Laboratory Studies of Atmospheric Heterogeneous Chemistry

NASA Technical Reports Server (NTRS)

Keyser, L. F.; Leu, M-T.

1993-01-01

In the laboratory, ice films formed by freezing from the liquid or more frequently by deposition from the vapor phase have been used to simulate stratospheric cloud surfaces for measurements of reaction and uptake rates. To obtain intrinsic surface reaction probabilities that can be used in atmospheric models, the area of the film surface that actually takes part in the reaction must be known. It is important to know not only the total surface area but also the film morphology in order to determine where and how the surface is situated and, thus, what fraction of it is available for reaction. Information on the structure of these ice films has been obtained by using several experimental methods. In the sections that follow, these methods will be discussed, then the results will be used to construct a working model of the ice films, and finally the model will be applied to an experimental study of HC1 uptake by H_2O ice.

Water dissociation on Ni(100), Ni(110), and Ni(111) surfaces: Reaction path approach to mode selectivity

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

Seenivasan, H.; Jackson, Bret; Tiwari, Ashwani K.

We performed a comparative study of mode-selectivity of water dissociation on Ni(100), Ni(110), and Ni(111) surfaces at the same level of theory using a fully quantum approach based on the reaction path Hamiltonian. Calculations show that the barrier to water dissociation on the Ni(110) surface is significantly lower compared to its close-packed counterparts. Transition states for this reaction on all three surfaces involve the elongation of one of the O–H bonds. Furthermore, a significant decrease in the symmetric stretching and bending mode frequencies near the transition state is observed in all three cases and in the vibrational adiabatic approximation, excitationmore » of these softened modes results in a significant enhancement in reactivity. Inclusion of non-adiabatic couplings between modes results in the asymmetric stretching mode showing a similar enhancement of reactivity as the symmetric stretching mode. Dissociation probabilities calculated at a surface temperature of 300 K showed higher reactivity at lower collision energies compared to that of the static surface case, underlining the importance of lattice motion in enhancing reactivity. Mode selective behavior is similar on all the surfaces. Molecules with one-quantum of vibrational excitation in the symmetric stretch, at lower energies (up to 0.45 eV), are more reactive on Ni(110) than the Ni(100) and Ni(111) surfaces. But, the dissociation probabilities approach saturation on all the surfaces at higher incident energy values. Ultimately, Ni(110) is found to be highly reactive toward water dissociation among the low-index nickel surfaces owing to a low reaction barrier resulting from the openness and corrugation of the surface. These results show that the mode-selective behavior does not vary with different crystal facets of Ni qualitatively, but there is a significant quantitative effect.« less

Water dissociation on Ni(100), Ni(110), and Ni(111) surfaces: Reaction path approach to mode selectivity

DOE PAGES

Seenivasan, H.; Jackson, Bret; Tiwari, Ashwani K.

2017-02-17

We performed a comparative study of mode-selectivity of water dissociation on Ni(100), Ni(110), and Ni(111) surfaces at the same level of theory using a fully quantum approach based on the reaction path Hamiltonian. Calculations show that the barrier to water dissociation on the Ni(110) surface is significantly lower compared to its close-packed counterparts. Transition states for this reaction on all three surfaces involve the elongation of one of the O–H bonds. Furthermore, a significant decrease in the symmetric stretching and bending mode frequencies near the transition state is observed in all three cases and in the vibrational adiabatic approximation, excitationmore » of these softened modes results in a significant enhancement in reactivity. Inclusion of non-adiabatic couplings between modes results in the asymmetric stretching mode showing a similar enhancement of reactivity as the symmetric stretching mode. Dissociation probabilities calculated at a surface temperature of 300 K showed higher reactivity at lower collision energies compared to that of the static surface case, underlining the importance of lattice motion in enhancing reactivity. Mode selective behavior is similar on all the surfaces. Molecules with one-quantum of vibrational excitation in the symmetric stretch, at lower energies (up to 0.45 eV), are more reactive on Ni(110) than the Ni(100) and Ni(111) surfaces. But, the dissociation probabilities approach saturation on all the surfaces at higher incident energy values. Ultimately, Ni(110) is found to be highly reactive toward water dissociation among the low-index nickel surfaces owing to a low reaction barrier resulting from the openness and corrugation of the surface. These results show that the mode-selective behavior does not vary with different crystal facets of Ni qualitatively, but there is a significant quantitative effect.« less

Vibrational Mode-Specific Reaction of Methane on a Nickel Surface

NASA Astrophysics Data System (ADS)

Beck, Rainer D.; Maroni, Plinio; Papageorgopoulos, Dimitrios C.; Dang, Tung T.; Schmid, Mathieu P.; Rizzo, Thomas R.

2003-10-01

The dissociation of methane on a nickel catalyst is a key step in steam reforming of natural gas for hydrogen production. Despite substantial effort in both experiment and theory, there is still no atomic-scale description of this important gas-surface reaction. We report quantum state-resolved studies, using pulsed laser and molecular beam techniques, of vibrationally excited methane reacting on the nickel (100) surface. For doubly deuterated methane (CD2H2), we observed that the reaction probability with two quanta of excitation in one C-H bond was greater (by as much as a factor of 5) than with one quantum in each of two C-H bonds. These results clearly exclude the possibility of statistical models correctly describing the mechanism of this process and attest to the importance of full-dimensional calculations of the reaction dynamics.

Vibrational mode-specific reaction of methane on a nickel surface.

PubMed

Beck, Rainer D; Maroni, Plinio; Papageorgopoulos, Dimitrios C; Dang, Tung T; Schmid, Mathieu P; Rizzo, Thomas R

2003-10-03

The dissociation of methane on a nickel catalyst is a key step in steam reforming of natural gas for hydrogen production. Despite substantial effort in both experiment and theory, there is still no atomic-scale description of this important gas-surface reaction. We report quantum state-resolved studies, using pulsed laser and molecular beam techniques, of vibrationally excited methane reacting on the nickel (100) surface. For doubly deuterated methane (CD2H2), we observed that the reaction probability with two quanta of excitation in one C-H bond was greater (by as much as a factor of 5) than with one quantum in each of two C-H bonds. These results clearly exclude the possibility of statistical models correctly describing the mechanism of this process and attest to the importance of full-dimensional calculations of the reaction dynamics.

Heterogeneous reactions in aircraft gas turbine engines

NASA Astrophysics Data System (ADS)

Brown, R. C.; Miake-Lye, R. C.; Lukachko, S. P.; Waitz, I. A.

2002-05-01

One-dimensional flow models and unity probability heterogeneous rate parameters are used to estimate the maximum effect of heterogeneous reactions on trace species evolution in aircraft gas turbines. The analysis includes reactions on soot particulates and turbine/nozzle material surfaces. Results for a representative advanced subsonic engine indicate the net change in reactant mixing ratios due to heterogeneous reactions is <10-6 for O2, CO2, and H2O, and <10-10 for minor combustion products such as SO2 and NO2. The change in the mixing ratios relative to the initial values is <0.01%. Since these estimates are based on heterogeneous reaction probabilities of unity, the actual changes will be even lower. Thus, heterogeneous chemistry within the engine cannot explain the high conversion of SO2 to SO3 which some wake models require to explain the observed levels of volatile aerosols. Furthermore, turbine heterogeneous processes will not effect exhaust NOx or NOy levels.

Fragmentation and reactivity in collisions of protonated diglycine with chemically modified perfluorinated alkylthiolate-self-assembled monolayer surfaces

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

Barnes, George L.; Yang Li; Hase, William L.

2011-03-07

Direct dynamics simulations are reported for quantum mechanical (QM)/molecular mechanical (MM) trajectories of N-protonated diglycine (gly{sub 2}-H{sup +}) colliding with chemically modified perfluorinated octanethiolate self-assembled monolayer (SAM) surfaces. The RM1 semiempirical theory is used for the QM component of the trajectories. RM1 activation and reaction energies were compared with those determined from higher-level ab initio theories. Two chemical modifications are considered in which a head group (-COCl or -CHO) is substituted on the terminal carbon of a single chain of the SAM. These surfaces are designated as the COCl-SAM and CHO-SAM, respectively. Fragmentation, peptide reaction with the SAM, and covalentmore » linkage of the peptide or its fragments with the SAM surface are observed. Peptide fragmentation via concerted CH{sub 2}-CO bond breakage is the dominant pathway for both surfaces. HCl formation is the dominant species produced by reaction with the COCl-SAM, while for the CHO-SAM a concerted H-atom transfer from the CHO-SAM to the peptide combined with either a H-atom or radical transfer from the peptide to the surface to form singlet reaction products is the dominant pathway. A strong collision energy dependence is found for the probability of peptide fragmentation, its reactivity, and linkage with the SAM. Surface deposition, i.e., covalent linkage between the surface and the peptide, is compared to recent experimental observations of such bonding by Laskin and co-workers [Phys. Chem. Chem. Phys. 10, 1512 (2008)]. Qualitative differences in reactivity are seen between the COCl-SAM and CHO-SAM showing that chemical identity is important for surface reactivity. The probability of reactive surface deposition, which is most closely analogous to experimental observables, peaks at a value of around 20% for a collision energy of 50 eV.« less

Heterotypic antibodies in Liberian sera causing anomalous reactions when using a commercial haemagglutination test for hepatitis-B surface antigen.

PubMed

Willcox, M C

1976-04-01

Agglutinins reacting with normal and tanned sheep erythrocytes were the probable cause of false positive reactions given by 51 of 214 Liberian sera when using a commercial passive-haemagglutination test for hepatitis-B surface antigen. Absorption showed these agglutinins to be identical to those described earlier in Nigerian sera. Rheumatoid factor and anti-sheep-serum antibodies although present in 12 and five per cent respectively of all sera were not responsible for any false positive reactions. The practical conclusion is that such tests, based on sheep erythrocytes are unsuitable for screening this population.

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

PubMed

Wang, Xiaohong; Bowman, Joel M

2013-02-12

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

Effect of Electronic Excitation on Hydrogen Atom Transfer (Tautomerization) Reactions for the DNA Base Adenine

NASA Technical Reports Server (NTRS)

Chaban, Galina M.; Salter, Latasha M.; Kwak, Dochan (Technical Monitor)

2002-01-01

Geometrical structures and energetic properties for four different tautomers of adenine are calculated in this study, using multi-configurational wave functions. Both the ground and the lowest single excited state potential energy surface are studied. The energetic order of the tautomers on the ground state potential surface is 9H less than 7H less than 3H less than 1H, while on the excited state surface this order is found to be different: 3H less than 1H less than 9H less than 7H. Minimum energy reaction paths are obtained for hydrogen atom transfer (9 yields 3 tautomerization) reactions in the ground and the lowest excited electronic state. It is found that the barrier heights and the shapes of the reaction paths are different for the ground and the excited electronic state, suggesting that the probability of such tautomerization reaction is higher on the excited state potential energy surface. The barrier for this reaction in the excited state may become very low in the presence of water or other polar solvent molecules, and therefore such tautomerization reaction may play an important role in the solution phase photochemistry of adenine.

Mass spectrometric studies of phosphine pyrolysis and OMVPE growth of InP. [organometallic vapor phase epitaxy

NASA Technical Reports Server (NTRS)

Larsen, C. A.; Buchan, N. I.; Stringfellow, G. B.

1987-01-01

The mechanism of PH3 decomposition was studied by using D2 as a carrier gas and analyzing the reaction products with a mass spectrometer. The effects of InP and silica surfaces were investigated. The only gaseous product below 600 C is H2. Since any gas-phase H atoms would produce HD, the reaction occurs entirely on the surface. The slow step is the unimolecular removal of the first hydrogen atom, with an activation energy of 36.0 kcal/mole on InP surfaces. The reaction on InP is first-order for PH3 concentrations as high as 15 percent, so the surface is not saturated at those conditions. When trimethylindium (TMIn) is added to the gas mixture, the mechanism changes dramatically, probably proceeding via an unstable intermediate adduct of TMIn and PH3 which eliminates CH4 upon formation. This concerted reaction lowers the pyrolysis temperatures of both PH3 and TMIn.

The manifestation of vibrational excitation effect in reactions C + SH(v = 0-20, j = 0) \\rightarrow H + CS, S + CH

NASA Astrophysics Data System (ADS)

Zhang, Lulu; Gao, Shoubao; Song, Yuzhi; Meng, Qingtian

2018-03-01

The dependence of the cross section for the C + SH \\to H + CS, S + CH reactions on the vibrational excitation of SH(v = 0-20, j = 0) is analyzed in detail at the collision energies of 0.3 and 0.8 eV by using the quasi-classical trajectory method and the new potential energy surface (Song et al 2016 Sci. Rep. 6 37734) of the {{HCS}}({{X}}{}2{{A}}\\prime ). The efficiency of vibrational excitation to promote the reaction is investigated through the analysis of the cross section and its v dependence in terms of the reaction probability, maximum impact parameter, and the features of the potential energy surface. The differential cross sections obtained show that at higher vibrational levels, the products (CS, CH) are mainly forward scattered, and the sideward and backward scatterings are quite weak. In addition to the scalar properties, the stereodynamical attributes, such as angle distribution functions P(θ r ), P(ϕ r ) and P(θ r , ϕ r ) at different vibrational levels are explored in detail. Furthermore, through the investigation of the state-to-state dynamics for the titled reaction, it is clear that the vibrational excitation of the product for C + SH \\to H + CS reaction is quite strong, with the most probable population appearing at high vibration numbers.

Theoretical investigation of the gas-phase reactions of CrO(+) with ethylene.

PubMed

Scupp, Thomas M; Dudley, Timothy J

2010-01-21

The potential energy surfaces associated with the reactions of chromium oxide cation (CrO(+)) with ethylene have been characterized using density functional, coupled-cluster, and multireference methods. Our calculations show that the most probable reaction involves the formation of acetaldehyde and Cr(+) via a hydride transfer involving the metal center. Our calculations support previous experimental hypotheses that a four-membered ring intermediate plays an important role in the reactivity of the system. We have also characterized a number of viable reaction pathways that lead to other products, including ethylene oxide. Due to the experimental observation that CrO(+) can activate carbon-carbon bonds, a reaction pathway involving C-C bond cleavage has also been characterized. Since many of the reactions involve a change in the spin state in going from reactants to products, locations of these spin surface crossings are presented and discussed. The applicability of methods based on Hartree-Fock orbitals is also discussed.

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

Wagner, Albert F., E-mail: wagner@anl.gov; Dawes, Richard; Continetti, Robert E.

The measured H(D)OCO survival fractions of the photoelectron-photofragment coincidence experiments by the Continetti group are qualitatively reproduced by tunneling calculations to H(D) + CO{sub 2} on several recent ab initio potential energy surfaces for the HOCO system. The tunneling calculations involve effective one-dimensional barriers based on steepest descent paths computed on each potential energy surface. The resulting tunneling probabilities are converted into H(D)OCO survival fractions using a model developed by the Continetti group in which every oscillation of the H(D)-OCO stretch provides an opportunity to tunnel. Four different potential energy surfaces are examined with the best qualitative agreement with experimentmore » occurring for the PIP-NN surface based on UCCSD(T)-F12a/AVTZ electronic structure calculations and also a partial surface constructed for this study based on CASPT2/AVDZ electronic structure calculations. These two surfaces differ in barrier height by 1.6 kcal/mol but when matched at the saddle point have an almost identical shape along their reaction paths. The PIP surface is a less accurate fit to a smaller ab initio data set than that used for PIP-NN and its computed survival fractions are somewhat inferior to PIP-NN. The LTSH potential energy surface is the oldest surface examined and is qualitatively incompatible with experiment. This surface also has a small discontinuity that is easily repaired. On each surface, four different approximate tunneling methods are compared but only the small curvature tunneling method and the improved semiclassical transition state method produce useful results on all four surfaces. The results of these two methods are generally comparable and in qualitative agreement with experiment on the PIP-NN and CASPT2 surfaces. The original semiclassical transition state theory method produces qualitatively incorrect tunneling probabilities on all surfaces except the PIP. The Eckart tunneling method uses the least amount of information about the reaction path and produces too high a tunneling probability on PIP-NN surface, leading to survival fractions that peak at half their measured values.« less

Impact of physical properties on ozone removal by several porous materials.

PubMed

Gall, Elliott T; Corsi, Richard L; Siegel, Jeffrey A

2014-04-01

Models of reactive uptake of ozone in indoor environments generally describe materials through aerial (horizontal) projections of surface area, a potentially limiting assumption for porous materials. We investigated the effect of changing porosity/pore size, material thickness, and chamber fluid mechanic conditions on the reactive uptake of ozone to five materials: two cellulose filter papers, two cementitious materials, and an activated carbon cloth. Results include (1) material porosity and pore size distributions, (2) effective diffusion coefficients for ozone in materials, and (3) material-ozone deposition velocities and reaction probabilities. At small length scales (0.02-0.16 cm) increasing thickness caused increases in estimated reaction probabilities from 1 × 10(-6) to 5 × 10(-6) for one type of filter paper and from 1 × 10(-6) to 1 × 10(-5) for a second type of filter paper, an effect not observed for materials tested at larger thicknesses. For high porosity materials, increasing chamber transport-limited deposition velocities resulted in increases in reaction probabilities by factors of 1.4-2.0. The impact of physical properties and transport effects on values of the Thiele modulus, ranging across all materials from 0.03 to 13, is discussed in terms of the challenges in estimating reaction probabilities to porous materials in scenarios relevant to indoor environments.

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

NASA Astrophysics Data System (ADS)

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

1999-08-01

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

Substrate Vibrations as Promoters of Chemical Reactivity on Metal Surfaces.

PubMed

Campbell, Victoria L; Chen, Nan; Guo, Han; Jackson, Bret; Utz, Arthur L

2015-12-17

Studies exploring how vibrational energy (Evib) promotes chemical reactivity most often focus on molecular reagents, leaving the role of substrate atom motion in heterogeneous interfacial chemistry underexplored. This combined theoretical and experimental study of methane dissociation on Ni(111) shows that lattice atom motion modulates the reaction barrier height during each surface atom's vibrational period, which leads to a strong variation in the reaction probability (S0) with surface temperature (Tsurf). State-resolved beam-surface scattering studies at Tsurf = 90 K show a sharp threshold in S0 at translational energy (Etrans) = 42 kJ/mol. When Etrans decreases from 42 kJ/mol to 34 kJ/mol, S0 decreases 1000-fold at Tsurf = 90 K, but only 2-fold at Tsurf = 475 K. Results highlight the mechanism for this effect, provide benchmarks for DFT calculations, and suggest the potential importance of surface atom induced barrier height modulation in heterogeneously catalyzed reactions, particularly on structurally labile nanoscale particles and defect sites.

Heterogeneous Reactions of ClONO2, HCl, and HOCl on Liquid Sulfuric Acid Surfaces

NASA Technical Reports Server (NTRS)

Zhang, Renyi; Leu, Ming-Taun; Keyser, Leon F.

1994-01-01

The heterogeneous reactions of ClONO2 + H2O yields HNO3 + HOCl (1), ClONO2 + HCl yields C12 + HNO3 (2), and HOCl + HCl yields Cl2 + H2O (3) on liquid sulfuric acid surfaces have been studied using a fast flow reactor coupled to a quadrupole mass spectrometer. The main objectives of the study are to investigate: (a) the temperature dependence of these reactions at a fixed H2O partial pressure typical of the lower stratosphere (that is, by changing temperature at a constant water partial pressure, the H2SO4 content of the surfaces is also changed), (b) the relative importance or competition between reactions 1 and 2, and (c) the effect of HNO3 on the reaction probabilities due to the formation of a H2SO4/HNO3/H2O ternary system. The measurements show that all the reactions depend markedly on temperature at a fixed H2O partial pressure: they proceed efficiently at temperatures near 200 K and much slower at temperatures near 220 K. The reaction probability (gamma(sub 1)) for ClONO2 hydrolysis approaches 0.01 at temperatures below 200 K, whereas the values for gamma(sub 2) and gamma(sub 3) are on the order of a few tenths at 200 K. Although detailed mechanisms for these reactions are still unknown, the present data indicate that the competition between ClONO2 hydrolysis and ClONO2 reaction with HCl may depend on temperature (or H2SO4 Wt %): in the presence of gaseous HCl at stratospheric concentrations, reaction 2 is dominant at lower temperatures (less than 200 K), but reaction 1 becomes important at temperatures above 210 K. Furthermore, reaction probability measurements performed on the H2SO4/HNO3/ H2O ternary solutions do not exhibit noticeable deviation from those performed on the H2SO4/H2O binary system, suggesting little effect of HNO3 in sulfate aerosols on the ClONO2 and HOCl reactions with HCl. The results reveal that significant reductions in the chlorine-containing reservoir species (such as ClONO2 and HCl) can take place on stratospheric sulfate aerosols at high latitudes in winter and early spring, even at temperatures too warm for Polar Stratospheric Clouds (PSCs) to form or in regions where nucleation of PSCs is sparse. This is particularly true under elevated sulfuric acid loading, such as that after the eruption of Mt. Pinatubo. Comparisons between our results and those presently available have also been made.

Field ion microscopic studies of the CO oxidation on platinum: Field ion imaging and titration reactions

NASA Astrophysics Data System (ADS)

Gorodetskii, V.; Drachsel, W.; Block, J. H.

1994-05-01

Elementary steps of the CO oxidation—which are important for understanding the oscillatory behavior of this catalytic reaction—are investigated simultaneously on different Pt-single crystal surfaces by field ion microscopy. Due to preferential ionization probabilities of oxygen as imaging gas on those surface sites, which are adsorbed with oxygen, these sites can be imaged in a lateral resolution on the atomic scale. In the titration reaction a COad-precovered field emitter surface reacts with gaseous oxygen adsorbed from the gas phase or, vice versa, the Oad-precovered surface with carbon monoxide adsorbed from the gas phase. The competition of the manifold of single crystal planes exposed to the titration reaction at the field emitter tip is studied. The surface specificity can be documented in the specific reaction delay times of the different planes and in the propagation rates of the reaction-diffusion wave fronts measured on these individual planes during the titration reaction with a time resolution of 40 ms. At 300 K the COad-precovered surfaces display the {011} regions, precisely the {331} planes as the most active, followed by {012}, {122}, {001}, and finally by {111}. Reaction wave fronts move with a velocity of 8 Å/s at {012}, with ≊0.8 Å/s at {111}, and have a very fast ``switch-on'' reaction at the (001) plane with 500 Å/s. At higher temperature, T=350 K, an acceleration of reaction rates is combined with shorter delay times. The titration reaction of a precovered Oad surface with COgas at T=373 K shows the formation of CO islands starting in the {011} regions with a quickly moving reaction front into the other surface areas without showing particular delay times for different surface symmetries. The two reverse titration reactions have a largely different character. The titration of COad with oxygen adsorbed from the gas phase consists of three different steps, (i) the induction times, (ii) the highly surface specific reaction, and (iii) different rates of wave front propagation. The reaction of COgas with a precovered Oad layer on the other hand starts with nucleating islands around the {011} planes from where the whole emitter surface is populated with COad without pronounced surface specifity.

Heterogeneous Reaction of ClONO2(g) + NaCl(s) to Cl2(g) + NaNO3(s)

NASA Technical Reports Server (NTRS)

Timonen, Raimo S.; Chu, Liang T.; Leu, Ming-Taun; Keyser, Leon F.

1994-01-01

The heterogeneous reaction of ClON02 + NaCl yields Cl2 + NaNO3 (eq 1) was investigated over a temperature range 220-300 K in a flow-tube reactor interfaced with a differentially pumped quadrupole mass spectrometer. Partial pressures of ClON02 in the range 10(exp -8) - 10(exp -5) Torr were used. Granule sizes and surface roughness of the NaCl substrates were determined by using a scanning electron microscope, and in separate experiments, surface areas of the substrates were measured by using BET analysis of gas-adsorption isotherms. For dry NaCl substrates, both the decay rates of ClON02 and the growth rates Of C12 were used to obtain reaction probabilities, gamma(sub l) = (4.6 +/- 3.0) x 10(exp -3) at 296 K and (6.7 +/- 3.2) x 10(exp -1) at 225 K, after considering the internal surface area, The error bars represent 1 standard deviation. The Cl2 yield based on the ClONO2 reacted was measured to be 1.0 +/- 0.2. In order to mimic the conditions encountered in the lower stratosphere, the effect of water vapor pressures between 5 x 10(exp -5) and 3 x 10(exp -4) Torr on reaction 1 was also studied. With added H20, reaction probabilities, gamma = (4.1 +/- 2.1) x 10(exp -3) at 296 K and (4.7 +/- 2.9) x 10(exp -3) at 225 K, were obtained. A trace of HOCl, the reaction product from the ClON02 + H20 yield HOCl + HN03 reaction, was observed in addition to the C12 product from reaction 1. The implications of this result for the enhancement of hydrogen chloride in the stratosphere after the El Chichon volcanic eruption and for the marine troposphere are discussed.

HCl Vapour Pressures and Reaction Probabilities for ClONO2 + HCl on Liquid H2SO4-HNO3-HCl-H20 Solutions

NASA Technical Reports Server (NTRS)

Elrod, M. J.; Koch, R. E.; Kim, J. E.; Molina, M. J.

1995-01-01

Henry's Law solubility constants for HCl have been measured for liquid H2SO4-HNO3-HCl-H2O solutions; the results are in good agreement with predictions from published semiempirical models. The ClONO2 + HCl reaction on the surfaces of such solutions with compositions simulating those of stratospheric aerosols has been investigated; as the composition changes following the temperature drop characteristic of the high-latitude stratosphere the reaction probability gamma increases rapidly. Furthermore, the gamma values remain essentially unchanged when HN03 uptake is neglected; the controlling factor appears to be the solubility of HCl. These results corroborate our earlier suggestion that supercooled liquid sulfate aerosols promote chlorine activation at low temperatures as efficiently as solid polar stratospheric cloud particles.

On the possibility of negative activation energies in bimolecular reactions

NASA Technical Reports Server (NTRS)

Jaffe, R. L.

1978-01-01

The temperature dependence of the rate constants for model reacting systems was studied to understand some recent experimental measurements which imply the existence of negative activation energies. A collision theory model and classical trajectory calculations are used to demonstrate that the reaction probability can vary inversely with collision energy for bimolecular reactions occurring on attractive potential energy surfaces. However, this is not a sufficient condition to ensure that the rate constant has a negative temperature dependence. On the basis of these calculations, it seems unlikely that a true bimolecular reaction between neutral molecules will have a negative activation energy.

Vibrational Mode-Specific Reaction of Methane with a Nickel Surface

NASA Astrophysics Data System (ADS)

Beck, Rainer

2004-03-01

The dissociation of methane on a nickel catalyst is a key step in steam reforming of natural gas for hydrogen production. Despite substantial effort in both experiment and theory, there is still no atomic scale description of this important gas-surface reaction. To elucidate its dynamics, we have performed quantum state resolved studies of vibrationally excited methane reacting on the Ni(100) surface using pulsed laser and molecular beam techniques. We observed up to a factor of 5 greater reaction probability for methane-d2 with two quanta of excitation in one C-H bond versus a nearly isoenergetic state with one quanta in each of two C-H bonds. The observed reactivities point to a transition state structure which has one of the C-H bonds significantly elongated. Our results also clearly exclude the possibility of statistical models correctly describing the mechanism of this process and emphasize the importance of full-dimensional calculations of the reaction dynamics.

Reaction of gas phase OH with unsaturated self-assembled monolayers and relevance to atmospheric organic oxidations.

PubMed

Moussa, Samar G; Finlayson-Pitts, Barbara J

2010-08-28

The kinetics and mechanisms of the reaction of gas phase OH radicals with organics on surfaces are of fundamental chemical interest, as well as relevant to understanding the degradation of organics on tropospheric surfaces or when they are components of airborne particles. We report here studies of the oxidation of a terminal alkene self-assembled monolayer (7-octenyltrichlorosilane, C8= SAM) on a germanium attenuated total reflectance crystal by OH radicals at a concentration of 2.1 x 10(5) cm(-3) at 1 atm total pressure and 298 K in air. Loss of the reactant SAM and the formation of surface products were followed in real time using infrared spectroscopy. From the rate of loss of the C=C bond, a reaction probability within experimental error of unity was derived. The products formed on the surface include organic nitrates and carbonyl compounds, with yields of 10 +/- 4% and < or = 7 +/- 4%, respectively, and there is evidence for the formation of organic products with C-O bonds such as alcohols, ethers and/or alkyl peroxides and possibly peroxynitrates. The yield of organic nitrates relative to carbonyl compounds is higher than expected based on analogous gas phase mechanisms, suggesting that the branching ratio for the RO(2) + NO reaction is shifted to favor the formation of organic nitrates when the reaction occurs on a surface. Water uptake onto the surface was only slightly enhanced upon oxidation, suggesting that oxidation per se cannot be taken as a predictor of increased hydrophilicity of atmospheric organics. These experiments indicate that the mechanisms for the surface reactions are different from gas phase reactions, but the OH oxidation of surface species will still be a significant contributor to determining their lifetimes in air.

Quantal Study of the Exchange Reaction for N + N2 using an ab initio Potential Energy Surface

NASA Technical Reports Server (NTRS)

Wang, Dunyou; Stallcop, James R.; Huo, Winifred M.; Dateo, Christopher E.; Schwenke, David W.; Partridge, Harry; Kwak, Dochan (Technical Monitor)

2002-01-01

The N + N2 exchange rate is calculated using a time-dependent quantum dynamics method on a newly determined ab initio potential energy surface (PES) for the ground A" state. This ab initio PES shows a double barrier feature in the interaction region with the barrier height at 47.2 kcal/mol, and a shallow well between these two barriers, with the minimum at 43.7 kcal/mol. A quantum dynamics wave packet calculation has been carried out using the fitted PES to compute the cumulative reaction probability for the exchange reaction of N + N2(J=O). The J - K shift method is then employed to obtain the rate constant for this reaction. The calculated rate constant is compared with experimental data and a recent quasi-classical calculation using a LEPS PES. Significant differences are found between the present and quasiclassical results. The present rate calculation is the first accurate 3D quantal dynamics study for N + N2 reaction system and the ab initio PES reported here is the first such surface for N3.

HCl dissociating on a rigid Au(111) surface: A six-dimensional quantum mechanical study on a new potential energy surface based on the RPBE functional.

PubMed

Liu, Tianhui; Fu, Bina; Zhang, Dong H

2017-04-28

The dissociative chemisorption of HCl on the Au(111) surface has recently been an interesting and important subject, regarding the discrepancy between the theoretical dissociation probabilities and the experimental sticking probabilities. We here constructed an accurate full-dimensional (six-dimensional (6D)) potential energy surface (PES) based on the density functional theory (DFT) with the revised Perdew-Burke-Ernzerhof (RPBE) functional, and performed 6D quantum mechanical (QM) calculations for HCl dissociating on a rigid Au(111) surface. The effects of vibrational excitations, rotational orientations, and site-averaging approximation on the present RPBE PES are investigated. Due to the much higher barrier height obtained on the RPBE PES than on the PW91 PES, the agreement between the present theoretical and experimental results is greatly improved. In particular, at the very low kinetic energy, the QM-RPBE dissociation probability agrees well with the experimental data. However, the computed QM-RPBE reaction probabilities are still markedly different from the experimental values at most of the energy regions. In addition, the QM-RPBE results achieve good agreement with the recent ab initio molecular dynamics calculations based on the RPBE functional at high kinetic energies.

Theoretical/experimental comparison of deep tunneling decay of quasi-bound H(D)OCO to H(D) + CO₂.

PubMed

Wagner, Albert F; Dawes, Richard; Continetti, Robert E; Guo, Hua

2014-08-07

The measured H(D)OCO survival fractions of the photoelectron-photofragment coincidence experiments by the Continetti group are qualitatively reproduced by tunneling calculations to H(D) + CO2 on several recent ab initio potential energy surfaces for the HOCO system. The tunneling calculations involve effective one-dimensional barriers based on steepest descent paths computed on each potential energy surface. The resulting tunneling probabilities are converted into H(D)OCO survival fractions using a model developed by the Continetti group in which every oscillation of the H(D)-OCO stretch provides an opportunity to tunnel. Four different potential energy surfaces are examined with the best qualitative agreement with experiment occurring for the PIP-NN surface based on UCCSD(T)-F12a/AVTZ electronic structure calculations and also a partial surface constructed for this study based on CASPT2/AVDZ electronic structure calculations. These two surfaces differ in barrier height by 1.6 kcal/mol but when matched at the saddle point have an almost identical shape along their reaction paths. The PIP surface is a less accurate fit to a smaller ab initio data set than that used for PIP-NN and its computed survival fractions are somewhat inferior to PIP-NN. The LTSH potential energy surface is the oldest surface examined and is qualitatively incompatible with experiment. This surface also has a small discontinuity that is easily repaired. On each surface, four different approximate tunneling methods are compared but only the small curvature tunneling method and the improved semiclassical transition state method produce useful results on all four surfaces. The results of these two methods are generally comparable and in qualitative agreement with experiment on the PIP-NN and CASPT2 surfaces. The original semiclassical transition state theory method produces qualitatively incorrect tunneling probabilities on all surfaces except the PIP. The Eckart tunneling method uses the least amount of information about the reaction path and produces too high a tunneling probability on PIP-NN surface, leading to survival fractions that peak at half their measured values.

Theoretical and Experimental Studies in Reactive Scattering.

DTIC Science & Technology

1986-08-11

dynamics 3. Three-dimensional reaction dynamics 4. Anisotropic potentials for He + C02, OCS, CS2 .. 5. Production of a high intensity-high energy beam of...involving beams of He atoms, H atoms and metastable H molecules aimed at the determination of potential energy surfaces involving these systems. 2... energy of 0.3 ’, Kcal/mole below the top of the barrier, the reaction probability from ground S"t vibrational state reagent to ground vibrational

Boost-phase discrimination research activities

NASA Technical Reports Server (NTRS)

Cooper, David M.; Deiwert, George S.

1989-01-01

Theoretical research in two areas was performed. The aerothermodynamics research focused on the hard-body and rocket plume flows. Analytical real gas models to describe finite rate chemistry were developed and incorporated into the three-dimensional flow codes. New numerical algorithms capable of treating multi-species reacting gas equations and treating flows with large gradients were also developed. The computational chemistry research focused on the determination of spectral radiative intensity factors, transport properties and reaction rates. Ab initio solutions to the Schrodinger equation provided potential energy curves transition moments (radiative probabilities and strengths) and potential energy surfaces. These surfaces were then coupled with classical particle reactive trajectories to compute reaction cross-sections and rates.

Time scale of random sequential adsorption.

PubMed

Erban, Radek; Chapman, S Jonathan

2007-04-01

A simple multiscale approach to the diffusion-driven adsorption from a solution to a solid surface is presented. The model combines two important features of the adsorption process: (i) The kinetics of the chemical reaction between adsorbing molecules and the surface and (ii) geometrical constraints on the surface made by molecules which are already adsorbed. The process (i) is modeled in a diffusion-driven context, i.e., the conditional probability of adsorbing a molecule provided that the molecule hits the surface is related to the macroscopic surface reaction rate. The geometrical constraint (ii) is modeled using random sequential adsorption (RSA), which is the sequential addition of molecules at random positions on a surface; one attempt to attach a molecule is made per one RSA simulation time step. By coupling RSA with the diffusion of molecules in the solution above the surface the RSA simulation time step is related to the real physical time. The method is illustrated on a model of chemisorption of reactive polymers to a virus surface.

Statistical modeling of the reactions Fe(+) + N2O → FeO(+) + N2 and FeO(+) + CO → Fe(+) + CO2.

PubMed

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

2015-08-14

The rates of the reactions Fe(+) + N2O → FeO(+) + N2 and FeO(+) + CO → Fe(+) + CO2 are modeled by statistical rate theory accounting for energy- and angular momentum-specific rate constants for formation of the primary and secondary cationic adducts and their backward and forward reactions. The reactions are both suggested to proceed on sextet and quartet potential energy surfaces with efficient, but probably not complete, equilibration by spin-inversion of the populations of the sextet and quartet adducts. The influence of spin-inversion on the overall reaction rate is investigated. The differences of the two reaction rates mostly are due to different numbers of entrance states (atom + linear rotor or linear rotor + linear rotor, respectively). The reaction Fe(+) + N2O was studied either with (6)Fe(+) or with (4)Fe(+) reactants. Differences in the rate constants of (6)Fe(+) and (4)Fe(+) reacting with N2O are attributed to different contributions from electronically excited potential energy surfaces, such as they originate from the open-electronic shell reactants.

Zirconium fluoride glass - Surface crystals formed by reaction with water

NASA Technical Reports Server (NTRS)

Doremus, R. H.; Bansal, N. P.; Bradner, T.; Murphy, D.

1984-01-01

The hydrated surfaces of a zirconium barium fluoride glass, which has potential for application in optical fibers and other optical elements, were observed by scanning electron microscopy. Crystalline zirconium fluoride was identified by analysis of X-ray diffraction patterns of the surface crystals and found to be the main constituent of the surface material. It was also found that hydrated zirconium fluorides form only in highly acidic fluoride solutions. It is possible that the zirconium fluoride crystals form directly on the glass surface as a result of its depletion of other ions. The solubility of zirconium fluoride is suggested to be probably much lower than that of barium fluoride (0.16 g/100 cu cm at 18 C). Dissolution was determined to be the predominant process in the initial stages of the reaction of the glass with water. Penetration of water into the glass has little effect.

EFFECT OF AN ACID RAIN ENVIRONMENT ON LIMESTONE SURFACES.

USGS Publications Warehouse

Mossotti, Victor G.; Lindsay, James R.; Hochella, Michael F.

1987-01-01

Salem limestone samples were exposed to weathering for 1 y in several urban and one rural environments. Samples exposed in the rural location were chemically indistinguishable from the freshly quarried limestone, whereas all samples collected from urban exposure sites developed gypsum stains on the ground-facing surfaces where the stones were not washed by precipitation. The gas-solid reaction of SO//2 with calcite was selected for detailed consideration. It appears from the model that under arid conditions, the quantity of stain deposited on an unwashed surface is independent of atmospheric SO//2 concentration once the surface has been saturated with gypsum. Under wet conditions, surface sulfation and weight loss are probably dominated by mechanisms involving wet stone. However, if the rain events are frequent and delimited by periods of dryness, the quantity of gypsum produced by a gas-solid reaction mechanism should correlate with both the frequency of rain events and the atmospheric SO//2 level.

Controlling Heterogeneous Catalysis of Water Dissociation Using Cu-Ni Bimetallic Alloy Surfaces: A Quantum Dynamics Study.

PubMed

Ray, Dhiman; Ghosh, Smita; Tiwari, Ashwani Kumar

2018-06-07

Copper-Nickel bimetallic alloys are emerging heterogeneous catalysts for water dissociation which is the rate determining step of industrially important Water Gas Shift (WGS) reaction. Yet, the detailed quantum dynamics studies of water-surface scattering in literature are limited to pure metal surfaces. We present here, a three dimensional wave-packet dynamics study of water dissociation on Cu-Ni alloy surfaces, using a pseudo diatomic model of water on a London-Eyring-Polanyi-Sato (LEPS) potential energy surface in order to study the effect of initial vibration, rotation and orientation of water molecule on reactivity. For all the chosen surfaces reactivity increases significantly with vibrational excitation. In general, for lower vibrational states the reactivity increases with increasing rotational excitation but it decreases in higher vibrational states. Molecular orientation strongly affects reactivity by helping the molecule to align along the reaction path at higher vibrational states. For different alloys, the reaction probability follows the trend of barrier heights and the surfaces having all Ni atoms in the uppermost layer are much more reactive than the ones with Cu atoms. Hence the nature of the alloy surface and initial quantum state of the incoming molecule significantly influence the reactivity in surface catalyzed water dissociation.

Energy Dissipation and Nonthermal Diffusion on Interstellar Ice Grains

NASA Astrophysics Data System (ADS)

Fredon, A.; Lamberts, T.; Cuppen, H. M.

2017-11-01

Interstellar dust grains are known to facilitate chemical reactions by acting as a meeting place and adsorbing energy. This process strongly depends on the ability of the reactive species to effectively diffuse over the surface. The cold temperatures around 10 K strongly hamper this for species other than H and H2. However, complex organic molecules have been observed in the gas phase at these cold conditions, indicating that their formation, as well as their return to the gas phase, should be effective. Here, we show how the energy released following surface reactions can be employed to solve both problems by inducing desorption or diffusion. To this purpose, we have performed thousands of Molecular Dynamics simulations to quantify the outcome of an energy dissipation process. Admolecules on top of a crystalline water surface have been given translational energy between 0.5 and 5 eV. Three different surface species are considered (CO2, H2O, and CH4), spanning a range in binding energies, number of internal degrees of freedom, and molecular weights. The admolecules are found to be able to travel up to several hundreds of angstroms before coming to a stand still, allowing for follow-up reactions en route. The probability of travel beyond any particular radius, as determined by our simulations, shows the same r dependence for all three admolecule species. Furthermore, we have been able to quantify the desorption probability, which depends on the binding energy of the species and the translational excitation. We provide expressions that can be incorporated in astrochemical models to predict grain surface formation and return into the gas phase of these products.

[Scanning microscopy aspects of the corneal endothelium in disciform keratitis and graft rejection].

PubMed

Renard, G; Pouliquen, Y

1975-05-01

Scanning electron microscopic study of corneal endothelium in two cases of corneal disease. In one case of herpetic keratitis with stromal oedema and anterior uveitis an important cellular reaction is found with different cells forming a retrocorneal membrane. In a case of graft rejection there are two different aspects. On somes places there is an inflammatory reaction with lymphocytes and macrophages. The main surface of the graft is covered with indifferenciated cells whose origine is probably the receiver's endothelium.

Effect of anodic treatment on the electrocatalytic activity of superficial Raney nickel catalyst in cathodic hydrogen

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

Korovin, N.V.; Kozlova, N.I.; Kumenko, M.V.

This work is concerned with the effect of oxidation on the activity of Raney nickel catalyst in cathodic hydrogen evolution. The superficial Raney nickel catalyst (nickel SRC) was prepared by a previously described procedure. The surface of the nickel SRC was oxidized by applying an anodic sweep over the potential range from 0.25 to 1.00 V with a potential sweep rate of 1 mV/sec. The rate of cathodic hydrogen evolution increases after pretreatment of the surface of nickel SRC by application of an anodic pulse. A significant increase in the reaction rate most probably is due to oxygen adsorption onmore » the nickel SRC surface. The largest increase in the amount of weakly bound hydrogen corresponds to the most active electrode. Oxidation of the nickel surface by an anodic pulse causes both an acceleration and a retardation of the cathodic hydrogen evolution reaction.« less

Modeling of molecular nitrogen collisions and dissociation processes for direct simulation Monte Carlo.

PubMed

Parsons, Neal; Levin, Deborah A; van Duin, Adri C T; Zhu, Tong

2014-12-21

The Direct Simulation Monte Carlo (DSMC) method typically used for simulating hypersonic Earth re-entry flows requires accurate total collision cross sections and reaction probabilities. However, total cross sections are often determined from extrapolations of relatively low-temperature viscosity data, so their reliability is unknown for the high temperatures observed in hypersonic flows. Existing DSMC reaction models accurately reproduce experimental equilibrium reaction rates, but the applicability of these rates to the strong thermal nonequilibrium observed in hypersonic shocks is unknown. For hypersonic flows, these modeling issues are particularly relevant for nitrogen, the dominant species of air. To rectify this deficiency, the Molecular Dynamics/Quasi-Classical Trajectories (MD/QCT) method is used to accurately compute collision and reaction cross sections for the N2(Σg+1)-N2(Σg+1) collision pair for conditions expected in hypersonic shocks using a new potential energy surface developed using a ReaxFF fit to recent advanced ab initio calculations. The MD/QCT-computed reaction probabilities were found to exhibit better physical behavior and predict less dissociation than the baseline total collision energy reaction model for strong nonequilibrium conditions expected in a shock. The MD/QCT reaction model compared well with computed equilibrium reaction rates and shock-tube data. In addition, the MD/QCT-computed total cross sections were found to agree well with established variable hard sphere total cross sections.

Theoretical aspects of methyl acetate and methanol activation on MgO(100) and (501) catalyst surfaces with application in FAME production

NASA Astrophysics Data System (ADS)

Man, Isabela-Costinela; Soriga, Stefan Gabriel; Parvulescu, Vasile

2017-01-01

Density functional theory (DFT) calculations were carried out to study the activation of methyl acetate and methanol on MgO(100) and MgO(501) surfaces and integrated in the context of transesterification, interesterification and glycerolysis reactions used in biodiesel industry. First results indicate the importance of including of dispersion forces in the calculations. On MgO(100) the reverse reactions steps of Csbnd O and Csbnd H dissociations and on MgO(501) the same reverse reaction step of Csbnd H dissociations of methyl acetate are energetically favorable, while the dissociation of Csbnd O bond into methoxide and acetate fragments on the edge of MgO(501) was found to be exothermic with a low activation energy. For methanol, the dissociation of Osbnd H bond on MgO(100) surface in the presence of the second coadsorbed methanol molecule becomes more energetically favoured compared to the isolated molecule, due to the fact that the methoxide fragment is stabilized by intermolecular hydrogen bonding. This is reflected by the decrease of the activation energy of the forward reaction step and the increase of the activation energy of the backward reaction step, increasing the probability to have dissociated molecules among the undissociated ones. These results represent a step forward for better understanding from atomistic point of view the paths of these reactions on these surfaces for the corresponding catalytic processes.

Low-pressure oxidation of Cb-1Zr alloy.

NASA Technical Reports Server (NTRS)

Lyon, T. F.

1971-01-01

Resistively heated strip specimens of Cb-1Zr alloy were exposed at 927 C in a vacuum chamber at various levels of total pressure in the 1-microtorr range and at various oxygen partial pressures in the .1-microtorr range. Oxygen reaction rates (sticking probabilities) were found to depend on whether or not the specimens were annealed immediately before the test exposure. It is shown that a normally undetectable oxide film exists on the Cb-1Zr surface as a result of oxidation by ambient air, and this film reduces the sticking probability as compared with a clean metal surface. The alloy is considerably strengthened by addition of oxygen to a level of about 6000 ppm, while still maintaining reasonably good room temperature ductility.

Volatile element chemistry of selected lunar, meteoritic, and terrestrial samples

NASA Technical Reports Server (NTRS)

Simoneit, B. R.; Christiansen, P. C.; Burlingame, A. L.

1973-01-01

Using vacuum pyrolysis and high resolution mass spectrometry, a study is made of the gas release patterns of representative lunar samples, meteorites, terrestrial samples, and synthetic samples doped with various sources of carbon and nitrogen. The pyrolytic gas evolution patterns were intercorrelated, allowing an assessment of the possible sources of the volatilizable material in the lunar samples to be made. Lightly surface adsorbed species and more strongly chemisorbed species are released from ambient to 300 C and from 300 to 500 C, respectively. The low-temperature volatiles (less than 500 C) derived from various chondrites correlate well with the gas evolution patterns of volatile-rich samples, as for example 74220 and 61221. Solar wind entrapped species and molecules derived from reactions probably in the grain surfaces are evolved from about 500 to 700 C, respectively. Solar wind implanted C, N, and S species are generated from 750 to 1150 C, probably by reaction with the mineral matrix during the annealing process. Possible indigenous and/or refractory carbide, nitride, and sulfide C, N, and S are released in the region from 1200 C to fusion.

Reactive collisions of sulfur dioxide with molten carbonates

PubMed Central

Krebs, Thomas; Nathanson, Gilbert M.

