the surface structure is presented for each method of deposition. The influences of various discharge parameters on the film surface properties are discussed based upon the experimental results. The coalescence process via the diffusion of adsorbed carbon species is responsible for the formation of hydrogen-free DLC films with rough surfaces. The films with surface roughness at an atomic level can be deposited by energetic ion impacts in a highly ionized carbon plasma. The dangling bonds created by atomic hydrogen lead to the uniform growth of hydrocarbon species at the a-C:H film surfaces of the ECR or DBD plasmas.

Deep eutectic solvents: similia similibus solvuntur?

PubMed

Zahn, Stefan

2017-02-01

Deep eutectic solvents, mixtures of an organic compound and a salt with a deep eutectic melting point, are promising cheap and eco-friendly alternatives to ionic liquids. Ab initio molecular dynamics simulations of reline, a mixture consisting of urea and choline chloride, reveal that not solely hydrogen bonds allow similar interactions between both constituents. The chloride anion and the oxygen atom of urea also show a similar spatial distribution close to the cationic core of choline due to a similar charge located on both atoms. As a result of multiple similar interactions, clusters migrating together cannot be observed in reline which supports the hypothesis similia similibus solvuntur. In contrast to previous suggestions, the interaction of the hydroxyl group of choline with a hydrogen bond acceptor is overall rigid. Fast hydrogen bond acceptor dynamics is facilitated by the hydrogen atoms in the trans position to the carbonyl group of urea which contributes to the low melting point of reline.

Hydrogen molecules and chains in a superstrong magnetic field

NASA Technical Reports Server (NTRS)

Lai, Dong; Salpeter, Edwin E.; Shapiro, Stuart L.

1992-01-01

The electronic structures of hydrogen polymolecules H(n) (n = 2,3,4,...) is studied in a superstrong magnetic field (B greater than about 10 exp 12 G) typically found on the surface of a neutron star. Simple analytical scaling relations for several limiting cases (e.g., large n, high B field) are derived. The binding energies of H(n) molecules are numerically calculated for various magnetic-field strengths. For a given magnetic-field strength, the binding energy per atom in the H(n) molecules is found to approach a constant value as n increases. For typical field strengths of interest, energy saturation is essentially achieved once n exceeds 3 to 4. Also considered is the structure of negative H ions in a high magnetic field. For B about 10 exp 12 G, the dissociation energy of an atom in a hydrogen chain and the ionization potential of H(-) are smaller than the ionization potential of neutral atomic hydrogen.

2,3-Diamino-pyridinium sorbate-sorbic acid (1/1).

PubMed

Hemamalini, Madhukar; Goh, Jia Hao; Fun, Hoong-Kun

2012-01-01

In the title mol-ecular salt-adduct, C(5)H(8)N(3) (+)·C(6)H(7)O(2) (-)·C(6)H(8)O(2), the 2,3-diamino-pyridinium cation is essentially planar, with a maximum deviation of 0.013 (2) Å, and is protanated at its pyridine N atom. The sorbate anion and sorbic acid mol-ecules exist in extended conformations. In the crystal, the protonated N atom and one of the two amino-group H atoms are hydrogen bonded to the sorbate anion through a pair of N-H⋯O hydrogen bonds, forming an R(1) (2)(6) ring motif. The carboxyl groups of the sorbic acid mol-ecules and the carboxyl-ate groups of the sorbate anions are connected via O-H⋯O hydrogen bonds. Furthermore, the ion pairs and neutral mol-ecules are connected via inter-molecular N-H⋯O hydrogen bonds, forming sheets lying parallel to (100).

Molecular dynamics simulations of trihalomethanes removal from water using boron nitride nanosheets.

PubMed

Azamat, Jafar; Khataee, Alireza; Joo, Sang Woo

2016-04-01

Molecular dynamics simulations were performed to investigate the separation of trihalomethanes (THMs) from water using boron nitride nanosheets (BNNSs). The studied systems included THM molecules and a functionalized BNNS membrane immersed in an aqueous solution. An external pressure was applied to the z axis of the systems. Two functionalized BNNSs with large fluorinated-hydrogenated pore (F-H-pores) and small hydrogen-hydroxyl pore (H-OH-pores) were used. The pores of the BNNS membrane were obtained by passivating each nitrogen and boron atoms at the pore edges with fluorine and hydrogen atoms in the large pore or with hydroxyl and hydrogen atoms in the small pore. The results show that the BNNS with a small functionalized pore was impermeable to THM molecules, in contrast to the BNNS with a large functionalized pore. Using these membranes, water contaminants can be removed at lower cost.

Dissociation of CH4 by electron impact: Production of metastable hydrogen and carbon fragments

NASA Technical Reports Server (NTRS)

Finn, T. G.; Carnahan, B. L.; Zipf, E. C.

1974-01-01

Metastable fragments produced by electron impact excitation of CH4 have been investigated for incident electron energies from threshold to 300 eV. Only metastable hydrogen and carbon atoms were observed. Onset energies for the production of metastable hydrogen atoms were observed at electron impact energies of 22.0 + or - .5 eV, 25.5 + or - .6 eV, 36.7 + or - .6 eV and 66 + or - 3 eV, and at 26.6 + or - .6 eV for the production of metastable carbon atoms. Most of the fragments appear to have been formed in high-lying Rydberg states. The total metastable hydrogen cross section reaches a maximum value of approximately 1 X 10 to the minus 18th power sq cm at 100 eV. At the same energy, the metastable carbon cross section is 2 x 10 to the minus 19th power sq cm.

Evolution behavior of nanohardness after thermal-aging and hydrogen-charging on austenite and strain-induced martensite in pre-strained austenitic stainless steel

NASA Astrophysics Data System (ADS)

Zheng, Yuanyuan; Zhou, Chengshuang; Hong, Yuanjian; Zheng, Jinyang; Zhang, Lin

2018-05-01

Nanoindentation has been used to study the effects of thermal-aging and hydrogen on the mechanical property of the metastable austenitic stainless steel. Thermal-aging at 473 K decreases the nanohardness of austenite, while it increases the nanohardness of strain-induced ɑ‧ martensite. Hydrogen-charging at 473 K increases the nanohardness of austenite, while it decreases the nanohardness of strain-induced ɑ‧ martensite. The opposite effect on austenite and ɑ‧ martensite is first found in the same pre-strained sample. This abnormal evolution behavior of hardness can be attributed to the interaction between dislocation and solute atoms (carbon and hydrogen). Carbon atoms are difficult to move and redistribute in austenite compared with ɑ‧ martensite. Therefore, the difference in the diffusivity of solute atoms between austenite and ɑ‧ martensite may result in the change of hardness.

The interaction of hydrogen with the {010} surfaces of Mg and Fe olivine as models for interstellar dust grains: a density functional theory study

PubMed Central

Downing, C. A.; Ahmady, B.; Catlow, C. R. A.; de Leeuw, N. H.

2013-01-01

There is no consensus as yet to account for the significant presence of water on the terrestrial planets, but suggested sources include direct hydrogen adsorption from the parent molecular cloud after the planets’ formation, and delivery of hydrous material via comets or asteroids external to the zone of the terrestrial planets. Alternatively, a more recent idea is that water may have directly adsorbed onto the interstellar dust grains involved in planetary formation. In this work, we use electronic structure calculations based on the density functional theory to investigate and compare the bulk and {010} surface structures of the magnesium and iron end-members of the silicate mineral olivine, namely forsterite and fayalite, respectively. We also report our results on the adsorption of atomic hydrogen at the mineral surfaces, where our calculations show that there is no activation barrier to the adsorption of atomic hydrogen at these surfaces. Furthermore, different surface sites activate the atom to form either adsorbed hydride or proton species in the form of hydroxy groups on the same surface, which indicates that these mineral surfaces may have acted as catalytic sites in the immobilization and reaction of hydrogen atoms to form dihydrogen gas or water molecules. PMID:23734054

Deuterium supersaturation in low-energy plasma-loaded tungsten surfaces

NASA Astrophysics Data System (ADS)

Gao, L.; Jacob, W.; von Toussaint, U.; Manhard, A.; Balden, M.; Schmid, K.; Schwarz-Selinger, T.