2010-01-01

Molecular beam scattering experiments are used to investigate reactions of SO2 at the surface of a molten alkali carbonate eutectic at 683 K. We find that two-thirds of the SO2 molecules that thermalize at the surface of the melt are converted to gaseous CO2 via the reaction . The CO2 product is formed from SO2 in less than 10-6 s, implying that the reaction takes place in a shallow liquid region less than 100 Å deep. The reaction probability does not vary between 683 and 883 K, further implying a compensation between decreasing SO2 residence time in the near-interfacial region and increasing reactivity at higher temperatures. These results demonstrate the remarkable efficiency of SO2 → CO2 conversion by molten carbonates, which appear to be much more reactive than dry calcium carbonate or wet slurries commonly used for flue gas desulfurization in coal-burning power plants. PMID:20133648

A Limited Comparison of the Thermal Durability of Polyimide Candidate Matrix Polymers with PMR-15

NASA Technical Reports Server (NTRS)

Bowles, Kenneth J.; Papadopoulos, Demetrios S.; Scheiman, Daniel A.; Inghram, Linda L.; McCorkle, Linda S.; Klans, Ojars V.

2003-01-01

Studies were conducted with six different candidate high-temperature neat matrix resin specimens of varied geometric shapes to investigate the mechanisms involved in the thermal degradation of polyimides like PMR-15. The metrics for assessing the quality of these candidates were chosen to be glass transition temperature (T(sub g)), thermo-oxidative stability, dynamic mechanical properties, microstructural changes, and dimensional stability. The processing and mechanical properties were not investigated in the study reported herein. The dimensional changes and surface layer growth were measured and recorded. The data were in agreement with earlier published data. An initial weight increase reaction was observed to be dominating at the lower temperatures. However, at the more elevated temperatures, the weight loss reactions were prevalent and probably masked the weight gain reaction. These data confirmed the findings of the existence of an initial weight gain reaction previously reported. Surface- and core-dependent weight losses were shown to control the polymer degradation at the higher temperatures.

Water dissociating on rigid Ni(100): A quantum dynamics study on a full-dimensional potential energy surface

NASA Astrophysics Data System (ADS)

Liu, Tianhui; Chen, Jun; Zhang, Zhaojun; Shen, Xiangjian; Fu, Bina; Zhang, Dong H.

2018-04-01

We constructed a nine-dimensional (9D) potential energy surface (PES) for the dissociative chemisorption of H2O on a rigid Ni(100) surface using the neural network method based on roughly 110 000 energies obtained from extensive density functional theory (DFT) calculations. The resulting PES is accurate and smooth, based on the small fitting errors and the good agreement between the fitted PES and the direct DFT calculations. Time dependent wave packet calculations also showed that the PES is very well converged with respect to the fitting procedure. The dissociation probabilities of H2O initially in the ground rovibrational state from 9D quantum dynamics calculations are quite different from the site-specific results from the seven-dimensional (7D) calculations, indicating the importance of full-dimensional quantum dynamics to quantitatively characterize this gas-surface reaction. It is found that the validity of the site-averaging approximation with exact potential holds well, where the site-averaging dissociation probability over 15 fixed impact sites obtained from 7D quantum dynamics calculations can accurately approximate the 9D dissociation probability for H2O in the ground rovibrational state.

The Effect of the Spin-Forbidden Co((sup 1) Sigma plus) plus O((sup 3) P) Yields CO2 (1 Sigma (sub G) plus) Recombination Reaction on Afterbody Heating of Mars Entry Vehicles

NASA Technical Reports Server (NTRS)

Xu, Lu T.; Jaffe, Richard L.; Schwenke, David W.; Panesi, Marco

2017-01-01

Vibrationally excited CO2, formed by two-body recombination from CO((sup 1) sigma plus) and O((sup 3) P) in the wake behind spacecraft entering the Martian atmosphere reaction, is potentially responsible for the higher than anticipated radiative heating of the backshell, compared to pre-flight predictions. This process involves a spin-forbidden transition of the transient triplet CO2 molecule to the longer-lived singlet. To accurately predict the singlet-triplet transition probability and estimate the thermal rate coefficient of the recombination reaction, ab initio methods were used to compute the first singlet and three lowest triplet CO2 potential energy surfaces and the spin-orbit coupling matrix elements between these states. Analytical fits to these four potential energy surfaces were generated for surface hopping trajectory calculations, using Tully's fewest switches surface hopping algorithm. Preliminary results for the trajectory calculations are presented. The calculated probability of a CO((sup 1) sigma plus) and O((sup 3) P) collision leading to singlet CO2 formation is on the order of 10 (sup -4). The predicted flowfield conditions for various Mars entry scenarios predict temperatures in the range of 1000 degrees Kelvin - 4000 degrees Kelvin and pressures in the range of 300-2500 pascals at the shoulder and in the wake, which is consistent with a heavy-particle collision frequency of 10 (sup 6) to 10 (sup 7) per second. Owing to this low collision frequency, it is likely that CO((sup 1) sigma plus) molecules formed by this mechanism will mostly be frozen in a highly nonequilibrium rovibrational energy state until they relax by photoemission.

The formation of diethyl ether via the reaction of iodoethane with atomic oxygen on the Ag(110) surface

NASA Astrophysics Data System (ADS)

Jones, G. Scott; Barteau, Mark A.; Vohs, John M.

1999-01-01

The reactions of iodoethane (ICH 2CH 3) on clean and oxygen-covered Ag(110) surfaces were investigated using temperature-programmed desorption (TPD) and high-resolution electron energy-loss spectroscopy (HREELS). Iodoethane adsorbs dissociatively at 150 K to produce surface ethyl groups on both clean and oxygen-covered Ag(110) surfaces. The ethyl species couple to form butane on both surfaces, with the desorption peak maximum located between 218 and 238 K, depending on the ethyl coverage. In addition to butane, a number of oxidation products including diethyl ether, ethanol, acetaldehyde, surface acetate, ethylene, carbon dioxide and water were formed on the oxygen-dosed Ag(110) surface. Diethyl ether was the major oxygenate produced at all ethyl:oxygen ratios, and the peak temperature for ether evolution varied from 220 to 266 K depending on the relative coverages of these reactants. The total combustion products, CO 2 and H 2O, were primarily formed at low ethyl coverages in the presence of excess oxygen. The formation of ethylene near 240 K probably involves an oxygen-assisted dehydrogenation pathway since ethylene is not formed from ethyl groups on the clean surface. Acetaldehyde and ethanol evolve coincidentally with a peak centered at 270-280 K, and are attributed to the reactions of surface ethoxide species. The surface acetate which decomposes near 620 K is formed from subsequent reactions of acetaldehyde with oxygen atoms. The addition of ethyl to oxygen to form surface ethoxides was verified by HREELS results. The yields of all products exhibited a strong dependence on the relative coverages of ethyl and oxygen.

Surface-mediated nucleation in the solid-state polymorph transformation of terephthalic acid.

PubMed

Beckham, Gregg T; Peters, Baron; Starbuck, Cindy; Variankaval, Narayan; Trout, Bernhardt L

2007-04-18

A molecular mechanism for nucleation for the solid-state polymorph transformation of terephthalic acid is presented. New methods recently developed in our group, aimless shooting and likelihood maximization, are employed to construct a model for the reaction coordinate for the two system sizes studied. The reaction coordinate approximation is validated using the committor probability analysis. The transformation proceeds via a localized, elongated nucleus along the crystal edge formed by fluctuations in the supramolecular synthons, suggesting a nucleation and growth mechanism in the macroscopic system.

F + H2 collisions on two electronic potential energy surfaces - Quantum-mechanical study of the collinear reaction

NASA Technical Reports Server (NTRS)

Zimmerman, I. H.; Baer, M.; George, T. F.

1979-01-01

Collinear quantum calculations are carried out for reactive F + H2 collisions on two electronic potential energy surfaces. The resulting transmission and reflection probabilities exhibit much greater variation with energy than single-surface studies would lead us to anticipate. Transmission to low-lying product channels is increased by orders of magnitude by the presence of the second surface; however, branching ratios among product states are found to be independent of the initial electronic state of the reactants. These apparently contradictory aspects of the calculation are discussed and a tentative explanation put forward to resolve them.

Catalytic ozonation of paracetamol using commercial and Pt-supported nanocomposites of Al2O3: The impact of ultrasound.

PubMed

Ziylan-Yavaş, Asu; Ince, Nilsun H

2018-01-01

The study is the assessment of commercial γ-Al 2 O 3 and its sonolytically modified nanocomposite in catalytic ozonation of paracetamol (PCT), which is an emerging water contaminant and a highly reactive compound with ozone. The results showed that commercial alumina was ineffective regardless of the solution pH, due to the low affinity of the catalyst surface for PCT and the high reactivity of the solute with molecular ozone. The modified catalyst, which was synthesized by decoration of the original surface with nanoparticles of platinum provided considerable improvement in the performance of the catalyst, particularly in mineralization of the target compound. The presence of OH scavenging agents in solution markedly retarded the rate of PCT oxidation and organic carbon decay, to signal the importance of radical-mediated reaction mechanisms on the degradation of the compound. Finally, the attempt to accelerate the reactions by running them in the presence of ultrasound was found inadequate for the early oxidation, but highly adequate for the longer mineralization process. The failure was attributed to the diffusion of a large fraction of ozone into the gaseous cavity bubbles (reduced probability of direct reactions) and the extreme conditions of cavitation collapse that partially damaged the catalyst surface. The success (in mineralization) was explained by the shift of the reaction site from the bulk solution (poor adsorption on catalyst surfaces) to the solid surface and the gaseous cavity bubbles (via enhanced hydrophobicity), both being considerably more active reaction media. Copyright © 2017 Elsevier B.V. All rights reserved.

Oligomerization of glycine and alanine catalyzed by iron oxides: implications for prebiotic chemistry.

PubMed

Shanker, Uma; Bhushan, Brij; Bhattacharjee, G; Kamaluddin

2012-02-01

Iron oxide minerals are probable constituents of the sediments present in geothermal regions of the primitive earth. They might have adsorbed different organic monomers (amino acids, nucleotides etc.) and catalyzed polymerization processes leading to the formation of the first living cell. In the present work we tested the catalytic activity of three forms of iron oxides (Goethite, Akaganeite and Hematite) in the intermolecular condensation of each of the amino acids glycine and L-alanine. The effect of zinc oxide and titanium dioxide on the oligomerization has also been studied. Oligomerization studies were performed for 35 days at three different temperatures 50, 90 and 120°C without applying drying/wetting cycling. The products formed were characterized by HPLC and ESI-MS techniques. All three forms of iron oxides catalyzed peptide bond formation (23.2% of gly2 and 10.65% of ala2). The reaction was monitored every 7 days. Formation of peptides was observed to start after 7 days at 50°C. Maximum yield of peptides was found after 35 days at 90°C. Reaction at 120°C favors formation of diketopiperazine derivatives. It is also important to note that after 35 days of reaction, goethite produced dimer and trimer with the highest yield among the oxides tested. We suggest that the activity of goethite could probably be due to its high surface area and surface acidity.

Reactions of singlet oxygen with pine pollen.

NASA Technical Reports Server (NTRS)

Dowty, B.; Laseter, J. L.; Griffin, G. W.; Politzer, I. R.; Walkinshaw, C. H.

1973-01-01

A study was initiated to determine whether viable atmospheric particles such as plant pollens and fungal spores containing unsaturated lipids can interact with singlet oxygen to give oxygenated products that are potentially toxic. The results obtained confirm that surface and near surface components of common viable particulate matter in the atmosphere may be subject to rapid oxidation by singlet oxygen, leading to products which are probably allylic hydroperoxides. In connection with increasing atmospheric pollution, it is important to note that materials toxic to mammalian lung tissue may be oxidatively produced on the surfaces of viable particulate matter.

Rate coefficients from quantum and quasi-classical cumulative reaction probabilities for the S(1D) + H2 reaction

NASA Astrophysics Data System (ADS)

Jambrina, P. G.; Lara, Manuel; Menéndez, M.; Launay, J.-M.; Aoiz, F. J.

2012-10-01

Cumulative reaction probabilities (CRPs) at various total angular momenta have been calculated for the barrierless reaction S(1D) + H2 → SH + H at total energies up to 1.2 eV using three different theoretical approaches: time-independent quantum mechanics (QM), quasiclassical trajectories (QCT), and statistical quasiclassical trajectories (SQCT). The calculations have been carried out on the widely used potential energy surface (PES) by Ho et al. [J. Chem. Phys. 116, 4124 (2002), 10.1063/1.1431280] as well as on the recent PES developed by Song et al. [J. Phys. Chem. A 113, 9213 (2009), 10.1021/jp903790h]. The results show that the differences between these two PES are relatively minor and mostly related to the different topologies of the well. In addition, the agreement between the three theoretical methodologies is good, even for the highest total angular momenta and energies. In particular, the good accordance between the CRPs obtained with dynamical methods (QM and QCT) and the statistical model (SQCT) indicates that the reaction can be considered statistical in the whole range of energies in contrast with the findings for other prototypical barrierless reactions. In addition, total CRPs and rate coefficients in the range of 20-1000 K have been calculated using the QCT and SQCT methods and have been found somewhat smaller than the experimental total removal rates of S(1D).

Collisions of slow polyatomic ions with surfaces: dissociation and chemical reactions of C2H2+*, C2H3+, C2H4+*, C2H5+, and their deuterated variants C2D2+* and C2D4+* on room-temperature and heated carbon surfaces.

PubMed

Jasík, Juraj; Zabka, Jan; Feketeova, Linda; Ipolyi, Imre; Märk, Tilmann D; Herman, Zdenek

2005-11-17

Interaction of C2Hn+ (n = 2-5) hydrocarbon ions and some of their isotopic variants with room-temperature and heated (600 degrees C) highly oriented pyrolytic graphite (HOPG) surfaces was investigated over the range of incident energies 11-46 eV and an incident angle of 60 degrees with respect to the surface normal. The work is an extension of our earlier research on surface interactions of CHn+ (n = 3-5) ions. Mass spectra, translational energy distributions, and angular distributions of product ions were measured. Collisions with the HOPG surface heated to 600 degrees C showed only partial or substantial dissociation of the projectile ions; translational energy distributions of the product ions peaked at about 50% of the incident energy. Interactions with the HOPG surface at room temperature showed both surface-induced dissociation of the projectiles and, in the case of radical cation projectiles C2H2+* and C2H4+*, chemical reactions with the hydrocarbons on the surface. These reactions were (i) H-atom transfer to the projectile, formation of protonated projectiles, and their subsequent fragmentation and (ii) formation of a carbon chain build-up product in reactions of the projectile ion with a terminal CH3-group of the surface hydrocarbons and subsequent fragmentation of the product ion to C3H3+. The product ions were formed in inelastic collisions in which the translational energy of the surface-excited projectile peaked at about 32% of the incident energy. Angular distributions of reaction products showed peaking at subspecular angles close to 68 degrees (heated surfaces) and 72 degrees (room-temperature surfaces). The absolute survival probability at the incident angle of 60 degrees was about 0.1% for C2H2+*, close to 1% for C2H4+* and C2H5+, and about 3-6% for C2H3+.

Validity of the site-averaging approximation for modeling the dissociative chemisorption of H{sub 2} on Cu(111) surface: A quantum dynamics study on two potential energy surfaces

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

Liu, Tianhui; Fu, Bina, E-mail: bina@dicp.ac.cn, E-mail: zhangdh@dicp.ac.cn; Zhang, Dong H., E-mail: bina@dicp.ac.cn, E-mail: zhangdh@dicp.ac.cn

A new finding of the site-averaging approximation was recently reported on the dissociative chemisorption of the HCl/DCl+Au(111) surface reaction [T. Liu, B. Fu, and D. H. Zhang, J. Chem. Phys. 139, 184705 (2013); T. Liu, B. Fu, and D. H. Zhang, J. Chem. Phys. 140, 144701 (2014)]. Here, in order to investigate the dependence of new site-averaging approximation on the initial vibrational state of H{sub 2} as well as the PES for the dissociative chemisorption of H{sub 2} on Cu(111) surface at normal incidence, we carried out six-dimensional quantum dynamics calculations using the initial state-selected time-dependent wave packet approach, withmore » H{sub 2} initially in its ground vibrational state and the first vibrational excited state. The corresponding four-dimensional site-specific dissociation probabilities are also calculated with H{sub 2} fixed at bridge, center, and top sites. These calculations are all performed based on two different potential energy surfaces (PESs). It is found that the site-averaging dissociation probability over 15 fixed sites obtained from four-dimensional quantum dynamics calculations can accurately reproduce the six-dimensional dissociation probability for H{sub 2} (v = 0) and (v = 1) on the two PESs.« less

Atomic-scale analysis of deposition and characterization of a-Si:H thin films grown from SiH radical precursor

NASA Astrophysics Data System (ADS)

Sriraman, Saravanapriyan; Aydil, Eray S.; Maroudas, Dimitrios

2002-07-01

Growth of hydrogenated amorphous silicon films (a-Si:H) on an initial H-terminated Si(001)(2 x1) substrate at T=500 K was studied through molecular-dynamics (MD) simulations of repeated impingement of SiH radicals to elucidate the effects of reactive minority species on the structural quality of the deposited films. The important reactions contributing to film growth were identified through detailed visualization of radical-surface interaction trajectories. These reactions include (i) insertion of SiH into Si-Si bonds, (ii) adsorption onto surface dangling bonds, (iii) surface H abstraction by impinging SiH radicals through an Eley-Rideal mechanism, (iv) surface adsorption by penetration into subsurface layers or dissociation leading to interstitial atomic hydrogen, (v) desorption of interstitial hydrogen into the gas phase, (vi) formation of higher surface hydrides through the exchange of hydrogen, and (vii) dangling-bond-mediated dissociation of surface hydrides into monohydrides. The MD simulations of a-Si:H film growth predict an overall surface reaction probability of 95% for the SiH radical that is in good agreement with experimental measurements. Structural and chemical characterization of the deposited films was based on the detailed analysis of evolution of the films' structure, surface morphology and roughness, surface reactivity, and surface composition. The analysis revealed that the deposited films exhibit high dangling bond densities and rough surface morphologies. In addition, the films are abundant in voids and columnar structures that are detrimental to producing device-quality a-Si:H thin films.

Dimethyl ether electro-oxidation on platinum surfaces

DOE PAGES

Roling, Luke T.; Herron, Jeffrey A.; Budiman, Winny; ...

2016-02-27

A first-principles density functional theory study was performed in this paper to elucidate the mechanism of dimethyl ether electro-oxidation on three low-index platinum surfaces (Pt(111), Pt(100), and Pt(211)). The goal of this study is to provide a fundamental explanation for the high activity observed experimentally on Pt(100) compared to Pt(111) and stepped surfaces. We determine that the enhanced activity of Pt(100) stems from more facile C–O bond breaking kinetics, as well as from easier removal of CO as a surface poison through activation of water. In general, the C–O bond (in CH xOCH y) becomes easier to break as dimethylmore » ether is dehydrogenated to a greater extent. In contrast, dehydrogenation becomes more difficult as more hydrogen atoms are removed. We perform two analyses of probable reaction pathways, which both identify CHOC and CO as the key reaction intermediates on these Pt surfaces. We show that the reaction mechanism on each surface is dependent on the cell operating potential, as increasing the potential facilitates C–H bond scission, in turn promoting the formation of intermediates for which C–O scission is more facile. We additionally demonstrate that CO oxidation determines the high overpotential required for electro-oxidation on Pt surfaces. Finally, at practical operating potentials (~0.60 V RHE), we determine that C–O bond breaking is most likely the most difficult step on all three Pt surfaces studied.« less

Hydrogenation at low temperatures does not always lead to saturation: the case of HNCO

NASA Astrophysics Data System (ADS)

Noble, J. A.; Theule, P.; Congiu, E.; Dulieu, F.; Bonnin, M.; Bassas, A.; Duvernay, F.; Danger, G.; Chiavassa, T.

2015-04-01

Context. It is generally agreed that hydrogenation reactions dominate chemistry on grain surfaces in cold, dense molecular cores, saturating the molecules present in ice mantles. Aims: We present a study of the low temperature reactivity of solid phase isocyanic acid (HNCO) with hydrogen atoms, with the aim of elucidating its reaction network. Methods: Fourier transform infrared spectroscopy and mass spectrometry were employed to follow the evolution of pure HNCO ice during bombardment with H atoms. Both multilayer and monolayer regimes were investigated. Results: The hydrogenation of HNCO does not produce detectable amounts of formamide (NH2CHO) as the major product. Experiments using deuterium reveal that deuteration of solid HNCO occurs rapidly, probably via cyclic reaction paths regenerating HNCO. Chemical desorption during these reaction cycles leads to loss of HNCO from the surface. Conclusions: It is unlikely that significant quantities of NH2CHO form from HNCO. In dense regions, however, deuteration of HNCO will occur. HNCO and DNCO will be introduced into the gas phase, even at low temperatures, as a result of chemical desorption.

Ozone reactions with indoor materials during building disinfection

NASA Astrophysics Data System (ADS)

Poppendieck, D.; Hubbard, H.; Ward, M.; Weschler, C.; Corsi, R. L.

There is scant information related to heterogeneous indoor chemistry at ozone concentrations necessary for the effective disinfection of buildings, i.e., hundreds to thousands of ppm. In the present study, 24 materials were exposed for 16 h to ozone concentrations of 1000-1200 ppm in the inlet streams of test chambers. Initial ozone deposition velocities were similar to those reported in the published literature for much lower ozone concentrations, but decayed rapidly as reaction sites on material surfaces were consumed. For every material, deposition velocities converged to a relatively constant, and typically low, value after approximately 11 h. The four materials with the highest sustained deposition velocities were ceiling tile, office partition, medium density fiberboard and gypsum wallboard backing. Analysis of ozone reaction probabilities indicated that throughout each experiment, and particularly after several hours of disinfection, surface reaction resistance dominated the overall resistance to ozone deposition for nearly all materials. Total building disinfection by-products (all carbonyls) were quantified per unit area of each material for the experimental period. Paper, office partition, and medium density fiberboard each released greater than 38 mg m -2 of by-products.

Synergistic reaction between SO2 and NO2 on mineral oxides: a potential formation pathway of sulfate aerosol.

PubMed

Liu, Chang; Ma, Qingxin; Liu, Yongchun; Ma, Jinzhu; He, Hong

2012-02-07

Sulfate is one of the most important aerosols in the atmosphere. A new sulfate formation pathway via synergistic reactions between SO(2) and NO(2) on mineral oxides was proposed. The heterogeneous reactions of SO(2) and NO(2) on CaO, α-Fe(2)O(3), ZnO, MgO, α-Al(2)O(3), TiO(2), and SiO(2) were investigated by in situ Diffuse Reflectance Infrared Fourier Transform Spectroscopy (in situ DRIFTS) at ambient temperature. Formation of sulfate from adsorbed SO(2) was promoted by the coexisting NO(2), while surface N(2)O(4) was observed as the crucial oxidant for the oxidation of surface sulfite. This process was significantly promoted by the presence of O(2). The synergistic effect between SO(2) and NO(2) was not observed on other mineral particles (such as CaCO(3) and CaSO(4)) probably due to the lack of the surface reactive oxygen sites. The synergistic reaction between SO(2) and NO(2) on mineral oxides resulted in the formation of internal mixtures of sulfate, nitrate, and mineral oxides. The change of mixture state will affect the physicochemical properties of atmospheric particles and therefore further influence their environmental and climate effects.

Atmospheric photochemistry at a fatty acid coated air/water interface

NASA Astrophysics Data System (ADS)

George, Christian; Rossignol, Stéphanie; Passananti, Monica; Tinel, Liselotte; Perrier, Sebastien; Kong, Lingdong; Brigante, Marcello; Bianco, Angelica; Chen, Jianmin; Donaldson, James

2017-04-01

Over the past 20 years, interfacial processes have become increasingly of interest in the field of atmospheric chemistry, with many studies showing that environmental surfaces display specific chemistry and photochemistry, enhancing certain reactions and acting as reactive sinks or sources for various atmospherically relevant species. Many molecules display a free energy minimum at the air-water interface, making it a favored venue for compound accumulation and reaction. Indeed, surface active molecules have been shown to undergo specific photochemistry at the air-water interface. This presentation will address some recent surprises. Indeed, while fatty acids are believed to be photochemically inert in the actinic region, complex volatile organic compounds (VOCs) are produced during illumination of an air-water interface coated solely with a monolayer of carboxylic acid. When aqueous solutions containing nonanoic acid (NA) at bulk concentrations that give rise to just over monolayer NA coverage are illuminated with actinic radiation, saturated and unsaturated aldehydes are seen in the gas phase and more highly oxygenated products appear in the aqueous phase. This chemistry is probably initiated by triplet state NA molecules excited by direct absorption of actinic light at the water surface. As fatty acids covered interfaces are ubiquitous in the environment, such photochemical processing will have a significant impact on local ozone and particle formation. In addition, it was shown recently that a heterogeneous reaction between SO2 and oleic acid (OA; an unsaturated fatty acid) takes place and leads efficiently to the formation of organosulfur products. Here, we demonstrate that this reaction proceeds photochemically on various unsaturated fatty acids compounds, and may therefore have a general environmental impact. This is probably due to the chromophoric nature of the SO2 adduct with C=C bonds, and means that the contribution of this direct addition of SO2 could be in excess of 5%.

Boehmite-An Efficient and Recyclable Acid-Base Bifunctional Catalyst for Aldol Condensation Reaction.

PubMed

Reshma, P C Rajan; Vikneshvaran, Sekar; Velmathi, Sivan

2018-06-01

In this work boehmite was used as an acid-base bifunctional catalyst for aldol condensation reactions of aromatic aldehydes and ketones. The catalyst was prepared by simple sol-gel method using Al(NO3)3·9H2O and NH4OH as precursors. The catalyst has been characterized by X-ray diffraction (XRD), Fourier Transform Infrared (FTIR), Scanning Electron Microscopy (SEM), UV-visible spectroscopy (DRS), BET surface area analyses. Boehmite is successfully applied as catalyst for the condensation reaction between 4-nitrobenzaldehyde and acetone as a model substrate giving α, β-unsaturated ketones without any side product. The scope of the reaction is extended for various substituted aldehydes. A probable mechanism has been suggested to explain the cooperative behavior of the acidic and basic sites. The catalyst is environmentally friendly and easily recovered from the reaction mixture. Also the catalyst is reusable up to 3 catalytic cycles.

Step Towards Modeling the Atmosphere of Titan: State-Selected Reactions of O+ with Methane.

PubMed

Hrušák, J; Paidarová, I

2016-11-01

Methane conversion and in particular the formation of the C-O bond is one of fundamental entries to organic chemistry and it appears to be essential for understanding parts of atmospheric chemistry of Titan, but, in broader terms it might be also relevant for Earth-like exoplanets. Theoretical study of the reactions of methane with atomic oxygen ion in its excited electronic states requires treating simultaneously at least 19 electronic states. Development of a computational strategy that would allow chemically reasonable and computationally feasible treatment of the CH 4 (X)/O + ( 2 D, 2 P) system is by far not trivial and it requires careful examination of all the complex features of the corresponding 19 potential energy surfaces. Before entering the discussion of the rich (photo) chemistry, inspection of the long range behavior of the system with focus on electric dipole transition moments is required. Our calculations show nonzero probability for the reactants to decay before entering the multiple avoided crossings region of the [CH 4  + O → products] + reaction. For the CH 4 /O + ( 2 P) system non-zero transition moment probabilities occur over the entire range of considered C-O distances (up to 15 Å), while for the CH 4 /O + ( 2 D) system these probabilities are lower by one order of magnitude and were found only at C-O distances smaller than 6 Å.

A proposed physical model for the impregnated tungsten cathode based on Auger surface studies of the Ba-O-W system

NASA Technical Reports Server (NTRS)

Forman, R.

1979-01-01

Auger spectra and work function measurements are used to study the surface reactions between tungsten surface and adsorbed layers of barium, and barium and oxygen. The barium on an impregnated tungsten cathod seems to be an intermediate state, probably a coadsorbed barium-oxygen layer on tungsten. A slightly revised version of the previously suggested (1976) impregnated tungsten cathode model is proposed. This revised model assumes that the cathode surface during life has an adsorbed surface layer of a monolayer or less of both barium and oxygen on the surface. At end of life, steep drop in electron emission and resultant cathode failure occur. Recent NASA life test results on TWT type tubes are reported and explained by the proposed model.

Surface chemical study on the covalent attachment of hydroxypropyltrimethyl ammonium chloride chitosan to titanium surfaces

NASA Astrophysics Data System (ADS)

Xu, Xiaofen; Wang, Ling; Guo, Shengrong; Lei, Lei; Tang, Tingting

2011-10-01

An anti-microbial and bioactive coating could not only reduce the probability of infection related to titanium implants but also support the growth of surrounding osteogenic cells. Our previous study has showed that hydroxypropyltrimethyl ammonium chloride chitosan (HACC) with a DS (degrees of substitution) of 18% had improved solubility and significantly higher antibacterial activities against three bacteria which were usually associated with infections in orthopaedics. In the current study, HACC with a DS of 18% coating was bonded to titanium surface by a three-step process. The titanium surface after each individual reaction step was analyzed by X-ray photoelectron spectroscopy (XPS) and attenuated total reflection (ATR) of Fourier-transformed infrared (FT-IR) spectroscopy. The XPS results demonstrated that there were great changes in the atomic ratios of C/Ti, O/Ti, and N/Ti after each reaction step. The XPS high resolution and corresponding devolution spectra of carbon, oxygen, nitrogen, and titanium were also in good coordination with the anticipated reaction steps. Additionally, the absorption bands around 3365 cm -1 (-OH vibration), 1664 cm -1 (Amide I), 1165 cm -1 ( νas, C-O-C bridge), and the broad absorption bands between 958 cm -1 and 1155 cm -1 (skeletal vibrations involving the C-O stretching of saccharide structure of HACC) verified that HACC was successfully attached to titanium surface.

Accelerating rejection-based simulation of biochemical reactions with bounded acceptance probability

NASA Astrophysics Data System (ADS)

Thanh, Vo Hong; Priami, Corrado; Zunino, Roberto

2016-06-01

Stochastic simulation of large biochemical reaction networks is often computationally expensive due to the disparate reaction rates and high variability of population of chemical species. An approach to accelerate the simulation is to allow multiple reaction firings before performing update by assuming that reaction propensities are changing of a negligible amount during a time interval. Species with small population in the firings of fast reactions significantly affect both performance and accuracy of this simulation approach. It is even worse when these small population species are involved in a large number of reactions. We present in this paper a new approximate algorithm to cope with this problem. It is based on bounding the acceptance probability of a reaction selected by the exact rejection-based simulation algorithm, which employs propensity bounds of reactions and the rejection-based mechanism to select next reaction firings. The reaction is ensured to be selected to fire with an acceptance rate greater than a predefined probability in which the selection becomes exact if the probability is set to one. Our new algorithm improves the computational cost for selecting the next reaction firing and reduces the updating the propensities of reactions.

Accelerating rejection-based simulation of biochemical reactions with bounded acceptance probability

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

Thanh, Vo Hong, E-mail: vo@cosbi.eu; Priami, Corrado, E-mail: priami@cosbi.eu; Department of Mathematics, University of Trento, Trento

Stochastic simulation of large biochemical reaction networks is often computationally expensive due to the disparate reaction rates and high variability of population of chemical species. An approach to accelerate the simulation is to allow multiple reaction firings before performing update by assuming that reaction propensities are changing of a negligible amount during a time interval. Species with small population in the firings of fast reactions significantly affect both performance and accuracy of this simulation approach. It is even worse when these small population species are involved in a large number of reactions. We present in this paper a new approximatemore » algorithm to cope with this problem. It is based on bounding the acceptance probability of a reaction selected by the exact rejection-based simulation algorithm, which employs propensity bounds of reactions and the rejection-based mechanism to select next reaction firings. The reaction is ensured to be selected to fire with an acceptance rate greater than a predefined probability in which the selection becomes exact if the probability is set to one. Our new algorithm improves the computational cost for selecting the next reaction firing and reduces the updating the propensities of reactions.« less

Atomic oxygen interaction at defect sights in protective coatings on polymers flown on LDEF

NASA Technical Reports Server (NTRS)

Banks, Bruce A.; Degroh, Kim K.; Auer, Bruce M.; Gebauer, Linda; Lamoreaux, Cynthia

1993-01-01

Although the Long Duration Exposure Facility (LDEF) has exposed materials with a fixed orientation relative to the ambient low-Earth-orbital environment, arrival of atomic oxygen is angularly distributed as a result of the atomic oxygen's high temperature Maxwellian velocity distribution and the LDEF's orbital inclination. Thus, atomic oxygen entering defects in protective coatings on polymeric surfaces can cause wider undercut cavities than the size of the defect in the protective coating. Because only a small fraction of atomic oxygen reacts upon first impact with most polymeric materials, secondary reactions with lower energy thermally accommodated atomic oxygen can occur. The secondary reactions of scattered and/or thermally accommodated atomic oxygen also contribute to widening the undercut cavity beneath the protective coating defect. As the undercut cavity enlarges, exposing more polymer, the probability of atomic oxygen reacting with underlying polymeric material increases because of multiple opportunities for reaction. Thus, the effective atomic oxygen erosion yield for atoms entering defects increases above that of the unprotected material. Based on the results of analytical modeling and computational modeling, aluminized Kapton multilayer insulation exposed to atomic oxygen on row 9 lost the entire externally exposed layer of polyimide Kapton, yet based on the results of this investigation, the bottom surface aluminum film must have remained in place, but crazed. Atomic oxygen undercutting at defect sites in protective coatings on graphite epoxy composites indicates that between 40 to 100 percent of the atomic oxygen thermally accommodates upon impact, and that the reaction probability of thermally accommodated atomic oxygen may range from 7.7 x 10(exp -6) to 2.1 x 10(exp -3), depending upon the degree of thermal accommodation upon each impact.

Quantum dynamics of the C(1D)+HD and C(1D)+n-D2 reactions on the ã 1A' and b 1A" surfaces.

PubMed

Defazio, Paolo; Gamallo, Pablo; González, Miguel; Akpinar, Sinan; Bussery-Honvault, Béatrice; Honvault, Pascal; Petrongolo, Carlo

2010-03-14

We present the Born-Oppenheimer, quantum dynamics of the reactions C((1)D)+HD and C((1)D)+n-D(2) on the uncoupled potential energy surfaces ã (1)A' and b (1)A", considering the Coriolis interactions and the nuclear-spin statistics. Using the real wavepacket method, we obtain initial-state-resolved probabilities, cross sections, isotopic branching ratios, and rate constants. Similarly to the C+n-H(2) reaction, the probabilities present many ã (1)A' or few b (1)A" sharp resonances, and the cross sections are very large at small collision energies and decrease at higher energies. At any initial condition, the C+HD reaction gives preferentially the CD+H products. Thermal cross sections, isotopic branching ratios, and rate constant k vary slightly with temperature and agree very well with the experimental values. At 300 K, we obtain for the various products k(CH+H)=(2.45+/-0.08) x 10(-10), k(CD+H)=(1.19+/-0.04) x 10(-10), k(CH+D)=(0.71+/-0.02) x 10(-10), k(CD+D)=(1.59+/-0.05) x 10(-10) cm(3) s(-1), and k(CD+H)/k(CH+D)=1.68+/-0.01. The b (1)A" contribution to cross sections and rate constants is always large, up to a maximum value of 62% for a rotationally resolved C+D(2) rate constant. The upper b (1)A" state is thus quite important in the C((1)D) collision with H(2) and its deuterated isotopes, as the agreement between theory and experiment shows.

Measurement of surface recombination velocity for silicon solar cells using a scanning electron microscope with pulsed beam

NASA Technical Reports Server (NTRS)

Daud, T.; Cheng, L. J.

1981-01-01

The role of surface recombination velocity in the design and fabrication of silicon solar cells is discussed. A scanning electron microscope with pulsed electron beam was used to measure this parameter of silicon surfaces. It is shown that the surface recombination velocity, s, increases by an order of magnitude when an etched surface degrades, probably as a result of environmental reaction. A textured front-surface-field cell with a high-low junction near the surface shows the effect of minority carrier reflection and an apparent reduction of s, whereas a tandem-junction cell shows an increasing s value. Electric fields at junction interfaces in front-surface-field and tandem-junction cells acting as minority carrier reflectors or sinks tend to alter the value of effective surface recombination velocity for different beam penetration depths. A range of values of s was calculated for different surfaces.

Cooperative communication within and between single nanocatalysts

NASA Astrophysics Data System (ADS)

Zou, Ningmu; Zhou, Xiaochun; Chen, Guanqun; Andoy, Nesha May; Jung, Won; Liu, Guokun; Chen, Peng

2018-06-01

Enzymes often show catalytic allostery in which reactions occurring at different sites communicate cooperatively over distances of up to a few nanometres. Whether such effects can occur with non-biological nanocatalysts remains unclear, even though these nanocatalysts can undergo restructuring and molecules can diffuse over catalyst surfaces. Here we report that phenomenologically similar, but mechanistically distinct, cooperative effects indeed exist for nanocatalysts. Using spatiotemporally resolved single-molecule catalysis imaging, we find that catalytic reactions on a single Pd or Au nanocatalyst can communicate with each other, probably via hopping of positively charged holes on the catalyst surface, over 102 nanometres and with a temporal memory of 101 to 102 seconds, giving rise to positive cooperativity among its surface active sites. Similar communication is also observed between individual nanocatalysts, however it operates via a molecular diffusion mechanism involving negatively charged product molecules, and its communication distance is many micrometres. Generalization of these long-range intra- and interparticle catalytic communication mechanisms may introduce a novel conceptual framework for understanding nanoscale catalysis.

Electrochemical oxidation of ampicillin antibiotic at boron-doped diamond electrodes and process optimization using response surface methodology.

PubMed

Körbahti, Bahadır K; Taşyürek, Selin

2015-03-01

Electrochemical oxidation and process optimization of ampicillin antibiotic at boron-doped diamond electrodes (BDD) were investigated in a batch electrochemical reactor. The influence of operating parameters, such as ampicillin concentration, electrolyte concentration, current density, and reaction temperature, on ampicillin removal, COD removal, and energy consumption was analyzed in order to optimize the electrochemical oxidation process under specified cost-driven constraints using response surface methodology. Quadratic models for the responses satisfied the assumptions of the analysis of variance well according to normal probability, studentized residuals, and outlier t residual plots. Residual plots followed a normal distribution, and outlier t values indicated that the approximations of the fitted models to the quadratic response surfaces were very good. Optimum operating conditions were determined at 618 mg/L ampicillin concentration, 3.6 g/L electrolyte concentration, 13.4 mA/cm(2) current density, and 36 °C reaction temperature. Under response surface optimized conditions, ampicillin removal, COD removal, and energy consumption were obtained as 97.1 %, 92.5 %, and 71.7 kWh/kg CODr, respectively.

Quantum Dynamics Study of the Isotopic Effect on Capture Reactions: HD, D2 + CH3

NASA Technical Reports Server (NTRS)

Wang, Dunyou; Kwak, Dochan (Technical Monitor)

2002-01-01

Time-dependent wave-packet-propagation calculations are reported for the isotopic reactions, HD + CH3 and D2 + CH3, in six degrees of freedom and for zero total angular momentum. Initial state selected reaction probabilities for different initial rotational-vibrational states are presented in this study. This study shows that excitations of the HD(D2) enhances the reactivities; whereas the excitations of the CH3 umbrella mode have the opposite effects. This is consistent with the reaction of H2 + CH3. The comparison of these three isotopic reactions also shows the isotopic effects in the initial-state-selected reaction probabilities. The cumulative reaction probabilities (CRP) are obtained by summing over initial-state-selected reaction probabilities. The energy-shift approximation to account for the contribution of degrees of freedom missing in the six dimensionality calculation is employed to obtain approximate full-dimensional CRPs. The rate constant comparison shows H2 + CH3 reaction has the biggest reactivity, then HD + CH3, and D2 + CH3 has the smallest.

High Contrast CRT.

DTIC Science & Technology

1980-02-01

barium dioxide contains about 0.02% iron. For economical reasons, glass manufacturer’s probably use materials of lesser purity than reagent grade...otherwise the same procedure is followed. 2.4 Nonreflecting (NR) Film The NR film is a light abosrbing inhomogeneous film utilized to achieve a high...hour. No surface distortion of the disc occurred, thus ruling out any reaction between the carbon support plate and the glass disc that might have

Potential Impacts from Using Photoactive Roads as AN Air Quality Mitigation Strategy

NASA Astrophysics Data System (ADS)

Toro, C.; Jobson, B. T.; Shen, S.; Chung, S. H.; Haselbach, L.

2013-12-01

Mobile sources are major contributors to photochemical air pollution in urban areas. It has been proposed that the use of TiO2 coated roadways ('photoactive roads') could be an effective approach to reduce mobile source emissions by oxidizing NOx and VOC emissions at the roadway surface. However, studies have shown that formation of HONO and aldehydes can occur from some TiO2 treated surfaces during the photocatalytic oxidation of NOx and VOC, respectively. By changing the NOx-to-VOC ratio and generating photolabile HOx radical precursors, photoactive roads may enhance ozone formation rates in urban areas. In this work we present results that quantify NOx and VOC loss rates onto TiO2 treated asphalt and concrete samples, as well as HONO and aldehydes yields that result from the photocatalytic process. The treatment used a commercially available product. These objectives are relevant considering that the quantification of pollutant loss rates and yields of byproducts have not been determined for asphalt and that in the US more than 90% of the roadway surface is made of this material. Surface reaction probabilities (γ) and byproduct yields were determined using a CSTR photochemical chamber under varying conditions of water vapor and UV-A light intensity. Our results indicate that asphalt surfaces have a significantly higher molar yield of HONO compared to concrete surfaces with similar TiO2 loading. Concrete surfaces have reaction probabilities with NO one order of magnitude higher than asphalt samples. Fresh asphalt samples showed negligible photocatalytic activity, presumably due to absorption of TiO2 into the bitumen substrate. Laboratory-prepared asphalt samples with a higher degree of exposed aggregates showed increased HONO molar yields when compared to real-road asphalt samples, whose HONO molar yield was ~1%. Preliminary results for aldehydes formation showed similar molar yields between aged asphalt and concrete, even though aged asphalt samples had twice the TiO2 loading than concrete samples.

Ultrafast Dynamics of Plasmon-Exciton Interaction of Ag Nanowire- Graphene Hybrids for Surface Catalytic Reactions

PubMed Central

Ding, Qianqian; Shi, Ying; Chen, Maodu; Li, Hui; Yang, Xianzhong; Qu, Yingqi; Liang, Wenjie; Sun, Mengtao

2016-01-01

Using the ultrafast pump-probe transient absorption spectroscopy, the femtosecond-resolved plasmon-exciton interaction of graphene-Ag nanowire hybrids is experimentally investigated, in the VIS-NIR region. The plasmonic lifetime of Ag nanowire is about 150 ± 7 femtosecond (fs). For a single layer of graphene, the fast dynamic process at 275 ± 77 fs is due to the excitation of graphene excitons, and the slow process at 1.4 ± 0.3 picosecond (ps) is due to the plasmonic hot electron interaction with phonons of graphene. For the graphene-Ag nanowire hybrids, the time scale of the plasmon-induced hot electron transferring to graphene is 534 ± 108 fs, and the metal plasmon enhanced graphene plasmon is about 3.2 ± 0.8 ps in the VIS region. The graphene-Ag nanowire hybrids can be used for plasmon-driven chemical reactions. This graphene-mediated surface-enhanced Raman scattering substrate significantly increases the probability and efficiency of surface catalytic reactions co-driven by graphene-Ag nanowire hybridization, in comparison with reactions individually driven by monolayer graphene or single Ag nanowire. This implies that the graphene-Ag nanowire hybrids can not only lead to a significant accumulation of high-density hot electrons, but also significantly increase the plasmon-to-electron conversion efficiency, due to strong plasmon-exciton coupling. PMID:27601199

Mode-selective chemistry on metal surfaces: The dissociative chemisorption of CH 4 on Pt(111)

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

Guo, Han; Jackson, Bret

A quantum approach based on an expansion in vibrationally adiabatic eigenstates is used to explore CH 4 dissociation on Pt(111). Computed sticking probabilities for molecules in the ground, 1v 3 and 2v 3, states are in very good agreement with the available experimental data, reproducing the variation in reactivity with collision energy and vibrational state. As was found in similar studies on Ni(100) and Ni(111), exciting the 1v 1 symmetric stretch of CH 4 is more effective at promoting the dissociative chemisorption of CH 4 than exciting the 1v 3 antisymmetric stretch. This behavior is explained in terms of symmetry,more » mode-softening, and nonadiabatic transitions between vibrationally adiabatic states. We find that the efficacies of the bending modes for promoting reaction are reasonably large, and similar to the 1v 3 state. The vibrational efficacies for promoting reaction on Ni(111) are larger than for reaction on Pt(111), due to the larger nonadiabatic couplings. As a result, our computed sticking probabilities are in good agreement with results from recent ab initio molecular dynamics and reactive force field studies.« less

Mode-selective chemistry on metal surfaces: The dissociative chemisorption of CH{sub 4} on Pt(111)

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

Guo, Han; Jackson, Bret, E-mail: jackson@chem.umass.edu

A quantum approach based on an expansion in vibrationally adiabatic eigenstates is used to explore CH{sub 4} dissociation on Pt(111). Computed sticking probabilities for molecules in the ground, 1v{sub 3} and 2v{sub 3}, states are in very good agreement with the available experimental data, reproducing the variation in reactivity with collision energy and vibrational state. As was found in similar studies on Ni(100) and Ni(111), exciting the 1v{sub 1} symmetric stretch of CH{sub 4} is more effective at promoting the dissociative chemisorption of CH{sub 4} than exciting the 1v{sub 3} antisymmetric stretch. This behavior is explained in terms of symmetry,more » mode-softening, and nonadiabatic transitions between vibrationally adiabatic states. We find that the efficacies of the bending modes for promoting reaction are reasonably large, and similar to the 1v{sub 3} state. The vibrational efficacies for promoting reaction on Ni(111) are larger than for reaction on Pt(111), due to the larger nonadiabatic couplings. Our computed sticking probabilities are in good agreement with results from recent ab initio molecular dynamics and reactive force field studies.« less

Mode-selective chemistry on metal surfaces: The dissociative chemisorption of CH 4 on Pt(111)

DOE PAGES

Guo, Han; Jackson, Bret

2016-05-13

A quantum approach based on an expansion in vibrationally adiabatic eigenstates is used to explore CH 4 dissociation on Pt(111). Computed sticking probabilities for molecules in the ground, 1v 3 and 2v 3, states are in very good agreement with the available experimental data, reproducing the variation in reactivity with collision energy and vibrational state. As was found in similar studies on Ni(100) and Ni(111), exciting the 1v 1 symmetric stretch of CH 4 is more effective at promoting the dissociative chemisorption of CH 4 than exciting the 1v 3 antisymmetric stretch. This behavior is explained in terms of symmetry,more » mode-softening, and nonadiabatic transitions between vibrationally adiabatic states. We find that the efficacies of the bending modes for promoting reaction are reasonably large, and similar to the 1v 3 state. The vibrational efficacies for promoting reaction on Ni(111) are larger than for reaction on Pt(111), due to the larger nonadiabatic couplings. As a result, our computed sticking probabilities are in good agreement with results from recent ab initio molecular dynamics and reactive force field studies.« less

Time-independent quantum dynamics for diatom-surface scattering

NASA Astrophysics Data System (ADS)

Saalfrank, Peter; Miller, William H.

1993-06-01

Two time-independent quantum reactive scattering methods, namely, the S-matrix Kohn technique to compute the full S-matrix, and the absorbing boundary Green's function method to compute cumulative reaction probabilities, are applied here to the case of diatom-surface scattering. In both cases a discrete variable representation for the operators is used. We test the methods for two- and three-dimensional uncorrugated potential energy surfaces, which have been used earlier by Halstead et al. [J. Chem. Phys. 93, 2359 (1990)] and by Sheng et al. [J. Chem. Phys. 97, 684 (1992)] in studies of H2 dissociating on metal substrates with theoretical techniques different from those applied here. We find overall but not always perfect agreement with these earlier studies. Based on ab initio data and experiment, a new, six-dimensional potential energy surface for the dissociative chemisorption of H2 on Ni(100) is proposed. Two- and three-dimensional cuts through the new potential are performed to illustrate special dynamical aspects of this particular molecule-surface reaction: (i) the role of corrugation effects, (ii) the importance of the ``cartwheel'' rotation of H2, and (iii) the role of the ``helicopter'' degree of freedom for the adsorbing molecule.