2017-01-01

Fundamental understanding of hydrogen-metal interactions is challenging due to a lack of knowledge on defect production and/or evolution upon hydrogen ingression, especially for metals undergoing hydrogen irradiation with ion energy below the displacement thresholds reported in literature. Here, applying a novel low-energy argon-sputter depth profiling method with significantly improved depth resolution for tungsten (W) surfaces exposed to deuterium (D) plasma at 300 K, we show the existence of a 10 nm thick D-supersaturated surface layer (DSSL) with an unexpectedly high D concentration of ~10 at.% after irradiation with ion energy of 215 eV. Electron back-scatter diffraction reveals that the W lattice within this DSSL is highly distorted, thus strongly blurring the Kikuchi pattern. We explain this strong damage by the synergistic interaction of energetic D ions and solute D atoms with the W lattice. Solute D atoms prevent the recombination of vacancies with interstitial W atoms, which are produced by collisions of energetic D ions with W lattice atoms (Frenkel pairs). This proposed damaging mechanism could also be active on other hydrogen-irradiated metal surfaces. The present work provides deep insight into hydrogen-induced lattice distortion at plasma-metal interfaces and sheds light on its modelling work.

E. S. R. determination of atomic hydrogen distribution in oxy-fuel flames burning at atmospheric pressure

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

Bregeon, B.G.; Kadirgan, M.A.N.; Lamy, C.

1981-01-01

The authors have derived an experimental technique, using ESR spectroscopy, that allows this determination. A quartz burner equipped with an appropriate cooling system is placed directly in the ESR cavity. We obtained the hydrogen resonance signal and studied its variation for different positions of the flame inside the cavity. Hydrogen concentrations cannot be calculated directly from experimental data; hence we proceed indirectly to deconvoluate the resonance signal. This allows us to overcome the present severe handicap in obtaining atomic hydrogen concentrations in oxy-fuel flames from ESR measurements. Data obtained in this work, after temperature correction, give us the axial distributionmore » of hydrogen radicals for different oxy-propane and hydrogen-oxygen flames. These results show clearly that for all flames, the hydrogen radical concentration is maximum in a zone immediately above the inner cone. 13 refs.« less

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.

Exact solution for the hydrogen atom confined by a dielectric continuum and the correct basis set to study many-electron atoms under similar confinements

NASA Astrophysics Data System (ADS)

Martínez-Sánchez, Michael-Adán; Aquino, Norberto; Vargas, Rubicelia; Garza, Jorge

2017-12-01

The Schrödinger equation associated to the hydrogen atom confined by a dielectric continuum is solved exactly and suggests the appropriate basis set to be used when an atom is immersed in a dielectric continuum. Exact results show that this kind of confinement spread the electron density, which is confirmed through the Shannon entropy. The basis set suggested by the exact results is similar to Slater type orbitals and it was applied on two-electron atoms, where the H- ion ejects one electron for moderate confinements for distances much larger than those commonly used to generate cavities in solvent models.

a Time-Dependent Many-Electron Approach to Atomic and Molecular Interactions

NASA Astrophysics Data System (ADS)