The surface reactivity of acrylonitrile with oxygen atoms on an analogue of interstellar dust grains

NASA Astrophysics Data System (ADS)

Kimber, Helen J.; Toscano, Jutta; Price, Stephen D.

2018-06-01

Experiments designed to reveal the low-temperature reactivity on the surfaces of interstellar dust grains are used to probe the heterogeneous reaction between oxygen atoms and acrylonitrile (C2H3CN, H2C=CH-CN). The reaction is studied at a series of fixed surface temperatures between 14 and 100 K. After dosing the reactants on to the surface, temperature-programmed desorption, coupled with time-of-flight mass spectrometry, reveals the formation of a product with the molecular formula C3H3NO. This product results from the addition of a single oxygen atom to the acrylonitrile reactant. The oxygen atom attack appears to occur exclusively at the C=C double bond, rather than involving the cyano(-CN) group. The absence of reactivity at the cyano site hints that full saturation of organic molecules on dust grains may not always occur in the interstellar medium. Modelling the experimental data provides a reaction probability of 0.007 ± 0.003 for a Langmuir-Hinshelwood style (diffusive) reaction mechanism. Desorption energies for acrylonitrile, oxygen atoms, and molecular oxygen, from the multilayer mixed ice their deposition forms, are also extracted from the kinetic model and are 22.7 ± 1.0 kJ mol-1 (2730 ± 120 K), 14.2 ± 1.0 kJ mol-1 (1710 ± 120 K), and 8.5 ± 0.8 kJ mol-1 (1020 ± 100 K), respectively. The kinetic parameters we extract from our experiments indicate that the reaction between atomic oxygen and acrylonitrile could occur on interstellar dust grains on an astrophysical time-scale.

Pocked surface neutron detector

DOEpatents

McGregor, Douglas; Klann, Raymond

2003-04-08

The detection efficiency, or sensitivity, of a neutron detector material such as of Si, SiC, amorphous Si, GaAs, or diamond is substantially increased by forming one or more cavities, or holes, in its surface. A neutron reactive material such as of elemental, or any compound of, .sup.10 B, .sup.6 Li, .sup.6 LiF, U, or Gd is deposited on the surface of the detector material so as to be disposed within the cavities therein. The portions of the neutron reactive material extending into the detector material substantially increase the probability of an energetic neutron reaction product in the form of a charged particle being directed into and detected by the neutron detector material.

Exposure-Relevant Ozone Chemistry in Occupied Spaces

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

Coleman, Beverly Kaye

2009-04-01

Ozone, an ambient pollutant, is transformed into other airborne pollutants in the indoor environment. In this dissertation, the type and amount of byproducts that result from ozone reactions with common indoor surfaces, surface residues, and vapors were determined, pollutant concentrations were related to occupant exposure, and frameworks were developed to predict byproduct concentrations under various indoor conditions. In Chapter 2, an analysis is presented of secondary organic aerosol formation from the reaction of ozone with gas-phase, terpene-containing consumer products in small chamber experiments under conditions relevant for residential and commercial buildings. The full particle size distribution was continuously monitored, andmore » ultrafine and fine particle concentrations were in the range of 10 to>300 mu g m -3. Particle nucleation and growth dynamics were characterized.Chapter 3 presents an investigation of ozone reactions with aircraft cabin surfaces including carpet, seat fabric, plastics, and laundered and worn clothing fabric. Small chamber experiments were used to determine ozone deposition velocities, ozone reaction probabilities, byproduct emission rates, and byproduct yields for each surface category. The most commonly detected byproducts included C1?C10 saturated aldehydes and skin oil oxidation products. For all materials, emission rates were higher with ozone than without. Experimental results were used to predict byproduct exposure in the cabin and compare to other environments. Byproduct levels are predicted to be similar to ozone levels in the cabin, which have been found to be tens to low hundreds of ppb in the absence of an ozone converter. In Chapter 4, a model is presented that predicts ozone uptake by and byproduct emission from residual chemicals on surfaces. The effects of input parameters (residue surface concentration, ozone concentration, reactivity of the residue and the surface, near-surface airflow conditions, and byproduct yield) were explored. In Chapter 5, the reaction of ozone with permethrin, a residual insecticide used in aircraft cabins, to form phosgene is investigated. A derivatization technique was developed to detect phosgene at low levels, and chamber experiments were conducted with permethrin-coated cabin materials. It was determined that phosgene formation, if it occurs in the aircraft cabin, is not likely to exceed the relevant, health-based phosgene exposure guidelines.« less

Interaction of aromatic amines with iron oxides: implications for prebiotic chemistry.

PubMed

Shanker, Uma; Singh, Gurinder; Kamaluddin

2013-06-01

The interaction of aromatic amines (aniline, p-chloroaniline, p-toludine and p-anisidine) with iron oxides (goethite, akaganeite and hematite) has been studied. Maximum uptake of amines was observed around pH 7. The adsorption data obtained at neutral pH were found to follow Langmuir adsorption. Anisidine was found to be a better adsorbate probably due to its higher basicity. In alkaline medium (pH > 8), amines reacted on goethite and akaganeite to give colored products. Analysis of the products by GC-MS showed benzoquinone and azobenzene as the reaction products of aniline while p-anisidine afforded a dimer. IR analysis of the amine-iron oxide hydroxide adduct suggests that the surface acidity of iron oxide hydroxides is responsible for the interaction. The present study suggests that iron oxide hydroxides might have played a role in the stabilization of organic molecules through their surface activity and in prebiotic condensation reactions.

The geochemical evolution of aqueous sodium in the Black Creek Aquifer, Horry and Georgetown counties, South Carolina

USGS Publications Warehouse

Zack, Allen L.; Roberts, Ivan

1988-01-01

The Black Creek aquifer contains dilute seawater near the North Carolina State line, probably the result of incomplete flushing of ancient seawater. Data do not indicate that the dilute seawater has migrated toward areas of fresh ground-water withdrawals. The concentration of chloride in ground-water samples ranges from 5 to 720 milligrams per liter and that of sodium from 160 to 690 milligrams per liter. Ion-exchange reactions (sodium for calcium and fluoride for hydroxyl) occur with the calcium carbonate dissolution reaction which produces calcium, bicarbonate, and hydroxyl ions. The reaction sequence and stoichiometry result in an aqueous solution in which the sum of bicarbonate and chloride equivalents per liter is equal to the equivalents per liter of sodium. Calcium ions are exchanged for sodium ions derived from sodium-rich clays upgradient of the dilute seawater. The cation-exchange reaction equilibrates at a sodium concentration of 280 milligrams per liter. Amounts of sodium greater than 280 milligrams per liter are contributed from dilute seawater. The cation-exchange reaction approaches an equilibrium which represents a mass-action limit in terms of the ratio of sodium to calcium in solution versus the ratio of exchangeable sodium to calcium on clay surfaces. Where the limit of calcium carbonate solubility is approached and dissolution ceases, some precipitation of calcite probably takes place. The dissolution of calcite exposes fossil shark teeth which release fluoride ions to the ground water through anion exchange with aqueous hydroxyl ions.

Preparation of the cortical reaction: maturation-dependent migration of SNARE proteins, clathrin, and complexin to the porcine oocyte's surface blocks membrane traffic until fertilization.

PubMed

Tsai, Pei-Shiue; van Haeften, Theo; Gadella, Bart M

2011-02-01

The cortical reaction is a calcium-dependent exocytotic process in which the content of secretory granules is released into the perivitellin space immediately after fertilization, which serves to prevent polyspermic fertilization. In this study, we investigated the involvement and the organization of SNARE (soluble N-ethylmaleimide-sensitive factor attachment protein receptor) proteins in the docking and fusion of the cortical granule membrane with the oolemma in porcine oocytes. During meiotic maturation, secretory vesicles that were labeled with a granule-specific binding lectin, peanut agglutinin (PNA), migrated toward the oocyte's surface. This surface-orientated redistribution behavior was also observed for the oocyte-specific SNARE proteins SNAP23 and VAMP1 that colocalized with the PNA-labeled structures in the cortex area just under the oolemma and with the exclusive localization area of complexin (a trans-SNARE complex-stabilizing protein). The coming together of these proteins serves to prevent the spontaneous secretion of the docked cortical granules and to prepare the oocyte's surface for the cortical reaction, which should probably be immediately compensated for by a clathrin-mediated endocytosis. In vitro fertilization resulted in the secretion of the cortical granule content and the concomitant release of complexin and clathrin into the oocyte's cytosol, and this is considered to stimulate the observed endocytosis of SNARE-containing membrane vesicles.

State-to-state reactive scattering in six dimensions using reactant-product decoupling: OH + H2 → H2O + H (J = 0).

PubMed

Cvitaš, Marko T; Althorpe, Stuart C

2011-01-14

We extend to full dimensionality a recently developed wave packet method [M. T. Cvitaš and S. C. Althorpe, J. Phys. Chem. A 113, 4557 (2009)] for computing the state-to-state quantum dynamics of AB + CD → ABC + D reactions and also increase the computational efficiency of the method. This is done by introducing a new set of product coordinates, by applying the Crank-Nicholson approximation to the angular kinetic energy part of the split-operator propagator and by using a symmetry-adapted basis-to-grid transformation to evaluate integrals over the potential energy surface. The newly extended method is tested on the benchmark OH + H(2) → H(2)O + H reaction, where it allows us to obtain accurately converged state-to-state reaction probabilities (on the Wu-Schatz-Fang-Lendvay-Harding potential energy surface) with modest computational effort. These methodological advances will make possible efficient calculations of state-to-state differential cross sections on this system in the near future.

A Time-Dependent Quantum Dynamics Study of the H2 + CH3 yields H + CH4 Reaction

NASA Technical Reports Server (NTRS)

Wang, Dunyou; Kwak, Dochan (Technical Monitor)

2002-01-01

We present a time-dependent wave-packet propagation calculation for the H2 + CH3 yields H + CH4 reaction in six degrees of freedom and for zero total angular momentum. Initial state selected reaction probability for different initial rotational-vibrational states are presented in this study. The cumulative reaction probability (CRP) is obtained by summing over initial-state-selected reaction probability. The energy-shift approximation to account for the contribution of degrees of freedom missing in the 6D calculation is employed to obtain an approximate full-dimensional CRP. Thermal rate constant is compared with different experiment results.

Heterogeneous reactions of HNO3(g) + NaCl(s) yields HCl(g) + NaNO3(s) and N2O5(g) + NaCl(s) yields ClNO2(g) + NaNO3(s)

NASA Technical Reports Server (NTRS)

Leu, Ming-Taun; Timonen, Raimo S.; Keyser, Leon F.; Yung, Yuk L.

1995-01-01

The heterogeneous reactions of HNO3(g) + NaCl(s) yields HCl(g) + NaNO3(s) (eq 1) and N2O5(g) + NaCl(s) yields ClNO2(g) + NaNO3(S) (eq 2) were investigated over the temperature range 223-296 K in a flow-tube reactor coupled to a quadrupole mass spectrometer. Either a chemical ionization mass spectrometer (CIMS) or an electron-impact ionization mass spectrometer (EIMS) was used to provide suitable detection sensitivity and selectivity. In order to mimic atmospheric conditions, partial pressures of HNO3 and N2O5 in the range 6 x 10(exp -8) - 2 x 10(exp -6) Torr were used. Granule sizes and surface roughness of the solid NaCl substrates were determined by using a scanning electron microscope. For dry NaCl substrates, decay rates of HNO3 were used to obtain gamma(1) = 0.013 +/- 0.004 (1sigma) at 296 K and > 0.008 at 223 K, respectively. The error quoted is the statistical error. After all corrections were made, the overall error, including systematic error, was estimated to be about a factor of 2. HCl was found to be the sole gas-phase product of reaction 1. The mechanism changed from heterogeneous reaction to predominantly physical adsorption when the reactor was cooled from 296 to 223 K. For reaction 2 using dry salts, gamma(2) was found to be less than 1.0 x 10(exp -4) at both 223 and 296 K. The gas-phase reaction product was identified as ClNO2 in previous studies using an infrared spectrometer. An enhancement in reaction probability was observed if water was not completely removed from salt surfaces, probably due to the reaction of N2O5(g) + H2O(s) yields 2HNO3(g). Our results are compared with previous literature values obtained using different experimental techniques and conditions. The implications of the present results for the enhancement of the hydrogen chloride column density in the lower stratosphere after the El Chichon volcanic eruption and for the chemistry of HCl and HNO3 in the marine troposphere are discussed.

Scattering study of the Ne + NeH+(v0 = 0, j0 = 0) → NeH+ + Ne reaction on an ab initio based analytical potential energy surface

NASA Astrophysics Data System (ADS)

Koner, Debasish; Barrios, Lizandra; González-Lezana, Tomás; Panda, Aditya N.

2016-01-01

Initial state selected dynamics of the Ne + NeH+(v0 = 0, j0 = 0) → NeH+ + Ne reaction is investigated by quantum and statistical quantum mechanical (SQM) methods on the ground electronic state. The three-body ab initio energies on a set of suitably chosen grid points have been computed at CCSD(T)/aug-cc-PVQZ level and analytically fitted. The fitting of the diatomic potentials, computed at the same level of theory, is performed by spline interpolation. A collinear [NeHNe]+ structure lying 0.72 eV below the Ne + NeH+ asymptote is found to be the most stable geometry for this system. Energies of low lying vibrational states have been computed for this stable complex. Reaction probabilities obtained from quantum calculations exhibit dense oscillatory structures, particularly in the low energy region and these get partially washed out in the integral cross section results. SQM predictions are devoid of oscillatory structures and remain close to 0.5 after the rise at the threshold thus giving a crude average description of the quantum probabilities. Statistical cross sections and rate constants are nevertheless in sufficiently good agreement with the quantum results to suggest an important role of a complex-forming dynamics for the title reaction.

Collisions of slow ions C3Hn+ and C3Dn+ (n = 2-8) with room temperature carbon surfaces: mass spectra of product ions and the ion survival probability.

PubMed

Pysanenko, Andriy; Zabka, Jan; Feketeová, Linda; Märk, Tilmann D; Herman, Zdenek

2008-01-01

Collisions of C3Hn+ (n = 2-8) ions and some of their per- deuterated analogs with room temperature carbon (HOPG) surfaces (hydrocarbon-covered) were investigated over the incident energy range 13-45 eV in beam scattering experiments. The mass spectra of product ions were measured and main fragmentation paths of the incident projectile ions, energized in the surface collision, were determined. The extent of fragmentation increased with increasing incident energy. Mass spectra of even-electron ions C3H7+ and C3H5+ showed only fragmentations, mass spectra of radical cations C3H8*+ and C3H6*+ showed both simple fragmentations of the projectile ion and formation of products of its surface chemical reaction (H-atom transfer between the projectile ion and hydrocarbons on the surface). No carbon-chain build-up reaction (formation of C4 hydrocarbons) was detected. The survival probability of the incident ions, S(a), was usually found to be about 1-2% for the radical cation projectile ions C3H8*+, C3H6*+, C3H4*+ and C3H2*+ and several percent up to about 20% for the even-electron projectile ions C3H7+, C3H5+, C3H3+. A plot of S(a) values of C1, C2, C3, some C7 hydrocarbon ions, Ar+ and CO2+ on hydrocarbon-covered carbon surfaces as a function of the ionization energies (IE) of the projectile species showed a drop from about 10% to about 1% and less at IE 8.5-9.5 eV and further decrease with increasing IE. A strong correlation was found between log S(a) and IE, a linear decrease over the entire range of IE investigated (7-16 eV), described by log S(a) = (3.9 +/- 0.5)-(0.39 +/- 0.04) IE.

Effect of Heterogeneous Chemical Reactions on the Köhler Activation of Aqueous Organic Aerosols.

PubMed

Djikaev, Yuri S; Ruckenstein, Eli

2018-05-03

We study some thermodynamic aspects of the activation of aqueous organic aerosols into cloud droplets considering the aerosols to consist of liquid solution of water and hydrophilic and hydrophobic organic compounds, taking into account the presence of reactive species in the air. The hydrophobic (surfactant) organic molecules on the surface of such an aerosol can be processed by chemical reactions with some atmospheric species; this affects the hygroscopicity of the aerosol and hence its ability to become a cloud droplet either via nucleation or via Köhler activation. The most probable pathway of such processing involves atmospheric hydroxyl radicals that abstract hydrogen atoms from hydrophobic organic molecules located on the aerosol surface (first step), the resulting radicals being quickly oxidized by ubiquitous atmospheric oxygen molecules to produce surface-bound peroxyl radicals (second step). These two reactions play a crucial role in the enhancement of the Köhler activation of the aerosol and its evolution into a cloud droplet. Taking them and a third reaction (next in the multistep chain of relevant heterogeneous reactions) into account, one can derive an explicit expression for the free energy of formation of a four-component aqueous droplet on a ternary aqueous organic aerosol as a function of four independent variables of state of a droplet. The results of numerical calculations suggest that the formation of cloud droplets on such (aqueous hydrophilic/hydrophobic organic) aerosols is most likely to occur as a Köhler activation-like process rather than via nucleation. The model allows one to determine the threshold parameters of the system necessary for the Köhler activation of such aerosols, which are predicted to be very sensitive to the equilibrium constant of the chain of three heterogeneous reactions involved in the chemical aging of aerosols.

Interfacial Cu + promoted surface reactivity: Carbon monoxide oxidation reaction over polycrystalline copper-titania catalysts

DOE PAGES

Senanayake, S. D.; Pappoe, N. A.; Nguyen-Phan, T. -D.; ...

2016-10-01

We have studied the catalytic carbon monoxide (CO) oxidation (CO+0.5O2 → CO2) reaction using a powder catalyst composed of both copper (5wt% loading) and titania (CuOx-TiO2). Our study was focused on revealing the role of Cu, and the interaction between Cu and TiO2, by systematic comparison between two nanocatalysts, CuOx-TiO2 and pure CuOx. We interrogated these catalysts under in situ conditions using X-ray Diffraction (XRD), X-ray Absorption Fine Structure (XAFS) and Diffuse Reflectance Infrared Fourier Transform Spectroscopy (DRIFTS) to probe the structure and electronic properties of the catalyst at all stages of the reaction and simultaneously probe the surface statesmore » or intermediates of this reaction. With the aid of several ex situ characterization techniques including Transmission Electron Microscopy (TEM), the local catalyst morphology and structure was also studied. Our results show that a CuOx-TiO2 system is more active than bulk CuOx for the CO oxidation reaction due to its lower onset temperature and better stability at higher temperatures. Our results also suggests that a surface Cu+ species observed in the CuOx-TiO2 interface are likely to be a key player in the CO oxidation mechanism, while implicating that the stabilization of this species is probably associated with the oxide-oxide interface. Both in situ DRIFTS and XAFS measurements reveal that there is likely to be a Cu(Ti)-O mixed oxide at this interface. We discuss the nature of this Cu(Ti)-O interface and interpret its role on the CO oxidation reaction.« less

Relationship between surface property and catalytic application of amorphous NiP/Hβ catalyst for n-hexane isomerization

NASA Astrophysics Data System (ADS)

Chen, Jinshe; Duan, Zunbin; Song, Zhaoyang; Zhu, Lijun; Zhou, Yulu; Xiang, Yuzhi; Xia, Daohong

2017-12-01

The amorphous NiP nanoparticles were synthesized and a novel amorphous NiP/Hβ catalyst was prepared successfully further. Due to the superior surface property of amorphous NiP/Hβ catalyst, it exhibited good catalytic application for n-hexane isomerization. The catalytic activity of amorphous NiP/Hβ catalyst was close to that of the prepared Pt/Hβ sample, and better than that of commercial catalyst and crystalline Ni2P/Hβ catalyst. What's more, the amorphous NiP/Hβ catalyst shows high resistance to different sulfur compounds and water on account of its unique surface property. The effect of loading amounts on surface property and catalytic performance was investigated, and the structure-function relationship among them was studied ulteriorly. The results demonstrate that loading amounts have effect on textural property and surface acid property, which further affect the catalytic performance. The 10 wt.% NiP/Hβ sample has appropriate pore structure and acid property with uniformly dispersed NiP nanoparticles on surface, which is helpful for providing suitable synergistic effect. The effects of reaction conditions on surface reactions and the mechanism for n-hexane isomerization were investigated further. Based on these results, the amorphous NiP/Hβ catalyst with superior surface property probably pavesa way to overcome the drawbacks of traditional noble metal catalyst, which shows good catalytic application prospects.

Surface reactions of ethanol over UO 2(100) thin film

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

S. D. Senanayake; Mudiyanselage, K.; Burrell, A. K.

2015-10-08

The study of the reactions of oxygenates on well-defined oxide surfaces is important for the fundamental understanding of heterogeneous chemical pathways that are influenced by atomic geometry, electronic structure, and chemical composition. In this work, an ordered uranium oxide thin film surface terminated in the (100) orientation is prepared on a LaAlO 3 substrate and studied for its reactivity with a C-2 oxygenate, ethanol (CH 3CH 2OH). With the use of synchrotron X-ray photoelectron spectroscopy (XPS), we have probed the adsorption and desorption processes observed in the valence band, C 1s, O 1s, and U 4f to investigate the bondingmore » mode, surface composition, electronic structure, and probable chemical changes to the stoichiometric-UO 2(100) [smooth-UO 2(100)] and Ar +-sputtered UO 2(100) [rough-UO 2(100)] surfaces. Unlike UO 2(111) single crystal and UO 2 thin film, Ar-ion-sputtering of this UO 2(100) did not result in noticeable reduction of U cations. Upon ethanol adsorption (saturation occurred at 0.5 ML), only the ethoxy (CH 3CH 2O –) species is formed on smooth-UO 2(100) whereas initially formed ethoxy species are partially oxidized to surface acetate (CH3COO–) on the Ar +-sputtered UO 2(100) surface. Furthermore, all ethoxy and acetate species are removed from the surface between 600 and 700 K.« less

Chemical desorption and diffusive dust chemistry

NASA Astrophysics Data System (ADS)

Dulieu, Francois; Pirronello, Valerio; Minissale, Marco; Congiu, Emanuele; Baouche, Saoud; Chaabouni, Henda; Moudens, Audrey; Accolla, Mario; Cazaux, Stephanie; Manicò, Giulio

In molecular clouds, gaseous species can accrete efficiently on the cold surfaces of dust grains. As for radical-radical reactions, the surface of the grains acts as a third body, and changes dramatically the efficiency of the reactions (i.e., H2 formation), or lowers considerably the barrier to formation (i.e., H2O synthesis) in comparison with gas phase reaction processes. These properties make dust grains efficient catalytic templates. However, the chemical role of dust grains depends on the diffusive properties of the reactive partners. Over the last years, we have developed experimental tools and methods to explore the chemistry occurring on cold (6-50K) surfaces. We have obtained some hints about the diffusivity of H on amorphous ice, and studied in detail the diffusion of O atoms. The latter species appears to have a hopping rate in the range 0.01-100 hops/sec. The diffusion rate of O atoms is dependent on the surface morphology and on the surface temperature. The diffusion law is compatible with a diffusion dominated by quantum tunnelling rather than classical thermal hopping. Using H, O, N atoms and, indirectly, OH and HCO radicals, we have begun to explore many chemical reactive networks. In this presentation, I will focus on the formation of H2O and CO2, and will propose many possible formation routes to obtain these chemical traps. The molecules formed on surfaces have a certain probability of desorbing upon their formation. This non-thermal desorption mechanism, or chemical desorption, has been proposed to explain why some molecules can be detected in the gas phase of those region where they were believed to be part of the icy mantles covering dust grains. We have shown that this process can be very efficient, but is very sensitive to the substrate and the surroundings of the reaction site, is dependent on the kind of molecule formed and its chemical pathway. In my presentation I will present how the surface coverage and the type of reaction can play a major role in the chemical desorption process. I will discuss of possible key parameters that rule this process.

State-specific catalytic recombination boundary condition for DSMC methods in aerospace applications

NASA Astrophysics Data System (ADS)

Bariselli, F.; Torres, E.; Magin, T. E.

2016-11-01

Accurate characterization of the hypersonic flow around a vehicle during its atmospheric entry is important for a precise quantification of heat flux margins. In some cases, exothermic reactions promoted by the catalytic properties of the surface material can significantly contribute to the overall heat flux. In this work, the effect of catalytic recombination of atomic nitrogen is examined within the framework of a state-specific DSMC implementation. State-to-state reaction cross sections are derived from a detailed quantum-chemical database for the N2(v, J) + N system. A coarse-grain model is used to reduce the number of internal states and state-specific reactions to a manageable level. The catalytic boundary condition is based on an phenomenological approach and the state-specific surface recombination probabilities can be imposed by the user. This can represent an important aspect in modelling catalysis, since experiments and molecular dynamics suggest that only part of the chemical energy is absorbed by the wall, with the formed molecules leaving the surface in an excited state. The implementation is verified in a simplified geometrical configuration by comparing the numerical results with an analytical solution, developed for a 1D diffusion problem in a binary mixture. Then, the effect of catalysis in a hypersonic flow along the stagnation line of a blunt body is studied.

Associative desorption of hydrogen isotopologues from copper surfaces: Characterization of two reaction mechanisms

NASA Astrophysics Data System (ADS)

Kaufmann, Sven; Shuai, Quan; Auerbach, Daniel J.; Schwarzer, Dirk; Wodtke, Alec M.

2018-05-01

We report quantum-state resolved measurements of angular and velocity distributions of the associative desorption of H2, HD, and D2 from Cu(111) and Cu(211) surfaces. The desorbing molecules have bimodal velocity distributions comprising a "fast" channel and a "slow" channel on both facets. The "fast channel" is promoted by both hydrogen incidence translational and vibrational energy, while the "slow channel" is promoted by vibrational energy but inhibited by translational energy. Using detailed balance, we determine state-specific reaction probabilities for dissociative adsorption and compare these to theoretical calculations. The results for the activation barrier for the "fast channel" on Cu(111) are in agreement with theory within "chemical accuracy" (1 kcal/mole). Results on the Cu(211) facet provide direct information on the effect of increasing step density, which is commonly believed to increase reactivity. Differences in reactivity on the (111) and (211) facets are subtle - quantum state specific reactivity on the (211) surface is characterized by a broader distribution of barrier heights whose average values are higher than for reaction on (111). We fully characterize the "slow channel," which has not been found in theoretical calculations although it makes up a large fraction of the reactivity in these experiments.

Resonances in the cumulative reaction probability for a model electronically nonadiabatic reaction

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

Qi, J.; Bowman, J.M.

1996-05-01

The cumulative reaction probability, flux{endash}flux correlation function, and rate constant are calculated for a model, two-state, electronically nonadiabatic reaction, given by Shin and Light [S. Shin and J. C. Light, J. Chem. Phys. {bold 101}, 2836 (1994)]. We apply straightforward generalizations of the flux matrix/absorbing boundary condition approach of Miller and co-workers to obtain these quantities. The upper adiabatic electronic potential supports bound states, and these manifest themselves as {open_quote}{open_quote}recrossing{close_quote}{close_quote} resonances in the cumulative reaction probability, at total energies above the barrier to reaction on the lower adiabatic potential. At energies below the barrier, the cumulative reaction probability for themore » coupled system is shifted to higher energies relative to the one obtained for the ground state potential. This is due to the effect of an additional effective barrier caused by the nuclear kinetic operator acting on the ground state, adiabatic electronic wave function, as discussed earlier by Shin and Light. Calculations are reported for five sets of electronically nonadiabatic coupling parameters. {copyright} {ital 1996 American Institute of Physics.}« less

Statistics for laminar flamelet modeling

NASA Technical Reports Server (NTRS)

Cant, R. S.; Rutland, C. J.; Trouve, A.

1990-01-01

Statistical information required to support modeling of turbulent premixed combustion by laminar flamelet methods is extracted from a database of the results of Direct Numerical Simulation of turbulent flames. The simulations were carried out previously by Rutland (1989) using a pseudo-spectral code on a three dimensional mesh of 128 points in each direction. One-step Arrhenius chemistry was employed together with small heat release. A framework for the interpretation of the data is provided by the Bray-Moss-Libby model for the mean turbulent reaction rate. Probability density functions are obtained over surfaces of the constant reaction progress variable for the tangential strain rate and the principal curvature. New insights are gained which will greatly aid the development of modeling approaches.

Wave packet and statistical quantum calculations for the He + NeH⁺ → HeH⁺ + Ne reaction on the ground electronic state.

PubMed

Koner, Debasish; Barrios, Lizandra; González-Lezana, Tomás; Panda, Aditya N

2014-09-21

A real wave packet based time-dependent method and a statistical quantum method have been used to study the He + NeH(+) (v, j) reaction with the reactant in various ro-vibrational states, on a recently calculated ab initio ground state potential energy surface. Both the wave packet and statistical quantum calculations were carried out within the centrifugal sudden approximation as well as using the exact Hamiltonian. Quantum reaction probabilities exhibit dense oscillatory pattern for smaller total angular momentum values, which is a signature of resonances in a complex forming mechanism for the title reaction. Significant differences, found between exact and approximate quantum reaction cross sections, highlight the importance of inclusion of Coriolis coupling in the calculations. Statistical results are in fairly good agreement with the exact quantum results, for ground ro-vibrational states of the reactant. Vibrational excitation greatly enhances the reaction cross sections, whereas rotational excitation has relatively small effect on the reaction. The nature of the reaction cross section curves is dependent on the initial vibrational state of the reactant and is typical of a late barrier type potential energy profile.

Fission and quasifission of composite systems with Z =108 -120 : Transition from heavy-ion reactions involving S and Ca to Ti and Ni ions

NASA Astrophysics Data System (ADS)

Kozulin, E. M.; Knyazheva, G. N.; Novikov, K. V.; Itkis, I. M.; Itkis, M. G.; Dmitriev, S. N.; Oganessian, Yu. Ts.; Bogachev, A. A.; Kozulina, N. I.; Harca, I.; Trzaska, W. H.; Ghosh, T. K.

2016-11-01

Background: Suppression of compound nucleus formation in the reactions with heavy ions by a quasifission process in dependence on the reaction entrance channel. Purpose: Investigation of fission and quasifission processes in the reactions 36S,48Ca,48Ti , and 64Ni+238U at energies around the Coulomb barrier. Methods: Mass-energy distributions of fissionlike fragments formed in the reaction 48Ti+238U at energies of 247, 258, and 271 MeV have been measured using the double-arm time-of-flight spectrometer CORSET at the U400 cyclotron of the Flerov Laboratory of Nuclear Reactions and compared with mass-energy distributions for the reactions 36S,48Ca,64Ni+238U . Results: The most probable fragment masses as well as total kinetic energies and their dispersions in dependence on the interaction energies have been investigated for asymmetric and symmetric fragments for the studied reactions. The fusion probabilities have been deduced from the analysis of mass-energy distributions. Conclusion: The estimated fusion probability for the reactions S, Ca, Ti, and Ni ions with actinide nuclei shows that it depends exponentially on the mean fissility parameter of the system. For the reactions with actinide nuclei leading to the formation of superheavy elements the fusion probabilities are of several orders of magnitude higher than in the case of cold fusion reactions.

Excimer laser induced surface chemical modification of polytetrafluoroethylene

NASA Astrophysics Data System (ADS)

Révész, K.; Hopp, B.; Bor, Z.

1997-02-01

Polytetrafluoroethylene has a notoriously non adhesive and non reactive character. Its successful surface photochemical modification was performed by irradiating the polytetrafluoroethylene/liquid triethylamine interface with an ArF excimer laser (λ=193 nm). Due to the photochemical treatment the polytetrafluoroethylene surface became more hydrophilic. The water receding contact angle decreased from 94° to 43°. The reaction cross section was determined from the decrease of the contact angles. It was found to be as high as 6.4×10-18 cm2. XPS measurements evidenced the removal of fluorine from the polytetrafluoroethylene, incorporation of alkyl carbon and nitrogen. Photochemical dissociation path of the triethylamine makes probable that it bonded to the fluoropolymer backbone via the α-carbon atom of an ethyl group. A radical, or a photoinduced electron transfer mechanism was suggested to describe this reaction. A selective area electroless plating of silver was performed after pretreating the sample with patterned photomodification. The increased adhesion of the sample was proved by gluing with epoxy resin. As a result of the surface modification the tensile strength of gluing increased by 210× and reached 24% of the value characteristic for the bulk material.

Balloon-Borne Measurements of CLO, NO and O3 in a Volcanic Cloud: An Analysis of Heterogeneous Chemistry between 20 and 30 KM

NASA Technical Reports Server (NTRS)

Dessler, A. E.; Stimpfle, R. M.; Daube, B. C.; Salawitch, R. J.; Weinstock, E. M.; Judah, D. M.; Burley, J. D.; Munger, J. W.; Wofsy, S. C.; Anderson, J. G.;

Preparation and application of nanoglued binary titania-silica aerogel.

PubMed

Luo, Liang; Cooper, Adrienne T; Fan, Maohong

2009-01-15

Nanoglued binary titania (TiO2)-silica (SiO2) aerogel, as a novel type of photocatalyst, has been synthesized on glass substrates. Using an about-to-gel SiO2 sol as nanoglue, anatase TiO2 aerogel was immobilized into a three-dimensional mesoporous network of the SiO2. Factorial designs were employed to optimize both TiO2 aerogel and binary TiO2-SiO2 aerogel synthesis. Characterization of the as-prepared TiO2 and binary samples by surface area, porosity, and surface chemical composition showed that the photocatalysts were high-surface-area nanoporous materials, with a Ti4+ valency. The binary aerogel exhibited high photocatalytic activity for the degradation of methylene blue (MB) under simulated solar light; the reaction followed the pseudo first-order Langmuir-Hinshelwood (L-H) kinetic model. Fluorescence spectroscopy revealed that the hydroxyl (*OH) radical was formed during the illumination of the binary TiO2-SiO2 aerogel in a solution of probe molecules, which corroborates the probable mechanism of hydroxyl radical oxidation of contaminants in photocatalytic reactions.

Full-dimensional quantum dynamics study of the H{sub 2} + C{sub 2}H → H + C{sub 2}H{sub 2} reaction on an ab initio potential energy surface

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

Chen, Liuyang; University of Chinese Academy of Sciences, Beijing 100049; Shao, Kejie

2016-05-21

This work performs a time-dependent wavepacket study of the H{sub 2} + C{sub 2}H → H + C{sub 2}H{sub 2} reaction on a new ab initio potential energy surface (PES). The PES is constructed using neural network method based on 68 478 geometries with energies calculated at UCCSD(T)-F12a/aug-cc-pVTZ level and covers H{sub 2} + C{sub 2}H↔H + C{sub 2}H{sub 2}, H + C{sub 2}H{sub 2} → HCCH{sub 2}, and HCCH{sub 2} radial isomerization reaction regions. The reaction dynamics of H{sub 2} + C{sub 2}H → H + C{sub 2}H{sub 2} are investigated using full-dimensional quantum dynamics method. The initial-state selected reactionmore » probabilities are calculated for reactants in eight vibrational states. The calculated results showed that the H{sub 2} vibrational excitation predominantly enhances the reactivity while the excitation of bending mode of C{sub 2}H slightly inhibits the reaction. The excitations of two stretching modes of C{sub 2}H molecule have negligible effect on the reactivity. The integral cross section is calculated with J-shift approximation and the mode selectivity in this reaction is discussed. The rate constants over 200-2000 K are calculated and agree well with the experimental measured values.« less

Kinetics of DNA-mediated docking reactions between vesicles tethered to supported lipid bilayers

PubMed Central

Chan, Yee-Hung M.; Lenz, Peter; Boxer, Steven G.

2007-01-01

Membrane–membrane recognition and binding are crucial in many biological processes. We report an approach to studying the dynamics of such reactions by using DNA-tethered vesicles as a general scaffold for displaying membrane components. This system was used to characterize the docking reaction between two populations of tethered vesicles that display complementary DNA. Deposition of vesicles onto a supported lipid bilayer was performed by using a microfluidic device to prevent mixing of the vesicles in bulk during sample preparation. Once tethered onto the surface, vesicles mixed via two-dimensional diffusion. DNA-mediated docking of two reacting vesicles results in their colocalization after collision and their subsequent tandem motion. Individual docking events and population kinetics were observed via epifluorescence microscopy. A lattice-diffusion simulation was implemented to extract from experimental data the probability, Pdock, that a collision leads to docking. For individual vesicles displaying small numbers of docking DNA, Pdock shows a first-order relationship with copy number as well as a strong dependence on the DNA sequence. Both trends are explained by a model that includes both tethered vesicle diffusion on the supported bilayer and docking DNA diffusion over each vesicle's surface. These results provide the basis for the application of tethered vesicles to study other membrane reactions including protein-mediated docking and fusion. PMID:18025472

Committor of elementary reactions on multistate systems

NASA Astrophysics Data System (ADS)

Király, Péter; Kiss, Dóra Judit; Tóth, Gergely

2018-04-01

In our study, we extend the committor concept on multi-minima systems, where more than one reaction may proceed, but the feasible data evaluation needs the projection onto partial reactions. The elementary reaction committor and the corresponding probability density of the reactive trajectories are defined and calculated on a three-hole two-dimensional model system explored by single-particle Langevin dynamics. We propose a method to visualize more elementary reaction committor functions or probability densities of reactive trajectories on a single plot that helps to identify the most important reaction channels and the nonreactive domains simultaneously. We suggest a weighting for the energy-committor plots that correctly shows the limits of both the minimal energy path and the average energy concepts. The methods also performed well on the analysis of molecular dynamics trajectories of 2-chlorobutane, where an elementary reaction committor, the probability densities, the potential energy/committor, and the free-energy/committor curves are presented.

Maruhn-Greiner Maximum of Uranium Fission for Confirmation of Low Energy Nuclear Reactions LENR via a Compound Nucleus with Double Magic Numbers

NASA Astrophysics Data System (ADS)

Hora, H.; Miley, G. H.

2007-12-01

One of the most convincing facts about LENR due to deuterons of very high concentration in host metals as palladium is the measurement of the large scale minimum of the reaction probability depending on the nucleon number A of generated elements at A = 153 where a local maximum was measured. This is similar to the fission of uranium at A = 119 where the local maximum follows from the Maruhn-Greiner theory if the splitting nuclei are excited to about MeV energy. The LENR generated elements can be documented any time after the reaction by SIMS or K-shell X-ray excitation to show the very unique distribution with the local maximum. An explanation is based on the strong Debye screening of the Maxwellian deuterons within the degenerate rigid electron background especially within the swimming electron layer at the metal surface or at interfaces. The deuterons behave like neutrals at distances of about 2 picometers. They may form clusters due to soft attraction in the range above thermal energy. Clusters of 10 pm diameter may react over long time probabilities (megaseconds) with Pd nuclei leading to a double magic number compound nucleus which splits like in fission to the A = 153 element distribution.

Quantum scattering studies of spin-orbit effects in the Cl({sup 2}P) + HCl {yields} ClH + Cl({sup 2}P) reaction

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

Schatz, G.C.; McCabe, P.; Connor, J.N.L.

1998-07-01

The authors present quantum scattering calculations for the Cl + HCl {yields} ClH + Cl reaction in which they include the three electronic states that correlate asymptotically to the ground state of Cl({sup 2}P) + HCl(X{sup 1}{Sigma}{sup +}). The potential surfaces and couplings are taken from the recent work of C.S. Maierle, G.C. Schatz, M.S. Gordon, P. McCabe and J.N.L. Connor, J. Chem. Soc. Farad. Trans. (1997). They are based on extensive ab initio calculations for geometries in the vicinity of the lowest energy saddle point, and on an electrostatic expansion (plus empirical dispersion and repulsion) for long range geometriesmore » including the van der Waals wells. Spin-orbit coupling has been included using a spin-orbit coupling parameter {lambda} that is assumed to be independent of nuclear geometry, and Coriolis interactions are incorporated accurately. The scattering calculations use a hyperspherical coordinate coupled channel method in full dimensionality. AJ-shifting approximation is employed to convert cumulative reaction probabilities for total angular momentum quantum number J = 1/2 into state selected and thermal rate coefficients. Two issues have been studied: (a) the influence of the magnitude of {lambda} on the fine-structure resolved cumulative probabilities and rate coefficients (the authors consider {lambda}`s that vary from 0 to {+-}100% of the true Cl value), and (b) the transition state resonance spectrum, and its variation with {lambda} and with other parameters in the calculations. Cl + HCl is a simple hydrogen transfer reaction which serves as a canonical model both for heavy-light-heavy atom reactions, and for the reactions of halogen atoms with closed shell molecules.« less

Communication: Energy transfer and reaction dynamics for DCl scattering on Au(111): An ab initio molecular dynamics study.

PubMed

Kolb, Brian; Guo, Hua

2016-07-07

Scattering and dissociative chemisorption of DCl on Au(111) are investigated using ab initio molecular dynamics with a slab model, in which the top two layers of Au are mobile. Substantial kinetic energy loss in the scattered DCl is found, but the amount of energy transfer is notably smaller than that observed in the experiment. On the other hand, the dissociative chemisorption probability reproduces the experimental trend with respect to the initial kinetic energy, but is about one order of magnitude larger than the reported initial sticking probability. While the theory-experiment agreement is significantly improved from the previous rigid surface model, the remaining discrepancies are still substantial, calling for further scrutiny in both theory and experiment.

Monte Carlo based protocol for cell survival and tumour control probability in BNCT.

PubMed

Ye, S J

1999-02-01

A mathematical model to calculate the theoretical cell survival probability (nominally, the cell survival fraction) is developed to evaluate preclinical treatment conditions for boron neutron capture therapy (BNCT). A treatment condition is characterized by the neutron beam spectra, single or bilateral exposure, and the choice of boron carrier drug (boronophenylalanine (BPA) or boron sulfhydryl hydride (BSH)). The cell survival probability defined from Poisson statistics is expressed with the cell-killing yield, the 10B(n,alpha)7Li reaction density, and the tolerable neutron fluence. The radiation transport calculation from the neutron source to tumours is carried out using Monte Carlo methods: (i) reactor-based BNCT facility modelling to yield the neutron beam library at an irradiation port; (ii) dosimetry to limit the neutron fluence below a tolerance dose (10.5 Gy-Eq); (iii) calculation of the 10B(n,alpha)7Li reaction density in tumours. A shallow surface tumour could be effectively treated by single exposure producing an average cell survival probability of 10(-3)-10(-5) for probable ranges of the cell-killing yield for the two drugs, while a deep tumour will require bilateral exposure to achieve comparable cell kills at depth. With very pure epithermal beams eliminating thermal, low epithermal and fast neutrons, the cell survival can be decreased by factors of 2-10 compared with the unmodified neutron spectrum. A dominant effect of cell-killing yield on tumour cell survival demonstrates the importance of choice of boron carrier drug. However, these calculations do not indicate an unambiguous preference for one drug, due to the large overlap of tumour cell survival in the probable ranges of the cell-killing yield for the two drugs. The cell survival value averaged over a bulky tumour volume is used to predict the overall BNCT therapeutic efficacy, using a simple model of tumour control probability (TCP).

Natural flows of H2-rich fluids in the ophiolites of Oman and the Philippines: Tectonic control of migration pathways and associated diagenetic processes

NASA Astrophysics Data System (ADS)

Deville, E. P.; Prinzhofer, A.; Vacquand, C.; Chavagnac, V.; Monnin, C.; Ceuleneer, G.; Arcilla, C. A.

2009-12-01

We compare the geological environments of sites of emission of natural hydrogen in the Oman ophiolite and the Zambales ophiolite (Luzon, Philippines). The genesis of natural H2 results from the interaction between ultrabasic rocks and aqueous solutions circulating in deep fracture networks, by oxidation of metals (Fe2+, Mn2+) and reduction of water, probably under high temperature conditions. This process generates very reducing conditions capable of destabilizing other molecules (notably reduction of deep CO2 being transformed into CH4 by Fisher-Tropsch type reactions). Nitrogen is also commonly associated to the H2-rich fluids. H2 flows are associated with the expulsion of hyperalkaline waters rich in ions OH- and Ca2+ and characterized by high pH (between 11 and 12). Most alkaline springs are found in the vicinity of major faults and/or lithological discontinuities like the basal thrust plane of the ophiolites and the peridotite-gabbro contact (Moho). Within the fracture networks, gas and water separate probably at shallow depth, i.e. close to the top of the upper aquifer level. Locally high flows of gas migrate vertically through fracture pathways and they are able to inflame spontaneously on the surface. Aqueous fluids tends to migrate laterally in the fracture network toward the creeks where most of the hyperalkaline springs are found. This water circulation induces a chain of diagenetic reactions starting in the fracture systems and continuing at the surface where it leads to the precipitation of calcite, aragonite, brucite and more rarely portlandite. This chain of diagenetic reactions is associated with the capture of the atmospheric CO2 during the precipitation of carbonates.

Fabrication and condensation characteristics of metallic superhydrophobic surface with hierarchical micro-nano structures

NASA Astrophysics Data System (ADS)

Chu, Fuqiang; Wu, Xiaomin

2016-05-01

Metallic superhydrophobic surfaces have various applications in aerospace, refrigeration and other engineering fields due to their excellent water repellent characteristics. This study considers a simple but widely applicable fabrication method using a two simultaneous chemical reactions method to prepare the acid-salt mixed solutions to process the metal surfaces with surface deposition and surface etching to construct hierarchical micro-nano structures on the surface and then modify the surface with low surface-energy materials. Al-based and Cu-based superhydrophobic surfaces were fabricated using this method. The Al-based superhydrophobic surface had a water contact angle of 164° with hierarchical micro-nano structures similar to the lotus leaves. The Cu-based surface had a water contact angle of 157° with moss-like hierarchical micro-nano structures. Droplet condensation experiments were also performed on these two superhydrophobic surfaces to investigate their condensation characteristics. The results show that the Al-based superhydrophobic surface has lower droplet density, higher droplet jumping probability, slower droplet growth rate and lower surface coverage due to the more structured hierarchical structures.

Phototransformation of the sunlight filter benzophenone-3 (2-hydroxy-4-methoxybenzophenone) under conditions relevant to surface waters.

PubMed

Vione, Davide; Caringella, Rosalinda; De Laurentiis, Elisa; Pazzi, Marco; Minero, Claudio

2013-10-01

The UV filter benzophenone-3 (BP3) has UV photolysis quantum yield ΦBP3=(3.1±0.3)·10(-5) and the following second-order reaction rate constants: with (•)OH, k(BP3,(•)OH)=(2.0±0.4)·10(10) M(-1) s(-1); with the triplet states of chromophoric dissolved organic matter ((3)CDOM*), K(BP3,(3)CDOM*)=(1.1±0.1)·10(9) M(-1) s(-1); with (1)O2, k(BP3,(1)O2)=(2.0±0.1)·10(5) M(-1) s(-1), and with CO3(-•), k(BP3,CO3(-•))<5·10(7) M(-1) s(-1). These data allow the modelling of BP3 photochemical transformation, which helps filling the knowledge gap about the environmental persistence of this compound. Under typical surface-water conditions, direct photolysis and reactions with (•)OH and (3)CDOM* would be the main processes of BP3 phototransformation. Reaction with (•)OH would prevail at low DOC, direct photolysis at intermediate DOC (around 5 mg C L(-1)), and reaction with (3)CDOM* at high DOC. If the reaction rate constant with CO3(-•) is near the upper limit of experimental measures (5·10(7) M(-1) s(-1)), the CO3(-•) degradation process could be somewhat important for DOC<1 mg C L(-1). The predicted half-life time of BP3 in surface waters under summertime conditions would be of some weeks, and it would increase with increasing depth and DOC. BP3 transformation intermediates were detected upon reaction with (•)OH. Two methylated derivatives were tentatively identified, and they were probably produced by reaction between BP3 and fragments arising from photodegradation. The other intermediates were benzoic acid (maximum concentration ~10% of initial BP3) and benzaldehyde (1%). Copyright © 2013 Elsevier B.V. All rights reserved.

Scattering study of the Ne + NeH{sup +}(v{sub 0} = 0, j{sub 0} = 0) → NeH{sup +} + Ne reaction on an ab initio based analytical potential energy surface

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

Koner, Debasish; Panda, Aditya N., E-mail: adi07@iitg.ernet.in; Barrios, Lizandra

2016-01-21

Initial state selected dynamics of the Ne + NeH{sup +}(v{sub 0} = 0, j{sub 0} = 0) → NeH{sup +} + Ne reaction is investigated by quantum and statistical quantum mechanical (SQM) methods on the ground electronic state. The three-body ab initio energies on a set of suitably chosen grid points have been computed at CCSD(T)/aug-cc-PVQZ level and analytically fitted. The fitting of the diatomic potentials, computed at the same level of theory, is performed by spline interpolation. A collinear [NeHNe]{sup +} structure lying 0.72 eV below the Ne + NeH{sup +} asymptote is found to be the most stablemore » geometry for this system. Energies of low lying vibrational states have been computed for this stable complex. Reaction probabilities obtained from quantum calculations exhibit dense oscillatory structures, particularly in the low energy region and these get partially washed out in the integral cross section results. SQM predictions are devoid of oscillatory structures and remain close to 0.5 after the rise at the threshold thus giving a crude average description of the quantum probabilities. Statistical cross sections and rate constants are nevertheless in sufficiently good agreement with the quantum results to suggest an important role of a complex-forming dynamics for the title reaction.« less

Chlorine dioxide reactions with indoor materials during building disinfection: surface uptake.

PubMed

Hubbard, Heidi; Poppendieck, Dustin; Corsi, Richard L

2009-03-01

Chlorine dioxide received attention as a building disinfectant in the wake of Bacillus anthracis contamination of several large buildings in the fall of 2001. It is increasingly used for the disinfection of homes and other indoor environments afflicted by mold. However, little is known regarding the interaction of chlorine dioxide and indoor materials, particularly as related to the removal of chlorine dioxide from air. Such removal may be undesirable with respect to the subsequent formation of localized zones of depleted disinfectant concentrations and potential reductions in disinfection effectiveness in a building. The focus of this paper is on chlorine dioxide removal from air to each of 24 different indoor materials. Experiments were completed with materials housed in flow-through 48-L stainless steel chambers under standard conditions of 700 ppm chlorine dioxide inlet concentration, 75% relative humidity, 24 degrees C, and 0.5 h(-1) air changes. Chlorine dioxide concentration profiles, deposition velocities, and reaction probabilities are described in this paper. Deposition velocities and reaction probabilities varied over approximately 2 orders of magnitude across all materials. For most materials, deposition velocity decreased significantly over a 16-h disinfection period; that is, materials became smaller sinks for chlorine dioxide with time. Four materials (office partition, ceiling tile, medium density fiberboard, and gypsum wallboard) accounted for the most short- and long-term consumption of chlorine dioxide. Deposition velocity was observed to be a strong function of chlorine dioxide inlet concentration, suggesting the potential importance of chemical reactions on or within test materials.

The H2 + + He proton transfer reaction: quantum reactive differential cross sections to be linked with future velocity mapping experiments

NASA Astrophysics Data System (ADS)

Hernández Vera, Mario; Wester, Roland; Gianturco, Francesco Antonio

2018-01-01

We construct the velocity map images of the proton transfer reaction between helium and molecular hydrogen ion {{{H}}}2+. We perform simulations of imaging experiments at one representative total collision energy taking into account the inherent aberrations of the velocity mapping in order to explore the feasibility of direct comparisons between theory and future experiments planned in our laboratory. The asymptotic angular distributions of the fragments in a 3D velocity space is determined from the quantum state-to-state differential reactive cross sections and reaction probabilities which are computed by using the time-independent coupled channel hyperspherical coordinate method. The calculations employ an earlier ab initio potential energy surface computed at the FCI/cc-pVQZ level of theory. The present simulations indicate that the planned experiments would be selective enough to differentiate between product distributions resulting from different initial internal states of the reactants.

An eight-dimensional quantum dynamics study of the Cl + CH{sub 4}→ HCl + CH{sub 3} reaction

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

Liu, Na; Yang, Minghui, E-mail: yangmh@wipm.ac.cn

2015-10-07

In this work, the later-barrier reaction Cl + CH{sub 4} → HCl + CH{sub 3} is investigated with an eight-dimensional quantum dynamics method [R. Liu et al., J. Chem. Phys. 137, 174113 (2012)] on the ab initio potential energy surface of Czakó and Bowman [J. Chem. Phys. 136, 044307 (2012)]. The reaction probabilities with CH{sub 4} initially in its ground and vibrationally excited states are calculated with a time-dependent wavepacket method. The theoretical integral cross sections (ICSs) are extensively compared with the available experimental measurements. For the ground state reaction, the theoretical ICSs excellently agree with the experimental ones. Themore » good agreements are also achieved for ratios between ICSs of excited reactions. For ICS ratios between various states, the theoretical values are also consistent with the experimental observations. The rate constants over 200-2000 K are calculated and the non-Arrhenius effect has been observed which is coincident with the previous experimental observations and theoretical calculations.« less

In situ spectroscopic and solution analyses of the reductive dissolution of Mn02 by Fe(II)

USGS Publications Warehouse

Villinski, John E.; O'Day, Peggy A.; Corley, Timothy L.; Conklin, Martha H.

2001-01-01

The reductive dissolution of MnO2 by Fe(II) under conditions simulating acid mine drainage (pH 3, 100 mM SO42-) was investigated by utilizing a flow-through reaction cell and synchrotron X-ray absorption spectroscopy. This configuration allows collection of in situ, real-time X-ray absorption near-edge structure (XANES) spectra and bulk solution samples. Analysis of the solution chemistry suggests that the reaction mechanism changed (decreased reaction rate) as MnO2 was reduced and Fe(III) precipitated, primarily as ferrihydrite. Simultaneously, we observed an additional phase, with the local structure of jacobsite (MnFe2O4), in the Mn XANES spectra of reactants and products. The X-ray absorbance of this intermediate phase increased during the experiment, implying an increase in concentration. The presence of this phase, which probably formed as a surface coating, helps to explain the reduced rate of dissolution of manganese(IV) oxide. In natural environments affected by acid mine drainage, the formation of complex intermediate solid phases on mineral surfaces undergoing reductive dissolution may likewise influence the rate of release of metals to solution.

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.

Mercury profiles in sediment from the marginal high of Arabian Sea: an indicator of increasing anthropogenic Hg input.

PubMed

Chakraborty, Parthasarathi; Vudamala, Krushna; Chennuri, Kartheek; Armoury, Kazip; Linsy, P; Ramteke, Darwin; Sebastian, Tyson; Jayachandran, Saranya; Naik, Chandan; Naik, Richita; Nath, B Nagender

2016-05-01

Total Hg distributions and its speciation were determined in two sediment cores collected from the western continental marginal high of India. Total Hg content in the sediment was found to gradually increase (by approximately two times) towards the surface in both the cores. It was found that Hg was preferentially bound to sulfide under anoxic condition. However, redox-mediated reactions in the upper part of the core influenced the total Hg content in the sediment cores. This study suggests that probable increase in authigenic and allogenic Hg deposition attributed to the increasing Hg concentration in the surface sediment in the study area.

Microbial control of silicate weathering in organic-rich ground water

USGS Publications Warehouse

Hiebert, Franz K.; Bennett, Philip C.

1992-01-01

An in situ microcosm study of the influence of surface-adhering bacteria on silicate diagenesis in a shallow petroleum-contaminated aquifer showed that minerals were colonized by indigenous bacteria and chemically weathered at a rate faster than theoretically predicted. Feldspar and quartz fragments were placed in anoxic, organic-rich ground water, left for 14 months, recovered, and compared to unreacted controls with scanning electron microscopy. Ground-water geochemistry was characterized before and after the experiment. Localized mineral etching probably occurred in a reaction zone at the bacteria-mineral interface where high concentrations of organic acids, formed by bacteria during metabolism of hydrocarbon, selectively mobilized silica and aluminum from the mineral surface.

Time-resolved chromatographic analysis and mechanisms in adsorption and catalysis.

PubMed

Roubani-Kalantzopoulou, Fani

2009-03-06

The main object of this review is the study of fundamentals of adsorption and heterogeneous catalysis, a benefit for the understanding of adsorptive and catalytic properties. This work aims to define and record, with the utmost accuracy, the phenomena and the possible reactions. A new methodology for the study of the adsorption is presented, which is a version of the well-known inverse gas chromatography. This reversed-flow inverse gas chromatography (RF-IGC) is technically very simple, and it is combined with a mathematical analysis that gives the possibility for the estimation of various physicochemical parameters related to adsorbent or catalyst characterization, under conditions compatible with the operation of real adsorbents and catalysts. On this base, this methodology has been successfully applied to the study of the impact of air pollutants, volatile organic and/or inorganic, on many solids such as marbles, ceramics, oxide-pigments of works of art, building materials, authentic statues of the Greek Archaeological Museums. Moreover, this methodology proved to be a powerful tool for studying the topography of active sites of heterogeneous surfaces in the nano-scale domain. Thus, some very important local quantities for the surface chemistry have been determined experimentally for many solids including thin films. These physicochemical local quantities (among which adsorption energy and entropy, surface diffusion coefficient, probability density function) have been determined from the experimental pairs of height of extra chromatographic peaks and time by a nonlinear least-squares method, through personal computer programs written in GW BASIC and lately in FORTRAN. Through the time-resolved analysis the surface characterization of the examined materials took place. In addition, the kinetic constants responsible for adsorption/desorption and surface chemical reactions have also been calculated. Thus, important answers have been provided to the following essential questions: (1) Can RF-IGC define the gnostic regions of adsorption/desorption, surface diffusion, surface reaction? Yes, irrefutably and undeniably. (2) Can RF-IGC deal with issues of catalysis, the existence of more than one reaction? Certainly yes. Indeed, it is impressive to observe the reactions "on line". (3) Can RF-IGC identify peaks of products and reactants simultaneously? Certainly yes. (4) Can RF-IGC be applied to thin films in a nano-scale domain? The answer is "definitely yes". (5) Can it kinetically follow the above? Yes, again.

Sticking and recombination of the SiH 3 radical on hydrogenated amorphous silicon: The catalytic effect of diborane

NASA Astrophysics Data System (ADS)

Perrin, Jérôme; Takeda, Yoshihiko; Hirano, Naoto; Takeuchi, Yoshiaki; Matsuda, Akihisa

1989-03-01

The deposition rate of hydrogenated amorphous silicon films in SiH 4 glow-discharge is drastically enhanced upon addition of B 2H 6 when the gas-phase concentration exceeds 10 -4. This cannot be attributed to gas-phase reactions and must be interpreted as an increase of the sticking probability of the dominant SiH 3 radical. However, the total surface loss probability ( β) of SiH 3 which includes both sticking ( s) and recombination ( γ) increases only above 10 -2 B 2H 6 concentration, which reveals that between 10 -4 and 10 -2 the ratio {s}/{β} increases. A precursor-state model is proposed in which SiH 3 first physisorbs on the H-covered surface and migrates until it recombines, or chemisorbs on a free dangling bond site. At a typical deposition temperature of 200° C, the only mechanism of creation of dangling bonds in the absence of B 2H 6 is precisely the recombination of SiH 3 as SiH 4 by H abstraction, which limits the sticking probability to a fraction of β. This restriction is overcome with the help of hydroboron radicals, presumably BH 3, which catalyze H 2 desorption.

Chemoselective Hydrogenation with Supported Organoplatinum(IV) Catalyst on Zn(II)-Modified Silica

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

Camacho-Bunquin, Jeffrey; Ferrandon, Magali; Sohn, Hyuntae

For this research, well-defined organoplatinum(IV) sites were grafted on a Zn(II)-modified SiO 2 support via surface organometallic chemistry in toluene at room temperature. Solid-state spectroscopies including XAS, DRIFTS, DRUV–vis, and solid-state (SS) NMR enhanced by dynamic nuclear polarization (DNP), as well as TPR-H 2 and TEM techniques revealed highly dispersed (methylcyclopentadienyl)methylplatinum(IV) sites on the surface ((MeCp)PtMe/Zn/SiO 2, 1). In addition, computational modeling suggests that the surface reaction of (MeCp)PtMe 3 with Zn(II)-modified SiO 2 support is thermodynamically favorable (ΔG = -12.4 kcal/mol), likely due to the increased acidity of the hydroxyl group, as indicated by NH 3-TPD and DNP-enhanced 17O{more » 1H} SSNMR. In situ DRIFTS and XAS hydrogenation experiments reveal the probable formation of a surface Pt(IV)-H upon hydrogenolysis of Pt-Me groups. The heterogenized organoplatinum(IV)-hydride sites catalyze the selective partial hydrogenation of 1,3-butadiene to butenes (up to 95%) and the reduction of nitrobenzene derivatives to anilines (up to 99%) with excellent tolerance of reduction-sensitive functional groups (olefin, carbonyl, nitrile, halogens) under mild reaction conditions.« less

Electron-hole pair effects in methane dissociative chemisorption on Ni(111)

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

Luo, Xuan; Jiang, Bin, E-mail: bjiangch@ustc.edu.cn; Juaristi, J. Iñaki

The dissociative chemisorption of methane on metal surfaces has attracted much attention in recent years as a prototype of gas-surface reactions in understanding the mode specific and bond selective chemistry. In this work, we systematically investigate the influence of electron-hole pair excitations on the dissociative chemisorption of CH{sub 4}/CH{sub 3}D/CHD{sub 3} on Ni(111). The energy dissipation induced by surface electron-hole pair excitations is modeled as a friction force introduced in the generalized Langevin equation, in which the independent atomic friction coefficients are determined within the local-density friction approximation. Quasi-classical trajectory calculations for CH{sub 4}/CH{sub 3}D/CHD{sub 3} have been carried outmore » on a recently developed twelve-dimensional potential energy surface. Comparing the dissociation probabilities obtained with and without friction, our results clearly indicate that the electron-hole pair effects are generally small, both on absolute reactivity of each vibrational state and on the mode specificity and bond selectivity. Given similar observations in both water and methane dissociation processes, we conclude that electron-hole pair excitations would not play an important role as long as the reaction is direct and the interaction time between the molecule and metal electrons is relatively short.« less

Chemoselective Hydrogenation with Supported Organoplatinum(IV) Catalyst on Zn(II)-Modified Silica

DOE PAGES

Camacho-Bunquin, Jeffrey; Ferrandon, Magali; Sohn, Hyuntae; ...

2018-02-27

For this research, well-defined organoplatinum(IV) sites were grafted on a Zn(II)-modified SiO 2 support via surface organometallic chemistry in toluene at room temperature. Solid-state spectroscopies including XAS, DRIFTS, DRUV–vis, and solid-state (SS) NMR enhanced by dynamic nuclear polarization (DNP), as well as TPR-H 2 and TEM techniques revealed highly dispersed (methylcyclopentadienyl)methylplatinum(IV) sites on the surface ((MeCp)PtMe/Zn/SiO 2, 1). In addition, computational modeling suggests that the surface reaction of (MeCp)PtMe 3 with Zn(II)-modified SiO 2 support is thermodynamically favorable (ΔG = -12.4 kcal/mol), likely due to the increased acidity of the hydroxyl group, as indicated by NH 3-TPD and DNP-enhanced 17O{more » 1H} SSNMR. In situ DRIFTS and XAS hydrogenation experiments reveal the probable formation of a surface Pt(IV)-H upon hydrogenolysis of Pt-Me groups. The heterogenized organoplatinum(IV)-hydride sites catalyze the selective partial hydrogenation of 1,3-butadiene to butenes (up to 95%) and the reduction of nitrobenzene derivatives to anilines (up to 99%) with excellent tolerance of reduction-sensitive functional groups (olefin, carbonyl, nitrile, halogens) under mild reaction conditions.« less

Kinetics of Heterogeneous Reaction of Sulfur Dioxide on Authentic Mineral Dust: Effects of Relative Humidity and Hydrogen Peroxide.

PubMed

Huang, Liubin; Zhao, Yue; Li, Huan; Chen, Zhongming

2015-09-15

Heterogeneous reaction of SO2 on mineral dust seems to be an important sink for SO2. However, kinetic data about this reaction on authentic mineral dust are scarce and are mainly limited to low relative humidity (RH) conditions. In addition, little is known about the role of hydrogen peroxide (H2O2) in this reaction. Here, we investigated the uptake kinetics of SO2 on three authentic mineral dusts (i.e., Asian mineral dust (AMD), Tengger desert dust (TDD), and Arizona test dust (ATD)) in the absence and presence of H2O2 at different RHs using a filter-based flow reactor, and applied a parameter (effectiveness factor) to the estimation of the effective surface area of particles for the calculation of the corrected uptake coefficient (γc). We found that with increasing RH, the γc decreases on AMD particles, but increases on ATD and TDD particles. This discrepancy is probably due to the different mineralogy compositions and aging extents of these dust samples. Furthermore, the presence of H2O2 can promote the uptake of SO2 on mineral dust at different RHs. The probable explanations are that H2O2 rapidly reacts with SO2 on mineral dust in the presence of adsorbed water, and OH radicals, which can be produced from the heterogeneous decomposition of H2O2 on the mineral dust, immediately react with adsorbed SO2 as well. Our results suggest that the removal of SO2 via the heterogeneous reaction on mineral dust is an important sink for SO2 and has the potential to alter the physicochemical properties (e.g., ice nucleation ability) of mineral dust particles in the atmosphere.

Influence of the vehicle on elicitation of contact allergic reactions to acrylic compounds in the guinea pig.

PubMed

Björkner, B; Niklasson, B

1984-11-01

Many factors can influence the elicitation of hypersensitivity reactions in guinea pigs and humans. The effect which the vehicle might have on the test response in guinea pigs sensitized with various acrylic compounds, using the "guinea pig maximization test", has been investigated. A marked decrease in the number of positive animals was seen when acetone was used as test vehicle, compared to petrolatum. The same result was seen with alcohol as vehicle, when neopentyl glycol diacrylate (NPGDA) was used as an acrylic monomer model. The patch test locations on the guinea pig flank, also affected the test response. Half of the animals did not react when challenged near the abdomen, compared to a test site near the back. By means of HPLC-analysis, the possible adsorption of the acrylic monomer to the aluminium chamber or filter paper disc, was analysed. Our findings did not indicate that adsorption occurs. A decrease in the amount of acrylic monomer in the chamber with increasing time, was noted. There was a marked difference in the monomer residue between solutions with (darkness) and without (daylight) inhibitor. The monomer decrease was also more affected by an aluminium surface than a glass or filter paper surface. Aluminium oxide probably enhances the polymerization process. The discrepancy between the test results in this study, when petrolatum and acetone were used as test vehicles, is due to a polymerization process of the acrylic compounds. Thus, the petrolatum vehicle probably prevents polymerization of the acrylic monomer.

[Effects of prefrontal ablations on the reaction of the active choice of feeder under different probability and value of the reinforcement on dog].

PubMed

Preobrazhenskaia, L A; Ioffe, M E; Mats, V N

2004-01-01

The role of the prefrontal cortex was investigated on the reaction of the active choice of the two feeders under changes value and probability reinforcement. The experiments were performed on 2 dogs with prefrontal ablation (g. proreus). Before the lesions the dogs were taught to receive food in two different feeders to conditioned stimuli with equally probable alimentary reinforcement. After ablation in the inter-trial intervals the dogs were running from the one feeder to another. In the answer to conditioned stimuli for many times the dogs choose the same feeder. The disturbance of the behavior after some times completely restored. In the experiments with competition of probability events and values of reinforcement the dogs chose the feeder with low-probability but better quality of reinforcement. In the experiments with equal value but different probability the intact dogs chose the feeder with higher probability. In our experiments the dogs with prefrontal lesions chose the each feeder equiprobably. Thus in condition of free behavior one of different functions of the prefrontal cortex is the reactions choose with more probability of reinforcement.

Photocatalytic Conversion of Nitrobenzene to Aniline through Sequential Proton-Coupled One-Electron Transfers from a Cadmium Sulfide Quantum Dot

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

Jensen, Stephen C.; Bettis Homan, Stephanie; Weiss, Emily A.

2016-01-28

This paper describes the use of cadmium sulfide quantum dots (CdS QDs) as visible-light photocatalysts for the reduction of nitrobenzene to aniline through six sequential photoinduced, proton-coupled electron transfers. At pH 3.6–4.3, the internal quantum yield of photons-to-reducing electrons is 37.1% over 54 h of illumination, with no apparent decrease in catalyst activity. Monitoring of the QD exciton by transient absorption reveals that, for each step in the catalytic cycle, the sacrificial reductant, 3-mercaptopropionic acid, scavenges the excitonic hole in ~5 ps to form QD•–; electron transfer to nitrobenzene or the intermediates nitrosobenzene and phenylhydroxylamine then occurs on the nanosecondmore » time scale. The rate constants for the single-electron transfer reactions are correlated with the driving forces for the corresponding proton-coupled electron transfers. This result suggests, but does not prove, that electron transfer, not proton transfer, is rate-limiting for these reactions. Nuclear magnetic resonance analysis of the QD–molecule systems shows that the photoproduct aniline, left unprotonated, serves as a poison for the QD catalyst by adsorbing to its surface. Performing the reaction at an acidic pH not only encourages aniline to desorb but also increases the probability of protonated intermediates; the latter effect probably ensures that recruitment of protons is not rate-limiting.« less

Heterogeneous Interactions of ClONO2 and HCl with Sulfuric Acid Tetrahydrate: Implications for the Stratosphere

NASA Technical Reports Server (NTRS)

Zhang, Renyi; Jayne, John T.; Molina, Mario J.

1994-01-01

The reaction probabilities for ClONO2+H2O- HOCl + HNO3 and ClONO2+ HCl Cl2 +HNO3 have been investigated on sulfuric acid tetrahydrate (SAT, H2SO4-4H2O)surfaces at temperatures between 190 and 230 K and at reactant concentrations that are typical in the lower stratosphere, using a fast-flow reactor coupled to a quadrupole mass spectrometer. The results indicate that the reaction probabilities as well as HCl uptake depend strongly on the thermodynamic state of SAT surface: they decrease significantly with decreasing H2O partial pressure at a given temperature, and decrease with increasing temperature at a given H2O partial pressure, as the SAT changes from the H2O-rich form to the H2SO4-rich form. For H2O-rich SAT at 195 K gamma(sub 1) approx. = -0.01 and gamma(sub 2) greater or equal to 0.1, whereas the values for H2SO4-rich SAT decrease by more than 2 orders of magnitude. At low concentrations of HCl, close to those found in the stratosphere, the amount of HCl taken up by H2O-rich SAT films corresponds to a coverage of the order of a tenth of a monolayer (approx. = 10(exp 14) molecules/sq cm); H2SO4-rich SAT films take up 2 orders of magnitude less HCl (les than 10(exp 12) molecules/sq cm). Substantial HCl uptake at high HCl concentrations is also observed, as a result of surface melting. The data reveal that frozen stratospheric sulfate aerosols may play an important role in chlorine activation in the winter polar stratosphere via processes similar to those occurring on the surfaces of polar stratospheric cloud particles.

A study on the probability of twin plane formation during the nucleation of AgBr and AgCl crystals in the aqueous gelatin solution

NASA Astrophysics Data System (ADS)

Ohzeki, Katsuhisa; Hosoya, Yoichi

2007-07-01

A study was made on the probability of twin plane formation during the nucleation of AgBr and AgCl crystals. The growth condition was controlled to keep the number of the nuclei, neither decreasing owing to their dissolution, nor increasing owing to the formation of a new nucleus during the growth process. Under the condition, the nuclei were grown to have {1 1 1} faces on their surfaces by controlling pAg in a reaction solution and by use of growth modifier in case of AgCl crystal formation. The number of twin planes in each crystal was judged according to a conventional way on the basis of its morphology. The dependence of the number of twin planes per crystal on the probability of twin plain formation was in accordance with Poisson distribution, indicating the random formation of a twin plane on the {1 1 1} faces of a nucleus. The result that the ratio of number of AgCl crystals with parallel twin planes to all the multiply twinned crystals was about 10% supports the random formation of a twin plane and suggests that the twin plane formation took place on {1 1 1} surfaces at the possible eight corner of a nucleus. On the other hand, the ratio of the number of AgBr crystals with parallel twin planes to all the multiply twinned crystals was more than 50%. The result was explained by the anisotropic growth of a singly twinned nucleus according to the higher growth rate of {1 0 0} surfaces than that of {1 1 1} surfaces.

The aqueous photolysis of α-pinene in solution with humic acid

USGS Publications Warehouse

Goldberg, Marvin C.; Cunningham, Kirkwood M.; Aiken, George R.; Weiner, Eugene R.; ,

1992-01-01

Terpenes are produced abundantly by environmental processes but are found in very low concentrations in natural waters. Aqueous photolysis of solutions containing α-pinene, a representative terpene, in the presence of humic acid resulted in degradation of the pinene. Comparison of this reaction to photolysis of α-pinene in the presence of methylene blue leads to the conclusion that the reactive pathway for the abiotic degradation of α-pinene is due to reaction with singlet oxygen produced by irradiation of the humic material. The initial product of single oxygen and α-pinene is a hydroperoxide. Since humic materials are prevalent in most natural waters, this mechanism of photodecomposition for α-pinene probably also applies to other terpenes in surface waters and may be reasonably considered to contribute to their low environmental concentration.

Concentrations of Reactive Trace Gases In The Interstitial Air of Surface Snow

NASA Astrophysics Data System (ADS)

Jacobi, H.-W.; Honrath, R. E.; Peterson, M. C.; Lu, Y.; Dibb, J. E.; Arsenault, M. A.; Swanson, A. L.; Blake, N. J.; Bales, R. C.; Schrems, O.

Several measurements at Arctic and Antarctic sites have demonstrated that unexpected photochemical reactions occur in irradiated surface snow influencing the composi- tion of the boundary layer over snow-covered areas. The results of these reactions are probably most obvious in the interstitial air of the surface snow since it constitutes the interface between the surface snow and the boundary layer. Therefore, measurements of concentrations of nitrogen oxide and dioxide, nitrous acid, formaldehyde, hydro- gen peroxide, formic acid, acetic acid, and other organic compounds were performed in the interstitial air of the surface snow of the Greenland ice sheet. Concentrations were measured at variable depths between - 10 cm and - 50 cm during the summer field season in 2000 at the Summit Environmental Observatory. At shallow depths, the system NO-NO2-O3 exhibits large deviations from the calculated photostationary state. Using steady-state analyses applied to OH-HO2-CH3O2 cycling indicated the presence of high concentrations of OH and peroxy radicals in the firn air. Maximum concentrations calculated for a depth of - 10 cm are in the order of 6 105 molecules cm-3 and 1.4 * 107 molecules cm-3 for OH and HO2, respectively, although radia- tion levels at - 10 cm are reduced by approximately 50 % compared to levels above the snow surface. By far the most important OH source is the photolysis of HONO while the photolysis of ozone contributes less than 2 % to the overall production of OH in the firn air.

Growth of methanogens on a Mars soil simulant.

PubMed

Kral, Timothy A; Bekkum, Curtis R; McKay, Christopher P

2004-12-01

Currently, the surface of Mars is probably too cold, too dry, and too oxidizing for life, as we know it, to exist. But the subsurface is another matter. Life forms that might exist below the surface could not obtain their energy from photosynthesis, but rather they would have to utilize chemical energy. Methanogens are one type of microorganism that might be able to survive below the surface of Mars. A potential habitat for existence of methanogens on Mars might be a geothermal source of hydrogen, possibly due to volcanic or hydrothermal activity, or the reaction of basalt and anaerobic water, carbon dioxide, which is abundant in the martian atmosphere, and of course, subsurface liquid water. We report here that certain methanogens can grow on a Mars soil simulant when supplied with carbon dioxide, molecular hydrogen, and varying amounts of water.

Survival-mediated capture and fusion cross sections for heavy-element synthesis

NASA Astrophysics Data System (ADS)

Yao, L.; Loveland, W.

2018-01-01

The cross section for producing a heavy evaporation residue σEVR in a fusion reaction can be written as a product of three nonseparable factors, i.e., the capture cross section, the fusion probability PCN, and the survival probability Wsur. Each of these factors is dependent on the spin. However, one must remember that the Wsur term is zero or very small for higher spin values, thus effectively limiting the capture and fusion terms. For a series of ˜287 reactions leading to heavy evaporation residues with ZCN≤110 , we point out the implications of this fact for capture cross sections for heavy element formation reactions. From a comparison of calculated and measured evaporation residue cross sections we deduce values of the fusion probability PCN for some of these reactions.

Slow-muon study of quaternary solar-cell materials: Single layers and p -n junctions

NASA Astrophysics Data System (ADS)

Alberto, H. V.; Vilão, R. C.; Vieira, R. B. L.; Gil, J. M.; Weidinger, A.; Sousa, M. G.; Teixeira, J. P.; da Cunha, A. F.; Leitão, J. P.; Salomé, P. M. P.; Fernandes, P. A.; Törndahl, T.; Prokscha, T.; Suter, A.; Salman, Z.

2018-02-01

Thin films and p -n junctions for solar cells based on the absorber materials Cu (In ,G a ) Se2 and Cu2ZnSnS4 were investigated as a function of depth using implanted low energy muons. The most significant result is a clear decrease of the formation probability of the Mu+ state at the heterojunction interface as well as at the surface of the Cu (In ,G a ) Se2 film. This reduction is attributed to a reduced bonding reaction of the muon in the absorber defect layer at its surface. In addition, the activation energies for the conversion from a muon in an atomiclike configuration to a anion-bound position are determined from temperature-dependence measurements. It is concluded that the muon probe provides a measurement of the effective surface defect layer width, both at the heterojunctions and at the films. The CIGS surface defect layer is crucial for solar-cell electrical performance and additional information can be used for further optimizations of the surface.

The dissociative chemisorption of methane on Ni(100) and Ni(111): Classical and quantum studies based on the reaction path Hamiltonian

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

Mastromatteo, Michael; Jackson, Bret, E-mail: jackson@chem.umass.edu

Electronic structure methods based on density functional theory are used to construct a reaction path Hamiltonian for CH{sub 4} dissociation on the Ni(100) and Ni(111) surfaces. Both quantum and quasi-classical trajectory approaches are used to compute dissociative sticking probabilities, including all molecular degrees of freedom and the effects of lattice motion. Both approaches show a large enhancement in sticking when the incident molecule is vibrationally excited, and both can reproduce the mode specificity observed in experiments. However, the quasi-classical calculations significantly overestimate the ground state dissociative sticking at all energies, and the magnitude of the enhancement in sticking with vibrationalmore » excitation is much smaller than that computed using the quantum approach or observed in the experiments. The origin of this behavior is an unphysical flow of zero point energy from the nine normal vibrational modes into the reaction coordinate, giving large values for reaction at energies below the activation energy. Perturbative assumptions made in the quantum studies are shown to be accurate at all energies studied.« less

Field-to-laboratory analysis of clay wall coatings as passive removal materials for ozone in buildings.

PubMed

Darling, E; Corsi, R L

2017-05-01

Ozone reacts readily with many indoor materials, as well as with compounds in indoor air. These reactions lead to lower indoor than outdoor ozone concentrations when outdoor air is the major contributor to indoor ozone. However, the products of indoor ozone reactions may be irritating or harmful to building occupants. While active technologies exist to reduce indoor ozone concentrations (i.e, in-duct filtration using activated carbon), they can be cost-prohibitive for some and/or infeasible for dwellings that do not have heating, ventilating, and air-conditioning systems. In this study, the potential for passive reduction of indoor ozone by two different clay-based interior surface coatings was explored. These coatings were exposed to occupied residential indoor environments and tested bimonthly in environmental chambers for quantification of ozone reaction probabilities and reaction product emission rates over a 6-month period. Results indicate that clay-based coatings may be effective as passive removal materials, with relatively low by-product emission rates that decay rapidly within 2 months. © 2016 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.

The Chemistry of Inorganic Precursors during the Chemical Deposition of Films on Solid Surfaces.

PubMed

Barry, Seán T; Teplyakov, Andrew V; Zaera, Francisco

2018-03-20

The deposition of thin solid films is central to many industrial applications, and chemical vapor deposition (CVD) methods are particularly useful for this task. For one, the isotropic nature of the adsorption of chemical species affords even coverages on surfaces with rough topographies, an increasingly common requirement in microelectronics. Furthermore, by splitting the overall film-depositing reactions into two or more complementary and self-limiting steps, as it is done in atomic layer depositions (ALD), film thicknesses can be controlled down to the sub-monolayer level. Thanks to the availability of a vast array of inorganic and metalorganic precursors, CVD and ALD are quite versatile and can be engineered to deposit virtually any type of solid material. On the negative side, the surface chemistry that takes place in these processes is often complex, and can include undesirable side reactions leading to the incorporation of impurities in the growing films. Appropriate precursors and deposition conditions need to be chosen to minimize these problems, and that requires a proper understanding of the underlying surface chemistry. The precursors for CVD and ALD are often designed and chosen based on their known thermal chemistry from inorganic chemistry studies, taking advantage of the vast knowledge developed in that field over the years. Although a good first approximation, however, this approach can lead to wrong choices, because the reactions of these precursors at gas-solid interfaces can be quite different from what is seen in solution. For one, solvents often aid in the displacement of ligands in metalorganic compounds, providing the right dielectric environment, temporarily coordinating to the metal, or facilitating multiple ligand-complex interactions to increase reaction probabilities; these options are not available in the gas-solid reactions associated with CVD and ALD. Moreover, solid surfaces act as unique "ligands", if these reactions are to be viewed from the point of view of the metalorganic complexes used as precursors: they are bulky and rigid, can provide multiple binding sites for a single reaction, and can promote unique bonding modes, especially on metals, which have delocalized electronic structures. The differences between the molecular and surface chemistry of CVD and ALD precursors can result in significant variations in their reactivity, ultimately leading to unpredictable properties in the newly grown films. In this Account, we discuss some of the main similarities and differences in chemistry that CVD/ALD precursors follow on surfaces when contrasted against their known behavior in solution, with emphasis on our own work but also referencing other key contributions. Our approach is unique in that it combines expertise from the inorganic, surface science, and quantum-mechanics fields to better understand the mechanistic details of the chemistry of CVD and ALD processes and to identify new criteria to consider when designing CVD/ALD precursors.

Investigating ozone-induced decomposition of surface-bound permethrin for conditions in aircraft cabins.

PubMed

Coleman, B K; Wells, J R; Nazaroff, W W

2010-02-01

The reaction of ozone with permethrin can potentially form phosgene. Published evidence on ozone levels and permethrin surface concentrations in aircraft cabins indicated that significant phosgene formation might occur in this setting. A derivatization technique was developed to detect phosgene with a lower limit of detection of 2 ppb. Chamber experiments were conducted with permethrin-coated materials (glass, carpet, seat fabric, and plastic) exposed to ozone under cabin-relevant conditions (150 ppb O(3), 4.5/h air exchange rate, <1% relative humidity, 1700 ng/cm(2) of permethrin). Phosgene was not detected in these experiments. Reaction of ozone with permethrin appears to be hindered by the electron-withdrawing chlorine atoms adjacent to the double bond in permethrin. Experimental results indicate that the upper limit on the reaction probability of ozone with surface-bound permethrin is approximately 10(-7). Extrapolation by means of material-balance modeling indicates that the upper limit on the phosgene level in aircraft cabins resulting from this chemistry is approximately 1 microg/m(3) or approximately 0.3 ppb. It was thus determined that phosgene formation, if it occurs in aircraft cabins, is not likely to exceed relevant, health-based phosgene exposure guidelines. Phosgene formation from ozone-initiated oxidation of permethrin in the aircraft cabin environment, if it occurs, is estimated to generate levels below the California Office of Environmental Health Hazard Assessment acute reference exposure level of 4 microg/m(3) or approximately 1 ppb.

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

PubMed

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

2015-12-17

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

Photo-induced reactions from efficient molecular dynamics with electronic transitions using the FIREBALL local-orbital density functional theory formalism.

PubMed

Zobač, Vladimír; Lewis, James P; Abad, Enrique; Mendieta-Moreno, Jesús I; Hapala, Prokop; Jelínek, Pavel; Ortega, José

2015-05-08

The computational simulation of photo-induced processes in large molecular systems is a very challenging problem. Firstly, to properly simulate photo-induced reactions the potential energy surfaces corresponding to excited states must be appropriately accessed; secondly, understanding the mechanisms of these processes requires the exploration of complex configurational spaces and the localization of conical intersections; finally, photo-induced reactions are probability events, that require the simulation of hundreds of trajectories to obtain the statistical information for the analysis of the reaction profiles. Here, we present a detailed description of our implementation of a molecular dynamics with electronic transitions algorithm within the local-orbital density functional theory code FIREBALL, suitable for the computational study of these problems. As an example of the application of this approach, we also report results on the [2 + 2] cycloaddition of ethylene with maleic anhydride and on the [2 + 2] photo-induced polymerization reaction of two C60 molecules. We identify different deactivation channels of the initial electron excitation, depending on the time of the electronic transition from LUMO to HOMO, and the character of the HOMO after the transition.

Mechanism of formation of humus coatings on mineral surfaces 1. Evidence for multidentate binding of organic acids from compost leachate on alumina

USGS Publications Warehouse

Wershaw, R. L.; Leenheer, J.A.; Sperline, R.P.; Song, Yuan; Noll, L.A.; Melvin, R.L.; Rigatti, G.P.

1995-01-01

Measurements of the infrared linear dichroism of carboxylate groups of organic acids from compost leachate adsorbed to an alumina surface and the enthalpy of adsorption of this reaction have been made. The linear dichroism measurements indicated that the carboxylate groups are not free to rotate. This limited rotation probably results from bidentate binding of the carboxylate groups. The molar enthalpy of adsorption of the acids is approximately −100 kJ mol−1. This high value for enthalpy of adsorption may best be explained by assuming that two or more carboxylate groups on a single dissolved organic carbon (DOC) molecule coordinate to the surficial aluminium ions.

Evaluation of naranjo adverse drug reactions probability scale in causality assessment of drug-induced liver injury.

PubMed

García-Cortés, M; Lucena, M I; Pachkoria, K; Borraz, Y; Hidalgo, R; Andrade, R J

2008-05-01

Causality assessment in hepatotoxicity is challenging. The current standard liver-specific Council for International Organizations of Medical Sciences/Roussel Uclaf Causality Assessment Method scale is complex and difficult to implement in daily practice. The Naranjo Adverse Drug Reactions Probability Scale is a simple and widely used nonspecific scale, which has not been specifically evaluated in drug-induced liver injury. To compare the Naranjo method with the standard liver-specific Council for International Organizations of Medical Sciences/Roussel Uclaf Causality Assessment Method scale in evaluating the accuracy and reproducibility of Naranjo Adverse Drug Reactions Probability Scale in the diagnosis of hepatotoxicity. Two hundred and twenty-five cases of suspected hepatotoxicity submitted to a national registry were evaluated by two independent observers and assessed for between-observer and between-scale differences using percentages of agreement and the weighted kappa (kappa(w)) test. A total of 249 ratings were generated. Between-observer agreement was 45% with a kappa(w) value of 0.17 for the Naranjo Adverse Drug Reactions Probability Scale, while there was a higher agreement when using the Council for International Organizations of Medical Sciences/Roussel Uclaf Causality Assessment Method scale (72%, kappa(w): 0.71). Concordance between the two scales was 24% (kappa(w): 0.15). The Naranjo Adverse Drug Reactions Probability Scale had low sensitivity (54%) and poor negative predictive value (29%) and showed a limited capability to distinguish between adjacent categories of probability. The Naranjo scale lacks validity and reproducibility in the attribution of causality in hepatotoxicity.

Microwaves in chemistry: Another way of heating reaction mixtures

NASA Astrophysics Data System (ADS)

Berlan, J.

1995-04-01

The question of a possible "microwave activation" of chemical reaction is discussed. In fact two cases should be distinguished: homogeneous or heterogeneous reaction mixtures. In homogeneous mixtures there are no (or very low) rate enhancements compared to a conventional heating, but some influence on chemioselectivity has been observed. These effects derive from fast and mass heating of microwaves, and probably, especially under reflux, from different boiling rates and/or overheating. With heterogeneous mixtures non conventional effects probably derive from mass heating and selective overheating. This is illustrated with several reactions: Diels-Alder, naphthalene sulphonation, preparation of cyanuric acid, hydrolysis of nitriles, transposition reaction on solid support.

A Finite-Rate-Catalytic Model For Hypersonic Flows Informed By Molecular Dynamics

NASA Astrophysics Data System (ADS)

Schwartzentruber, T. E.; Valentini, P.; Norman, P.; Sorensen, C.

2011-05-01

The implementation of a finite-rate catalytic (FRC) wall boundary condition within a general 3D unstructured CFD solver is described. A set of one-step gas-surface chemical equations and atomistic parameters that deter- mine the reaction rates must be prescribed as input to the model. The chemical rate equations are solved at each wall face in the CFD simulation and result in a net production of species at the wall. In order for a finite- rate gas-surface reaction model to be consistent at equilibrium, it is determined that not all forward and back- ward rates can be specified arbitrarily. Provided that the forward rates for each surface recombination are as- signed, the backward rates must be determined using equilibrium constants that are consistent with the gas- phase chemistry model and thermodynamics. Reactive molecular dynamics (MD) simulations are performed us- ing the ReaxFFSiO potential to investigate oxygen-silica interactions. β-quartz and amorphous SiO2 surfaces are accommodated to a high temperature gas via MD simulation and reach a steady-state surface coverage. In addition to stable surface reconstructions a number of active sites are observed on which recombination occurs. Single collision MD simulations are performed where gas-phase oxygen atoms interact with the most dominant active site. Probabilities of recombination are found to have an exponential trend with gas-surface system temperature. The MD simulations are used to determine the activation energy for Eley-Rideal recombination of oxygen on a specific silica active site which is an important input parameter for the FRC model.

Antarctic stratospheric chemistry of chlorine nitrate, hydrogen chloride, and ice - Release of active chlorine

NASA Technical Reports Server (NTRS)

Molina, Mario J.; Tso, Tai-Ly; Molina, Luisa T.; Wang, Frank C.-Y.

1987-01-01

The reaction rate between atmospheric hydrogen chloride (HCl) and chlorine nitrate (ClONO2) is greatly enhanced in the presence of ice particles; HCl dissolves readily into ice, and the collisional reaction probability for ClONO2 on the surface of ice with HCl in the mole fraction range from about 0.003 to 0.010 is in the range from about 0.05 to 0.1 for temperatures near 200 K. Chlorine is released into the gas phase on a time scale of at most a few milliseconds, whereas nitric acid (HNO3), the other product, remains in the condensed phase. This reaction could play an important role in explaining the observed depletion of ozone over Antarctica; it releases photolytically active chlorine from its most abundant reservoir species, and it promotes the formation of HNO3 and thus removes nitrogen dioxide from the gas phase. Hence it establishes the necessary conditions for the efficient catalytic destruction of ozone by halogenated free radicals.

Two-dimensional lithium diffusion behavior and probable hybrid phase transformation kinetics in olivine lithium iron phosphate

DOE PAGES

Hong, Liang; Li, Linsen; Chen-Wiegart, Yuchen-Karen; ...

2017-10-30

Olivine lithium iron phosphate is a technologically important electrode material for lithium-ion batteries and a model system for studying electrochemically driven phase transformations. Despite extensive studies, many aspects of the phase transformation and lithium transport in this material are still not well understood. Here we combine operando hard X-ray spectroscopic imaging and phase-field modeling to elucidate the delithiation dynamics of single-crystal lithium iron phosphate microrods with long-axis along the [010] direction. Lithium diffusivity is found to be two-dimensional in microsized particles containing ~3%lithium-iron anti-site defects. Our study provides direct evidence for the previously predicted surface reaction-limited phase-boundary migration mechanism andmore » the potential operation of a hybrid mode of phase growth, in which phase-boundary movement is controlled by surface reaction or lithium diffusion in different crystallographic directions. These findings uncover the rich phase-transformation behaviors in lithium iron phosphate and intercalation com-pounds in general and can help guide the design of better electrodes.« less

Two-dimensional lithium diffusion behavior and probable hybrid phase transformation kinetics in olivine lithium iron phosphate

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

Hong, Liang; Li, Linsen; Chen-Wiegart, Yuchen-Karen

Olivine lithium iron phosphate is a technologically important electrode material for lithium-ion batteries and a model system for studying electrochemically driven phase transformations. Despite extensive studies, many aspects of the phase transformation and lithium transport in this material are still not well understood. Here we combine operando hard X-ray spectroscopic imaging and phase-field modeling to elucidate the delithiation dynamics of single-crystal lithium iron phosphate microrods with long-axis along the [010] direction. Lithium diffusivity is found to be two-dimensional in microsized particles containing ~3%lithium-iron anti-site defects. Our study provides direct evidence for the previously predicted surface reaction-limited phase-boundary migration mechanism andmore » the potential operation of a hybrid mode of phase growth, in which phase-boundary movement is controlled by surface reaction or lithium diffusion in different crystallographic directions. These findings uncover the rich phase-transformation behaviors in lithium iron phosphate and intercalation com-pounds in general and can help guide the design of better electrodes.« less

Two-dimensional lithium diffusion behavior and probable hybrid phase transformation kinetics in olivine lithium iron phosphate

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

Hong, Liang; Chen-Wiegart, Yu-Chen K.

2017-10-30

Olivine lithium iron phosphate is a technologically important electrode material for lithium-ion batteries and a model system for studying electrochemically driven phase transformations. Despite extensive studies, many aspects of the phase transformation and lithium transport in this material are still not well understood. Here we combine operando hard X-ray spectroscopic imaging and phase-field modeling to elucidate the delithiation dynamics of single-crystal lithium iron phosphate microrods with long-axis along the [010] direction. Lithium diffusivity is found to be two-dimensional in microsized particles containing ~3%lithium-iron anti-site defects. Our study provides direct evidence for the previously predicted surface reaction-limited phase-boundary migration mechanism andmore » the potential operation of a hybrid mode of phase growth, in which phase-boundary movement is controlled by surface reaction or lithium diffusion in different crystallographic directions. These findings uncover the rich phase-transformation behaviors in lithium iron phosphate and intercalation com-pounds in general and can help guide the design of better electrodes.« less

Layer-by-layer assembly of TiO(2) colloids onto diatomite to build hierarchical porous materials.

PubMed

Jia, Yuxin; Han, Wei; Xiong, Guoxing; Yang, Weishen

2008-07-15

TiO(2) colloids with the most probably particle size of 10 nm were deposited on the surface of macroporous diatomite by a layer-by-layer (LBL) assembly method with using phytic acid as molecular binder. For preparation of colloidal TiO(2), titanium(IV) isopropoxide (Ti(C(3)H(7)O)(4)) was used as titanium precursor, nitric acid (HNO(3)) as peptizing agent and deionized water and isopropanol (C(3)H(7)OH) as solvent. Scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), N(2) adsorption-desorption, and UV-vis spectra are used to assess the morphology and physical chemistry properties of the resulting TiO(2) coated diatomite. It was shown that the mesoporosity has been introduced into macroporous diatomite by LBL deposition. The mesoporosity was originated from close-packing of the uniform TiO(2) nanoparticles. More TiO(2) could be coated on the surface of diatomite by increasing the deposition cycles. This hierarchical porous material has potential for applications in catalytic reactions involved diffusion limit, especially in photocatalytic reactions.

Electron-beam generated porous dextran gels: experimental and quantum chemical studies.

PubMed

Naumov, Sergej; Knolle, Wolfgang; Becher, Jana; Schnabelrauch, Matthias; Reichelt, Senta

2014-06-01

The aim of this work was to investigate the reaction mechanism of electron-beam generated macroporous dextran cryogels by quantum chemical calculation and electron paramagnetic resonance measurements. Electron-beam radiation was used to initiate the cross-linking reaction of methacrylated dextran in semifrozen aqueous solutions. The pore morphology of the resulting cryogels was visualized by scanning electron microscopy. Quantum chemical calculations and electron paramagnetic resonance studies provided information on the most probable reaction pathway and the chain growth radicals. The most probable reaction pathway was a ring opening reaction and the addition of a C-atom to the double-bond of the methacrylated dextran molecule. First detailed quantum chemical calculation on the reaction mechanism of electron-beam initiated cross-linking reaction of methacrylated dextran are presented.