Runge, Keith

A new methodology is developed for the description of electronic rearrangement in atomic and molecular collisions. Using the eikonal representation of the total wavefunction, time -dependent equations are derived for the electronic densities within the time-dependent Hartree-Fock approximation. An averaged effective potential which ensures time reversal invariance is used to describe the effect of the fast electronic transitions on the slower nuclear motions. Electron translation factors (ETF) are introduced to eliminate spurious asymptotic couplings, and a local ETF is incorporated into a basis of traveling atomic orbitals. A reference density is used to describe local electronic relaxation and to account for the time propagation of fast and slow motions, and is shown to lead to an efficient integration scheme. Expressions for time-dependent electronic populations and polarization parameters are given. Electronic integrals over Gaussians including ETFs are derived to extend electronic state calculations to dynamical phenomena. Results of the method are in good agreement with experimental data for charge transfer integral cross sections over a projectile energy range of three orders of magnitude in the proton-Hydrogen atom system. The more demanding calculations of integral alignment, state-to-state integral cross sections, and differential cross sections are found to agree well with experimental data provided care is taken to include ETFs in the calculation of electronic integrals and to choose the appropriate effective potential. The method is found to be in good agreement with experimental data for the calculation of charge transfer integral cross sections and state-to-state integral cross sections in the one-electron heteronuclear Helium(2+)-Hydrogen atom system and in the two-electron system, Hydrogen atom-Hydrogen atom. Time-dependent electronic populations are seen to oscillate rapidly in the midst of collision event. In particular, multiple exchanges of the electron are seen to occur in the proton-Hydrogen atom system at low collision energies. The concepts and results derived from the approach provide new insight into the dynamics of nuclear screening and electronic rearrangement in atomic collisions.

First principles study of gallium cleaning for hydrogen-contaminated α-Al2O3(0001) surfaces.

PubMed

Yang, Rui; Rendell, Alistair P

2013-05-15

The use of gallium for cleaning hydrogen-contaminated Al2O3 surfaces is explored by performing first principles density functional calculations of gallium adsorption on a hydrogen-contaminated Al-terminated α-Al2O3(0001) surface. Both physisorbed and chemisorbed H-contaminated α-Al2O3(0001) surfaces with one monolayer (ML) gallium coverage are investigated. The thermodynamics of gallium cleaning are considered for a variety of different asymptotic products, and are found to be favorable in all cases. Physisorbed H atoms have very weak interactions with the Al2O3 surface and can be removed easily by the Ga ML. Chemisorbed H atoms form stronger interactions with the surface Al atoms. Bonding energy analysis and departure simulations indicate, however, that chemisorbed H atoms can be effectively removed by the Ga ML. Copyright © 2013 Wiley Periodicals, Inc.

(2E,5E)-2,5-Bis(4-hy­droxy-3-meth­oxy­benzyl­idene)cyclo­penta­none ethanol monosolvate

PubMed Central

Da’i, Muhammad; Yanuar, Arry; Meiyanto, Edy; Jenie, Umar Anggara; Supardjan, Amir Margono

2013-01-01

In the title structure, C21H20O5·C2H5OH, the curcumine-type mol­ecule has a double E conformation for the two benzyl­idene double bonds [C=C = 1.342 (4) and 1.349 (4) Å] and is nearly planar with respect to the non-H atoms (r.m.s. deviation from planarity = 0.069 Å). The two phenolic OH groups form bifurcated hydrogen bonds with intra­molecular branches to adjacent meth­oxy O atoms and inter­molecular branches to either a neighbouring mol­ecule or an ethanol solvent mol­ecule. The ethanol O atom donates a hydrogen bond to the keto O atom. These hydrogen bonds link the constituents into layers parallel to (101) in the crystal structure. PMID:23634071

Scattered Ion Energetics for H atoms Impinging a Copper Surface

NASA Astrophysics Data System (ADS)

Defazio, J. N.; Stephen, T. M.; Peko, B. L.

2002-05-01

The energy loss and charge state of atomic hydrogen scattered from surfaces is important in a broad range of scientific endeavors. These include the charging of spacecraft, the detection of low energy neutrals in the space environment, energy transfer from magnetically confined plasmas and the modeling of low energy electric discharges. Measurements of scattered ions resulting from low energy (20 - 1000 eV) atomic hydrogen impacting a copper surface have been accomplished. Differential energy distributions and yields for H- and H+ resulting from these collisions are presented. The data show that the energy distributions develop a universal dependence, when scaled by the incident energy. These results are compared with studies involving incident hydrogen ions. For incident energies less than 100eV, there are obvious differences in the scattered ion energy distributions resulting from impacting atoms when compared to those resulting from ions.