DISCUSSION OF "DETECTION OF CRYPTOSPORIDIUM PARVUM IN SECONDARY EFFLUENTS USING A MOST PROBABLE NUMBER-POLYMERASE CHAIN REACTION ASSAY"

EPA Science Inventory

The emphasis of this paper is to show that most probable number-polymerase chain reaction (MPNPCR) assay can be used to detect Cryptosporidium parvum in WWTP effluents as an alternative to immunfluorescent assay (IFA). I am concerned, however, that the paper suggests that all WW...

Surface-Activated Coupling Reactions Confined on a Surface.

PubMed

Dong, Lei; Liu, Pei Nian; Lin, Nian

2015-10-20

Chemical reactions may take place in a pure phase of gas or liquid or at the interface of two phases (gas-solid or liquid-solid). Recently, the emerging field of "surface-confined coupling reactions" has attracted intensive attention. In this process, reactants, intermediates, and products of a coupling reaction are adsorbed on a solid-vacuum or a solid-liquid interface. The solid surface restricts all reaction steps on the interface, in other words, the reaction takes place within a lower-dimensional, for example, two-dimensional, space. Surface atoms that are fixed in the surface and adatoms that move on the surface often activate the surface-confined coupling reactions. The synergy of surface morphology and activity allow some reactions that are inefficient or prohibited in the gas or liquid phase to proceed efficiently when the reactions are confined on a surface. Over the past decade, dozens of well-known "textbook" coupling reactions have been shown to proceed as surface-confined coupling reactions. In most cases, the surface-confined coupling reactions were discovered by trial and error, and the reaction pathways are largely unknown. It is thus highly desirable to unravel the mechanisms, mechanisms of surface activation in particular, of the surface-confined coupling reactions. Because the reactions take place on surfaces, advanced surface science techniques can be applied to study the surface-confined coupling reactions. Among them, scanning tunneling microscopy (STM) and X-ray photoelectron spectroscopy (XPS) are the two most extensively used experimental tools. The former resolves submolecular structures of individual reactants, intermediates, and products in real space, while the latter monitors the chemical states during the reactions in real time. Combination of the two methods provides unprecedented spatial and temporal information on the reaction pathways. The experimental findings are complemented by theoretical modeling. In particular, density-functional theory (DFT) transition-state calculations have been used to shed light on reaction mechanisms and to unravel the trends of different surface materials. In this Account, we discuss recent progress made in two widely studied surface-confined coupling reactions, aryl-aryl (Ullmann-type) coupling and alkyne-alkyne (Glaser-type) coupling, and focus on surface activation effects. Combined experimental and theoretical studies on the same reactions taking place on different metal surfaces have clearly demonstrated that different surfaces not only reduce the reaction barrier differently and render different reaction pathways but also control the morphology of the reaction products and, to some degree, select the reaction products. We end the Account with a list of questions to be addressed in the future. Satisfactorily answering these questions may lead to using the surface-confined coupling reactions to synthesize predefined products with high yield.

Femtosecond-laser induced dynamics of CO on Ru(0001): Deep insights from a hot-electron friction model including surface motion

NASA Astrophysics Data System (ADS)

Scholz, Robert; Floß, Gereon; Saalfrank, Peter; Füchsel, Gernot; Lončarić, Ivor; Juaristi, J. I.

2016-10-01

A Langevin model accounting for all six molecular degrees of freedom is applied to femtosecond-laser induced, hot-electron driven dynamics of Ru(0001)(2 ×2 ):CO. In our molecular dynamics with electronic friction approach, a recently developed potential energy surface based on gradient-corrected density functional theory accounting for van der Waals interactions is adopted. Electronic friction due to the coupling of molecular degrees of freedom to electron-hole pairs in the metal are included via a local density friction approximation, and surface phonons by a generalized Langevin oscillator model. The action of ultrashort laser pulses enters through a substrate-mediated, hot-electron mechanism via a time-dependent electronic temperature (derived from a two-temperature model), causing random forces acting on the molecule. The model is applied to laser induced lateral diffusion of CO on the surface, "hot adsorbate" formation, and laser induced desorption. Reaction probabilities are strongly enhanced compared to purely thermal processes, both for diffusion and desorption. Reaction yields depend in a characteristic (nonlinear) fashion on the applied laser fluence, as well as branching ratios for various reaction channels. Computed two-pulse correlation traces for desorption and other indicators suggest that aside from electron-hole pairs, phonons play a non-negligible role for laser induced dynamics in this system, acting on a surprisingly short time scale. Our simulations on precomputed potentials allow for good statistics and the treatment of long-time dynamics (300 ps), giving insight into this system which hitherto has not been reached. We find generally good agreement with experimental data where available and make predictions in addition. A recently proposed laser induced population of physisorbed precursor states could not be observed with the present low-coverage model.

Evaporation and condensation at a liquid surface. I. Argon

NASA Astrophysics Data System (ADS)

Yasuoka, Kenji; Matsumoto, Mitsuhiro; Kataoka, Yosuke

1994-11-01

Molecular dynamics computer simulations were carried out to investigate the dynamics of evaporation and condensation for argon at the temperature of 80 and 100 K. From the decrease of the survival probability of vapor molecules, the ratio of self reflection to collision is estimated to be 12%-15%, only weakly dependent on the temperature. This suggests that argon vapor molecules are in the condition of almost complete capture, and the condensation is considered to be a barrierless process. The total ratio of reflection which is evaluated with the flux correlation of condensation and evaporation is 20% at both temperature. The difference between these two ratios of reflection is ascribed to a phenomenon that vapor molecules colliding with the surface drive out other liquid molecules. This molecule exchange at the surface is as important as the self-reflection, and the conventional picture of condensation as a unimolecular chemical reaction is not appropriate.

Active site densities, oxygen activation and adsorbed reactive oxygen in alcohol activation on npAu catalysts

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

Wang, Lu-Cun; Friend, C. M.; Fushimi, Rebecca

The activation of molecular O 2as well as the reactivity of adsorbed oxygen species is of central importance in aerobic selective oxidation chemistry on Au-based catalysts. Herein, we address the issue of O 2activation on unsupported nanoporous gold (npAu) catalysts by applying a transient pressure technique, a temporal analysis of products (TAP) reactor, to measure the saturation coverage of atomic oxygen, its collisional dissociation probability, the activation barrier for O 2dissociation, and the facility with which adsorbed O species activate methanol, the initial step in the catalytic cycle of esterification. The results from these experiments indicate that molecular O 2dissociationmore » is associated with surface silver, that the density of reactive sites is quite low, that adsorbed oxygen atoms do not spill over from the sites of activation onto the surrounding surface, and that methanol reacts quite facilely with the adsorbed oxygen atoms. In addition, the O species from O 2dissociation exhibits reactivity for the selective oxidation of methanol but not for CO. The TAP experiments also revealed that the surface of the npAu catalyst is saturated with adsorbed O under steady state reaction conditions, at least for the pulse reaction.« less

Present status of titanium removable dentures--a review of the literature.

PubMed

Ohkubo, C; Hanatani, S; Hosoi, T

2008-09-01

Although porcelain and zirconium oxide might be used for fixed partial dental prostheses instead of conventional dental metals in the near future, removable partial denture (RPD) frameworks will probably continue to be cast with biocompatible metals. Commercially pure (CP) titanium has appropriate mechanical properties, it is lightweight (low density) compared with conventional dental alloys, and has outstanding biocompatibility that prevents metal allergic reactions. This literature review describes the laboratory conditions needed for fabricating titanium frameworks and the present status of titanium removable prostheses. The use of titanium for the production of cast RPD frameworks has gradually increased. There are no reports about metallic allergy apparently caused by CP titanium dentures. The laboratory drawbacks still remain, such as the lengthy burn-out, inferior castability and machinability, reaction layer formed on the cast surface, difficulty of polishing, and high initial costs. However, the clinical problems, such as discoloration of the titanium surfaces, unpleasant metal taste, decrease of clasp retention, tendency for plaque to adhere to the surface, detachment of the denture base resin, and severe wear of titanium teeth, have gradually been resolved. Titanium RPD frameworks have never been reported to fail catastrophically. Thus, titanium is recommended as protection against metal allergy, particularly for large-sized prostheses such as RPDs or complete dentures.

Active site densities, oxygen activation and adsorbed reactive oxygen in alcohol activation on npAu catalysts

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

Wang, Lu-Cun; Friend, C. M.; Fushimi, Rebecca

2016-01-01

The activation of molecular O 2as well as the reactivity of adsorbed oxygen species is of central importance in aerobic selective oxidation chemistry on Au-based catalysts. Herein, we address the issue of O 2activation on unsupported nanoporous gold (npAu) catalysts by applying a transient pressure technique, a temporal analysis of products (TAP) reactor, to measure the saturation coverage of atomic oxygen, its collisional dissociation probability, the activation barrier for O 2dissociation, and the facility with which adsorbed O species activate methanol, the initial step in the catalytic cycle of esterification. The results from these experiments indicate that molecular O 2dissociationmore » is associated with surface silver, that the density of reactive sites is quite low, that adsorbed oxygen atoms do not spill over from the sites of activation onto the surrounding surface, and that methanol reacts quite facilely with the adsorbed oxygen atoms. In addition, the O species from O 2dissociation exhibits reactivity for the selective oxidation of methanol but not for CO. The TAP experiments also revealed that the surface of the npAu catalyst is saturated with adsorbed O under steady state reaction conditions, at least for the pulse reaction.« less

Preparation and Characterization of Cu and Ni on Alumina Supports and Their Use in the Synthesis of Low-Temperature Metal-Phthalocyanine Using a Parallel-Plate Reactor.

PubMed

Sánchez-De la Torre, Fernando; De la Rosa, Javier Rivera; Kharisov, Boris I; Lucio-Ortiz, Carlos J

2013-09-30

Ni- and Cu/alumina powders were prepared and characterized by X-ray diffraction (XRD), scanning electronic microscope (SEM), and N₂ physisorption isotherms were also determined. The Ni/Al₂O₃ sample reveled agglomerated (1 μm) of nanoparticles of Ni (30-80 nm) however, NiO particles were also identified, probably for the low temperature during the H 2 reduction treatment (350 °C), the Cu/Al₂O₃ sample presented agglomerates (1-1.5 μm) of nanoparticles (70-150 nm), but only of pure copper. Both surface morphologies were different, but resulted in mesoporous material, with a higher specificity for the Ni sample. The surfaces were used in a new proposal for producing copper and nickel phthalocyanines using a parallel-plate reactor. Phthalonitrile was used and metallic particles were deposited on alumina in ethanol solution with CH₃ONa at low temperatures; ≤60 °C. The mass-transfer was evaluated in reaction testing with a recent three-resistance model. The kinetics were studied with a Langmuir-Hinshelwood model. The activation energy and Thiele modulus revealed a slow surface reaction. The nickel sample was the most active, influenced by the NiO morphology and phthalonitrile adsorption.

Communication: Reactivity borrowing in the mode selective chemistry of H + CHD3 → H2 + CD3

NASA Astrophysics Data System (ADS)

Ellerbrock, Roman; Manthe, Uwe

2017-12-01

Quantum state-resolved reaction probabilities for the H + CHD3 → H2 + CD3 reaction are calculated by accurate full-dimensional quantum dynamics calculations using the multi-layer multi-configurational time-dependent Hartree approach and the quantum transition state concept. Reaction probabilities of various ro-vibrational states of the CHD3 reactant are investigated for vanishing total angular momentum. While the reactivity of the different vibrational states of CHD3 mostly follows intuitive patterns, an unusually large reaction probability is found for CHD3 molecules triply excited in the CD3 umbrella-bending vibration. This surprising reactivity can be explained by a Fermi resonance-type mixing of the single CH-stretch excited and the triple CD3 umbrella-bend excited vibrational states of CHD3. These findings show that resonant energy transfer can significantly affect the mode-selective chemistry of CHD3 and result in counter-intuitive reactivity patterns.

Adaptively biased sequential importance sampling for rare events in reaction networks with comparison to exact solutions from finite buffer dCME method

PubMed Central

Cao, Youfang; Liang, Jie

2013-01-01

Critical events that occur rarely in biological processes are of great importance, but are challenging to study using Monte Carlo simulation. By introducing biases to reaction selection and reaction rates, weighted stochastic simulation algorithms based on importance sampling allow rare events to be sampled more effectively. However, existing methods do not address the important issue of barrier crossing, which often arises from multistable networks and systems with complex probability landscape. In addition, the proliferation of parameters and the associated computing cost pose significant problems. Here we introduce a general theoretical framework for obtaining optimized biases in sampling individual reactions for estimating probabilities of rare events. We further describe a practical algorithm called adaptively biased sequential importance sampling (ABSIS) method for efficient probability estimation. By adopting a look-ahead strategy and by enumerating short paths from the current state, we estimate the reaction-specific and state-specific forward and backward moving probabilities of the system, which are then used to bias reaction selections. The ABSIS algorithm can automatically detect barrier-crossing regions, and can adjust bias adaptively at different steps of the sampling process, with bias determined by the outcome of exhaustively generated short paths. In addition, there are only two bias parameters to be determined, regardless of the number of the reactions and the complexity of the network. We have applied the ABSIS method to four biochemical networks: the birth-death process, the reversible isomerization, the bistable Schlögl model, and the enzymatic futile cycle model. For comparison, we have also applied the finite buffer discrete chemical master equation (dCME) method recently developed to obtain exact numerical solutions of the underlying discrete chemical master equations of these problems. This allows us to assess sampling results objectively by comparing simulation results with true answers. Overall, ABSIS can accurately and efficiently estimate rare event probabilities for all examples, often with smaller variance than other importance sampling algorithms. The ABSIS method is general and can be applied to study rare events of other stochastic networks with complex probability landscape. PMID:23862966

Adaptively biased sequential importance sampling for rare events in reaction networks with comparison to exact solutions from finite buffer dCME method

NASA Astrophysics Data System (ADS)

Cao, Youfang; Liang, Jie

2013-07-01

Critical events that occur rarely in biological processes are of great importance, but are challenging to study using Monte Carlo simulation. By introducing biases to reaction selection and reaction rates, weighted stochastic simulation algorithms based on importance sampling allow rare events to be sampled more effectively. However, existing methods do not address the important issue of barrier crossing, which often arises from multistable networks and systems with complex probability landscape. In addition, the proliferation of parameters and the associated computing cost pose significant problems. Here we introduce a general theoretical framework for obtaining optimized biases in sampling individual reactions for estimating probabilities of rare events. We further describe a practical algorithm called adaptively biased sequential importance sampling (ABSIS) method for efficient probability estimation. By adopting a look-ahead strategy and by enumerating short paths from the current state, we estimate the reaction-specific and state-specific forward and backward moving probabilities of the system, which are then used to bias reaction selections. The ABSIS algorithm can automatically detect barrier-crossing regions, and can adjust bias adaptively at different steps of the sampling process, with bias determined by the outcome of exhaustively generated short paths. In addition, there are only two bias parameters to be determined, regardless of the number of the reactions and the complexity of the network. We have applied the ABSIS method to four biochemical networks: the birth-death process, the reversible isomerization, the bistable Schlögl model, and the enzymatic futile cycle model. For comparison, we have also applied the finite buffer discrete chemical master equation (dCME) method recently developed to obtain exact numerical solutions of the underlying discrete chemical master equations of these problems. This allows us to assess sampling results objectively by comparing simulation results with true answers. Overall, ABSIS can accurately and efficiently estimate rare event probabilities for all examples, often with smaller variance than other importance sampling algorithms. The ABSIS method is general and can be applied to study rare events of other stochastic networks with complex probability landscape.

Adaptively biased sequential importance sampling for rare events in reaction networks with comparison to exact solutions from finite buffer dCME method.

PubMed

Cao, Youfang; Liang, Jie

2013-07-14

Critical events that occur rarely in biological processes are of great importance, but are challenging to study using Monte Carlo simulation. By introducing biases to reaction selection and reaction rates, weighted stochastic simulation algorithms based on importance sampling allow rare events to be sampled more effectively. However, existing methods do not address the important issue of barrier crossing, which often arises from multistable networks and systems with complex probability landscape. In addition, the proliferation of parameters and the associated computing cost pose significant problems. Here we introduce a general theoretical framework for obtaining optimized biases in sampling individual reactions for estimating probabilities of rare events. We further describe a practical algorithm called adaptively biased sequential importance sampling (ABSIS) method for efficient probability estimation. By adopting a look-ahead strategy and by enumerating short paths from the current state, we estimate the reaction-specific and state-specific forward and backward moving probabilities of the system, which are then used to bias reaction selections. The ABSIS algorithm can automatically detect barrier-crossing regions, and can adjust bias adaptively at different steps of the sampling process, with bias determined by the outcome of exhaustively generated short paths. In addition, there are only two bias parameters to be determined, regardless of the number of the reactions and the complexity of the network. We have applied the ABSIS method to four biochemical networks: the birth-death process, the reversible isomerization, the bistable Schlögl model, and the enzymatic futile cycle model. For comparison, we have also applied the finite buffer discrete chemical master equation (dCME) method recently developed to obtain exact numerical solutions of the underlying discrete chemical master equations of these problems. This allows us to assess sampling results objectively by comparing simulation results with true answers. Overall, ABSIS can accurately and efficiently estimate rare event probabilities for all examples, often with smaller variance than other importance sampling algorithms. The ABSIS method is general and can be applied to study rare events of other stochastic networks with complex probability landscape.

Optimal reconstruction of the folding landscape using differential energy surface analysis

NASA Astrophysics Data System (ADS)

La Porta, Arthur; Denesyuk, Natalia A.; de Messieres, Michel

2013-03-01

In experiments and in simulations, the free energy of a state of a system can be determined from the probability that the state is occupied. However, it is often necessary to impose a biasing potential on the system so that high energy states are sampled with sufficient frequency. The unbiased energy is typically obtained from the data using the weighted histogram analysis method (WHAM). Here we present differential energy surface analysis (DESA), in which the gradient of the energy surface, dE/dx, is extracted from data taken with a series of harmonic biasing potentials. It is shown that DESA produces a maximum likelihood estimate of the folding landscape gradient. DESA is demonstrated by analyzing data from a simulated system as well as data from a single-molecule unfolding experiment in which the end-to-end distance of a DNA hairpin is measured. It is shown that the energy surface obtained from DESA is indistinguishable from the energy surface obtained when WHAM is applied to the same data. Two criteria are defined which indicate whether the DESA results are self-consistent. It is found that these criteria can detect a situation where the energy is not a single-valued function of the measured reaction coordinate. The criteria were found to be satisfied for the experimental data analyzed, confirming that end-to-end distance is a good reaction coordinate for the experimental system. The combination of DESA and the optical trap assay in which a structure is disrupted under harmonic constraint facilitates an extremely accurate measurement of the folding energy surface.

An ab initio study of the potential energy surface in the S 1 state of 2-hydroxypyridine

NASA Astrophysics Data System (ADS)

Sobolewski, Andrzej L.; Adamowicz, Ludwik

1996-12-01

The potential energy (PE) surface of the lowest excited singlet state relevant to the photophysics of interconversion of the 2-hydroxypyridine/2 (1H)-pyridinone (2HP/2PY) system is characterized by ab initio calculations. The geometry optimizations in the S 1 state performed at the CIS/6-31G (d,p) level confirm the experimental findings that the 2HP form is planar in this state whereas the 2PY form is significantly out-of-plane distorted. The lowest-energy first-order saddle-points which are relevant to the photophysics of the "mobile" hydrogen atom on the S 1 PE surface lead toward its dissociation from the molecule. There is no saddle-point for a "direct" proton transfer reaction on the S 1 PE surface leading from the 2HP form to the 2PY form. The results confirm the hypothesis that the photo-induced dissociation-association (PIDA) mechanism is probably responsible for the excited-state tautomerization observed in this system.

Quasi-classical trajectory study of the role of vibrational and translational energy in the Cl(2P) + NH3 reaction.

PubMed

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

2012-05-28

A detailed state-to-state dynamics study was performed to analyze the effects of vibrational excitation and translational energy on the dynamics of the Cl((2)P) + NH(3)(v) gas-phase reaction, effects which are connected to such issues as mode selectivity and Polanyi's rules. This reaction evolves along two deep wells in the entry and exit channels. At low and high collision energies quasi-classical trajectory calculations were performed on an analytical potential energy surface previously developed by our group, together with a simplified model surface in which the reactant well is removed to analyze the influence of this well. While at high energy the independent vibrational excitation of all NH(3)(v) modes increases the reactivity by a factor ≈1.1-2.9 with respect to the vibrational ground-state, at low energy the opposite behaviour is found (factor ≈ 0.4-0.9). However, when the simplified model surface is used at low energy the independent vibrational excitation of all NH(3)(v) modes increases the reactivity, showing that the behaviour at low energies is a direct consequence of the existence of the reactant well. Moreover, we find that this reaction exhibits negligible mode selectivity, first because the independent excitation of the N-H symmetric and asymmetric stretch modes, which lie within 200 cm(-1) of each other, leads to reactions with similar reaction probabilities, and second because the vibrational excitation of the reactive N-H stretch mode is only partially retained in the products. For this "late transition-state" reaction, we also find that vibrational energy is more effective in driving the reaction than an equivalent amount of energy in translation, consistent with an extension of Polanyi's rules. Finally, we find that the non-reactive events, Cl((2)P)+NH(3)(v) → Cl((2)P) + NH(3)(v'), lead to a great number of populated vibrational states in the NH(3)(v') product, even starting from the NH(3)(v = 0) vibrational ground state at low energies, which is unphysical in a quantum world. This result is interpreted on the basis of non-conservation of the ZPE per mode.

Lattice based Kinetic Monte Carlo Simulations of a complex chemical reaction network

NASA Astrophysics Data System (ADS)

Danielson, Thomas; Savara, Aditya; Hin, Celine

Lattice Kinetic Monte Carlo (KMC) simulations offer a powerful alternative to using ordinary differential equations for the simulation of complex chemical reaction networks. Lattice KMC provides the ability to account for local spatial configurations of species in the reaction network, resulting in a more detailed description of the reaction pathway. In KMC simulations with a large number of reactions, the range of transition probabilities can span many orders of magnitude, creating subsets of processes that occur more frequently or more rarely. Consequently, processes that have a high probability of occurring may be selected repeatedly without actually progressing the system (i.e. the forward and reverse process for the same reaction). In order to avoid the repeated occurrence of fast frivolous processes, it is necessary to throttle the transition probabilities in such a way that avoids altering the overall selectivity. Likewise, as the reaction progresses, new frequently occurring species and reactions may be introduced, making a dynamic throttling algorithm a necessity. We present a dynamic steady-state detection scheme with the goal of accurately throttling rate constants in order to optimize the KMC run time without compromising the selectivity of the reaction network. The algorithm has been applied to a large catalytic chemical reaction network, specifically that of methanol oxidative dehydrogenation, as well as additional pathways on CeO2(111) resulting in formaldehyde, CO, methanol, CO2, H2 and H2O as gas products.

Modeling the Non-Equilibrium Process of the Chemical Adsorption of Ammonia on GaN(0001) Reconstructed Surfaces Based on Steepest-Entropy-Ascent Quantum Thermodynamics.

PubMed

Kusaba, Akira; Li, Guanchen; von Spakovsky, Michael R; Kangawa, Yoshihiro; Kakimoto, Koichi

2017-08-15

Clearly understanding elementary growth processes that depend on surface reconstruction is essential to controlling vapor-phase epitaxy more precisely. In this study, ammonia chemical adsorption on GaN(0001) reconstructed surfaces under metalorganic vapor phase epitaxy (MOVPE) conditions (3Ga-H and N ad -H + Ga-H on a 2 × 2 unit cell) is investigated using steepest-entropy-ascent quantum thermodynamics (SEAQT). SEAQT is a thermodynamic-ensemble based, first-principles framework that can predict the behavior of non-equilibrium processes, even those far from equilibrium where the state evolution is a combination of reversible and irreversible dynamics. SEAQT is an ideal choice to handle this problem on a first-principles basis since the chemical adsorption process starts from a highly non-equilibrium state. A result of the analysis shows that the probability of adsorption on 3Ga-H is significantly higher than that on N ad -H + Ga-H. Additionally, the growth temperature dependence of these adsorption probabilities and the temperature increase due to the heat of reaction is determined. The non-equilibrium thermodynamic modeling applied can lead to better control of the MOVPE process through the selection of preferable reconstructed surfaces. The modeling also demonstrates the efficacy of DFT-SEAQT coupling for determining detailed non-equilibrium process characteristics with a much smaller computational burden than would be entailed with mechanics-based, microscopic-mesoscopic approaches.

Modeling the Non-Equilibrium Process of the Chemical Adsorption of Ammonia on GaN(0001) Reconstructed Surfaces Based on Steepest-Entropy-Ascent Quantum Thermodynamics

PubMed Central

Kusaba, Akira; von Spakovsky, Michael R.; Kangawa, Yoshihiro; Kakimoto, Koichi

2017-01-01

Clearly understanding elementary growth processes that depend on surface reconstruction is essential to controlling vapor-phase epitaxy more precisely. In this study, ammonia chemical adsorption on GaN(0001) reconstructed surfaces under metalorganic vapor phase epitaxy (MOVPE) conditions (3Ga-H and Nad-H + Ga-H on a 2 × 2 unit cell) is investigated using steepest-entropy-ascent quantum thermodynamics (SEAQT). SEAQT is a thermodynamic-ensemble based, first-principles framework that can predict the behavior of non-equilibrium processes, even those far from equilibrium where the state evolution is a combination of reversible and irreversible dynamics. SEAQT is an ideal choice to handle this problem on a first-principles basis since the chemical adsorption process starts from a highly non-equilibrium state. A result of the analysis shows that the probability of adsorption on 3Ga-H is significantly higher than that on Nad-H + Ga-H. Additionally, the growth temperature dependence of these adsorption probabilities and the temperature increase due to the heat of reaction is determined. The non-equilibrium thermodynamic modeling applied can lead to better control of the MOVPE process through the selection of preferable reconstructed surfaces. The modeling also demonstrates the efficacy of DFT-SEAQT coupling for determining detailed non-equilibrium process characteristics with a much smaller computational burden than would be entailed with mechanics-based, microscopic-mesoscopic approaches. PMID:28809816

Activation energy for diamond growth from the carbon-hydrogen gas system at low substrate temperatures

NASA Astrophysics Data System (ADS)

Stiegler, J.; Lang, T.; von Kaenel, Y.; Michler, J.; Blank, E.

1997-01-01

The growth kinetics of diamond films deposited at low substrate temperatures (600-400 °C) from the carbon-hydrogen gas system have been studied. When the substrate temperature alone was varied, independently of all other process parameters in the microwave plasma reactor, an activation energy in the order of 7 kcal/mol was observed. This value did not change with different carbon concentrations in hydrogen. It is supposed that growth kinetics in this temperature range are controlled by a single chemical reaction, probably the abstraction of surface bonded hydrogen by gas phase atomic hydrogen.

Hydrogenated amorphous silicon formation by flux control and hydrogen effects on the growth mechanism

NASA Astrophysics Data System (ADS)

Toyoda, H.; Sugai, H.; Kato, K.; Yoshida, A.; Okuda, T.

1986-06-01

The composition of particle flux to deposit hydrogenated amorphous silicon films in a glow discharge is controlled by a combined electrostatic-magnetic deflection technique. As a result, the films are formed firstly without hydrogen ion flux, secondly by neutral flux only, and thirdly by all species fluxes. Comparison of these films reveals the significant role of hydrogen in the surface reactions. Hydrogen breaks the Si-Si bond, decreases the sticking probability of the Si atom, and replaces the SiH bond by a SiH2 bond to increase the hydrogen content of the films.

H2 formation on interstellar dust grains: The viewpoints of theory, experiments, models and observations

NASA Astrophysics Data System (ADS)

Wakelam, Valentine; Bron, Emeric; Cazaux, Stephanie; Dulieu, Francois; Gry, Cécile; Guillard, Pierre; Habart, Emilie; Hornekær, Liv; Morisset, Sabine; Nyman, Gunnar; Pirronello, Valerio; Price, Stephen D.; Valdivia, Valeska; Vidali, Gianfranco; Watanabe, Naoki

2017-12-01

Molecular hydrogen is the most abundant molecule in the universe. It is the first one to form and survive photo-dissociation in tenuous environments. Its formation involves catalytic reactions on the surface of interstellar grains. The micro-physics of the formation process has been investigated intensively in the last 20 years, in parallel of new astrophysical observational and modeling progresses. In the perspectives of the probable revolution brought by the future satellite JWST, this article has been written to present what we think we know about the H2 formation in a variety of interstellar environments.

Investigation of possibility of surface rupture derived from PFDHA and calculation of surface displacement based on dislocation

NASA Astrophysics Data System (ADS)

Inoue, N.; Kitada, N.; Irikura, K.

2013-12-01

A probability of surface rupture is important to configure the seismic source, such as area sources or fault models, for a seismic hazard evaluation. In Japan, Takemura (1998) estimated the probability based on the historical earthquake data. Kagawa et al. (2004) evaluated the probability based on a numerical simulation of surface displacements. The estimated probability indicates a sigmoid curve and increases between Mj (the local magnitude defined and calculated by Japan Meteorological Agency) =6.5 and Mj=7.0. The probability of surface rupture is also used in a probabilistic fault displacement analysis (PFDHA). The probability is determined from the collected earthquake catalog, which were classified into two categories: with surface rupture or without surface rupture. The logistic regression is performed for the classified earthquake data. Youngs et al. (2003), Ross and Moss (2011) and Petersen et al. (2011) indicate the logistic curves of the probability of surface rupture by normal, reverse and strike-slip faults, respectively. Takao et al. (2013) shows the logistic curve derived from only Japanese earthquake data. The Japanese probability curve shows the sharply increasing in narrow magnitude range by comparison with other curves. In this study, we estimated the probability of surface rupture applying the logistic analysis to the surface displacement derived from a surface displacement calculation. A source fault was defined in according to the procedure of Kagawa et al. (2004), which determined a seismic moment from a magnitude and estimated the area size of the asperity and the amount of slip. Strike slip and reverse faults were considered as source faults. We applied Wang et al. (2003) for calculations. The surface displacements with defined source faults were calculated by varying the depth of the fault. A threshold value as 5cm of surface displacement was used to evaluate whether a surface rupture reach or do not reach to the surface. We carried out the logistic regression analysis to the calculated displacements, which were classified by the above threshold. The estimated probability curve indicated the similar trend to the result of Takao et al. (2013). The probability of revere faults is larger than that of strike slip faults. On the other hand, PFDHA results show different trends. The probability of reverse faults at higher magnitude is lower than that of strike slip and normal faults. Ross and Moss (2011) suggested that the sediment and/or rock over the fault compress and not reach the displacement to the surface enough. The numerical theory applied in this study cannot deal with a complex initial situation such as topography.

Modeling of enhanced catalysis in multienzyme nanostructures: effect of molecular scaffolds, spatial organization, and concentration.

PubMed

Roberts, Christopher C; Chang, Chia-en A

2015-01-13

Colocalized multistep enzymatic reaction pathways within biological catabolic and metabolic processes occur with high yield and specificity. Spatial organization on membranes or surfaces may be associated with increased efficiency of intermediate substrate transfer. Using a new Brownian dynamics package, GeomBD, we explored the geometric features of a surface-anchored enzyme system by parallel coarse-grained Brownian dynamics simulations of substrate diffusion over microsecond (μs) to millisecond (ms) time scales. We focused on a recently developed glucose oxidase (GOx), horseradish peroxidase (HRP), and DNA origami-scaffold enzyme system, where the H2O2 substrate of HRP is produced by GOx. The results revealed and explained a significant advantage in catalytic enhancement by optimizing interenzyme distance and orientation in the presence of the scaffold model. The planar scaffold colocalized the enzymes and provided a diffusive barrier that enhanced substrate transfer probability, becoming more relevant with increasing interenzyme distance. The results highlight the importance of protein geometry in the proper assessment of distance and orientation dependence on the probability of substrate transfer. They shed light on strategies for engineering multienzyme complexes and further investigation of enhanced catalytic efficiency for substrate diffusion between membrane-anchoring proteins.

Statistical methods for thermonuclear reaction rates and nucleosynthesis simulations

NASA Astrophysics Data System (ADS)

Iliadis, Christian; Longland, Richard; Coc, Alain; Timmes, F. X.; Champagne, Art E.

2015-03-01

Rigorous statistical methods for estimating thermonuclear reaction rates and nucleosynthesis are becoming increasingly established in nuclear astrophysics. The main challenge being faced is that experimental reaction rates are highly complex quantities derived from a multitude of different measured nuclear parameters (e.g., astrophysical S-factors, resonance energies and strengths, particle and γ-ray partial widths). We discuss the application of the Monte Carlo method to two distinct, but related, questions. First, given a set of measured nuclear parameters, how can one best estimate the resulting thermonuclear reaction rates and associated uncertainties? Second, given a set of appropriate reaction rates, how can one best estimate the abundances from nucleosynthesis (i.e., reaction network) calculations? The techniques described here provide probability density functions that can be used to derive statistically meaningful reaction rates and final abundances for any desired coverage probability. Examples are given for applications to s-process neutron sources, core-collapse supernovae, classical novae, and Big Bang nucleosynthesis.

An operando Raman study of molecular structure and reactivity of molybdenum(VI) oxide supported on anatase for the oxidative dehydrogenation of ethane.

PubMed

Tsilomelekis, George; Boghosian, Soghomon

2012-02-21

Supported molybdenum oxide catalysts on TiO(2) (anatase) with surface densities in the range of 1.8-17.0 Mo per nm(2) were studied at temperatures of 410-480 °C for unraveling the configuration and molecular structure of the deposited (MoO(x))(n) species and examining their behavior for the ethane oxidative dehydrogenation (ODH). In situ Raman and in situ FTIR spectra under oxidizing conditions combined with (18)O/(16)O isotope exchange studies provide the first sound evidence for mono-oxo configuration for the deposited (MoO(x))(n) species on anatase. Isolated O=Mo(-O-)(3) tetra-coordinated species in C(3v)-like symmetry prevail at all surface coverages with a low presence of associated (polymeric) species (probably penta-coordinated) evidenced at high coverages, below the approximate monolayer of 6 Mo per nm(2). A mechanistic scenario for (18)O/(16)O isotope exchange and next-nearest-neighbor vibrational isotope effect is proposed at the molecular level to account for the pertinent spectral observations. Catalytic measurements for ethane ODH with simultaneous monitoring of operando Raman spectra were performed. The selectivity to ethylene increases with increasing surface density up to the monolayer coverage, where primary steps of ethane activation follow selective reaction pathways leading to ∼100% C(2)H(4) selectivity. The operando Raman spectra and a quantitative exploitation of the relative normalized Mo=O band intensities for surface densities of 1.8-5.9 Mo per nm(2) and various residence times show that the terminal Mo=O sites are involved in non-selective reaction turnovers. Reaction routes follow primarily non-selective pathways at low coverage and selective pathways at high coverage. Trends in the initial rates of ethane consumption (apparent reactivity per Mo) as a function of Mo surface density are discussed on the basis of several factors.

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

PubMed

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

2012-09-07

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

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

NASA Astrophysics Data System (ADS)

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

2012-09-01

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

Effects of surface motion and electron-hole pair excitations in CO2 dissociation and scattering on Ni(100)

NASA Astrophysics Data System (ADS)

Luo, Xuan; Zhou, Xueyao; Jiang, Bin

2018-05-01

The energy transfer between different channels is an important aspect in chemical reactions at surfaces. We investigate here in detail the energy transfer dynamics in a prototypical system, i.e., reactive and nonreactive scattering of CO2 on Ni(100), which is related to heterogeneous catalytic processes with Ni-based catalysts for CO2 reduction. On the basis of our earlier nine-dimensional potential energy surface for CO2/Ni(100), dynamical calculations have been done using the generalized Langevin oscillator (GLO) model combined with local density friction approximation (LDFA), in which the former accounts for the surface motion and the latter accounts for the low-energy electron-hole pair (EHP) excitation. In spite of its simplicity, it is found that the GLO model yields quite satisfactory results, including the significant energy loss and product energy disposal, trapping, and steering dynamics, all of which agree well with the ab initio molecular dynamics ones where many surface atoms are explicitly involved with high computational cost. However, the GLO model fails to describe the reactivity enhancement due to the lattice motion because it intrinsically does not incorporate the variance of barrier height on the surface atom displacement. On the other hand, in LDFA, the energy transferred to EHPs is found to play a minor role and barely alter the dynamics, except for slightly reducing the dissociation probabilities. In addition, vibrational state-selected dissociative sticking probabilities are calculated and previously observed strong mode specificity is confirmed. Our work suggests that further improvement of the GLO model is needed to consider the lattice-induced barrier lowering.

Measurement of 240Pu Angular Momentum Dependent Fission Probabilities Using the (α ,α') Reaction

NASA Astrophysics Data System (ADS)

Koglin, Johnathon; Burke, Jason; Fisher, Scott; Jovanovic, Igor

2017-09-01

The surrogate reaction method often lacks the theoretical framework and necessary experimental data to constrain models especially when rectifying differences between angular momentum state differences between the desired and surrogate reaction. In this work, dual arrays of silicon telescope particle identification detectors and photovoltaic (solar) cell fission fragment detectors have been used to measure the fission probability of the 240Pu(α ,α' f) reaction - a surrogate for the 239Pu(n , f) - and fission fragment angular distributions. Fission probability measurements were performed at a beam energy of 35.9(2) MeV at eleven scattering angles from 40° to 140°e in 10° intervals and at nuclear excitation energies up to 16 MeV. Fission fragment angular distributions were measured in six bins from 4.5 MeV to 8.0 MeV and fit to expected distributions dependent on the vibrational and rotational excitations at the saddle point. In this way, the contributions to the total fission probability from specific states of K angular momentum projection on the symmetry axis are extracted. A sizable data collection is presented to be considered when constraining microscopic cross section calculations.

Early anaerobic metabolisms

PubMed Central

Canfield, Don E; Rosing, Minik T; Bjerrum, Christian

2006-01-01

Before the advent of oxygenic photosynthesis, the biosphere was driven by anaerobic metabolisms. We catalogue and quantify the source strengths of the most probable electron donors and electron acceptors that would have been available to fuel early-Earth ecosystems. The most active ecosystems were probably driven by the cycling of H2 and Fe2+ through primary production conducted by anoxygenic phototrophs. Interesting and dynamic ecosystems would have also been driven by the microbial cycling of sulphur and nitrogen species, but their activity levels were probably not so great. Despite the diversity of potential early ecosystems, rates of primary production in the early-Earth anaerobic biosphere were probably well below those rates observed in the marine environment. We shift our attention to the Earth environment at 3.8 Gyr ago, where the earliest marine sediments are preserved. We calculate, consistent with the carbon isotope record and other considerations of the carbon cycle, that marine rates of primary production at this time were probably an order of magnitude (or more) less than today. We conclude that the flux of reduced species to the Earth surface at this time may have been sufficient to drive anaerobic ecosystems of sufficient activity to be consistent with the carbon isotope record. Conversely, an ecosystem based on oxygenic photosynthesis was also possible with complete removal of the oxygen by reaction with reduced species from the mantle. PMID:17008221

Determination of Martian soil mineralogy and water content using the Thermal Analyzer for Planetary Soils (TAPS)

NASA Technical Reports Server (NTRS)

Gooding, James L.; Ming, Douglas W.; Allton, Judith H.; Byers, Terry B.; Dunn, Robert P.; Gibbons, Frank L.; Pate, Daniel B.; Polette, Thomas M.

1992-01-01

Physical and chemical interactions between the surface and atmosphere of Mars can be expected to embody a strong cause-and-effect relationship with the minerals comprising the martian regolith. Many of the minerals in soils and sediments are probably products of chemical weathering (involving surface/atmosphere or surface/hydrosphere reactions) that could be expected to subsequently influence the sorption of atmospheric gases and water vapor. Therefore, identification of the minerals in martian surface soils and sediments is essential for understanding both past and present interactions between the Mars surface and atmosphere. Clearly, the most definitive mineral analyses would be achieved with well-preserved samples returned to Earth-based laboratories. In advance of a Mars sample return mission, however, significant progress could be made with in situ experiments that fill current voids in knowledge about the presence or abundance of key soil minerals such as clays (layered-structured silicates), zeolites, and various salts, including carbonates. TAPS is intended to answer that challenge by providing first-order identification of soil and sediment minerals.

Remarkable nanoconfinement effects on chemical equilibrium manifested in nucleotide dimerization and H-D exchange reactions.

PubMed

Polak, Micha; Rubinovich, Leonid

2011-10-06

Nanoconfinement entropic effects on chemical equilibrium involving a small number of molecules, which we term NCECE, are revealed by two widely diverse types of reactions. Employing statistical-mechanical principles, we show how the NCECE effect stabilizes nucleotide dimerization observed within self-assembled molecular cages. Furthermore, the effect provides the basis for dimerization even under an aqueous environment inside the nanocage. Likewise, the NCECE effect is pertinent to a longstanding issue in astrochemistry, namely the extra deuteration commonly observed for molecules reacting on interstellar dust grain surfaces. The origin of the NCECE effect is elucidated by means of the probability distributions of the reaction extent and related variations in the reactant-product mixing entropy. Theoretical modelling beyond our previous preliminary work highlights the role of the nanospace size in addition to that of the nanosystem size, namely the limited amount of molecules in the reaction mixture. Furthermore, the NCECE effect can depend also on the reaction mechanism, and on deviations from stoichiometry. The NCECE effect, leading to enhanced, greatly variable equilibrium "constants", constitutes a unique physical-chemical phenomenon, distinguished from the usual thermodynamical properties of macroscopically large systems. Being significant particularly for weakly exothermic reactions, the effects should stabilize products in other closed nanoscale structures, and thus can have notable implications for the growing nanotechnological utilization of chemical syntheses conducted within confined nanoreactors.

Modeling Cl2/O2/Ar inductively coupled plasmas used for silicon etching: effects of SiO2 chamber wall coating

NASA Astrophysics Data System (ADS)

Tinck, S.; Boullart, W.; Bogaerts, A.

2011-08-01

In this paper, simulations are performed to gain a better insight into the properties of a Cl2/Ar plasma, with and without O2, during plasma etching of Si. Both plasma and surface properties are calculated in a self-consistent manner. Special attention is paid to the behavior of etch products coming from the wafer or the walls, and how the chamber walls can affect the plasma and the resulting etch process. Two modeling cases are considered. In the first case, the reactor walls are defined as clean (Al2O3), whereas in the second case a SiO2 coating is introduced on the reactor walls before the etching process, so that oxygen will be sputtered from the walls and introduced into the plasma. For this reason, a detailed reaction set is presented for a Cl2/O2/Ar plasma containing etched species, as well as an extensive reaction set for surface processes, including physical and chemical sputtering, chemical etching and deposition processes. Density and flux profiles of various species are presented for a better understanding of the bulk plasma during the etching process. Detailed information is also given on the composition of the surfaces at various locations of the reactor, on the etch products in the plasma and on the surface loss probabilities of the plasma species at the walls, with different compositions. It is found that in the clean chamber, walls are mostly chlorinated (Al2Cl3), with a thin layer of etch products residing on the wall. In the coated chamber, an oxy-chloride layer is grown on the walls for a few nanometers during the etching process. The Cl atom wall loss probability is found to decrease significantly in the coated chamber, hence increasing the etch rate. SiCl2, SiCl4 and SiCl3 are found to be the main etch products in the plasma, with the fraction of SiCl2 being always slightly higher. The simulation results compare well with experimental data available from the literature.

Communication: Mechanochemical fluctuation theorem and thermodynamics of self-phoretic motors

NASA Astrophysics Data System (ADS)

Gaspard, Pierre; Kapral, Raymond

2017-12-01

Microscopic dynamical aspects of the propulsion of nanomotors by self-phoretic mechanisms are considered. Propulsion by self-diffusiophoresis relies on the mechanochemical coupling between the fluid velocity field and the concentration fields induced by asymmetric catalytic reactions on the motor surface. The consistency between the thermodynamics of this coupling and the microscopic reversibility of the underlying molecular dynamics is investigated. For this purpose, a mechanochemical fluctuation theorem for the joint probability to find the motor at position r after n reactive events have occurred during the time interval t is derived, starting from coupled Langevin equations for the translational, rotational, and chemical fluctuations of self-phoretic motors. An important result that follows from this analysis is the identification of an effect that is reciprocal to self-propulsion by diffusiophoresis, which leads to a dependence of the reaction rate on the value of an externally applied force.

Theoretical investigation of exchange and recombination reactions in O(3P)+NO(2Π) collisions

NASA Astrophysics Data System (ADS)

Ivanov, M. V.; Zhu, H.; Schinke, R.

2007-02-01

We present a detailed dynamical study of the kinetics of O(P3)+NO(Π2) collisions including O atom exchange reactions and the recombination of NO2. The classical trajectory calculations are performed on the lowest A'2 and A″2 potential energy surfaces, which were calculated by ab initio methods. The calculated room temperature exchange reaction rate coefficient, kex, is in very good agreement with the measured one. The high-pressure recombination rate coefficient, which is given by the formation rate coefficient and to a good approximation equals 2kex, overestimates the experimental data by merely 20%. The pressure dependence of the recombination rate, kr, is described within the strong-collision model by assigning a stabilization probability to each individual trajectory. The measured falloff curve is well reproduced over five orders of magnitude by a single parameter, i.e., the strong-collision stabilization frequency. The calculations also yield the correct temperature dependence, kr∝T-1.5, of the low-pressure recombination rate coefficient. The dependence of the rate coefficients on the oxygen isotopes are investigated by incorporating the difference of the zero-point energies between the reactant and product NO radicals, ΔZPE, into the potential energy surface. Similar isotope effects as for ozone are predicted for both the exchange reaction and the recombination. Finally, we estimate that the chaperon mechanism is not important for the recombination of NO2, which is in accord with the overall T-1.4 dependence of the measured recombination rate even in the low temperature range.

Army ants algorithm for rare event sampling of delocalized nonadiabatic transitions by trajectory surface hopping and the estimation of sampling errors by the bootstrap method.

PubMed

Nangia, Shikha; Jasper, Ahren W; Miller, Thomas F; Truhlar, Donald G

2004-02-22

The most widely used algorithm for Monte Carlo sampling of electronic transitions in trajectory surface hopping (TSH) calculations is the so-called anteater algorithm, which is inefficient for sampling low-probability nonadiabatic events. We present a new sampling scheme (called the army ants algorithm) for carrying out TSH calculations that is applicable to systems with any strength of coupling. The army ants algorithm is a form of rare event sampling whose efficiency is controlled by an input parameter. By choosing a suitable value of the input parameter the army ants algorithm can be reduced to the anteater algorithm (which is efficient for strongly coupled cases), and by optimizing the parameter the army ants algorithm may be efficiently applied to systems with low-probability events. To demonstrate the efficiency of the army ants algorithm, we performed atom-diatom scattering calculations on a model system involving weakly coupled electronic states. Fully converged quantum mechanical calculations were performed, and the probabilities for nonadiabatic reaction and nonreactive deexcitation (quenching) were found to be on the order of 10(-8). For such low-probability events the anteater sampling scheme requires a large number of trajectories ( approximately 10(10)) to obtain good statistics and converged semiclassical results. In contrast by using the new army ants algorithm converged results were obtained by running 10(5) trajectories. Furthermore, the results were found to be in excellent agreement with the quantum mechanical results. Sampling errors were estimated using the bootstrap method, which is validated for use with the army ants algorithm. (c) 2004 American Institute of Physics.

How to Make Data a Blessing to Parametric Uncertainty Quantification and Reduction?

NASA Astrophysics Data System (ADS)

Ye, M.; Shi, X.; Curtis, G. P.; Kohler, M.; Wu, J.

2013-12-01

In a Bayesian point of view, probability of model parameters and predictions are conditioned on data used for parameter inference and prediction analysis. It is critical to use appropriate data for quantifying parametric uncertainty and its propagation to model predictions. However, data are always limited and imperfect. When a dataset cannot properly constrain model parameters, it may lead to inaccurate uncertainty quantification. While in this case data appears to be a curse to uncertainty quantification, a comprehensive modeling analysis may help understand the cause and characteristics of parametric uncertainty and thus turns data into a blessing. In this study, we illustrate impacts of data on uncertainty quantification and reduction using an example of surface complexation model (SCM) developed to simulate uranyl (U(VI)) adsorption. The model includes two adsorption sites, referred to as strong and weak sites. The amount of uranium adsorption on these sites determines both the mean arrival time and the long tail of the breakthrough curves. There is one reaction on the weak site but two reactions on the strong site. The unknown parameters include fractions of the total surface site density of the two sites and surface complex formation constants of the three reactions. A total of seven experiments were conducted with different geochemical conditions to estimate these parameters. The experiments with low initial concentration of U(VI) result in a large amount of parametric uncertainty. A modeling analysis shows that it is because the experiments cannot distinguish the relative adsorption affinity of the strong and weak sites on uranium adsorption. Therefore, the experiments with high initial concentration of U(VI) are needed, because in the experiments the strong site is nearly saturated and the weak site can be determined. The experiments with high initial concentration of U(VI) are a blessing to uncertainty quantification, and the experiments with low initial concentration help modelers turn a curse into a blessing. The data impacts on uncertainty quantification and reduction are quantified using probability density functions of model parameters obtained from Markov Chain Monte Carlo simulation using the DREAM algorithm. This study provides insights to model calibration, uncertainty quantification, experiment design, and data collection in groundwater reactive transport modeling and other environmental modeling.

Rate acceleration of the heterogeneous reaction of ozone with a model alkene at the air-ice interface at low temperatures.

PubMed

Ray, Debajyoti; Malongwe, Joseph K'Ekuboni; Klán, Petr

2013-07-02

The kinetics of the ozonation reaction of 1,1-diphenylethylene (DPE) on the surface of ice grains (also called "artificial snow"), produced by shock-freezing of DPE aqueous solutions or DPE vapor-deposition on pure ice grains, was studied in the temperature range of 268 to 188 K. A remarkable and unexpected increase in the apparent ozonation rates with decreasing temperature was evaluated using the Langmuir-Hinshelwood and Eley-Rideal kinetic models, and by estimating the apparent specific surface area of the ice grains. We suggest that an increase of the number of surface reactive sites, and possibly higher ozone uptake coefficients are responsible for the apparent rate acceleration of DPE ozonation at the air-ice interface at lower temperatures. The increasing number of reactive sites is probably related to the fact that organic molecules are displaced more to the top of a disordered interface (or quasi-liquid) layer on the ice surface, which makes them more accessible to the gas-phase reactants. The effect of NaCl as a cocontaminant on ozonation rates was also investigated. The environmental implications of this phenomenon for natural ice/snow are discussed. DPE was selected as an example of environmentally relevant species which can react with ozone. For typical atmospheric ozone concentrations in polar areas (20 ppbv), we estimated that its half-life on the ice surface would decrease from ∼5 days at 258 K to ∼13 h at 188 K at submonolayer DPE loadings.

Modeling marine oily wastewater treatment by a probabilistic agent-based approach.

PubMed

Jing, Liang; Chen, Bing; Zhang, Baiyu; Ye, Xudong

2018-02-01

This study developed a novel probabilistic agent-based approach for modeling of marine oily wastewater treatment processes. It begins first by constructing a probability-based agent simulation model, followed by a global sensitivity analysis and a genetic algorithm-based calibration. The proposed modeling approach was tested through a case study of the removal of naphthalene from marine oily wastewater using UV irradiation. The removal of naphthalene was described by an agent-based simulation model using 8 types of agents and 11 reactions. Each reaction was governed by a probability parameter to determine its occurrence. The modeling results showed that the root mean square errors between modeled and observed removal rates were 8.73 and 11.03% for calibration and validation runs, respectively. Reaction competition was analyzed by comparing agent-based reaction probabilities, while agents' heterogeneity was visualized by plotting their real-time spatial distribution, showing a strong potential for reactor design and process optimization. Copyright © 2017 Elsevier Ltd. All rights reserved.

Zirconium and Yttrium (p, d) Surrogate Nuclear Reactions: Measurement and determination of gamma-ray probabilities: Experimental Physics Report

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

Burke, J. T.; Hughes, R. O.; Escher, J. E.

This technical report documents the surrogate reaction method and experimental results used to determine the desired neutron induced cross sections of 87Y(n,g) and the known 90Zr(n,g) cross section. This experiment was performed at the STARLiTeR apparatus located at Texas A&M Cyclotron Institute using the K150 Cyclotron which produced a 28.56 MeV proton beam. The proton beam impinged on Y and Zr targets to produce the nuclear reactions 89Y(p,d) 88Y and 92Zr(p,d) 91Zr. Both particle singles data and particle-gamma ray coincident data were measured during the experiment. This data was used to determine the γ-ray probability as a function of energymore » for these reactions. The results for the γ-ray probabilities as a function of energy for both these nuclei are documented here. For completeness, extensive tabulated and graphical results are provided in the appendices.« less

Trapped surfaces and emergent curved space in the Bose-Hubbard model

NASA Astrophysics Data System (ADS)

Caravelli, Francesco; Hamma, Alioscia; Markopoulou, Fotini; Riera, Arnau

2012-02-01

A Bose-Hubbard model on a dynamical lattice was introduced in previous work as a spin system analogue of emergent geometry and gravity. Graphs with regions of high connectivity in the lattice were identified as candidate analogues of spacetime geometries that contain trapped surfaces. We carry out a detailed study of these systems and show explicitly that the highly connected subgraphs trap matter. We do this by solving the model in the limit of no back-reaction of the matter on the lattice, and for states with certain symmetries that are natural for our problem. We find that in this case the problem reduces to a one-dimensional Hubbard model on a lattice with variable vertex degree and multiple edges between the same two vertices. In addition, we obtain a (discrete) differential equation for the evolution of the probability density of particles which is closed in the classical regime. This is a wave equation in which the vertex degree is related to the local speed of propagation of probability. This allows an interpretation of the probability density of particles similar to that in analogue gravity systems: matter inside this analogue system sees a curved spacetime. We verify our analytic results by numerical simulations. Finally, we analyze the dependence of localization on a gradual, rather than abrupt, falloff of the vertex degree on the boundary of the highly connected region and find that matter is localized in and around that region.

Membrane events in the acrosomal reaction of Limulus sperm. Membrane fusion, filament-membrane particle attachment, and the source and formation of new membrane surface

PubMed Central

1979-01-01

The membranes of Limulus (horseshoe crab) sperm were examined before and during the acrosomal reaction by using the technique of freeze- fracturing and thin sectioning. We focused on three areas. First, we examined stages in the fusion of the acrosomal vacuole with the cell surface. Fusion takes place in a particle-free zone which is surrounded by a circlet of particles on the P face of the plasma membrane and an underlying circlet of particles on the P face of the acrosomal vauole membrane. These circlets of particles are present before induction. Up to nine focal points of fusion occur within the particle-free zone. Second, we describe a system of fine filaments, each 30 A in diameter, which lies between the acrosomal vacuole and the plasma membrane. These filaments change their orientation as the vacuole opens, a process that takes place in less than 50 ms. Membrane particles seen on the P face of the acrosomal vacuole membrane change their orientation at the same time and in the same way as do the filaments, thus indicating that the membrane particles and filaments are probably connected. Third, we examined the source and the point of fusion of new membrane needed to cover the acrosomal process. This new membrane is almost certainly derived from the outer nuclear envelope and appears to insert into the plasma membrane in a particle-free area adjacent to an area rich in particles. The latter is the region where the particles are probably connected to the cytoplasmic filaments. The relevance of these observations in relation to the process of fertilization of this fantastic sperm is discussed. PMID:582596

Measurement of Plutonium-240 Angular Momentum Dependent Fission Probabilities Using the Alpha-Alpha' Reaction

NASA Astrophysics Data System (ADS)

Koglin, Johnathon

Accurate nuclear reaction data from a few keV to tens of MeV and across the table of nuclides is essential to a number of applications of nuclear physics, including national security, nuclear forensics, nuclear astrophysics, and nuclear energy. Precise determination of (n, f) and neutron capture cross sections for reactions in high- ux environments are particularly important for a proper understanding of nuclear reactor performance and stellar nucleosynthesis. In these extreme environments reactions on short-lived and otherwise difficult-to-produce isotopes play a significant role in system evolution and provide insights into the types of nuclear processes taking place; a detailed understanding of these processes is necessary to properly determine cross sections far from stability. Indirect methods are often attempted to measure cross sections on isotopes that are difficult to separate in a laboratory setting. Using the surrogate approach, the same compound nucleus from the reaction of interest is created through a "surrogate" reaction on a different isotope and the resulting decay is measured. This result is combined with appropriate reaction theory for compound nucleus population, from which the desired cross sections can be inferred. This method has shown promise, but the theoretical framework often lacks necessary experimental data to constrain models. In this work, dual arrays of silicon telescope particle identification detectors and photovoltaic (solar) cell fission fragment detectors have been used to measure the fission probability of the 240Pu(alpha, alpha'f) reaction - a surrogate for the 239Pu(n, f) - and fission of 35.9(2)MeV at eleven scattering angles from 40° to 140° in 10° intervals and at nuclear excitation energies up to 16MeV. Within experimental uncertainty, the maximum fission probability was observed at the neutron separation energy for each alpha scattering angle. Fission probabilities were separated into five 500 keV bins from 5:5MeV to 8:0MeV and one bin from 4:5MeV to 5:5MeV. Across energy bins the fission probability increases approximately linearly with increasing alpha' scattering angle. At 90° the fission probability increases from 0:069(6) in the lowest energy bin to 0:59(2) in the highest. Likewise, within a single energy bin the fission probability increases with alpha' scattering angle. Within the 6:5MeV and 7:0MeV energy bin, the fission probability increased from 0:41(1) at 60° to 0:81(10) at 140°. Fission fragment angular distributions were also measured integrated over each energy bin. These distributions were fit to theoretical distributions based on combinations of transitional nuclear vibrational and rotational excitations at the saddle point. Contributions from specific K vibrational states were extracted and combined with fission probability measurements to determine the relative fission probability of each state as a function of nuclear excitation energy. Within a given excitation energy bin, it is found that contributions from K states greater than the minimum K = 0 state tend to increase with the increasing alpha' scattering angle. This is attributed to an increase in the transferred angular momentum associated with larger scattering angles. The 90° alpha' scattering angle produced the highest quality results. The relative contributions of K states do not show a discernible trend across the energy spectrum. The energy-binned results confirm existing measurements that place a K = 2 state in the first energy bin with the opening of K = 1 and K = 4 states at energies above 5:5MeV. This experiment represents the first of its kind in which fission probabilities and angular distributions are simultaneously measured at a large number of scattering angles. The acquired fission probability, angular distribution, and K state contribution provide a diverse dataset against which microscopic fission models can be constrained and further the understanding of the properties of the 240Pu fission.

Effect of Coatings on the Uptake Rate and HONO Yield in Heterogeneous Reaction of Soot with NO2

NASA Astrophysics Data System (ADS)

Cruz-Quiñones, M.; Khalizov, A. F.; Zhang, R.

2009-12-01

Heterogeneous reaction of nitrogen dioxide on carbon soot aerosols has been suggested as a possible source of nighttime nitrous acid (HONO) in atmosphere boundary layer. Available laboratory data show significant variability in the measured reaction probabilities and HONO yields, making it difficult to asses the atmospheric significance of this process. Moreover, little is known of how aging of soot aerosol through internal mixing with other atmospheric trace constituents will affect the heterogeneous reactivity and HONO production. In this work, the heterogeneous reaction of NO2 on fresh and aged soot films leading to HONO formation was studied through a series of kinetic uptake experiments and HONO yield measurements. Soot samples were prepared by incomplete combustion of propane and kerosene fuels under lean and rich flame conditions. Experiments were performed in a low-pressure, fast-flow reactor coupled to a chemical ionization mass spectrometer (CIMS), using atmospheric-level NO2 concentrations. Heterogeneous uptake coefficients, γ(geom) and γ(BET), were calculated using geometric and internal BET soot surface areas, respectively. The uptake coefficient and the HONO yield depend on the type of fuel and combustion regime and are the highest for soot samples prepared using rich kerosene flame. Although, the internal surface area of soot measured by BET method is a factor of 50 to 500 larger than the geometric surface area, only the top soot layers are involved in heterogeneous reaction with NO2 as follows from the observed weak dependence of γ(geom) and decrease in γ(BET) with increasing sample mass. Heating the soot samples before exposure to NO2 increases the BET surface area, the HONO yield, and the NO2 uptake coefficient due to the removal of the organic fraction from the soot backbone that unblocks active sites and makes them accessible for physical adsorption and chemical reactions. Our results support the oxidation-reduction mechanism involving adsorptive and reactive centers on soot surface where NO2 is converted into HONO and other products. Coating the soot surface by different materials to simulate atmospheric aging has a strong impact on the reactivity of soot toward NO2. Sulfuric acid coating reduces the uptake coefficient and HONO production by physically blocking the soot active sites and initiating decomposition of HONO in the aqueous acid layer. Furthermore, the HONO yield can be reduced to zero after exposure to elevated relative humidity or partially restored when sulfuric acid is removed by heating. Coatings made of glutaric and succinic acids increase HONO yields and NO2 uptake coefficients, similarly as in the case of pre-heated soot samples. We propose that the organic acids change the top layer morphology, opening up the pores and making the internal soot surface more accessible for heterogeneous interaction with NO2. The implications of our study regarding the contribution of freshly emitted and aged soot aerosols to nighttime HONO production will be discussed.

Single-molecule stochastic times in a reversible bimolecular reaction

NASA Astrophysics Data System (ADS)

Keller, Peter; Valleriani, Angelo

2012-08-01

In this work, we consider the reversible reaction between reactants of species A and B to form the product C. We consider this reaction as a prototype of many pseudobiomolecular reactions in biology, such as for instance molecular motors. We derive the exact probability density for the stochastic waiting time that a molecule of species A needs until the reaction with a molecule of species B takes place. We perform this computation taking fully into account the stochastic fluctuations in the number of molecules of species B. We show that at low numbers of participating molecules, the exact probability density differs from the exponential density derived by assuming the law of mass action. Finally, we discuss the condition of detailed balance in the exact stochastic and in the approximate treatment.

State-resolved differential and integral cross sections for the Ne + H{sub 2}{sup +} (v = 0–2, j = 0) → NeH{sup +} + H reaction

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

Wu, Hui; Yao, Cui-Xia; He, Xiao-Hu

State-to-state quantum dynamic calculations for the proton transfer reaction Ne + H{sub 2}{sup +} (v = 0–2, j = 0) are performed on the most accurate LZHH potential energy surface, with the product Jacobi coordinate based time-dependent wave packet method including the Coriolis coupling. The J = 0 reaction probabilities for the title reaction agree well with previous results in a wide range of collision energy of 0.2-1.2 eV. Total integral cross sections are in reasonable agreement with the available experiment data. Vibrational excitation of the reactant is much more efficient in enhancing the reaction cross sections than translational andmore » rotational excitation. Total differential cross sections are found to be forward-backward peaked with strong oscillations, which is the indication of the complex-forming mechanism. As the collision energy increases, state-resolved differential cross section changes from forward-backward symmetric peaked to forward scattering biased. This forward bias can be attributed to the larger J partial waves, which makes the reaction like an abstraction process. Differential cross sections summed over two different sets of J partial waves for the v = 0 reaction at the collision energy of 1.2 eV are plotted to illustrate the importance of large J partial waves in the forward bias of the differential cross sections.« less

Chemical quenching of positronium in Fe 2O 3/Al 2O 3 catalysts

NASA Astrophysics Data System (ADS)

Li, C.; Zhang, H. J.; Chen, Z. Q.

2010-09-01

Fe 2O 3/Al 2O 3 catalysts were prepared by solid state reaction method using α-Fe 2O 3 and γ-Al 2O 3 nano powders. The microstructure and surface properties of the catalyst were studied using positron lifetime and coincidence Doppler broadening annihilation radiation measurements. The positron lifetime spectrum shows four components. The two long lifetimes τ3 and τ4 are attributed to positronium annihilation in two types of pores distributed inside Al 2O 3 grain and between the grains, respectively. With increasing Fe 2O 3 content from 3 wt% to 40 wt%, the lifetime τ3 keeps nearly unchanged, while the longest lifetime τ4 shows decrease from 96 ns to 64 ns. Its intensity decreases drastically from 24% to less than 8%. The Doppler broadening S parameter shows also a continuous decrease. Further analysis of the Doppler broadening spectra reveals a decrease in the p-Ps intensity with increasing Fe 2O 3 content, which rules out the possibility of spin-conversion of positronium. Therefore the decrease of τ4 is most probably due to the chemical quenching reaction of positronium with Fe ions on the surface of the large pores.

Mechanistic exploration of the catalytic cycles for the CO oxidation by O2 over FeO(1-3) application of the energetic span model.

PubMed

Wang, Huan-Jiang; Wang, Yong-Cheng

2014-06-01

Carbon monoxide (CO) and oxygen (O2) catalyzed by small neutral iron oxide clusters (FeO(1-3)) was investigated at the density functional level of theory using the Becke-Perdew-Wang functional (BPW91). Three reaction pathways along with singlet, triplet and quintet states were calculated for ascertaining the presence of some spin inversion during the catalytic cycle. The catalytic cycle was found to be "two state reactivity" resulting from the crossing among the multistate energetic profiles. The Landau-Zener equation was used to calculate the thermally-averaged spin transition probabilities for the non-adiabatic surface crossing reaction. In order to predict the efficiency of catalyst the energetic span model developed by Kozuch was implemented, whereas this model is not suitable for handling the diabatic reaction, this feature we must take into consideration. To this end, a kinetic assessment is carried out with an expansion of the energetic span model, including the spin-crossing effects. This approximation enables one to measure the efficiency of catalytic cycle including spin-crossing effects by quantum mechanical computation.

Dissolution kinetics of small amounts of oxygen in tantalum alloy T-111 and internal oxide displacement reactions during annealing

NASA Technical Reports Server (NTRS)

Stecura, S.

1976-01-01

Oxygen was added to T-111 (Ta-8W-2Hf, wt. %) at 820 and 990 C at an oxygen pressure of about 0.0003 torr. The technique employed permitted predetermined and reproducible doping of T-111 up to 3.0 at. % oxygen. Based on the temperature dependence of the doping reaction, it is concluded that the initial rates of oxygen pickup are probably controlled by solution of oxygen into the T-111 lattice. Although hafnium oxides are more stable than those of tantalum or tungsten, analyses of extracted residues indicate that the latter oxides predominate in the as-doped specimens, presumably because of the higher concentrations of tantalum and tungsten in the alloy. However, high-temperature annealing promotes gettering of dissolved oxygen and of other oxides to form hafnium oxides. Small amounts of tantalum and tungsten oxides were still present after high-temperature annealing. Tungsten oxide (WO3) volatilizes slightly from the surface of T-111 at 990 C. The vaporization of WO3 has no apparent affect on the doping reaction.

Kinetic intermediates of unfolding of dimeric prostatic phosphatase.

PubMed

Kuciel, Radosława; Mazurkiewicz, Aleksandra; Dudzik, Paulina

2007-01-01

Kinetics of guanidine hydrochloride (GdnHCl)-induced unfolding of human prostatic acid phosphatase (hPAP), a homodimer of 50 kDa subunit molecular mass was investigated with enzyme activity measurements, capacity for binding an external hydrophobic probe, 1-anilinonaphtalene-8-sulfonate (ANS), accessibility of thiols to reaction with 5,5'-dithiobis(2-nitrobenzoic acid) (DTNB) and 2-(4'-maleimidylanilino)naphthalene-6-sulfonate (MIANS) and ability to bind Congo red dye. Kinetic analysis was performed to describe a possible mechanism of hPAP unfolding and dissociation that leads to generation of an inactive monomeric intermediate that resembles, in solution of 1.25 M GdnHCl pH 7.5, at 20 degrees C, in equilibrium, a molten globule state. The reaction of hPAP inactivation in 1.25 M GdnHCl followed first order kinetics with the reaction rate constant 0.0715 +/- 0.0024 min(-1) . The rate constants of similar range were found for the pseudo-first-order reactions of ANS and Congo red binding: 0.0366 +/- 0.0018 min(-1) and 0.0409 +/- 0.0052 min(-1), respectively. Free thiol groups, inaccessible in the native protein, were gradually becoming, with the progress of unfolding, exposed for the reactions with DTNB and MIANS, with the pseudo-first-order reaction rate constants 0.327 +/- 0.014 min(-1) and 0.216 +/- 0.010 min(-1), respectively. The data indicated that in the course of hPAP denaturation exposure of thiol groups to reagents took place faster than the enzyme inactivation and exposure of the protein hydrophobic surface. This suggested the existence of a catalytically active, partially unfolded, but probably dimeric kinetic intermediate in the process of hPAP unfolding. On the other hand, the protein inactivation was accompanied by exposure of a hydrophobic, ANS-binding surface, and with an increased capacity to bind Congo red. Together with previous studies these results suggest that the stability of the catalytically active conformation of the enzyme depends mainly on the dimeric structure of the native hPAP.

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

Stanislav S. Gornostayev; Jouko J. Haerkki

Examinations of polished and dry cut sections of feed and tuyere coke revealed some possible mechanisms for the physical influence of mineral compounds on the reactivity and strength of coke. It was observed that rounded particles of mineral phases that are exposed to the pore walls and surface of coke at high temperature create an inorganic cover, thus reducing the surface available for gas-solid reactions. The particles of mineral matter that have a low melting point and viscosity can affect the coke at earlier stages in the blast furnace process, acting in the upper parts of the blast furnace (BF).more » The temperature-driven redistribution of mineral phases within the coke matrix probably leads to the creation of weak spots and in general to anisotropy in its properties, thus reducing its strength. 9 refs., 2 figs., 1 tab.« less

Clay catalysis of oligonucleotide formation: kinetics of the reaction of the 5'-phosphorimidazolides of nucleotides with the non-basic heterocycles uracil and hypoxanthine

NASA Technical Reports Server (NTRS)

Kawamura, K.; Ferris, J. P.

1999-01-01

The montmorillonite clay catalyzed condensation of activated monocleotides to oligomers of RNA is a possible first step in the formation of the proposed RNA world. The rate constants for the condensation of the phosphorimidazolide of adenosine were measured previously and these studies have been extended to the phosphorimidazolides of inosine and uridine in the present work to determine of substitution of neutral heterocycles for the basic adenine ring changes the reaction rate or regioselectivity. The oligomerization reactions of the 5'-phosphoromidazolides of uridine (ImpU) and inosine (ImpI) on montmorillonite yield oligo(U)s and oligo(I)s as long as heptamers. The rate constants for oligonucleotide formation were determined by measuring the rates of formation of the oligomers by HPLC. Both the apparent rate constants in the reaction mixture and the rate constants on the clay surface were calculated using the partition coefficients of the oligomers between the aqueous and clay phases. The rate constants for trimer formation are much greater than those dimer synthesis but there was little difference in the rate constants for the formation of trimers and higher oligomers. The overall rates of oligomerization of the phosphorimidazolides of purine and pyrimidine nucleosides in the presence of montmorillonite clay are the same suggesting that RNA formed on the primitive Earth could have contained a variety of heterocyclic bases. The rate constants for oligomerization of pyrimidine nucleotides on the clay surface are significantly higher than those of purine nucleotides since the pyrimidine nucleotides bind less strongly to the clay than do the purine nucleotides. The differences in the binding is probably due to Van der Waals interactions between the purine bases and the clay surface. Differences in the basicity of the heterocyclic ring in the nucleotide have little effect on the oligomerization process.

The Janus face of iron on anoxic worlds: iron oxides are both protective and destructive to life on the early Earth and present-day Mars.

PubMed

Wadsworth, Jennifer; Cockell, Charles S

2017-05-01

The surface of the early Earth was probably subjected to a higher flux of ultraviolet (UV) radiation than today. UV radiation is known to severely damage DNA and other key molecules of life. Using a liquid culture and a rock analogue system, we investigated the interplay of protective and deleterious effects of iron oxides under UV radiation on the viability of the model organism, Bacillus subtilis. In the presence of hydrogen peroxide, there exists a fine balance between iron oxide's protective effects against this radiation and its deleterious effects caused by Photo-Fenton reactions. The maximum damage was caused by a concentration of hematite of ∼1 mg/mL. Concentrations above this confer increasing protection by physical blockage of the UV radiation, concentrations below this cause less effective UV radiation blockage, but also a correspondingly less effective Photo-Fenton reaction, providing an overall advantage. These results show that on anoxic worlds, surface habitability under a high UV flux leaves life precariously poised between the beneficial and deleterious effects of iron oxides. These results have relevance to the Archean Earth, but also the habitability of the Martian surface, where high levels of UV radiation in combination with iron oxides and hydrogen peroxide can be found. © FEMS 2017. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.

Preparation and Characterization of Cu and Ni on Alumina Supports and Their Use in the Synthesis of Low-Temperature Metal-Phthalocyanine Using a Parallel-Plate Reactor

PubMed Central

Sánchez-De la Torre, Fernando; De la Rosa, Javier Rivera; Kharisov, Boris I.; Lucio-Ortiz, Carlos J.

2013-01-01

Ni- and Cu/alumina powders were prepared and characterized by X-ray diffraction (XRD), scanning electronic microscope (SEM), and N2 physisorption isotherms were also determined. The Ni/Al2O3 sample reveled agglomerated (1 μm) of nanoparticles of Ni (30–80 nm) however, NiO particles were also identified, probably for the low temperature during the H2 reduction treatment (350 °C), the Cu/Al2O3 sample presented agglomerates (1–1.5 μm) of nanoparticles (70–150 nm), but only of pure copper. Both surface morphologies were different, but resulted in mesoporous material, with a higher specificity for the Ni sample. The surfaces were used in a new proposal for producing copper and nickel phthalocyanines using a parallel-plate reactor. Phthalonitrile was used and metallic particles were deposited on alumina in ethanol solution with CH3ONa at low temperatures; ≤60 °C. The mass-transfer was evaluated in reaction testing with a recent three-resistance model. The kinetics were studied with a Langmuir-Hinshelwood model. The activation energy and Thiele modulus revealed a slow surface reaction. The nickel sample was the most active, influenced by the NiO morphology and phthalonitrile adsorption. PMID:28788334

Study on conditional probability of surface rupture: effect of fault dip and width of seismogenic layer

NASA Astrophysics Data System (ADS)

Inoue, N.

2017-12-01

The conditional probability of surface ruptures is affected by various factors, such as shallow material properties, process of earthquakes, ground motions and so on. Toda (2013) pointed out difference of the conditional probability of strike and reverse fault by considering the fault dip and width of seismogenic layer. This study evaluated conditional probability of surface rupture based on following procedures. Fault geometry was determined from the randomly generated magnitude based on The Headquarters for Earthquake Research Promotion (2017) method. If the defined fault plane was not saturated in the assumed width of the seismogenic layer, the fault plane depth was randomly provided within the seismogenic layer. The logistic analysis was performed to two data sets: surface displacement calculated by dislocation methods (Wang et al., 2003) from the defined source fault, the depth of top of the defined source fault. The estimated conditional probability from surface displacement indicated higher probability of reverse faults than that of strike faults, and this result coincides to previous similar studies (i.e. Kagawa et al., 2004; Kataoka and Kusakabe, 2005). On the contrary, the probability estimated from the depth of the source fault indicated higher probability of thrust faults than that of strike and reverse faults, and this trend is similar to the conditional probability of PFDHA results (Youngs et al., 2003; Moss and Ross, 2011). The probability of combined simulated results of thrust and reverse also shows low probability. The worldwide compiled reverse fault data include low fault dip angle earthquake. On the other hand, in the case of Japanese reverse fault, there is possibility that the conditional probability of reverse faults with less low dip angle earthquake shows low probability and indicates similar probability of strike fault (i.e. Takao et al., 2013). In the future, numerical simulation by considering failure condition of surface by the source fault would be performed in order to examine the amount of the displacement and conditional probability quantitatively.

On-surface synthesis on a bulk insulator surface

NASA Astrophysics Data System (ADS)

Richter, Antje; Floris, Andrea; Bechstein, Ralf; Kantorovich, Lev; Kühnle, Angelika

2018-04-01

On-surface synthesis has rapidly emerged as a most promising approach to prepare functional molecular structures directly on a support surface. Compared to solution synthesis, performing chemical reactions on a surface offers several exciting new options: due to the absence of a solvent, reactions can be envisioned that are otherwise not feasible due to the insolubility of the reaction product. Perhaps even more important, the confinement to a two-dimensional surface might enable reaction pathways that are not accessible otherwise. Consequently, on-surface synthesis has attracted great attention in the last decade, with an impressive number of classical reactions transferred to a surface as well as new reactions demonstrated that have no classical analogue. So far, the majority of the work has been carried out on conducting surfaces. However, when aiming for electronic decoupling of the resulting structures, e.g. for the use in future molecular electronic devices, non-conducting surfaces are highly desired. Here, we review the current status of on-surface reactions demonstrated on the (10.4) surface of the bulk insulator calcite. Besides thermally induced C-C coupling of halogen-substituted aryls, photochemically induced [2  +  2] cycloaddition has been proven possible on this surface. Moreover, experimental evidence exists for coupling of terminal alkynes as well as diacetylene polymerization. While imaging of the resulting structures with dynamic atomic force microscopy provides a direct means of reaction verification, the detailed reaction pathway often remains unclear. Especially in cases where the presence of metal atoms is known to catalyze the corresponding solution chemistry reaction (e.g. in the case of the Ullmann reaction), disclosing the precise reaction pathway is of importance to understand and generalize on-surface reactivity on a bulk insulator surface. To this end, density-functional theory calculations have proven to provide atomic-scale insights that have greatly contributed to unravelling the details of on-surface synthesis on a bulk insulator surface.

Vaccination with Dendritic Cell Myeloma Fusions in Conjunction with Stem Cell Transplantation and PD-1 Blockade

DTIC Science & Technology

2014-05-01

UNRELATED DEFINITE NONE RESOLVED PM34 Injection site reaction 9/5/2013 1 UNRELATED DEFINITE (GM-CSF) NONE RESOLVED PM35 Neutropenia 10/8/2013 3 PROBABLE...PROBABLE NONE RESOLVED PM35 Neutropenia 10/11/2013 4 PROBABLE PROBABLE NONE RESOLVED PM35 Neutropenia 10/15/2013 3 PROBABLE PROBABLE NONE RESOLVED...presented to clinic for week 2 follow-up after his second infusion of CT-011 with grade 4 neutropenia (expected, probably related to CT-011 and

Incorporating Skew into RMS Surface Roughness Probability Distribution

NASA Technical Reports Server (NTRS)

Stahl, Mark T.; Stahl, H. Philip.

2013-01-01

The standard treatment of RMS surface roughness data is the application of a Gaussian probability distribution. This handling of surface roughness ignores the skew present in the surface and overestimates the most probable RMS of the surface, the mode. Using experimental data we confirm the Gaussian distribution overestimates the mode and application of an asymmetric distribution provides a better fit. Implementing the proposed asymmetric distribution into the optical manufacturing process would reduce the polishing time required to meet surface roughness specifications.

Effects of the plasma-facing materials on the negative ion H ‑ density in an ECR (2.45 GHz) plasma

NASA Astrophysics Data System (ADS)

Bentounes, J.; Béchu, S.; Biggins, F.; Michau, A.; Gavilan, L.; Menu, J.; Bonny, L.; Fombaron, D.; Bès, A.; Lebedev, Yu A.; Shakhatov, V. A.; Svarnas, P.; Hassaine, T.; Lemaire, J. L.; Lacoste, A.

2018-05-01

Within the framework of fundamental research, the present work focuses on the role of surface material in the production of H ‑ negative ion, with a potential application of designing cesium-free H ‑ negative ion sources oriented to fusion application. It is widely accepted that the main reaction leading to H ‑ production, in the plasma volume, is the dissociative attachment of low-energy electrons (T e ≤ 1 eV) on highly ro-vibrationally excited hydrogen molecules. In parallel with other mechanisms, the density of these excited molecules may be enhanced by means of the recombinative desorption, i.e. the interaction between surface absorbed atoms with other atoms (surface adsorbed or not) through the path {H}{{ads}}+{H}{{gas}/{{ads}}}\\to {H}2{(v,J)}{{gas}}+{{Δ }}E. Accordingly, a systematic study on the role played by the surface in this reaction, with respect to the production of H ‑ ion in the plasma volume, is here performed. Thus, tantalum and tungsten (already known as H ‑ enhancers) and quartz (inert surface) materials are employed as inner surfaces of a test bench chamber. The plasma inside the chamber is produced by electron cyclotron resonance (ECR) driving and it is characterized with conventional electrostatic probes, laser photodetachment, and emission and absorption spectroscopy. Two different positions (close to and away from the ECR driving zone) are investigated under various conditions of pressure and power. The experimental results are supported by numerical data generated by a 1D model. The latter couples continuity and electron energy balance equations in the presence of magnetic field, and incorporates vibrational kinetics, H2 molecular reactions, H electronically excited states and ground-state species kinetics. In the light of this study, recombinative desorption has been evidenced as the most probable mechanism, among others, responsible for an enhancement by a factor of about 3.4, at 1.6 Pa and 175 W of microwave power, in the case of tantalum.

Systematic study of probable projectile-target combinations for the synthesis of the superheavy nucleus 302120

NASA Astrophysics Data System (ADS)

Santhosh, K. P.; Safoora, V.

2016-08-01

Probable projectile-target combinations for the synthesis of the superheavy element 302120 have been studied taking the Coulomb and proximity potential as the interaction barrier. The probabilities of the compound nucleus formation PCN for the projectile-target combinations found in the cold reaction valley of 302120 are estimated. At energies near and above the Coulomb barrier, we have calculated the capture, fusion, and evaporation residue cross sections for the reactions of all probable projectile-target combinations so as to predict the most promising projectile-target combinations for the synthesis of the superheavy element 302120 in heavy-ion fusion reactions. The calculated fusion and evaporation cross sections for the more asymmetric ("hotter") projectile-target combination is found to be higher than the less asymmetric ("colder") combination. It can be seen from the nature of the quasifission barrier height, mass asymmetry, the probability of compound nucleus formation, survival probability, and excitation energy, the systems 44Ar+258No , 46Ar+256No , 48Ca+254Fm , 50Ca+252Fm , 54Ti+248Cf , and 58Cr+244Cm in deep region I of the cold reaction valley and the systems 62Fe+240Pu , 64Fe+238Pu , 68Ni+234U , 70Ni+232U , 72Ni+230U , and 74Zn+228Th in the other cold valleys are identified as the better projectile-target combinations for the synthesis of 302120. Our predictions on the synthesis of 302120 superheavy nuclei using the combinations 54Cr+248Cm , 58Fe+244Pu , 64Ni+238U , and 50Ti+249Cf are compared with available experimental data and other theoretical predictions.

Determination and Use of the Local Recovery Factor for Calculating the Effectiveness Gas Temperature for Turbine Blades / Jack B. Esgar and Alfred L. Lea

NASA Technical Reports Server (NTRS)

Esgar, Jack B; Lea, Alfred L

1951-01-01

In an in experimental investigation of local recovery factors for a blade having a pressure distribution similar to that of a typical reaction-type turbine blade, it a was found that the recovery factors were essentially independent of Mach number, Reynolds number, pressure gradient, and position on the blade surface except for regions where the boundary layer was probably in the transition range from laminar to turbulent. The recommended value of local subsonic recovery factor for use in calculating the effective gas temperature for gas turbine blades was 0.89.

Low cost, surfactant-less, one pot synthesis of Cu 2O nano-octahedra at room temperature

NASA Astrophysics Data System (ADS)

Ahmed, Asar; Gajbhiye, Namdeo S.; Joshi, Amish G.

2011-08-01

Cu 2O octahedra were successfully synthesized via a novel wet-chemical method using D-glucose and hydrazine as reducing agent at room temperature without the presence of any other surfactant. Presence of D-glucose was important for the stabilization of the evolved copper octahedra and also for facilitating the reduction of the Cu(II) ions. The existence of glucose moieties on the surface as capping agent was confirmed by the FT-IR spectra while there was presence of excess oxygen atoms on the surface leading to the formation of a thin CuO layer at the octahedra surface, as confirmed by the XPS study, probably promoted by the capping glucose. Effect of NaOH concentration on the reaction and the formation of octahedra was also studied. The formation mechanism of obtained Cu 2O octahedra has been discussed. These octahedra were then studied for their photocatalytic properties in degradation of organic dyes, rhodamine B and methyl orange.

Polythiophene synthesis coupled to quartz crystal microbalance and Raman spectroscopy for detecting bacteria.

PubMed

Kengne-Momo, R P; Lagarde, F; Daniel, Ph; Pilard, J F; Durand, M J; Thouand, G

2012-12-01

A simple electrochemical procedure was used for the synthesis of a polythiophene containing para-benzenesulfonyl chloride groups. The obtained polymer was shown to be very reactive and directly able to covalently bind nucleophile biomolecules. Protein A and a specific antibody were then successively immobilized on the conductive polymer through a covalent bonding of Protein A with the as-prepared linker for bacteria trapping purpose. All reactions were controlled in situ by cyclic voltammetry, quartz crystal microbalance and Raman spectroscopy. The results were compared to those previously obtained on gold surface modified with the same chemical linker. The conductive polymer led to a very high rate of antibody recognition compared to the gold surface and to literature, probably due to a large available surface obtained after polymerization. One example of pathogenic bacteria "Salmonella enterica paratyphi" detection was successfully tested on the substrates. The presented results are promising for the future design of simple and inexpensive immunocapture-based sensors.

Brain mechanisms of emotions.

PubMed

Simonov, P V

1997-01-01

At the 23rd International Congress of Physiology Sciences (Tokyo, 1965) the results of experiment led us to the conclusion that emotions were determined by the actual need and estimation of probability (possibility) of its satisfaction. Low probability of need satisfaction leads to negative emotions actively minimized by the subject. Increased probability of satisfaction, as compared to the earlier forecast, generates positive emotions which the subject tries to maximize, that is, to enhance, to prolong, to repeat. We named our concept the Need-Informational Theory of Emotions. According to this theory, motivation, emotion, and estimation of probability have different neuromorphological substrates. Activation through the hypothalamic motivatiogenic structures of the frontal parts of the neocortex orients the behavior to signals with a high probability of their reinforcement. At the same time the hippocampus is necessary for reactions to signals of low probability events, which are typical for the emotionally excited brain. By comparison of motivational excitation with available stimuli or their engrams, the amygdala selects a dominant motivation, destined to be satisfied in the first instance. In the cases of classical conditioning and escape reaction the reinforcement was related to involvement of the negative emotion's hypothalamic neurons, while in the course of avoidance reaction the positive emotion's neurons were involved. The role of the left and right frontal neocortex in the appearance or positive or negative emotions depends on these informational (cognitive) functions.

[The brain mechanisms of emotions].

PubMed

Simonov, P V

1997-01-01

At the 23rd International Congress of Physiological Sciences (Tokyo, 1965) the results of experiment brought us to a conclusion that emotions were determined by the actual need and estimation of probability (possibility) of its satisfaction. Low probability of need satisfaction leads to negative emotions actively minimized by the subject. Increased probability of satisfaction, as compared to the earlier forecast, generates positive emotions which the subject tries to maximize, that is to enhance, to prolong, to repeat. We named our concept the Need-Informational Theory of Emotions. According to this theory, motivation, emotion and estimation of probability have different neuromorphological substrate. Activating by motivatiogenic structures of the hypothalamus the frontal parts of neocortex orients the behavior to signals with a high probability of their reinforcement. At the same time the hippocampus is necessary for reactions to signals of low probability events, which is typical for emotionally excited brain. By comparison of motivational excitation with available stimuli or their engrams the amygdala selects a dominant motivation, destined to be satisfied in the first instance. In the cases of classical conditioning and escape reaction the reinforcement was related to involvement of the negative emotion's hypothalamic neurons while in the course of avoidance reaction the positive emotion's neurons being involved. The role of the left and right frontal neocortex in the appearance of positive or negative emotions depends on this informational (cognitive) functions.

Stratospheric Sulfuric Acid and Black Carbon Aerosol Measured During POLARIS and its Role in Ozone Chemistry

NASA Technical Reports Server (NTRS)

Strawa, Anthony W.; Pueschel, R. F.; Drdla, K.; Verma, S.; Gore, Warren J. (Technical Monitor)

1998-01-01

Stratospheric aerosol can affect the environment in three ways. Sulfuric acid aerosol have been shown to act as sites for the reduction of reactive nitrogen and chlorine and as condensation sites to form Polar Stratospheric Clouds, under very cold conditions, which facilitate ozone depletion. Recently, modeling studies have suggested a link between BCA (Black Carbon Aerosol) and ozone chemistry. These studies suggest that HNO3, NO2, and O3 may be reduced heterogeneously on BCA particles. The ozone reaction converts ozone to oxygen molecules, while HNO3 and NO2 react to form NOx. Finally, a buildup of BCA could reduce the single-scatter albedo of aerosol below a value of 0.98, a critical value that has been postulated to change the effect of stratospheric aerosol from cooling to warming. Correlations between measured BCA amounts and aircraft usage have been reported. Attempts to link BCA to ozone chemistry and other stratospheric processes have been hindered by questions concerning the amount of BCA that exists in the stratosphere, the magnitude of reaction probabilities, and the scarcity of BCA measurements. The Ames Wire Impactors (AWI) participated in POLARIS as part of the complement of experiments on the NASA ER-2. One of our main objectives was to determine the amount of aerosol surface area, particularly BCA, available for reaction with stratospheric constituents and assess if possible, the importance of these reactions. The AWI collects aerosol and BCA particles on thin Palladium wires that are exposed to the ambient air in a controlled manner. The samples are returned to the laboratory for subsequent analysis. The product of the AWI analysis is the size, surface area, and volume distributions, morphology and elemental composition of aerosol and BCA. This paper presents results from our experiments during POLARIS and puts these measurements in the context of POLARIS and other missions in which we have participated. It describes modifications to the AWI data analysis procedures in which the collection of BCA is modeled as a fractal aggregate. The new analysis results in an increase in BCA surface area of approximately 24 and an increase in mass of 7-10 from the previous method. For the current study, BCA surface area is used in computer models that attempt to predict measured NOx/NOy ratios and O3 depletion rates. Inclusion of the HNO3 reaction with BCA in one model tends to improve the agreement of calculated to measured NOx/NOy ratio. However, it was found that these trends are viable only if the reactions are catalytic.

Semisupervised Gaussian Process for Automated Enzyme Search.

PubMed

Mellor, Joseph; Grigoras, Ioana; Carbonell, Pablo; Faulon, Jean-Loup

2016-06-17

Synthetic biology is today harnessing the design of novel and greener biosynthesis routes for the production of added-value chemicals and natural products. The design of novel pathways often requires a detailed selection of enzyme sequences to import into the chassis at each of the reaction steps. To address such design requirements in an automated way, we present here a tool for exploring the space of enzymatic reactions. Given a reaction and an enzyme the tool provides a probability estimate that the enzyme catalyzes the reaction. Our tool first considers the similarity of a reaction to known biochemical reactions with respect to signatures around their reaction centers. Signatures are defined based on chemical transformation rules by using extended connectivity fingerprint descriptors. A semisupervised Gaussian process model associated with the similar known reactions then provides the probability estimate. The Gaussian process model uses information about both the reaction and the enzyme in providing the estimate. These estimates were validated experimentally by the application of the Gaussian process model to a newly identified metabolite in Escherichia coli in order to search for the enzymes catalyzing its associated reactions. Furthermore, we show with several pathway design examples how such ability to assign probability estimates to enzymatic reactions provides the potential to assist in bioengineering applications, providing experimental validation to our proposed approach. To the best of our knowledge, the proposed approach is the first application of Gaussian processes dealing with biological sequences and chemicals, the use of a semisupervised Gaussian process framework is also novel in the context of machine learning applied to bioinformatics. However, the ability of an enzyme to catalyze a reaction depends on the affinity between the substrates of the reaction and the enzyme. This affinity is generally quantified by the Michaelis constant KM. Therefore, we also demonstrate using Gaussian process regression to predict KM given a substrate-enzyme pair.

Probability function of breaking-limited surface elevation. [wind generated waves of ocean

NASA Technical Reports Server (NTRS)

Tung, C. C.; Huang, N. E.; Yuan, Y.; Long, S. R.

1989-01-01

The effect of wave breaking on the probability function of surface elevation is examined. The surface elevation limited by wave breaking zeta sub b(t) is first related to the original wave elevation zeta(t) and its second derivative. An approximate, second-order, nonlinear, non-Gaussian model for zeta(t) of arbitrary but moderate bandwidth is presented, and an expression for the probability density function zeta sub b(t) is derived. The results show clearly that the effect of wave breaking on the probability density function of surface elevation is to introduce a secondary hump on the positive side of the probability density function, a phenomenon also observed in wind wave tank experiments.

Role of nuclear charge change and nuclear recoil on shaking processes and their possible implication on physical processes

NASA Astrophysics Data System (ADS)

Sharma, Prashant

2017-12-01

The probable role of the sudden nuclear charge change and nuclear recoil in the shaking processes during the neutron- or heavy-ion-induced nuclear reactions and weakly interacting massive particle-nucleus scattering has been investigated in the present work. Using hydrogenic wavefunctions, general analytical expressions of survival, shakeup/shakedown, and shakeoff probability have been derived for various subshells of hydrogen-like atomic systems. These expressions are employed to calculate the shaking, shakeup/shakedown, and shakeoff probabilities in some important cases of interest in the nuclear astrophysics and the dark matter search experiments. The results underline that the shaking processes are one of the probable channels of electronic transitions during the weakly interacting massive particle-nucleus scattering, which can be used to probe the dark matter in the sub-GeV regime. Further, it is found that the shaking processes initiating due to nuclear charge change and nuclear recoil during the nuclear reactions may influence the electronic configuration of the participating atomic systems and thus may affect the nuclear reaction measurements at astrophysically relevant energies.

High-level ab initio potential energy surface and dynamics of the F– + CH3I SN2 and proton-transfer reactions† †Electronic supplementary information (ESI) available: Benchmark classical and adiabatic relative energies (Table S1), vibrational frequencies of all the stationary points (Tables S2 and S3), direct/indirect trajectory separation function parameters (Table S4), entrance-channel potential (Fig. S1), structures of the minima and saddle points corresponding to the abstraction channel (Fig. S2), reaction probabilities (Fig. S3), trajectory integration time distributions (Fig. S4), trajectory integration time vs. I– velocity distributions (Fig. S5), and mechanism-specific reaction probabilities (Fig. S6). See DOI: 10.1039/c7sc00033b Click here for additional data file.