Metastability of isoformyl ions in collisions with helium and hydrogen. [in interstellar molecular clouds

NASA Technical Reports Server (NTRS)

Green, S.

1984-01-01

The stability of HOC(+) ions under conditions in interstellar molecular clouds is considered. In particular, the possibility that collisions with helium or hydrogen will induce isomerization to the stable HCO(+) form is examined theoretically. Portions of the electronic potential energy surfaces for interaction with He and H atoms are obtained from standard quantum mechanical calculations. Collisions with He atoms are found to be totally ineffective for inducing isomerization. Collisions with H atoms are found to be ineffective at low interstellar temperatures owing to a small (about 500 K) barrier in the entrance channel; at higher temperatures where this barrier can be overcome, however, collisions with hydrogen atoms do result in conversion to the stable HCO(+) form. Although detailed calculations are not presented, it is argued that low-energy collisions with H2 molecules are also ineffective in destroying the metastable ion.

Hα line shape in front of the limiter in the HT-6M tokamak

NASA Astrophysics Data System (ADS)

Wan, Baonian; Li, Jiangang; Luo, Jiarong; Xie, Jikang; Wu, Zhenwei; Zhang, Xianmei; HT-6M Group

1999-11-01

The Hα line shape in front of the limiter in the HT-6M tokamak is analysed by multi-Gaussian fitting. The energy distribution of neutral hydrogen atoms reveals that Hα radiation is contributed by Franck-Condon atoms, atoms reflected at the limiter surface and charge exchange. Multi-Gaussian fitting of the Hα spectral profile indicates contributions of 60% from reflection particles and 40% from molecule dissociation to recycling. Ion temperatures in central regions are obtained from the spectral width of charge exchange components. Dissociation of hydrogen molecules and reflection of particles at the limiter surface are dominant in edge recycling. Reduction of particle reflection at the limiter surface is important for controlling edge recycling. The measured profiles of neutral hydrogen atom density are reproduced by a particle continuity equation and a simplified one dimensional Monte Carlo simulation code.

Strain effect on the adsorption, diffusion, and molecular dissociation of hydrogen on Mg (0001) surface

NASA Astrophysics Data System (ADS)

Lei, Huaping; Wang, Caizhuang; Yao, Yongxin; Wang, Yangang; Hupalo, Myron; McDougall, Dan; Tringides, Michael; Ho, Kaiming

2013-12-01

The adsorption, diffusion, and molecular dissociation of hydrogen on the biaxially strained Mg (0001) surface have been systematically investigated by the first principle calculations based on density functional theory. When the strain changes from the compressive to tensile state, the adsorption energy of H atom linearly increases while its diffusion barrier linearly decreases oppositely. The dissociation barrier of H2 molecule linearly reduces in the tensile strain region. Through the chemical bonding analysis including the charge density difference, the projected density of states and the Mulliken population, the mechanism of the strain effect on the adsorption of H atom and the dissociation of H2 molecule has been elucidated by an s-p charge transfer model. With the reduction of the orbital overlap between the surface Mg atoms upon the lattice expansion, the charge transfers from p to s states of Mg atoms, which enhances the hybridization of H s and Mg s orbitals. Therefore, the bonding interaction of H with Mg surface is strengthened and then the atomic diffusion and molecular dissociation barriers of hydrogen decrease accordingly. Our works will be helpful to understand and to estimate the influence of the lattice deformation on the performance of Mg-containing hydrogen storage materials.