PubMed Central

Olasz, Balázs; Szabó, István

2017-01-01

Bimolecular nucleophilic substitution (SN2) and proton transfer are fundamental processes in chemistry and F– + CH3I is an important prototype of these reactions. Here we develop the first full-dimensional ab initio analytical potential energy surface (PES) for the F– + CH3I system using a permutationally invariant fit of high-level composite energies obtained with the combination of the explicitly-correlated CCSD(T)-F12b method, the aug-cc-pVTZ basis, core electron correlation effects, and a relativistic effective core potential for iodine. The PES accurately describes the SN2 channel producing I– + CH3F via Walden-inversion, front-side attack, and double-inversion pathways as well as the proton-transfer channel leading to HF + CH2I–. The relative energies of the stationary points on the PES agree well with the new explicitly-correlated all-electron CCSD(T)-F12b/QZ-quality benchmark values. Quasiclassical trajectory computations on the PES show that the proton transfer becomes significant at high collision energies and double-inversion as well as front-side attack trajectories can occur. The computed broad angular distributions and hot internal energy distributions indicate the dominance of indirect mechanisms at lower collision energies, which is confirmed by analyzing the integration time and leaving group velocity distributions. Comparison with available crossed-beam experiments shows usually good agreement. PMID:28507692

Disruptive effects of prefeeding and haloperidol administration on multiple measures of food-maintained behavior in rats

PubMed Central

Hayashi, Yusuke; Wirth, Oliver

2015-01-01

Four rats responded under a choice reaction-time procedure. At the beginning of each trial, the rats were required to hold down a center lever for a variable duration, release it following a high- or low-pitched tone, and press either a left or right lever, conditionally on the tone. Correct choices were reinforced with a probability of .95 or .05 under blinking or static houselights, respectively. After performance stabilized, disruptive effects of free access to food pellets prior to sessions (prefeeding) and intraperitoneal injection of haloperidol were examined on multiple behavioral measures (i.e., the number of trials completed, percent of correct responses, and reaction time). Resistance to prefeeding depended on the probability of food delivery for the number of trials completed and reaction time. Resistance to haloperidol, on the other hand, was not systematically affected by the probability of food delivery for all dependent measures. PMID:22209910

Response preparation and intra-individual reaction time variability in schizophrenia.

PubMed

Dankinas, Denisas; Mėlynytė, Sigita; Šiurkutė, Aldona; Dapšys, Kastytis

2016-01-01

Background. It is important to prepare response in advance to increase the efficiency of its execution. The process of response preparation is usually studied using the precueing paradigm. In this paradigm subjects have to employ the preceding information about further imperative stimulus to perform proper response preparation, which shortens the reaction time of subsequent response execution. Previous studies detected the impairment of response preparation in schizophrenia only with the help of electroencephalographic parameters, but not with the assessing of reaction time. Therefore, in this study we attempted to find a behavioural parameter that could detect impairment in response preparation of schizophrenia patients. It was recently found that appropriate response preparation not only shortens the reaction time but also increases its stability, which is measured with the intra-individual reaction time variability. It was also revealed that response stability could better find cognitive dysfunction in some studies of schizophrenia disorder than classical behavioural parameters. Hence, the main goal of this study was to verify if intra-individual reaction time variability could detect the impairment of response preparation in schizophrenia patients. Materials and methods. In order to achieve the main purpose, we carried out a study with 14 schizophrenia patients and 14 control group subjects. We used precueing paradigm in our research, in which participants had to employ information about stimulus probability for the proper response preparation. Results. Our main result showed that despite the responses of schizophrenia patients were faster to the high-probability stimulus than to the low-probability one ( F (1, 13) = 30.9, p < 0.001), intra-individual reaction time variability did not differ in this group between the responses to more and less probable stimuli ( F (1, 13) = 0.64, p = 0.44). Conclusions. Results of the study suggest that people with schizophrenia were able to use precueing probabilistic information only to shorten their reaction time, but not to increase response stability. Therefore, it was found that intra-individual reaction time variability parameter could detect response preparation impairment in schizophrenia, and could be used in clinical purposes.

Reactions of methyl groups on a non-reducible metal oxide: The reaction of iodomethane on stoichiometric α-Cr 2O 3(0001)

DOE PAGES

Dong, Yujung; Brooks, John D.; Chen, Tsung-Liang; ...

2015-06-10

The reaction of iodomethane on the nearly stoichiometric α-Cr 2O 3(0001) surface produces gas phase ethylene, methane, and surface iodine adatoms. The reaction is first initiated by the dissociation of iodomethane into surface methyl fragments, -CH 3, and iodine adatoms. Methyl fragments bound at surface Cr cation sites undergo a rate-limiting dehydrogenation reaction to methylene, =CH 2. The methylene intermediates formed from methyl dehydrogenation can then undergo coupling reactions to produce ethylene via two principle reaction pathways: (1) direct coupling of methylene and (2) methylene insertion into the methyl surface bond to form surface ethyl groups which undergo β-H eliminationmore » to produce ethylene. The liberated hydrogen also combines with methyl groups to form methane. Iodine adatoms from the dissociation of iodomethane deactivate the surface by simple site blocking of the surface Cr 3+ cations.« less

Warship Combat System Selection Methodology Based on Discrete Event Simulation

DTIC Science & Technology

2010-09-01

Platform (from Spanish) PD Damage Probability xiv PHit Hit Probability PKill Kill Probability RSM Response Surface Model SAM Surface-Air Missile...such a large target allows an assumption that the probability of a hit ( PHit ) is one. This structure can be considered as a bridge; therefore, the

Measurement of the fusion probability P{sub CN} for the reaction of {sup 50}Ti with {sup 208}Pb

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

Naik, R. S.; Loveland, W.; Sprunger, P. H.

2007-11-15

The capture cross sections and fission fragment angular distributions were measured for the reaction of {sup 50}Ti with {sup 208}Pb at center of mass projectile energies (E{sub c.m.}) of 183.7, 186.2, 190.2, 194.2, and 202.3 MeV (E*=14.2, 16.6, 20.6, 24.7, and 32.7 MeV). From fitting the backward angle fragment angular distributions, the cross sections for quasifission and fusion-fission and P{sub CN}, the probability that the colliding nuclei go from the contact configuration to inside the fission saddle point, were deduced. These quantities, along with the known values of the evaporation residue production cross sections for this reaction, were used tomore » deduce values of the survival probabilities, W{sub sur}, for this reaction as a function of excitation energy. The deduced values of P{sub CN} and W{sub sur} and their dependence on excitation energy differ from some current theoretical predictions of these quantities.« less

Electron-Induced Chemistry of Cobalt Tricarbonyl Nitrosyl (Co(CO)3NO) in Liquid Helium Nanodroplets

PubMed Central

2015-01-01

Electron addition to cobalt tricarbonyl nitrosyl (Co(CO3NO) and its clusters has been explored in helium nanodroplets. Anions were formed by adding electrons with controlled energies, and reaction products were identified by mass spectrometry. Dissociative electron attachment (DEA) to the Co(CO)3NO monomer gave reaction products similar to those reported in earlier gas phase experiments. However, loss of NO was more prevalent than loss of CO, in marked contrast to the gas phase. Since the Co–N bond is significantly stronger than the Co–C bond, this preference for NO loss must be driven by selective reaction dynamics at low temperature. For [Co(CO)3NO]N clusters, the DEA chemistry is similar to that of the monomer, but the anion yields as a function of electron energy show large differences, with the relatively sharp resonances of the monomer being replaced by broad profiles peaking at much higher electron energies. A third experiment involved DEA of Co(CO)3NO on a C60 molecule in an attempt to simulate the effect of a surface. Once again, broad ion yield curves are seen, but CO loss now becomes the most probable reaction channel. The implication of these findings for understanding focused electron beam induced deposition of cobalt is described. PMID:26401190

Triplet state dissolved organic matter in aquatic photochemistry: reaction mechanisms, substrate scope, and photophysical properties.

PubMed

McNeill, Kristopher; Canonica, Silvio

2016-11-09

Excited triplet states of chromophoric dissolved organic matter ( 3 CDOM*) play a major role among the reactive intermediates produced upon absorption of sunlight by surface waters. After more than two decades of research on the aquatic photochemistry of 3 CDOM*, the need for improving the knowledge about the photophysical and photochemical properties of these elusive reactive species remains considerable. This critical review examines the efforts to date to characterize 3 CDOM*. Information on 3 CDOM* relies mainly on the use of probe compounds because of the difficulties associated with directly observing 3 CDOM* using transient spectroscopic methods. Singlet molecular oxygen ( 1 O 2 ), which is a product of the reaction between 3 CDOM* and dissolved oxygen, is probably the simplest indicator that can be used to estimate steady-state concentrations of 3 CDOM*. There are two major modes of reaction of 3 CDOM* with substrates, namely triplet energy transfer or oxidation (via electron transfer, proton-coupled electron transfer or related mechanisms). Organic molecules, including several environmental contaminants, that are susceptible to degradation by these two different reaction modes are reviewed. It is proposed that through the use of appropriate sets of probe compounds and model photosensitizers an improved estimation of the distribution of triplet energies and one-electron reduction potentials of 3 CDOM* can be achieved.

SurfKin: an ab initio kinetic code for modeling surface reactions.

PubMed

Le, Thong Nguyen-Minh; Liu, Bin; Huynh, Lam K

2014-10-05

In this article, we describe a C/C++ program called SurfKin (Surface Kinetics) to construct microkinetic mechanisms for modeling gas-surface reactions. Thermodynamic properties of reaction species are estimated based on density functional theory calculations and statistical mechanics. Rate constants for elementary steps (including adsorption, desorption, and chemical reactions on surfaces) are calculated using the classical collision theory and transition state theory. Methane decomposition and water-gas shift reaction on Ni(111) surface were chosen as test cases to validate the code implementations. The good agreement with literature data suggests this is a powerful tool to facilitate the analysis of complex reactions on surfaces, and thus it helps to effectively construct detailed microkinetic mechanisms for such surface reactions. SurfKin also opens a possibility for designing nanoscale model catalysts. Copyright © 2014 Wiley Periodicals, Inc.

Insights into the mechanism of Piper betle leaf-induced contact leukomelanosis using C57BL/6 mice as the animal model and tyrosinase assays.

PubMed

Liu, Han-Nan; Liu, Tsung-Yun; Chen, Chih-Chiang; Lee, Ding-Dar; Chang, Yun-Ting

2011-08-01

Steamed piper betle leaves (PBL) were once used by many Taiwanese women to treat pigment disorders on the face. Most women claimed a quick, favourable response at first, only to be overcome with facial leukomelanosis later. C57BL/6 mice were randomly assigned to different groups to study if PBL could cause the following effects: contact dermatitis, leukomelanosis, or hair bleaching. Intracellular melanin content was measured by tyrosinase assays. Most steamed PBL-treated mice developed contact dermatitis and postinflammatory hyperpigmentation (PIH) on their shaved backs. About half developed bleached hair to varying extents. The steamed PBL did not only bleach the hairs, but also, unexpectedly, stimulated melanocyte replication, indicated by the fact that the number of functional melanocytes in the tail epidermis increased significantly after treatment (P = 0.007). Using tyrosinase assays PBL extract at the undiluted concentration showed limited inhibition of melanogenesis, probably via melanocytotoxicity. The leukomelanosis observed in patients might be the consequence of PIH combined with a mixed reaction (hyper- and hypopigmentation), probably due to the different volatile chemicals that surface after steaming the PBL. This conflicting mixed reaction suggests that counteractive ingredients might exist in PBL. PBL, if purified, might be a promising source of a novel bleaching agent. © 2011 The Authors; Australasian Journal of Dermatology © 2011 The Australasian College of Dermatologists.

Variations of electric resistance and H2 and Rn emissions of concrete blocks under increasing uniaxial compression

USGS Publications Warehouse

King, C.-Y.; Luo, G.

1990-01-01

Electric resistance and emissions of hydrogen and radon isotopes of concrete (which is somewhat similar to fault-zone materials) under increasing uniaxial compression were continuously monitored to check whether they show any pre- and post-failure changes that may correspond to similar changes reported for earthquakes. The results show that all these parameters generally begin to increase when the applied stresses reach 20% to 90% of the corresponding failure stresses, probably due to the occurrence and growth of dilatant microcracks in the specimens. The prefailure changes have different patterns for different specimens, probably because of differences in spatial and temporal distributions of the microcracks. The resistance shows large co-failure increases, and the gas emissions show large post-failure increases. The post-failure increase of radon persists longer and stays at a higher level than that of hydrogen, suggesting a difference in the emission mechanisms for these two kinds of gases. The H2 increase may be mainly due to chemical reaction at the crack surfaces while they are fresh, whereas the Rn increases may be mainly the result of the increased emanation area of such surfaces. The results suggest that monitoring of resistivity and gas emissions may be useful for predicting earthquakes and failures of concrete structures. ?? 1990 Birkha??user Verlag.

Probabilistic #D data fusion for multiresolution surface generation

NASA Technical Reports Server (NTRS)

Manduchi, R.; Johnson, A. E.

2002-01-01

In this paper we present an algorithm for adaptive resolution integration of 3D data collected from multiple distributed sensors. The input to the algorithm is a set of 3D surface points and associated sensor models. Using a probabilistic rule, a surface probability function is generated that represents the probability that a particular volume of space contains the surface. The surface probability function is represented using an octree data structure; regions of space with samples of large conariance are stored at a coarser level than regions of space containing samples with smaller covariance. The algorithm outputs an adaptive resolution surface generated by connecting points that lie on the ridge of surface probability with triangles scaled to match the local discretization of space given by the algorithm, we present results from 3D data generated by scanning lidar and structure from motion.

Do recent observations of very large electromagnetic dissociation cross sections signify a transition towards non-perturbative QED?

NASA Technical Reports Server (NTRS)

Norbury, John W.

1992-01-01

The very large electromagnetic dissociation (EMD) cross section recently observed by Hill, Wohn, Schwellenbach, and Smith do not agree with Weizsacker-Williams (WW) theory or any simple modification thereof. Calculations are presented for the reaction probabilities for this experiment and the entire single and double nucleon removal EMD data set. It is found that for those few reactions where theory and experiment disagree, the probabilities are exceptionally large. This indicates that WW theory is not valid for these reactions and that one must consider higher order corrections and perhaps even a non-perturbative approach to quantum electrodynamics (QED).

Study on reaction mechanism by analysis of kinetic energy spectra of light particles and formation of final products

NASA Astrophysics Data System (ADS)

Giardina, G.; Mandaglio, G.; Nasirov, A. K.; Anastasi, A.; Curciarello, F.; Fazio, G.

2018-05-01

The sensitivity of reaction mechanism in the formation of compound nucleus (CN) by the analysis of kinetic energy spectra of light particles and of reaction products are shown. The dependence of the P CN fusion probability of reactants and W sur survival probability of CN against fission at its deexcitation on the mass and charge symmetries in the entrance channel of heavy-ion collisions, as well as on the neutron numbers is discussed. The possibility of conducting a complex program of investigations of the complete fusion by reliable ways depends on the detailed and refined methods of experimental and theoretical analyses.

Origin of organic matter in the early solar system. VII - The organic polymer in carbonaceous chondrites

NASA Technical Reports Server (NTRS)

Hayatsu, R.; Matsuoka, S.; Anders, E.; Scott, R. G.; Studier, M. H.

1977-01-01

Degradation techniques, including pyrolysis, depolymerization, and oxidation, were used to study the insoluble polymer from the Murchison C2 chondrite. Oxidation with Cr2O7(2-) or O2/UV led to the identification of 15 aromatic ring systems. Of 11 aliphatic acids identified, three dicarboxylic acids presumably came from hydroaromatic portions of the polymer, whereas eight monocarboxylic acids probably derive from bridging groups or ring substituents. Depolymerization with CF3COO4 yielded some of the same ring systems, as well as alkanes (C1 through C8) and alkenes (C2 through C8), alkyl (C1 through C5) benzenes and naphthalenes, and methyl- or dimethyl -indene, -indane, -phenol, -pyrrole, and -pyridine. All these compounds were detected below 200 C, and are therefore probably indigenous constituents. The properties of the meteoritic polymer were compared with the properties of a synthetic polymer produced by the Fischer-Tropsch reaction. It is suggested that the meteoritic polymer was also produced by surface catalysis.

Mössbauer Studies of Stannous Fluoride Reactivity with Synthetic Tooth Enamel - A Model for the Tooth Cavity Protection Actions of Novel Dentifrices

NASA Astrophysics Data System (ADS)

Dénès, Georges; Muntasar, Abdualhafeed; Kozak, Kathy M.; Baig, Arif A.; White, Donald J.

2002-06-01

SnF2 is an important toothpaste ingredient, added for the provision of clinical efficacy for hard and soft tissue diseases and in breath protection. Synthetic calcium hydroxyapatite powders were exposed to liquid supernates (25 w/w% toothpaste water slurries, centrifuged) of Crest Gum Care® (SnF2) dentifrice. One-minute treatments were followed by 3x water washing, centrifugation and lyophilization. Post treatment, powders were analyzed by Mössbauer spectroscopy with 0.5-1 gram of treated apatite powder. Results show that tooth mineral stannous fluoride interactions include: (1) formation of surface reaction products with both Sn(II) and Sn(IV) oxidation states; (2) Sn-F binding on mineral surfaces with no evidence of SnO. The surface binding is, however, not pure Sn-F but contains contributions of other ligands, probably oxygens from surface phosphates or hydroxyl groups. Results also suggest that surface reacted stannous tin is oxidized with time, even when bound as a layer on the tooth surface. This study demonstrates for the first time the presence of Sn-F on tooth enamel post treatment and the contribution of passivation to long term stannous chemistry on tooth surfaces. The study also illustrates the practical applications of the Mössbauer technique.

Net Surface Flux Budget Over Tropical Oceans Estimated from the Tropical Rainfall Measuring Mission (TRMM)

NASA Astrophysics Data System (ADS)

Fan, Tai-Fang

We begin by defining the concept of `open' Markov processes, which are continuous-time Markov chains where probability can flow in and out through certain `boundary' states. We study open Markov processes which in the absence of such boundary flows admit equilibrium states satisfying detailed balance, meaning that the net flow of probability vanishes between all pairs of states. External couplings which fix the probabilities of boundary states can maintain such systems in non-equilibrium steady states in which non-zero probability currents flow. We show that these non-equilibrium steady states minimize a quadratic form which we call 'dissipation.' This is closely related to Prigogine's principle of minimum entropy production. We bound the rate of change of the entropy of a driven non-equilibrium steady state relative to the underlying equilibrium state in terms of the flow of probability through the boundary of the process. We then consider open Markov processes as morphisms in a symmetric monoidal category by splitting up their boundary states into certain sets of `inputs' and `outputs.' Composition corresponds to gluing the outputs of one such open Markov process onto the inputs of another so that the probability flowing out of the first process is equal to the probability flowing into the second. Tensoring in this category corresponds to placing two such systems side by side. We construct a `black-box' functor characterizing the behavior of an open Markov process in terms of the space of possible steady state probabilities and probability currents along the boundary. The fact that this is a functor means that the behavior of a composite open Markov process can be computed by composing the behaviors of the open Markov processes from which it is composed. We prove a similar black-boxing theorem for reaction networks whose dynamics are given by the non-linear rate equation. Along the way we describe a more general category of open dynamical systems where composition corresponds to gluing together open dynamical systems.

Sulfuric Acid Monohydrate: Formation and Heterogeneous Chemistry in the Stratosphere

NASA Technical Reports Server (NTRS)

Zhang, Renyi; Leu, Ming-Taun; Keyser, Leon F.

1995-01-01

We have investigated some thermodynamic properties (i.e., freezing/melting points) and heterogeneous chemistry of sulfuric acid monohydrate (SAM, H2SO4.H2O), using a fast flow reactor coupled to a quadrupole mass spectrometer. The freezing point observations of thin liquid sulfuric acid films show that for acid contents between 75 and 85 wt % the monohydrate crystallizes readily at temperatures between 220 and 240 K on a glass substrate. Once formed, SAM can be thermodynamically stable in the H2O partial pressure range of (1-4) x 10(exp -4) torr and in the temperature range of 220-240 K. For a constant H2O partial pressure, lowering the temperature causes SAM to melt when the temperature and water partial pressure conditions are out of its stability regime. The reaction probability measurements indicate that the hydrolysis of N2O5 is significantly suppressed owing to the formation of crystalline SAM: The reaction probability on water-rich SAM (with higher relative humidity, or RH) is of the order of 10(exp -3) at 210 K and decreases by more than an order of magnitude for the acid-rich form (with lower RH). The hydrolysis rate of ClONO2 on water-rich SAM is even smaller, of the order of 10(exp -4) at 195 K. These reported values on crystalline SAM are much smaller than those on liquid solutions. No enhancement of these reactions is observed in the presence of HCl vapor at the stratospheric concentrations. In addition, Brunauer, Emmett, and Teller analysis of gas adsorption isotherms and photomicrography have been performed to characterize the surface roughness and porosities of the SAM substrate. The results suggest the possible formation of SAM in some regions of the middle- or low-latitude stratosphere and, consequently, much slower heterogeneous reactions on the frozen aerosols.

Quantum Dynamics Scattering Study of AB+CDE Reactions: A Seven Dimensional Treatment for the H2+C2H Reaction

NASA Technical Reports Server (NTRS)

Wang, Dunyou

2003-01-01

A time-dependent wave-packet approach is presented for the quantum dynamics study of the AB+CDE reaction system for zero total angular momentum. A seven-degree-of-freedom calculation is employed to study the chemical reaction of H2+C2H yields H + C2H2 by treating C2H as a linear molecule. Initial state selected reaction probabilities are presented for various initial ro-vibrational states. This study shows that vibrational excitation of H2 enhances the reaction probability, whereas the excitation of C2H has only a small effect on the reactivity. An integral cross section is also reported for the initial ground states of H2 and C2H. The theoretical and experimental results agree with each other very well when the calculated seven dimensional results are adjusted to account for the lower transition state barrier heights found in recent ab initio calculations.

Sulfur-bearing coatings on fly ash from a coal-fired power plant: Composition, origin, and influence on ash alteration

USGS Publications Warehouse

Fishman, N.S.; Rice, C.A.; Breit, G.N.; Johnson, R.D.

1999-01-01

Fly ash samples collected from two locations in the exhaust stream of a coal-fired power plant differ markedly with respect to the abundance of thin (???0.1 ??m) sulfur-rich surface coatings that are observable by scanning electron microscopy. The coatings, tentatively identified as an aluminum-potassium-sulfate phase, probably form upon reaction between condensed sulfuric acid aerosols and glass surfaces, and are preferentially concentrated on ash exposed to exhaust stream gases for longer. The coatings are highly soluble and if sufficiently abundant, can impart an acidic pH to solutions initially in contact with ash. These observations suggest that proposals for ash use and predictions of ash behavior during disposal should consider the transient, acid-generating potential of some ash fractions and the possible effects on initial ash leachability and alteration. ?? 1998 Elsevier Science Ltd.

Mathematical modeling of chemical composition modification and etching of polymers under the atomic oxygen influence

NASA Astrophysics Data System (ADS)

Chirskaia, Natalia; Novikov, Lev; Voronina, Ekaterina

2016-07-01

Atomic oxygen (AO) of the upper atmosphere is one of the most important space factors that can cause degradation of spacecraft surface. In our previous mathematical model the Monte Carlo method and the "large particles" approximation were used for simulating processes of polymer etching under the influence of AO [1]. The interaction of enlarged AO particles with the polymer was described in terms of probabilities of reactions such as etching of polymer and specular and diffuse scattering of the AO particles on polymer. The effects of atomic oxygen on protected polymers and microfiller containing composites were simulated. The simulation results were in quite good agreement with the results of laboratory experiments on magnetoplasmadynamic accelerator of the oxygen plasma of SINP MSU [2]. In this paper we present a new model that describes the reactions of AO interactions with polymeric materials in more detail. Reactions of formation and further emission of chemical compounds such as CO, CO _{2}, H _{2}O, etc. cause the modification of the chemical composition of the polymer and change the probabilities of its consequent interaction with the AO. The simulation results are compared with the results of previous simulation and with the results of laboratory experiments. The reasons for the differences between the results of natural experiments on spacecraft, laboratory experiments and simulations are discussed. N. Chirskaya, M. Samokhina, Computer modeling of polymer structures degradation under the atomic oxygen exposure, WDS'12 Proceedings of Contributed Papers: Part III - Physics, Matfyzpress Prague, 2012, pp. 30-35. E. Voronina, L. Novikov, V. Chernik, N. Chirskaya, K. Vernigorov, G. Bondarenko, and A. Gaidar, Mathematical and experimental simulation of impact of atomic oxygen of the earth's upper atmosphere on nanostructures and polymer composites, Inorganic Materials: Applied Research, 2012, vol. 3, no. 2, pp. 95-101.

Renner-Teller quantum dynamics of NH(a(1)Delta) + H reactions on the NH(2) A(2)A(1) and X(2)B(1) coupled surfaces.

PubMed

Defazio, P; Gamallo, P; González, M; Petrongolo, C

2010-09-16

Four reactions NH(a1Delta) + H′(2S) are investigated by the quantum mechanical real wavepacket method, taking into account nonadiabatic Renner-Teller (RT) and rovibronic Coriolis couplings between the involved states. We consider depletion (d) to N(2D) + H2(X1Sigmag+), exchange (e) to NH′(a1Delta) + H(2S), quenching (q) to NH(X3Sigma-) + H′(2S), and exchange-quenching (eq) to NH′(X3Sigma-) + H(2S). We extend our RT theory to a general AB + C collision using a geometry-dependent but very simple and empirical RT matrix element. Reaction probabilities, cross sections, and rate constants are presented, and RT results are compared with Born-Oppenheimer (BO), experimental, and semiclassical data. The nonadiabatic couplings open two new channels, (q) and (eq), and increase the (d) and (e) reactivity with respect to the BO one, when NH(a1Delta) is rotationally excited. In this case, the quantum cross sections are larger than the semiclassical ones at low collision energies. The calculated rate constants at 300 K are k(d) = 3.06, k(e) = 3.32, k(q) = 1.44, and k(eq) = 1.70 in 10(-11) cm3 s(-1) compared with the measured values k(d) = (3.2 =/- 1.7), k(q + eq) = (1.7 +/- 0.3), and k(total) = (4.8 +/- 1.7). The theoretical depletion rate is thus in good agreement with the experimental value, but the quenching and total rates are overestimated, because the present RT couplings are too large. This discrepancy is probably due to our simple and empirical RT matrix element.

Determination of NH2 concentration on 3-aminopropyl tri-ethoxy silane layers and cyclopropylamine plasma polymers by liquid-phase derivatization with 5-iodo 2-furaldehyde

NASA Astrophysics Data System (ADS)

Manakhov, Anton; Čechal, Jan; Michlíček, Miroslav; Shtansky, Dmitry V.

2017-08-01

The quantification of concentration of primary amines, e.g. in plasma polymerized layers is a very important task for surface analysis. However, the commonly used procedure, such as gas phase derivatization with benzaldehydes, shows several drawbacks, the most important of which are the side reaction effects. In the present study we propose and validate a liquid phase derivatization using 5-iodo 2-furaldehyde (IFA). It was demonstrated that the content of NH2 groups can be determined from the atomic concentrations measured by X-ray photoelectron spectroscopy (XPS), in particular from the ratio of I 3d and N 1s peak intensities. First, we demonstrate the method on a prototypical system such as 3-aminopropyl tri-ethoxy silane (APTES) layer. Here the XPS analysis carried out after reaction of APTES layer with IFA gives the fraction of primary amines (NH2/N) of 38.3 ± 7.9%. Comparing this value with that obtained by N 1s curve fitting of APTES layer giving 40.9 ± 9.5% of amine groups, it can be concluded that all primary amines were derivatized by reaction with IFA. The second system to demonstrate the method comprises cyclopropylamine (CPA) plasma polymers that were free from conjugated imines. In this case the method gives the NH2 fraction ∼8.5%. This value is closely matching the NH2/N ratio estimated by 4-trifluoromethyl benzaldehyde (TFBA) derivatization. The reaction of IFA with CPA plasma polymer exhibiting high density of conjugated imines revealed the NH2/N fraction of ∼10.8%. This value was significantly lower compared to 17.3% estimated by TFBA derivatization. As the overestimated density of primary amines measured by TFBA derivatization is probably related to the side reaction of benzaldehydes with conjugated imines, the proposed IFA derivatization of primary amines can be an alternative procedure for the quantification of surface amine groups.

Physics and chemistry in the process of hot-wire deposition of thin film silicon

NASA Astrophysics Data System (ADS)

Zheng, Wengang

Hotwire Chemical Vapor Deposition (CVD) has been used in preparing high quality low hydrogen content hydrogenated amorphous or polycrystalline silicon thin film in recent years. Comparing to the most commonly used glow discharge method, Hotwire CVD has the potential of high speed deposition avoiding the damage caused by ion bombardment associated with plasma. Although device quality thin films have been prepared by this method, and some empirical optimized deposition conditions have been established, the mechanisms controlling this technique are not clear. A homebuild threshold ionization mass spectrometer was constructed in this lab, allowing the radicals to be observed with high sensitivity. Hydrogen dissociation on the hot metal surface was studied first both by the direct detection of hydrogen atoms from the hot surface and the temperature change due to the hydrogen dissociation, it was confirmed that the activation energy of this process is around 2.25eV, the same as the dissociation in the gas phase. Further, we observed a first order dependence of hydrogen dissociation probability on the hydrogen pressure. This observation contradicts previously reported models of second order desorption. The monosilicon radicals Si and SiH3 were observed. It was observed that the silane decomposition on the hot surface is mainly a function of filament temperature, but the species released from that surface also depend on the surface condition, and thus on the silane exposure history of that piece of filament. Si is believed to deteriorate the film quality, by comparing the depleted silane and the Si flux, it is observed that Si experienced a lot of gas phase reactions before reaching the substrate, which leads to less reactive precursors. This observation is consistence with Molenbroek's study on the optimization of deposition condition. The dominant disilicon radical is identified as Si2H2, which in the form of lowest energy isomer, is suppose to be much less reactive than Si, and thus contributes to good quality thin film deposition. The corresponding Si insert reaction Si + SiH4 was also studied and an effective reaction coefficient of KSeff = 5 x 10-12( cm3/s was established.

Selective scanning tunnelling microscope electron-induced reactions of single biphenyl molecules on a Si(100) surface.

PubMed

Riedel, Damien; Bocquet, Marie-Laure; Lesnard, Hervé; Lastapis, Mathieu; Lorente, Nicolas; Sonnet, Philippe; Dujardin, Gérald

2009-06-03

Selective electron-induced reactions of individual biphenyl molecules adsorbed in their weakly chemisorbed configuration on a Si(100) surface are investigated by using the tip of a low-temperature (5 K) scanning tunnelling microscope (STM) as an atomic size source of electrons. Selected types of molecular reactions are produced, depending on the polarity of the surface voltage during STM excitation. At negative surface voltages, the biphenyl molecule diffuses across the surface in its weakly chemisorbed configuration. At positive surface voltages, different types of molecular reactions are activated, which involve the change of adsorption configuration from the weakly chemisorbed to the strongly chemisorbed bistable and quadristable configurations. Calculated reaction pathways of the molecular reactions on the silicon surface, using the nudge elastic band method, provide evidence that the observed selectivity as a function of the surface voltage polarity cannot be ascribed to different activation energies. These results, together with the measured threshold surface voltages and the calculated molecular electronic structures via density functional theory, suggest that the electron-induced molecular reactions are driven by selective electron detachment (oxidation) or attachment (reduction) processes.

Kinetics and mechanism for degradation of dichlorvos by permanganate in drinking water treatment.

PubMed

Liu, Chao; Qiang, Zhimin; Adams, Craig; Tian, Fang; Zhang, Tao

2009-08-01

The degradation kinetics and mechanism of dichlorvos by permanganate during drinking water treatment were investigated. The reaction of dichlorvos with permanganate was of second-order overall with negligible pH dependence and an activation energy of 29.5 kJ x mol(-1). At pH 7.0 and 25 degrees C, the rate constant was 25.2+/-0.4M(-1)s(-1). Dichlorvos was first degraded to trimethyl phosphate (TMP) and dimethyl phosphate (DMP) simultaneously which approximately accounted for <5% and >or=95% with respect to phosphorus mass, respectively. Further oxidation of DMP generated a final byproduct, monomethyl phosphate (MMP). MMP was for the first time identified as a major byproduct in chemical oxidation of dichlorvos. The kinetic model based on degradation mechanism and determined reaction rate constants allowed us to predict the evolution of dichlorvos and its byproduct concentrations during permanganate pre-oxidation process at water treatment plants. These results suggest that even though the dichlorvos concentration in surface water complies with the surface water quality standards of China (50 microg L(-1)), its concentration after conventional water treatment will most probably exceed the drinking water quality standards (1 microg L(-1)). Moreover, luminescent bacteria test shows that the acute toxicity of dichlorvos solution evidently increased after permanganate oxidation.

Toward efficiency in heterogeneous multispecies reactive transport modeling: A particle-tracking solution for first-order network reactions

NASA Astrophysics Data System (ADS)

Henri, Christopher; Fernàndez-Garcia, Daniel

2015-04-01

Modeling multi-species reactive transport in natural systems with strong heterogeneities and complex biochemical reactions is a major challenge for assessing groundwater polluted sites with organic and inorganic contaminants. A large variety of these contaminants react according to serial-parallel reaction networks commonly simplified by a combination of first-order kinetic reactions. In this context, a random-walk particle tracking method is presented. This method is capable of efficiently simulating the motion of particles affected by first-order network reactions in three-dimensional systems, which are represented by spatially variable physical and biochemical coefficients described at high resolution. The approach is based on the development of transition probabilities that describe the likelihood that particles belonging to a given species and location at a given time will be transformed into and moved to another species and location afterwards. These probabilities are derived from the solution matrix of the spatial moments governing equations. The method is fully coupled with reactions, free of numerical dispersion and overcomes the inherent numerical problems stemming from the incorporation of heterogeneities to reactive transport codes. In doing this, we demonstrate that the motion of particles follows a standard random walk with time-dependent effective retardation and dispersion parameters that depend on the initial and final chemical state of the particle. The behavior of effective parameters develops as a result of differential retardation effects among species. Moreover, explicit analytic solutions of the transition probability matrix and related particle motions are provided for serial reactions. An example of the effect of heterogeneity on the dechlorination of organic solvents in a three-dimensional random porous media shows that the power-law behavior typically observed in conservative tracers breakthrough curves can be largely compromised by the effect of biochemical reactions.

Toward efficiency in heterogeneous multispecies reactive transport modeling: A particle-tracking solution for first-order network reactions

NASA Astrophysics Data System (ADS)

Henri, Christopher V.; Fernàndez-Garcia, Daniel

2014-09-01

Modeling multispecies reactive transport in natural systems with strong heterogeneities and complex biochemical reactions is a major challenge for assessing groundwater polluted sites with organic and inorganic contaminants. A large variety of these contaminants react according to serial-parallel reaction networks commonly simplified by a combination of first-order kinetic reactions. In this context, a random-walk particle tracking method is presented. This method is capable of efficiently simulating the motion of particles affected by first-order network reactions in three-dimensional systems, which are represented by spatially variable physical and biochemical coefficients described at high resolution. The approach is based on the development of transition probabilities that describe the likelihood that particles belonging to a given species and location at a given time will be transformed into and moved to another species and location afterward. These probabilities are derived from the solution matrix of the spatial moments governing equations. The method is fully coupled with reactions, free of numerical dispersion and overcomes the inherent numerical problems stemming from the incorporation of heterogeneities to reactive transport codes. In doing this, we demonstrate that the motion of particles follows a standard random walk with time-dependent effective retardation and dispersion parameters that depend on the initial and final chemical state of the particle. The behavior of effective parameters develops as a result of differential retardation effects among species. Moreover, explicit analytic solutions of the transition probability matrix and related particle motions are provided for serial reactions. An example of the effect of heterogeneity on the dechlorination of organic solvents in a three-dimensional random porous media shows that the power-law behavior typically observed in conservative tracers breakthrough curves can be largely compromised by the effect of biochemical reactions.

Some fundamental properties and reactions of ice surfaces at low temperatures.

PubMed

Park, Seong-Chan; Moon, Eui-Seong; Kang, Heon

2010-10-14

Ice surfaces offer a unique chemical environment in which reactions occur quite differently from those in liquid water or gas phases. In this article, we examine the basic properties of ice surfaces below the surface premelting temperature and discuss some of the recent investigations carried out on reactions at the ice surfaces. The static and dynamic properties of an ice surface as a reaction medium, such as its structure, molecule diffusion and proton transfer dynamics, and the surface preference of hydronium and hydroxide ions, are discussed in relation to the reactivity of the surface.

Results of experiments related to contact of mine-spoils water with coal, West Decker and Big Sky Mines, southeastern Montana

USGS Publications Warehouse

Davis, R.E.; Dodge, K.A.

1986-01-01

Batch-mixing experiments using spoils water and coal from the West Decker and Big Sky Mines were conducted to determine possible chemical changes in water moving from coal-mine spoils through a coal aquifer. The spoils water was combined with air-dried and oven-dried chunks of coal and air-dried and oven-dried crushed coal at a 1:1 weight ratio, mixed for 2 hr, and separated after a total contact time of 24 hr. The dissolved-solids concentration in water used in the experiments decreased an average 210 mg/liter (5-10%). Other chemical changes included general decreases in the concentrations of magnesium, potassium, and bicarbonate, and general increases in the concentrations of barium and boron. The magnitude of the changes increased as the surface area of the coal increased. The quantity of extractable cations and exchangeable cations on the post-mixing coal was larger than on the pre-mixing coal. Equilibrium and mass-transfer relations indicate that adsorption reactions or ion-exchange and precipitation reactions, or both, probably are the major reactions responsible for the chemical changes observed in the experiments. (Authors ' abstract)

When the Sun's Away, N2O5 Comes Out to Play: An Updated Analysis of Ambient N2O5 Heterogeneous Chemistry

NASA Astrophysics Data System (ADS)

McDuffie, E. E.; Brown, S. S.

2017-12-01

The heterogeneous chemistry of N2O5 impacts the budget of tropospheric oxidants, which directly controls air quality at Earth's surface. The reaction between gas-phase N2O5 and aerosol particles occurs largely at night, and is therefore more important during the less-intensively-studied winter season. Though N2O5-aerosol interactions are vital for the accurate understanding and simulation of tropospheric chemistry and air quality, many uncertainties persist in our understanding of how various environmental factors influence the reaction rate and probability. Quantitative and accurate evaluation of these factors directly improves the predictive capabilities of atmospheric models, used to inform mitigation strategies for wintertime air pollution. In an update to last year's presentation, The Wintertime Fate of N2O5: Observations and Box Model Analysis for the 2015 WINTER Aircraft Campaign, this presentation will focus on recent field results regarding new information about N2O5 heterogeneous chemistry and future research directions.

Gas-liquid countercurrent integration process for continuous biodiesel production using a microporous solid base KF/CaO as catalyst.

PubMed

Hu, Shengyang; Wen, Libai; Wang, Yun; Zheng, Xinsheng; Han, Heyou

2012-11-01

A continuous-flow integration process was developed for biodiesel production using rapeseed oil as feedstock, based on the countercurrent contact reaction between gas and liquid, separation of glycerol on-line and cyclic utilization of methanol. Orthogonal experimental design and response surface methodology were adopted to optimize technological parameters. A second-order polynomial model for the biodiesel yield was established and validated experimentally. The high determination coefficient (R(2)=98.98%) and the low probability value (Pr<0.0001) proved that the model matched the experimental data, and had a high predictive ability. The optimal technological parameters were: 81.5°C reaction temperature, 51.7cm fill height of catalyst KF/CaO and 105.98kPa system pressure. Under these conditions, the average yield of triplicate experiments was 93.7%, indicating the continuous-flow process has good potential in the manufacture of biodiesel. Copyright © 2012 Elsevier Ltd. All rights reserved.

Prevalence and factors associated to peanut allergy in Mexican school children.

PubMed

Bedolla-Barajas, M; Valdez-López, F; Alcalá-Padilla, G; Bedolla-Pulido, T I; Rivera-Mejia, V; Morales-Romero, J

In our country, the prevalence and the factors associated to peanut allergy are unknown, a health problem that has been emerging worldwide. To establish the prevalence and the factors that are associated to peanut allergy amongst school children. This is a population-based cross-sectional study. We included 756 children aged 6-7 years. The children's parents were questioned about their peanut intake habits. A structured questionnaire was applied, it included questions regarding peanut intake; family and personal history of asthma; rhinitis; and atopic dermatitis. Allergic reactions to peanuts were registered as: probable, convincing and systematic. The statistical analyses included logistical regression models to look for associated factors. Males were 356/756 (47.1%). Peanut allergy prevalence: probable reaction: 14/756 (1.8%), convincing reaction: 8/756 (1.1%) and systemic reaction: 3/756 (0.4%). Through multivariate analysis, the presence of symptoms of allergic rhinitis (OR=4.2 95% CI 1.3-13.2) and atopic dermatitis (OR=5.2; 95% CI 1.4-19.5) during the previous year, showed significant association to probable peanut reaction. The former year, the presence of atopic dermatitis was the only variable that was substantially associated to a convincing reaction (OR=7.5; 95% CI 1.4-38.4) and to a systematic reaction (OR=45.1; 95% CI 4.0-510.0), respectively. The reported prevalence of peanut allergy was consistent with that found in previous studies; symptoms of allergic rhinitis and atopic dermatitis were identified as associated factors to peanut allergy. Copyright © 2016 SEICAP. Published by Elsevier España, S.L.U. All rights reserved.

Multiscale Modeling of Ablation and Pyrolysis in PICA-Like materials

NASA Technical Reports Server (NTRS)

Lachaud, Jean; Mansour, Nagi N.

2008-01-01

During atmospheric entry of planetary probes, the thermal protection system (TIPS) of the probe is exposed to high temperatures under low pressures. In these conditions, carbonous fibrous TIPS materials may undergo oxidation leading to mass loss and wall recession called ablation. This work aims to improve the understanding of material/environment interactions through a study of the coupling between oxygen transport in the Knudsen regime, heterogeneous oxidation of carbon, and surface recession. A 3D Random Walk Monte Carlo simulation tool is used for this study. The fibrous architecture of a model material, consisting of high porosity random array of carbon fibers, is numerically represented on a 3D Cartesian grid. Mass transport in the Knudsen regime from the boundary layer to the surface, and inside this porous material is simulated by random walk. A reaction probability is used to simulate the heterogeneous oxidation reaction. The surface recession of the fibers is followed by front tracking using a simplified marching cube approach. The output data of the simulations are ablation velocity and dynamic evolution of the material porosity. A parametric study is carried out to analyze the material behavior as a function of Knudsen number for the porous media (length of the mean free path compared to the mean pore diameter) and the intrinsic reactivity of the carbon fibers. The model is applied to Stardust mission reentry conditions and explains the unexpected behavior of the TIPS material that underwent mass loss in volume.

Theory of rotational transition in atom-diatom chemical reaction

NASA Astrophysics Data System (ADS)

Nakamura, Masato; Nakamura, Hiroki

1989-05-01

Rotational transition in atom-diatom chemical reaction is theoretically studied. A new approximate theory (which we call IOS-DW approximation) is proposed on the basis of the physical idea that rotational transition in reaction is induced by the following two different mechanisms: rotationally inelastic half collision in both initial and final arrangement channels, and coordinate transformation in the reaction zone. This theory gives a fairy compact expression for the state-to-state transition probability. Introducing the additional physically reasonable assumption that reaction (particle rearrangement) takes place in a spatially localized region, we have reduced this expression into a simpler analytical form which can explicitly give overall rotational state distribution in reaction. Numerical application was made to the H+H2 reaction and demonstrated its effectiveness for the simplicity. A further simplified most naive approximation, i.e., independent events approximation was also proposed and demonstrated to work well in the test calculation of H+H2. The overall rotational state distribution is expressed simply by a product sum of the transition probabilities for the three consecutive processes in reaction: inelastic transition in the initial half collision, transition due to particle rearrangement, and inelastic transition in the final half collision.

Improved techniques for outgoing wave variational principle calculations of converged state-to-state transition probabilities for chemical reactions

NASA Technical Reports Server (NTRS)

Mielke, Steven L.; Truhlar, Donald G.; Schwenke, David W.

1991-01-01

Improved techniques and well-optimized basis sets are presented for application of the outgoing wave variational principle to calculate converged quantum mechanical reaction probabilities. They are illustrated with calculations for the reactions D + H2 yields HD + H with total angular momentum J = 3 and F + H2 yields HF + H with J = 0 and 3. The optimization involves the choice of distortion potential, the grid for calculating half-integrated Green's functions, the placement, width, and number of primitive distributed Gaussians, and the computationally most efficient partition between dynamically adapted and primitive basis functions. Benchmark calculations with 224-1064 channels are presented.

Multifocal Epithelial Hyperplasia of Oral Cavity Expressing HPV 16 Gene: A Rare Entity

PubMed Central

Prabhat, M. P. V.; Raja Lakshmi, Chintamaneni; Sai Madhavi, N.; Bhavana, Sujana Mulk; Sarat, Gummadapu; Ramamohan, Kodali

2013-01-01

Focal epithelial hyperplasia is a rare contagious disease caused by human papilloma virus. Usually HPV involves either cutaneous or mucosal surfaces, whereas concomitant mucocutaneous involvement is extremely rare. We report such a unique case of multifocal epithelial hyperplasia involving multiple sites of oral cavity along with skin lesions in a 65-year-old female. We also discuss the probable multifactorial etiology and variable clinical presentations of the lesions, including evidence of HPV 16 expression, as detected by polymerase chain reaction. The present report illustrates the need for careful examination and prompt diagnosis of the disease, as it might be associated with high risk genotypes such as HPV 16 and 18. PMID:24455323

Uncertainties and understanding of experimental and theoretical results regarding reactions forming heavy and superheavy nuclei

NASA Astrophysics Data System (ADS)

Giardina, G.; Mandaglio, G.; Nasirov, A. K.; Anastasi, A.; Curciarello, F.; Fazio, G.

2018-02-01

Experimental and theoretical results of the PCN fusion probability of reactants in the entrance channel and the Wsur survival probability against fission at deexcitation of the compound nucleus formed in heavy-ion collisions are discussed. The theoretical results for a set of nuclear reactions leading to formation of compound nuclei (CNs) with the charge number Z = 102- 122 reveal a strong sensitivity of PCN to the characteristics of colliding nuclei in the entrance channel, dynamics of the reaction mechanism, and excitation energy of the system. We discuss the validity of assumptions and procedures for analysis of experimental data, and also the limits of validity of theoretical results obtained by the use of phenomenological models. The comparison of results obtained in many investigated reactions reveals serious limits of validity of the data analysis and calculation procedures.

Studies on the synthesis of isotopes of superheavy element Lv (Z = 116)

NASA Astrophysics Data System (ADS)

Santhosh, K. P.; Safoora, V.

2017-11-01

The probable projectile-target combinations for the synthesis of superheavy nucleus 296Lv found in the cold valley of 296Lv have been identified by studying the interaction barrier of the colliding nuclei, probability of compound nucleus formation, P_{CN}, and survival probability W_{sur}. At energies near and above the Coulomb barrier, the capture, fusion and evaporation residue (ER) cross sections for the probable combinations for the hot and cold fusion reactions are systematically investigated. By considering intensities of the projectile beams, availabilities of the targets and half lives of the colliding nuclei, the combination 48Ca+248Cm is found to be the most probable projectile-target pair for the synthesis of 296Lv. The calculated maximum value of 2n, 3n, 4n and 5n channel cross section for the reaction 48Ca+248Cm are 0.599 pb, 5.957 pb, 4.805 pb, and 0.065 pb, respectively. Moreover, the production cross sections for the synthesis of isotopes 291-295,298Lv using 48Ca projectile on 243-247,250Cm targets are calculated. Among these reactions, the reactions 48Ca+247Cm → 295Lv and 48Ca+250Cm → 298Lv have maximum production cross section in 3n (10.697 pb) and 4n (12.006 pb) channel, respectively. Our studies on the SHE Lv using the combinations 48Ca+245Cm → 293Lv and 48Ca+248Cm → 296Lv are compared with available experimental data and with other theoretical studies. Our studies are in agreement with experimental data and we hope that these studies will be a guide for the future experiments to synthesize the isotopes of Lv.

2013 Chemical reactions at surfaces. Surfaces in Energy and the Environment. Gordon Research Conference and Gordon Research Seminar (April 28 - May 3, 2013 - Les Diablerets, Switzerland)

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

Stair, Peter C.

presentations on chemistry at solid and liquid surfaces of relevance to catalysis, synthesis, photochemistry, environmental science, and tribology. Topics include: Fundamental Surface Chemistry; Catalysis; Solid Liquid and Aerosol Interfaces; Surface Photochemistry; Synthesis of Surfaces; Environmental Interfaces; Hot Topics in Surface Chemical Reactions; Tribology; Gas-Surface Scattering and Reactions; Novel Materials and Environments.