On the temperature dependence of H-U{sub iso} in the riding hydrogen model

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

Lübben, Jens; Volkmann, Christian; Grabowsky, Simon

The temperature dependence of hydrogen U{sub iso} and parent U{sub eq} in the riding hydrogen model is investigated by neutron diffraction, aspherical-atom refinements and QM/MM and MO/MO cluster calculations. Fixed values of 1.2 or 1.5 appear to be underestimated, especially at temperatures below 100 K. The temperature dependence of H-U{sub iso} in N-acetyl-l-4-hydroxyproline monohydrate is investigated. Imposing a constant temperature-independent multiplier of 1.2 or 1.5 for the riding hydrogen model is found to be inaccurate, and severely underestimates H-U{sub iso} below 100 K. Neutron diffraction data at temperatures of 9, 150, 200 and 250 K provide benchmark results for thismore » study. X-ray diffraction data to high resolution, collected at temperatures of 9, 30, 50, 75, 100, 150, 200 and 250 K (synchrotron and home source), reproduce neutron results only when evaluated by aspherical-atom refinement models, since these take into account bonding and lone-pair electron density; both invariom and Hirshfeld-atom refinement models enable a more precise determination of the magnitude of H-atom displacements than independent-atom model refinements. Experimental efforts are complemented by computing displacement parameters following the TLS+ONIOM approach. A satisfactory agreement between all approaches is found.« less

Linking protein structure and dynamics to catalysis: the role of hydrogen tunnelling

PubMed Central

Klinman, Judith P

2006-01-01

Early studies of enzyme-catalysed hydride transfer reactions indicated kinetic anomalies that were initially interpreted in the context of a ‘tunnelling correction’. An alternate model for tunnelling emerged following studies of the hydrogen atom transfer catalysed by the enzyme soybean lipoxygenase. This invokes full tunnelling of all isotopes of hydrogen, with reaction barriers reflecting the heavy atom, environmental reorganization terms. Using the latter approach, we offer an integration of the aggregate data implicating hydrogen tunnelling in enzymes (i.e. deviations from Swain–Schaad relationships and the semi-classical temperature dependence of the hydrogen isotope effect). The impact of site-specific mutations of enzymes plays a critical role in our understanding of the factors that control tunnelling in enzyme reactions. PMID:16873120

Nature and Strength of the Inner-Core H⋅⋅⋅H Interactions in Porphyrinoids.

PubMed

Singh, Ankit; Sahoo, Dipak Kumar; Sethi, Srikant Kumar; Jena, Subhrakant; Biswal, Himansu S

2017-12-15

Several recent publications have illustrated that electrostatic attraction is not solely responsible for strong hydrogen bonds. Even electropositive and less electronegative atoms such as Te and Se are capable of forming strong H-bonds. Herein, we provide evidence for intramolecular homopolar dihydrogen bonds [HOMO-DHBs; X-N(C)-H δ+ ⋅⋅⋅ δ+ H-N(C)-Y] in porphyrins and related compounds for the first time; these bonds are revealed by careful Cambridge Structural Database (CSD) exploration, quantum theory of atoms in molecules, compliance constant calculations, and natural bond orbital and noncovalent interaction (NCI) analysis. A search of the CSD showed that the inner-core hydrogen atom distances were less than 2.5 Å (sum of the van der Waals radii of two hydrogen atoms is 2.4 Å) in porphyrinoids, i.e. about 75 % of the cases. This suggested an attractive interaction between hydrogen atoms carrying a positive charge, which was further supported by quantum-chemical calculations. The HOMO-DHB energy in some cases was found to be as much as around 20 kJ mol -1 , which is comparable to that of any conventional H-bond energy such as for the NH 3 dimer. The interplay between hyperconjugative attraction and steric constraint favorably decided the strength of the HOMO-DHBs. We expect that HOMO-DHBs could be revealed in many more systems, such as corroles, phlorins, crown ethers, and constrained systems having hydrogen atoms in close contact, and could be an important noncovalent interaction to consider in supramolecular chemistry. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Adsorption, hydrogenation and dehydrogenation of C2H on a CoCu bimetallic layer

NASA Astrophysics Data System (ADS)

Wu, Donghai; Yuan, Jinyun; Yang, Baocheng; Chen, Houyang

2018-05-01

In this paper, adsorption, hydrogenation and dehydrogenation of C2H on a single atomic layer of bimetallic CoCu were investigated using first-principles calculations. The CoCu bimetallic layer is formed by Cu replacement of partial Co atoms on the top layer of a Co(111) surface. Our adsorption and reaction results showed those sites, which have stronger adsorption energy of C2H, possess higher reactivity. The bimetallic layer possesses higher reactivity than either of the pure monometallic layer. A mechanism of higher reactivity of the bimetallic layer is proposed and identified, i.e. in the bimetallic catalyst, the catalytic performance of one component is promoted by the second component, and in our work, the catalytic performance of Co atoms in the bimetallic layer are improved by introducing Cu atoms, lowing the activation barrier of the reaction of C2H. The bimetallic layer could tune adsorption and reaction of C2H by modulating the ratio of Co and Cu. Results of adsorption energies and adsorption configurations reveal that C2H prefers to be adsorbed in parallel on both the pure Co metallic and CoCu bimetallic layers, and Co atoms in subsurface which support the metallic or bimetallic layer have little effect on C2H adsorption. For hydrogenation reactions, the products greatly depend on the concentration and initial positions of hydrogen atoms, and the C2H hydrogenation forming acetylene is more favorable than forming vinylidene in both thermodynamics and kinetics. This study would provide fundamental guidance for hydrocarbon reactions on Co-based and/or Cu-based bimetallic surface chemistry and for development of new bimetallic catalysts.

Laser stripping of hydrogen atoms by direct ionization

DOE PAGES

Brunetti, E.; Becker, W.; Bryant, H. C.; ...

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.

Laser stripping of hydrogen atoms by direct ionization

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

Brunetti, E.; Becker, W.; Bryant, H. C.

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.

Photoelectron emission yield experiments on evolution of sub-gap states in amorphous In-Ga-Zn-O thin films with post deposition hydrogen treatment

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

Hayashi, Kazushi, E-mail: hayashi.kazushi@kobelco.com; Hino, Aya; Tao, Hiroaki

Total photoyield emission spectroscopy (TPYS) was applied to study the evolution of sub-gap states in hydrogen-treated amorphous In-Ga-Zn-O (a-IGZO) thin films. The a-IGZO thin films were subjected to hydrogen radicals and subsequently annealed in ultra-high vacuum (UHV) conditions. A clear onset of the electron emission was observed at around 4.3 eV from the hydrogen-treated a-IGZO thin films. After successive UHV annealing at 300 °C, the onset in the TPYS spectra was shifted to 4.15 eV, and the photoelectron emission from the sub-gap states was decreased as the annealing temperature was increased. In conjunction with the results of thermal desorption spectrometer, it was deducedmore » that the hydrogen atoms incorporated in the a-IGZO thin films induced metastable sub-gap states at around 4.3 eV from vacuum level just after the hydrogenation. It was also suggested that the defect configuration was changed due to the higher temperature UHV annealing, and that the hydrogen atoms desorbed with the involvement of Zn atoms. These experiments produced direct evidence to show the formation of sub-gap states as a result of hydrogen incorporation into the a-IGZO thin films.« less

Prospects for hydrogen storage in graphene.

PubMed

Tozzini, Valentina; Pellegrini, Vittorio

2013-01-07

Hydrogen-based fuel cells are promising solutions for the efficient and clean delivery of electricity. Since hydrogen is an energy carrier, a key step for the development of a reliable hydrogen-based technology requires solving the issue of storage and transport of hydrogen. Several proposals based on the design of advanced materials such as metal hydrides and carbon structures have been made to overcome the limitations of the conventional solution of compressing or liquefying hydrogen in tanks. Nevertheless none of these systems are currently offering the required performances in terms of hydrogen storage capacity and control of adsorption/desorption processes. Therefore the problem of hydrogen storage remains so far unsolved and it continues to represent a significant bottleneck to the advancement and proliferation of fuel cell and hydrogen technologies. Recently, however, several studies on graphene, the one-atom-thick membrane of carbon atoms packed in a honeycomb lattice, have highlighted the potentialities of this material for hydrogen storage and raise new hopes for the development of an efficient solid-state hydrogen storage device. Here we review on-going efforts and studies on functionalized and nanostructured graphene for hydrogen storage and suggest possible developments for efficient storage/release of hydrogen under ambient conditions.

Hydrogen doping in HfO{sub 2} resistance change random access memory

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

Duncan, D.; Magyari-Köpe, B.; Nishi, Y.

2016-01-25

The structures and energies of hydrogen-doped monoclinic hafnium dioxide were calculated using density-functional theory. The electronic interactions are described within the LDA + U formalism, where on-site Coulomb corrections are applied to the 5d orbital electrons of Hf atoms and 2p orbital electrons of the O atoms. The effects of charge state, defect-defect interactions, and hydrogenation are investigated and compared with experiment. It is found that hydrogenation of HfO{sub 2} resistance-change random access memory devices energetically stabilizes the formation of oxygen vacancies and conductive vacancy filaments through multiple mechanisms, leading to improved switching characteristic and device yield.

Decomposition of silane on tungsten or other materials

DOEpatents

Wiesmann, H.J.

This invention relates to hydrogenated amorphous silicon produced by thermally decomposing silane (SiH/sub 4/) or other gases comprising H and Si, from a W or foil heated to a temperature of about 1400 to 1600/sup 0/C, in a vacuum of about 10-/sup 6/ to 10-/sup 4/ torr. A gaseous mixture is formed of atomic hydrogen and atomic silicon. The gaseous mixture is deposited onto a substrate independent of and outside the source of thermal decomposition. Hydrogenated amorphous silicon is formed. The presence of an ammonia atmosphere in the vacuum chamber enhances the photoconductivity of the hydrogenated amorphous silicon film.

The solubility of hydrogen in rhodium, ruthenium, iridium and nickel.

NASA Technical Reports Server (NTRS)

Mclellan, R. B.; Oates, W. A.

1973-01-01

The temperature variation of the solubility of hydrogen in rhodium, ruthenium, iridium, and nickel in equilibrium with H2 gas at 1 atm pressure has been measured by a technique involving saturating the solvent metal with hydrogen, quenching, and analyzing in resultant solid solutions. The solubilities determined are small (atom fraction of H is in the range from 0.0005 to 0.00001, and the results are consistent with the simple quasi-regular model for dilute interstitial solid solutions. The relative partial enthalpy and excess entropy of the dissolved hydrogen atoms have been calculated from the solubility data and compared with well-known correlations between these quantities.

Quantum mechanics models of the methanol dimer: OH⋯O hydrogen bonds of β-d-glucose moieties from crystallographic data.

PubMed

Cintrón, Michael Santiago; Johnson, Glenn P; French, Alfred D

2017-04-18

The interaction of two methanol molecules, simplified models of carbohydrates and cellulose, was examined using a variety of quantum mechanics (QM) levels of theory. Energy plots for hydrogen bonding distance (H⋯O) and angle (OH⋯O) were constructed. All but two experimental structures were located in stabilized areas on the vacuum phase energy plots. Each of the 399 models was analyzed with Bader's atoms-in-molecules (AIM) theory, which showed a widespread ability by the dimer models to form OH⋯O hydrogen bonds that have bond paths and Bond Critical Points. Continuum solvation calculations suggest that a portion of the energy-stabilized structures could occur in the presence of water. A survey of the Cambridge Structural Database (CSD) for all donor-acceptor interactions in β-D-glucose moieties examined the similarities and differences among the hydroxyl groups and acetal oxygen atoms that participate in hydrogen bonds. Comparable behavior was observed for the O2H, O3H, O4H, and O6H hydroxyls, acting either as acceptors or donors. Ring O atoms showed distinct hydrogen bonding behavior that favored mid-length hydrogen bonds. Published by Elsevier Ltd.