Vapor-deposited water and nitric acid ices

NASA Astrophysics Data System (ADS)

Leu, Ming-Taun; Keyser, Leon F.

Ices formed by vapor deposition have been the subject of numerous laboratory investigations in connection with snow and glaciers on the ground, ice clouds in the terrestrial atmosphere, surfaces of other planets and their satellites, and the interstellar medium. In this review we will focus on these specific subjects: (1) heterogeneous chemistry on the surfaces of polar stratospheric clouds (PSCs) and (2) surfaces of satellites of the outer planets in our solar system. Stratospheric ozone provides a protective shield for mankind and the global biosphere from harmful ultraviolet solar radiation. In past decades, theoretical atmospheric models for the calculation of ozone balance frequently used only homogeneous gas-phase reactions in their studies. Since the discovery of the Antarctic ozone hole in 1985, however, it has been demonstrated that knowledge of heterogeneous reactions on the surface of PSCs is definitely needed to understand this significant natural event due to the anthropogenic emission of chlorofluorocarbons (CFCs). We will briefly discuss the experimental techniques for the investigation of heterogeneous chemistry on ice surfaces carried out in our laboratories. The experimental apparatus used include: several flow-tube reactors, an electron-impact ionization mass spectrometer, a Fourier transform infrared spectrometer, a BET adsorption apparatus, and a scanning environmental electron microscope. The adsorption experiments and electron microscopic work have demonstrated that the vapor-deposited ices are highly porous. Therefore, it is necessary to develop theoretical models for the elucidation of the uptake and reactivity of trace gases in porous ice substrates. Several measurements of uptake and reaction probabilities of these trace gases on water ices and nitric acid ices have been performed under ambient conditions in the upper troposphere and lower stratosphere, mainly in the temperature range 180-220 K. The trace gases of atmospheric importance in heterogeneous chemistry include: ClONO2, HCl, HOCl, and HNO3. In addition, recent interest in the possible landing of a robotic spacecraft on the surface of Europa, one of the Galilean satellites of Jupiter, and ground based telescopic observations demand detailed knowledge of the physical properties of the icy surfaces of the outer planets and their satellites. Lower temperature studies in the range 77-150 K using both electron microscopy and adsorption isotherms (BET surface area measurements) have revealed some intriguing observations that may provide some insights for remote sensing of these satellite surfaces. Finally, we will attempt to summarize our recent results and suggest future research directions in both theoretical and laboratory investigations.

The use of clamping grips and friction pads by tree frogs for climbing curved surfaces

PubMed Central

Ji, Aihong; Yuan, Shanshan; Hill, Iain; Wang, Huan; Barnes, W. Jon P.; Dai, Zhendong; Sitti, Metin

2017-01-01

Most studies on the adhesive mechanisms of climbing animals have addressed attachment against flat surfaces, yet many animals can climb highly curved surfaces, like twigs and small branches. Here we investigated whether tree frogs use a clamping grip by recording the ground reaction forces on a cylindrical object with either a smooth or anti-adhesive, rough surface. Furthermore, we measured the contact area of fore and hindlimbs against differently sized transparent cylinders and the forces of individual pads and subarticular tubercles in restrained animals. Our study revealed that frogs use friction and normal forces of roughly a similar magnitude for holding on to cylindrical objects. When challenged with climbing a non-adhesive surface, the compressive forces between opposite legs nearly doubled, indicating a stronger clamping grip. In contrast to climbing flat surfaces, frogs increased the contact area on all limbs by engaging not just adhesive pads but also subarticular tubercles on curved surfaces. Our force measurements showed that tubercles can withstand larger shear stresses than pads. SEM images of tubercles revealed a similar structure to that of toe pads including the presence of nanopillars, though channels surrounding epithelial cells were less pronounced. The tubercles' smaller size, proximal location on the toes and shallow cells make them probably less prone to buckling and thus ideal for gripping curved surfaces. PMID:28228509

Sum over Histories Representation for Kinetic Sensitivity Analysis: How Chemical Pathways Change When Reaction Rate Coefficients Are Varied

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

Bai, Shirong; Davis, Michael J.; Skodje, Rex T.

2015-11-12

The sensitivity of kinetic observables is analyzed using a newly developed sum over histories representation of chemical kinetics. In the sum over histories representation, the concentrations of the chemical species are decomposed into the sum of probabilities for chemical pathways that follow molecules from reactants to products or intermediates. Unlike static flux methods for reaction path analysis, the sum over histories approach includes the explicit time dependence of the pathway probabilities. Using the sum over histories representation, the sensitivity of an observable with respect to a kinetic parameter such as a rate coefficient is then analyzed in terms of howmore » that parameter affects the chemical pathway probabilities. The method is illustrated for species concentration target functions in H-2 combustion where the rate coefficients are allowed to vary over their associated uncertainty ranges. It is found that large sensitivities are often associated with rate limiting steps along important chemical pathways or by reactions that control the branching of reactive flux« less

Consistent post-reaction vibrational energy redistribution in DSMC simulations using TCE model

NASA Astrophysics Data System (ADS)

Borges Sebastião, Israel; Alexeenko, Alina

2016-10-01

The direct simulation Monte Carlo (DSMC) method has been widely applied to study shockwaves, hypersonic reentry flows, and other nonequilibrium flow phenomena. Although there is currently active research on high-fidelity models based on ab initio data, the total collision energy (TCE) and Larsen-Borgnakke (LB) models remain the most often used chemistry and relaxation models in DSMC simulations, respectively. The conventional implementation of the discrete LB model, however, may not satisfy detailed balance when recombination and exchange reactions play an important role in the flow energy balance. This issue can become even more critical in reacting mixtures involving polyatomic molecules, such as in combustion. In this work, this important shortcoming is addressed and an empirical approach to consistently specify the post-reaction vibrational states close to thermochemical equilibrium conditions is proposed within the TCE framework. Following Bird's quantum-kinetic (QK) methodology for populating post-reaction states, the new TCE-based approach involves two main steps. The state-specific TCE reaction probabilities for a forward reaction are first pre-computed from equilibrium 0-D simulations. These probabilities are then employed to populate the post-reaction vibrational states of the corresponding reverse reaction. The new approach is illustrated by application to exchange and recombination reactions relevant to H2-O2 combustion processes.

Insight into Chemistry on Cloud/Aerosol Water Surfaces.

PubMed

Zhong, Jie; Kumar, Manoj; Francisco, Joseph S; Zeng, Xiao Cheng

2018-05-15

Cloud/aerosol water surfaces exert significant influence over atmospheric chemical processes. Atmospheric processes at the water surface are observed to follow mechanisms that are quite different from those in the gas phase. This Account summarizes our recent findings of new reaction pathways on the water surface. We have studied these surface reactions using Born-Oppenheimer molecular dynamics simulations. These studies provide useful information on the reaction time scale, the underlying mechanism of surface reactions, and the dynamic behavior of the product formed on the aqueous surface. According to these studies, the aerosol water surfaces confine the atmospheric species into a specific orientation depending on the hydrophilicity of atmospheric species or the hydrogen-bonding interactions between atmospheric species and interfacial water. As a result, atmospheric species are activated toward a particular reaction on the aerosol water surface. For example, the simplest Criegee intermediate (CH 2 OO) exhibits high reactivity toward the interfacial water and hydrogen sulfide, with the reaction times being a few picoseconds, 2-3 orders of magnitude faster than that in the gas phase. The presence of interfacial water molecules induces proton-transfer-based stepwise pathways for these reactions, which are not possible in the gas phase. The strong hydrophobicity of methyl substituents in larger Criegee intermediates (>C1), such as CH 3 CHOO and (CH 3 ) 2 COO, blocks the formation of the necessary prereaction complexes for the Criegee-water reaction to occur at the water droplet surface, which lowers their proton-transfer ability and hampers the reaction. The aerosol water surface provides a solvent medium for acids (e.g., HNO 3 and HCOOH) to participate in reactions via mechanisms that are different from those in the gas and bulk aqueous phases. For example, the anti-CH 3 CHOO-HNO 3 reaction in the gas phase follows a direct reaction between anti-CH 3 CHOO and HNO 3 , whereas on a water surface, the HNO 3 -mediated stepwise hydration of anti-CH 3 CHOO is dominantly observed. The high surface/volume ratio of interfacial water molecules at the aerosol water surface can significantly lower the energy barriers for the proton transfer reactions in the atmosphere. Such catalysis by the aerosol water surface is shown to cause the barrier-less formation of ammonium bisulfate from hydrated NH 3 and SO 3 molecules rather than from the reaction of H 2 SO 4 with NH 3 . Finally, an aerosol water droplet is a polar solvent, which would favorably interact with high polarity substrates. This can accelerate interconversion of different conformers (e.g., anti and syn) of atmospheric species, such as glyoxal, depending on their polarity. The results discussed here enable an improved understanding of atmospheric processes on the aerosol water surface.

A density functional theory study on the carbon chain growth of ethanol formation on Cu-Co (111) and (211) surfaces

NASA Astrophysics Data System (ADS)

Ren, Bohua; Dong, Xiuqin; Yu, Yingzhe; Wen, Guobin; Zhang, Minhua

2017-08-01

Calculations based on the first-principle density functional theory were carried out to study the most controversial reactions in ethanol formation from syngas on Cu-Co surfaces: CO dissociation mechanism and the key reactions of carbon chain growth of ethanol formation (HCO insertion reactions) on four model surfaces (Cu-Co (111) and (211) with Cu-rich or Co-rich surfaces) to investigate the synergy of the Cu and Co components since the complete reaction network of ethanol formation from syngas is a huge computational burden to calculate on four Cu-Co surface models. We investigated adsorption of important species involved in these reactions, activation barrier and reaction energy of H-assisted dissociation mechanism, directly dissociation of CO, and HCO insertion reactions (CHx + HCO → CHxCHO (x = 1-3)) on four Cu-Co surface models. It was found that reactions on Cu-rich (111) and (211) surfaces all have lower activation barrier in H-assisted dissociation and HCO insertion reactions, especially CH + HCO → CHCHO reaction. The PDOS of 4d orbitals of surface Cu and Co atoms of all surfaces were studied. Analysis of d-band center of Cu and Co atoms and the activation barrier data suggested the correlation between electronic property and catalytic performance. Cu-Co bimetallic with Cu-rich surface allows Co to have higher catalytic activity through the interaction of Cu and Co atom. Then it will improve the adsorption of CO and catalytic activity of Co. Thus it is more favorable to the carbon chain growth in ethanol formation. Our study revealed the factors influencing the carbon chain growth in ethanol production and explained the internal mechanism from electronic property aspect.

The influence of SrO and CaO in silicate and phosphate bioactive glasses on human gingival fibroblasts.

PubMed

Massera, J; Kokkari, A; Närhi, T; Hupa, L

2015-06-01

In this paper, we investigate the effect of substituting SrO for CaO in silicate and phosphate bioactive glasses on the human gingival fibroblast activity. In both materials the presence of SrO led to the formation of a CaP layer with partial Sr substitution for Ca. The layer at the surface of the silicate glass consisted of HAP whereas at the phosphate glasses it was close to the DCPD composition. In silicate glasses, SrO gave a faster initial dissolution and a thinner reaction layer probably allowing for a continuous ion release into the solution. In phosphate glasses, SrO decreased the dissolution process and gave a more strongly bonded reaction layer. Overall, the SrO-containing silicate glass led to a slight enhancement in the activity of the gingival fibroblasts cells when compared to the SrO-free reference glass, S53P4. The cell activity decreased up to 3 days of culturing for all phosphate glasses containing SrO. Whereas culturing together with the SrO-free phosphate glass led to complete cell death at 7 days. The glasses containing SrO showed rapid cell proliferation and growth between 7 and 14 days, reaching similar activity than glass S53P4. The addition of SrO in both silicate and phosphate glasses was assumed beneficial for proliferation and growth of human gingival fibroblasts due to Sr incorporation in the reaction layer at the glass surface and released in the cell culture medium.

A comprehensive model to determine the effects of temperature and species fluctuations on reaction rates in turbulent reacting flows

NASA Technical Reports Server (NTRS)

Chinitz, W.; Foy, E.; Rowan, G.; Goldstein, D.

1982-01-01

The use of probability theory to determine the effects of turbulent fluctuations on reaction rates in turbulent combustion systems is briefly reviewed. Results are presented for the effect of species fluctuations in particular. It is found that turbulent fluctuations of species act to reduce the reaction rates, in contrast with the temperature fluctuations previously determined to increase Arrhenius reaction rate constants. For the temperature fluctuations, a criterion is set forth for determining if, in a given region of a turbulent flow field, the temperature can be expected to exhibit ramp like fluctuations. Using the above results, along with results previously obtained, a model is described for testing the effects of turbulent fluctuations of temperature and species on reaction rates in computer programs dealing with turbulent reacting flows. An alternative model which employs three variable probability density functions (temperature and two species) and is currently being formulated is discussed as well.

The initial immune reaction to a new tumor antigen is always stimulatory and probably necessary for the tumor's growth.

PubMed

Prehn, Richmond T

2010-01-01

All nascent neoplasms probably elicit at least a weak immune reaction. However, the initial effect of the weak immune reaction on a nascent tumor is always stimulatory rather than inhibitory to tumor growth, assuming only that exposure to the tumor antigens did not antedate the initiation of the neoplasm (as may occur in some virally induced tumors). This conclusion derives from the observation that the relationship between the magnitude of an adaptive immune reaction and tumor growth is not linear but varies such that while large quantities of antitumor immune reactants tend to inhibit tumor growth, smaller quantities of the same reactants are, for unknown reasons, stimulatory. Any immune reaction must presumably be small before it can become large; hence the initial reaction to the first presentation of a tumor antigen must always be small and in the stimulatory portion of this nonlinear relationship. In mouse-skin carcinogenesis experiments it was found that premalignant papillomas were variously immunogenic, but that the carcinomas that arose in them were, presumably because of induced immune tolerance, nonimmunogenic in the animal of origin.

Insight into association reactions on metal surfaces: Density-functional theory studies of hydrogenation reactions on Rh(111)

NASA Astrophysics Data System (ADS)

Liu, Zhi-Pan; Hu, P.; Lee, Ming-Hsien

2003-09-01

Hydrogenation reaction, as one of the simplest association reactions on surfaces, is of great importance both scientifically and technologically. They are essential steps in many industrial processes in heterogeneous catalysis, such as ammonia synthesis (N2+3H2→2NH3). Many issues in hydrogenation reactions remain largely elusive. In this work, the NHx (x=0,1,2) hydrogenation reactions (N+H→NH, NH+H→NH2 and NH2+H→NH3) on Rh(111) are used as a model system to study the hydrogenation reactions on metal surfaces in general using density-functional theory. In addition, C and O hydrogenation (C+H→CH and O+H→OH) and several oxygenation reactions, i.e., C+O, N+O, O+O reactions, are also calculated in order to provide a further understanding of the barrier of association reactions. The reaction pathways and the barriers of all these reactions are determined and reported. For the C, N, NH, and O hydrogenation reactions, it is found that there is a linear relationship between the barrier and the valency of R (R=C, N, NH, and O). Detailed analyses are carried out to rationalize the barriers of the reactions, which shows that: (i) The interaction energy between two reactants in the transition state plays an important role in determining the trend in the barriers; (ii) there are two major components in the interaction energy: The bonding competition and the direct Pauli repulsion; and (iii) the Pauli repulsion effect is responsible for the linear valency-barrier trend in the C, N, NH, and O hydrogenation reactions. For the NH2+H reaction, which is different from other hydrogenation reactions studied, the energy cost of the NH2 activation from the IS to the TS is the main part of the barrier. The potential energy surface of the NH2 on metal surfaces is thus crucial to the barrier of NH2+H reaction. Three important factors that can affect the barrier of association reactions are generalized: (i) The bonding competition effect; (ii) the local charge densities of the reactants along the reaction direction; and (iii) the potential energy surface of the reactants on the surface. The lowest energy pathway for a surface association reaction should correspond to the one with the best compromise of these three factors.

The dissociative chemisorption of CO2 on Ni(100): A quantum dynamics study

NASA Astrophysics Data System (ADS)

Farjamnia, Azar; Jackson, Bret

2017-02-01

A quantum approach based on an expansion in vibrationally adiabatic eigenstates is used to explore the dissociative chemisorption of CO2 on Ni(100). The largest barrier to reaction corresponds to the formation of a bent anionic molecular precursor, bound to the surface by about 0.24 eV. The barrier to dissociation from this state is small. Our computed dissociative sticking probabilities on Ni(100) for molecules in the ground state are in very good agreement with available experimental data, reasonably reproducing the variation in reactivity with collision energy. Vibrational excitation of the incident CO2 can enhance reactivity, particularly for incident energies at or below threshold, and there is clear mode specific behavior. Both the vibrational enhancement and the increase in dissociative sticking with surface temperature are much weaker than that found in recent studies of methane and water dissociative chemisorption. The energetics for CO2 adsorption and dissociation on the stepped Ni(711) surface are found to be similar to that on Ni(100), except that the barrier to dissociation from the anionic precursor is even smaller on Ni(711). We predict that the dissociative sticking behavior is similar on the two surfaces.

The dissociative chemisorption of CO 2 on Ni(100): A quantum dynamics study

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

Farjamnia, Azar; Jackson, Bret

A quantum approach based on an expansion in vibrationally adiabatic eigenstates is used to explore the dissociative chemisorption of CO 2 on Ni(100). The largest barrier to reaction corresponds to the formation of a bent anionic molecular precursor, bound to the surface by about 0.24 eV. The barrier to dissociation from this state is small. In our computed dissociative sticking probabilities on Ni(100) for molecules, the ground states are in very good agreement with available experimental data, reasonably reproducing the variation in reactivity with collision energy. Vibrational excitation of the incident CO 2 can enhance reactivity, particularly for incident energiesmore » at or below threshold, and there is clear mode specific behavior. Both the vibrational enhancement and the increase in dissociative sticking with surface temperature are much weaker than that found in recent studies of methane and water dissociative chemisorption. The energetics for CO 2 adsorption and dissociation on the stepped Ni(711) surface are found to be similar to that on Ni(100), except that the barrier to dissociation from the anionic precursor is even smaller on Ni(711). Here, we predict that the dissociative sticking behavior is similar on the two surfaces.« less

The dissociative chemisorption of CO 2 on Ni(100): A quantum dynamics study

DOE PAGES

Farjamnia, Azar; Jackson, Bret

2017-02-21

A quantum approach based on an expansion in vibrationally adiabatic eigenstates is used to explore the dissociative chemisorption of CO 2 on Ni(100). The largest barrier to reaction corresponds to the formation of a bent anionic molecular precursor, bound to the surface by about 0.24 eV. The barrier to dissociation from this state is small. In our computed dissociative sticking probabilities on Ni(100) for molecules, the ground states are in very good agreement with available experimental data, reasonably reproducing the variation in reactivity with collision energy. Vibrational excitation of the incident CO 2 can enhance reactivity, particularly for incident energiesmore » at or below threshold, and there is clear mode specific behavior. Both the vibrational enhancement and the increase in dissociative sticking with surface temperature are much weaker than that found in recent studies of methane and water dissociative chemisorption. The energetics for CO 2 adsorption and dissociation on the stepped Ni(711) surface are found to be similar to that on Ni(100), except that the barrier to dissociation from the anionic precursor is even smaller on Ni(711). Here, we predict that the dissociative sticking behavior is similar on the two surfaces.« less

Dynamics of ionization of H2 by Ne*(3P) investigated by electron spectroscopy

NASA Astrophysics Data System (ADS)

Noroski, Joseph H.; Siska, P. E.

2006-10-01

The Penning ionization reaction Ne*(2p53sP3)+H2→[NeH2]++e- has been studied in crossed supersonic molecular beams with electron-energy analysis at four collision energies E =1.83, 2.50, 3.16, and 3.89kcal/mol. The electron kinetic-energy spectra, which directly reflect the ionizing transition region, show resolved peaks assignable to v'=0-4 of H2+. The vibrational populations deviate systematically from Franck-Condon behavior, suggesting that the discrete-continuum coupling increases with H2 bond stretching. Each peak displays both increasing breadth and increasing blueshift with increasing E, and the blueshift also increases with increasing v'. The first two properties are consistent with a predominantly repulsive excited-state potential-energy surface, while the last is speculated to be a reflection of the rHH dependence of the ionic surface. Quantum scattering calculations based on ab initio potential surfaces for the excited and ionic states in spherical and infinite-order-sudden rigid rotor approximations are in semiquantitative agreement with the measurements. Discrepancies suggest changes in the imaginary, absorptive part of the excited surface, which probably can be best effected by multiproperty fitting calculations.

The OH + D2 --> HOD + D angle-velocity distribution: quasi-classical trajectory calculations on the YZCL2 and WSLFH potential energy surfaces and comparison with experiments at ET = 0.28 eV.

PubMed

Sierra, José Daniel; Martínez, Rodrigo; Hernando, Jordi; González, Miguel

2009-12-28

The angle-velocity distribution (HOD) of the OH + D(2) reaction at a relative translational energy of 0.28 eV has been calculated using the quasi-classical trajectory (QCT) method on the two most recent potential energy surfaces available (YZCL2 and WSLFH PESs), widely extending a previous investigation of our group. Comparison with the high resolution experiments of Davis and co-workers (Science, 2000, 290, 958) shows that the structures (peaks) found in the relative translational energy distributions of products could not be satisfactorily reproduced in the calculations, probably due to the classical nature of the QCT method and the importance of quantum effects. The calculations, however, worked quite well for other properties. Overall, both surfaces led to similar results, although the YZCL2 surface is more accurate to describe the H(3)O PES, as derived from comparison with high level ab initio results. The differences observed in the QCT calculations were interpreted considering the somewhat larger anisotropy of the YZCL2 PES when compared with the WSLFH PES.

[Study on Tritium Content in Soil at Sites of Nuclear Explosions on the Territory of Semipalatinsk Test Site].

PubMed

Timonova, L V; Lyakhova, O N; Lukashenko, S N; Aidarkhanov, A O

2015-01-01

As a result of investigations carried out on the territory of Semipalatinsk Test Site, tritium was found in different environmental objects--surface and ground waters, vegetation, air environment, and snow cover. The analysis of the data obtained has shown that contamination of environmental objects at the Semipalatinsk Test Site with tritium is associated with the places where underground nuclear tests were performed. Since tritium can originate from an activation reaction and be trapped by pock particles during a test, it was decided to examine the soil in the sites where surface and excavation tests took place. It was found that the concentration of tritium in soil correlates with the concentration of europium. Probably, the concentration of tritium in the soil depends on the character and yield of the tests performed. Findings of the study have revealed that tritium can be found in soil in significant amounts not only in sites where underground nuclear tests took place but also in sites where surface and excavation nuclear tests were carried out.

Si1-yCy/Si(001) gas-source molecular beam epitaxy from Si2H6 and CH3SiH3: Surface reaction paths and growth kinetics

NASA Astrophysics Data System (ADS)

Foo, Y. L.; Bratland, K. A.; Cho, B.; Desjardins, P.; Greene, J. E.

2003-04-01

In situ surface probes and postdeposition analyses were used to follow surface reaction paths and growth kinetics of Si1-yCy alloys grown on Si(001) by gas-source molecular-beam epitaxy from Si2H6/CH3SiH3 mixtures as a function of C concentration y (0-2.6 at %) and temperature Ts (500-600 °C). High-resolution x-ray diffraction reciprocal lattice maps show that all layers are in tension and fully coherent with their substrates. Film growth rates R decrease with both y and Ts, and the rate of decrease in R as a function of y increases rapidly with Ts. In situ isotopically tagged D2 temperature-programmed desorption (TPD) measurements reveal that C segregation during steady-state Si1-yCy(001) growth results in charge transfer from Si surface dangling bonds to second-layer C atoms, which have a higher electronegativity than Si. From the TPD results, we obtain the coverage θSi*(y,Ts) of Si* surface sites with C backbonds as well as H2 desorption energies Ed from both Si and Si* surface sites. θSi* increases with increasing y and Ts in the kinetically limited segregation regime while Ed decreases from 2.52 eV for H2 desorption from Si surface sites with Si back bonds to 2.22 eV from Si* surface sites. This leads to an increase in the H2 desorption rate, and hence should yield higher film deposition rates, with increasing y and/or Ts during Si1-yCy(001) growth. The effect, however, is more than offset by the decrease in Si2H6 reactive sticking probabilities at Si* surface sites. Film growth rates R(Ts,JSi2H6,JCH3SiH3) calculated using a simple transition-state kinetic model, together with measured kinetic parameters, were found to be in excellent agreement with the experimental data.

Protolife on the Moon--A Neglected Mission

NASA Astrophysics Data System (ADS)

Green, J.

Fumaroles contain the ingredients for protolife on the earth and on the moon. Early Precambrian lunar fumaroles in shadow probably produced H_2O, HCHO, CO_2, CO, C_2N_2, HC_3N, NH3, COS, CH_4, HCN, S-bearing fluids and other compounds. Fumarolic water could have been more abundant in the early Precambrian on the moon based in part on fugacity data for the Apollo fire fountain beads. Formaldehyde formed "in the spark" on the moon in shadow would not be decomposed. Volcanism by flow charging and/or freezing by charge separation of some fumarolic fluids can readily provide the "spark". Only nanocurrents need be invoked. In shadow on the moon, most fumarolic fluids could be preserved as ices for up to billions of years at 40 Kelvin. Realistically, these ices would be discontinuously interlaminated or admixed with ejecta. Early formed amphiphilic compounds (lipids) probably formed double membraned vesicles. Miller-type reactions could possibly provide hydroxy amino acids, sugars, purines and pyrimidines. Cooling of ammonium cyanide compounds with formaldehyde in lunar shadow is presumed to have created hydrogen cyanide and adenine. Fischer-Tropsch reactions in fumaroles could result in aromatic and basic amino acids and on clay produce ribose. Ribose and adenine react to form adenosine which in turn could combine with soluble polyphosphates found in fumaroles to yield adenosine triphosphate. RNA evolving through intermediate compounds can polymerize even in an ice matrix (Monnard, 2002) as would be expected in lunar shadow. In the laboratory, RNA attached to montmorillonite template particles can be encapsulated within enlarged lipid vesicles or protocells (Hanczyc et al, 2003). Clay associated with RNA enhances the enzymatic activity of RNA (Marco, 1999). On earth, the evolution of the Archaea was dependent on tungsto-enzymes; fumaroles on earth are enriched in tungsten. Fumaroles within a distance of meters, exhibit a wide range of temperatures, pH, Eh, periods of desiccation, condensing agents, clay types, and hydrolytic reactivity. In addition, thermodynamically viable reactions involving hydrogen sulfide and troilite can produce biofilms. If methyl thiols are involved, resulting products include the prebiotic agents of formic and acetic acids. All of these parameters would be enhanced by lunar conditions of (1) lower lunar gravity and (2) surface vacuum. Lower lunar gravity would result in a deeper nucleation of bubbles in a fumarolic system with a slower bubble rise rate enhancing probabilities of reactivities of metabolites. Surface vacuum would result in lower boiling points of prebiotic agents such as formic acid producing temperatures more favorable for the formation of protolife. Assuming volcanism, targets for the search for protolife are discussed.

Prebiotic Evolution of Nitrogen Compounds

NASA Technical Reports Server (NTRS)

Arrhenius, G.

1999-01-01

Support from this four year grant has funded our research on two general problems. One involves attempts to model the abiotic formation of simple source compounds for functional biomolecules, their concentration from dilute state in the hydrosphere and, in several cases, surface induced reactions to form precursor monomers for bioactive end products (refs. 1-5). Because of the pervasiveness and antiquity of phosphate based biochemistry and the catalytic activity of RNA we have exploring the hypothesis of an RNA World as an early stage in the emergence of life. This concept is now rather generally considered, but has been questioned due to the earlier lack of an experimentally demonstrated successful scheme for the spontaneous formation of ribose phosphate, the key backbone molecule in RNA. That impediment has now been removed. This has been achieved by demonstrating probable sources of activated (condensed) highly soluble and strongly sorbed phosphates in nature (Refs. 1,2) and effective condensation of aldehyde phosphates to form ribose phosphate in high yield (ref.6), thereby placing the RNA World concept on a somewhat safer experimental footing. Like all work in this field these experiments are oversimplifications that largely ignore competing side reactions with other compounds expected to be present. None the less our choice of experimental conditions aim at selective processes that eliminate interfering reactions. We have also sought to narrow the credibility gap by simulating geophysically and geochemically plausible conditions surrounding the putative prebiotic reactions.

Catalysis of Nuclear Reactions by Electrons

NASA Astrophysics Data System (ADS)

Lipoglavšek, Matej

2018-01-01

Electron screening enhances nuclear reaction cross sections at low energies. We studied the nuclear reaction 1H(19F,αγ)16O in inverse kinematics in different solid hydrogen targets. Measured resonance strengths differed by up to a factor of 10 in different targets. We also studied the 2H(p,γ)3He fusion reaction and observed electrons emitted as reaction products instead of γ rays. In this case electron screening greatly enhances internal conversion probability.

Hybrid discrete/continuum algorithms for stochastic reaction networks

DOE PAGES

Safta, Cosmin; Sargsyan, Khachik; Debusschere, Bert; ...

2014-10-22

Direct solutions of the Chemical Master Equation (CME) governing Stochastic Reaction Networks (SRNs) are generally prohibitively expensive due to excessive numbers of possible discrete states in such systems. To enhance computational efficiency we develop a hybrid approach where the evolution of states with low molecule counts is treated with the discrete CME model while that of states with large molecule counts is modeled by the continuum Fokker-Planck equation. The Fokker-Planck equation is discretized using a 2nd order finite volume approach with appropriate treatment of flux components to avoid negative probability values. The numerical construction at the interface between the discretemore » and continuum regions implements the transfer of probability reaction by reaction according to the stoichiometry of the system. As a result, the performance of this novel hybrid approach is explored for a two-species circadian model with computational efficiency gains of about one order of magnitude.« less

Kinetics of dissolution of thorium and uranium doped britholite ceramics

NASA Astrophysics Data System (ADS)

Dacheux, N.; Du Fou de Kerdaniel, E.; Clavier, N.; Podor, R.; Aupiais, J.; Szenknect, S.

2010-09-01

In the field of immobilization of actinides in phosphate-based ceramics, several thorium and uranium doped britholite samples were submitted to leaching tests. The normalized dissolution rates determined for several pH values, temperatures and acidic media from the calcium release range from 4.7 × 10 -2 g m -2 d -1 to 21.6 g m -2 d -1. Their comparison with that determined for phosphorus, thorium and uranium revealed that the dissolution is clearly incongruent for all the conditions examined. Whatever the leaching solution considered, calcium and phosphorus elements were always released with higher RL values than the other elements (Nd, Th, U). Simultaneously, thorium was found to quickly precipitate as alteration product, leading to diffusion phenomena for uranium. For all the media considered, the uranium release is higher than that of thorium, probably due to its oxidation from tetravalent oxidation state to uranyl. Moreover, the evaluation of the partial order related to proton concentration and the apparent energy of activation suggest that the reaction of dissolution is probably controlled by surface chemical reactions occurring at the solid/liquid interface. Finally, comparative leaching tests performed in sulphuric acid solutions revealed a significant influence of such media on the chemical durability of the leached pellets, leading to higher normalized dissolution rates for all the elements considered. On the basis of the results of chemical speciation, this difference was mainly explained in the light of higher complexion constants by sulfate ions compared to nitrate, chloride and phosphate.

Cluster geometry and survival probability in systems driven by reaction diffusion dynamics

NASA Astrophysics Data System (ADS)

Windus, Alastair; Jensen, Henrik J.

2008-11-01

We consider a reaction-diffusion model incorporating the reactions A→phi, A→2A and 2A→3A. Depending on the relative rates for sexual and asexual reproduction of the quantity A, the model exhibits either a continuous or first-order absorbing phase transition to an extinct state. A tricritical point separates the two phase lines. While we comment on this critical behaviour, the main focus of the paper is on the geometry of the population clusters that form. We observe the different cluster structures that arise at criticality for the three different types of critical behaviour and show that there exists a linear relationship for the survival probability against initial cluster size at the tricritical point only.

Mass and angular distributions of the reaction products in heavy ion collisions

NASA Astrophysics Data System (ADS)

Nasirov, A. K.; Giardina, G.; Mandaglio, G.; Kayumov, B. M.; Tashkhodjaev, R. B.

2018-05-01

The optimal reactions and beam energies leading to synthesize superheavy elements is searched by studying mass and angular distributions of fission-like products in heavy-ion collisions since the evaporation residue cross section consists an ignorable small part of the fusion cross section. The intensity of the yield of fission-like products allows us to estimate the probability of the complete fusion of the interacting nuclei. The overlap of the mass and angular distributions of the fusion-fission and quasifission products causes difficulty at estimation of the correct value of the probability of the compound nucleus formation. A study of the mass and angular distributions of the reaction products is suitable key to understand the interaction mechanism of heavy ion collisions.

Probability distribution for the Gaussian curvature of the zero level surface of a random function

NASA Astrophysics Data System (ADS)

Hannay, J. H.

2018-04-01

A rather natural construction for a smooth random surface in space is the level surface of value zero, or ‘nodal’ surface f(x,y,z)  =  0, of a (real) random function f; the interface between positive and negative regions of the function. A physically significant local attribute at a point of a curved surface is its Gaussian curvature (the product of its principal curvatures) because, when integrated over the surface it gives the Euler characteristic. Here the probability distribution for the Gaussian curvature at a random point on the nodal surface f  =  0 is calculated for a statistically homogeneous (‘stationary’) and isotropic zero mean Gaussian random function f. Capitalizing on the isotropy, a ‘fixer’ device for axes supplies the probability distribution directly as a multiple integral. Its evaluation yields an explicit algebraic function with a simple average. Indeed, this average Gaussian curvature has long been known. For a non-zero level surface instead of the nodal one, the probability distribution is not fully tractable, but is supplied as an integral expression.

Pyrrole Hydrogenation over Rh(111) and Pt(111) Single-Crystal Surfaces and Hydrogenation Promotion Mediated by 1-Methylpyrrole: A Kinetic and Sum-Frequency Generation Vibrational Spectroscopy Study

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

Kliewer, Christopher J.; Bieri, Marco; Somorjai, Gabor A.

Sum-frequency generation (SFG) surface vibrational spectroscopy and kinetic measurements using gas chromatography have been used to study the adsorption and hydrogenation of pyrrole over both Pt(111) and Rh(111) single-crystal surfaces at Torr pressures (3 Torr pyrrole, 30 Torr H{sub 2}) to form pyrrolidine and the minor product butylamine. Over Pt(111) at 298 K it was found that pyrrole adsorbs in an upright geometry cleaving the N-H bond to bind through the nitrogen evidenced by SFG data. Over Rh(111) at 298 K pyrrole adsorbs in a tilted geometry relative to the surface through the p-aromatic system. A pyrroline surface reaction intermediate,more » which was not detected in the gas phase, was seen by SFG during the hydrogenation over both surfaces. Significant enhancement of the reaction rate was achieved over both metal surfaces by adsorbing 1-methylpyrrole before reaction. SFG vibrational spectroscopic results indicate that reaction promotion is achieved by weakening the bonding between the N-containing products and the metal surface because of lateral interactions on the surface between 1-methylpyrrole and the reaction species, reducing the desorption energy of the products. It was found that the ring-opening product butylamine was a reaction poison over both surfaces, but this effect can be minimized by treating the catalyst surfaces with 1-methylpyrrole before reaction. The reaction rate was not enhanced with elevated temperatures, and SFG suggests desorption of pyrrole at elevated temperatures.« less

Studying Reaction Intermediates Formed at Graphenic Surfaces

NASA Astrophysics Data System (ADS)

Sarkar, Depanjan; Sen Gupta, Soujit; Narayanan, Rahul; Pradeep, Thalappil

2014-03-01

We report in-situ production and detection of intermediates at graphenic surfaces, especially during alcohol oxidation. Alcohol oxidation to acid occurs on graphene oxide-coated paper surface, driven by an electrical potential, in a paper spray mass spectrometry experiment. As paper spray ionization is a fast process and the time scale matches with the reaction time scale, we were able to detect the intermediate, acetal. This is the first observation of acetal formed in surface oxidation. The process is not limited to alcohols and the reaction has been extended to aldehydes, amines, phosphenes, sugars, etc., where reaction products were detected instantaneously. By combining surface reactions with ambient ionization and mass spectrometry, we show that new insights into chemical reactions become feasible. We suggest that several other chemical transformations may be studied this way. This work opens up a new pathway for different industrially and energetically important reactions using different metal catalysts and modified substrate.

Correlation between discrete probability and reaction front propagation rate in heterogeneous mixtures

NASA Astrophysics Data System (ADS)

Naine, Tarun Bharath; Gundawar, Manoj Kumar

2017-09-01

We demonstrate a very powerful correlation between the discrete probability of distances of neighboring cells and thermal wave propagation rate, for a system of cells spread on a one-dimensional chain. A gamma distribution is employed to model the distances of neighboring cells. In the absence of an analytical solution and the differences in ignition times of adjacent reaction cells following non-Markovian statistics, invariably the solution for thermal wave propagation rate for a one-dimensional system with randomly distributed cells is obtained by numerical simulations. However, such simulations which are based on Monte-Carlo methods require several iterations of calculations for different realizations of distribution of adjacent cells. For several one-dimensional systems, differing in the value of shaping parameter of the gamma distribution, we show that the average reaction front propagation rates obtained by a discrete probability between two limits, shows excellent agreement with those obtained numerically. With the upper limit at 1.3, the lower limit depends on the non-dimensional ignition temperature. Additionally, this approach also facilitates the prediction of burning limits of heterogeneous thermal mixtures. The proposed method completely eliminates the need for laborious, time intensive numerical calculations where the thermal wave propagation rates can now be calculated based only on macroscopic entity of discrete probability.

Computational Study of Field Initiated Surface Reactions for Synthesis of Diamond and Silicon

NASA Technical Reports Server (NTRS)

Musgrave, Charles Bruce

1999-01-01

This project involves using quantum chemistry to simulate surface chemical reactions in the presence of an electric field for nanofabrication of diamond and silicon. A field delivered by a scanning tunneling microscope (STM) to a nanometer scale region of a surface affects chemical reaction potential energy surfaces (PES) to direct atomic scale surface modification to fabricate sub-nanometer structures. Our original hypothesis is that the applied voltage polarizes the charge distribution of the valence electrons and that these distorted molecular orbitals can be manipulated with the STM so as to change the relative stabilities of the electronic configurations over the reaction coordinates and thus the topology of the PES and reaction kinetics. Our objective is to investigate the effect of applied bias on surface reactions and the extent to which STM delivered fields can be used to direct surface chemical reactions on an atomic scale on diamond and silicon. To analyze the fundamentals of field induced chemistry and to investigate the application of this technique for the fabrication of nanostructures, we have employed methods capable of accurately describing molecular electronic structure. The methods we employ are density functional theory (DFT) quantum chemical (QC) methods. To determine the effect of applied bias on surface reactions we have calculated the QC PESs in various applied external fields for various reaction steps for depositing or etching diamond and silicon. We have chosen reactions which are thought to play a role in etching and the chemical vapor deposition growth of Si and diamond. The PESs of the elementary reaction steps involved are then calculated under the applied fields, which we vary in magnitude and configuration. We pay special attention to the change in the reaction barriers, and transition state locations, and search for low energy reaction channels which were inaccessible without the applied bias.

Comparisons of predicted steady-state levels in rooms with extended- and local-reaction bounding surfaces

NASA Astrophysics Data System (ADS)

Hodgson, Murray; Wareing, Andrew

2008-01-01

A combined beam-tracing and transfer-matrix model for predicting steady-state sound-pressure levels in rooms with multilayer bounding surfaces was used to compare the effect of extended- and local-reaction surfaces, and the accuracy of the local-reaction approximation. Three rooms—an office, a corridor and a workshop—with one or more multilayer test surfaces were considered. The test surfaces were a single-glass panel, a double-drywall panel, a carpeted floor, a suspended-acoustical ceiling, a double-steel panel, and glass fibre on a hard backing. Each test surface was modeled as of extended or of local reaction. Sound-pressure levels were predicted and compared to determine the significance of the surface-reaction assumption. The main conclusions were that the difference between modeling a room surface as of extended or of local reaction is not significant when the surface is a single plate or a single layer of material (solid or porous) with a hard backing. The difference is significant when the surface consists of multilayers of solid or porous material and includes a layer of fluid with a large thickness relative to the other layers. The results are partially explained by considering the surface-reflection coefficients at the first-reflection angles.

One-pot reaction for the preparation of biofunctionalized self-assembled monolayers on gold surfaces

NASA Astrophysics Data System (ADS)

Raigoza, Annette F.; Fies, Whitney; Lim, Amber; Onyirioha, Kristeen; Webb, Lauren J.

2017-02-01

The Huisgen cycloaddition reaction (;click; chemistry) has been used extensively to functionalize surfaces with macromolecules in a straightforward manner. We have previously developed a procedure using the copper(I)-catalyzed click reaction to tether synthetic α-helical peptides carrying two alkyne groups to a well-ordered azide-terminated alkanethiol self-assembled monolayer (SAM) on a Au(111) surface. While convenient, click-based strategies potentially pose significant problems from reagents, solvents, and reaction temperatures that may irreversibly damage some molecules or substrates. Tuning click chemistry conditions would allow individual optimization of reaction conditions for a wide variety of biomolecules and substrate materials. Here, we explore the utility of simultaneous SAM formation and peptide-attachment chemistry in a one-pot reaction. We demonstrate that a formerly multistep reaction can be successfully carried out concurrently by mixing azide-terminated alkanethiols, CuCl, and a propargylglycine-containing peptide over a bare gold surface in ethanol and reacting at 70 °C. X-ray photoelectron spectroscopy (XPS), surface infrared spectroscopy, surface circular dichroic (CD) spectroscopy, and scanning tunneling microscopy (STM) were used to determine that this one-pot reaction strategy resulted in a high density of surface-bound α-helices without aggregation. This work demonstrates the simplicity and versatility of a SAM-plus-click chemistry strategy for functionalizing Au surfaces with structured biomolecules.

Clustering and optimal arrangement of enzymes in reaction-diffusion systems.

PubMed

Buchner, Alexander; Tostevin, Filipe; Gerland, Ulrich

2013-05-17

Enzymes within biochemical pathways are often colocalized, yet the consequences of specific spatial enzyme arrangements remain poorly understood. We study the impact of enzyme arrangement on reaction efficiency within a reaction-diffusion model. The optimal arrangement transitions from a cluster to a distributed profile as a single parameter, which controls the probability of reaction versus diffusive loss of pathway intermediates, is varied. We introduce the concept of enzyme exposure to explain how this transition arises from the stochastic nature of molecular reactions and diffusion.

Photochemical modeling of the Antarctic stratosphere: Observational constraints from the airborne Antarctic ozone experiment and implications for ozone behavior

NASA Technical Reports Server (NTRS)

Rodriguez, Jose M.; Sze, Nien-Dak; Ko, Malcolm K. W.

1988-01-01

The rapid decrease in O3 column densities observed during Antarctic spring has been attributed to several chemical mechanisms involving nitrogen, bromine, or chlorine species, to dynamical mechanisms, or to a combination of the above. Chlorine-related theories, in particular, predict greatly elevated concentrations of ClO and OClO and suppressed abundances of NO2 below 22 km. The heterogeneous reactions and phase transitions proposed by these theories could also impact the concentrations of HCl, ClNO3 and HNO3 in this region. Observations of the above species have been carried out from the ground by the National Ozone Expedition (NOZE-I, 1986, and NOZE-II, 1987), and from aircrafts by the Airborne Antarctic Ozone Experiment (AAOE) during the austral spring of 1987. Observations of aerosol concentrations, size distribution and backscattering ratio from AAOE, and of aerosol extinction coefficients from the SAM-II satellite can also be used to deduce the altitude and temporal behavior of surfaces which catalyze heterogeneous mechanisms. All these observations provide important constraints on the photochemical processes suggested for the spring Antarctic stratosphere. Results are presented for the concentrations and time development of key trace gases in the Antarctic stratosphere, utilizing the AER photochemical model. This model includes complete gas-phase photochemistry, as well as heterogeneous reactions. Heterogeneous chemistry is parameterized in terms of surface concentrations of aerosols, collision frequencies between gas molecules and aerosol surfaces, concentrations of HCl/H2O in the frozen particles, and probability of reaction per collision (gamma). Values of gamma are taken from the latest laboratory measurements. The heterogeneous chemistry and phase transitions are assumed to occur between 12 and 22 km. The behavior of trace species at higher altitudes is calculated by the AER 2-D model without heterogeneous chemistry. Calculations are performed for solar illumination conditions typical of 60, 70, and 80 S, from July 15 to October 31.

Determining animal drug combinations based on efficacy and safety.

PubMed

Kratzer, D D; Geng, S

1986-08-01

A procedure for deriving drug combinations for animal health is used to derive an optimal combination of 200 mg of novobiocin and 650,000 IU of penicillin for nonlactating cow mastitis treatment. The procedure starts with an estimated second order polynomial response surface equation. That surface is translated into a probability surface with contours called isoprobs. The isoprobs show drug amounts that have equal probability to produce maximal efficacy. Safety factors are incorporated into the probability surface via a noncentrality parameter that causes the isoprobs to expand as safety decreases, resulting in lower amounts of drug being used.

Deep brain stimulation abolishes slowing of reactions to unlikely stimuli.

PubMed

Antoniades, Chrystalina A; Bogacz, Rafal; Kennard, Christopher; FitzGerald, James J; Aziz, Tipu; Green, Alexander L

2014-08-13

The cortico-basal-ganglia circuit plays a critical role in decision making on the basis of probabilistic information. Computational models have suggested how this circuit could compute the probabilities of actions being appropriate according to Bayes' theorem. These models predict that the subthalamic nucleus (STN) provides feedback that normalizes the neural representation of probabilities, such that if the probability of one action increases, the probabilities of all other available actions decrease. Here we report the results of an experiment testing a prediction of this theory that disrupting information processing in the STN with deep brain stimulation should abolish the normalization of the neural representation of probabilities. In our experiment, we asked patients with Parkinson's disease to saccade to a target that could appear in one of two locations, and the probability of the target appearing in each location was periodically changed. When the stimulator was switched off, the target probability affected the reaction times (RT) of patients in a similar way to healthy participants. Specifically, the RTs were shorter for more probable targets and, importantly, they were longer for the unlikely targets. When the stimulator was switched on, the patients were still faster for more probable targets, but critically they did not increase RTs as the target was becoming less likely. This pattern of results is consistent with the prediction of the model that the patients on DBS no longer normalized their neural representation of prior probabilities. We discuss alternative explanations for the data in the context of other published results. Copyright © 2014 the authors 0270-6474/14/3410844-09$15.00/0.

Born-Oppenheimer and Renner-Teller Quantum Dynamics of CH(X(2)Π) + D((2)S) Reactions on Three CHD Potential Surfaces.

PubMed

Gamallo, Pablo; Akpinar, Sinan; Defazio, Paolo; Petrongolo, Carlo

2015-11-19

The quantum dynamics of three CH(X(2)Π) + D((2)S) reactions is studied by means of the coupled-channel time-dependent real-wavepacket (WP) and flux methods at collision energy Ecol ≤ 0.6 eV and on three potential energy surfaces (PESs): the Born-Oppenheimer (BO) ground PES X̃(3)A″ and the excited ones ã(1)A' and b̃(1)A″, coupled by nonadiabatic (NA) Renner-Teller (RT) effects. This three-state model is suitable for obtaining initial-state-resolved observables, is based on a complete analysis of the correlation diagram of the lowest electronic states of the CHD intermediate and of their NA interactions, and neglects the smaller coupling effects due to the asymptotic electronic angular momenta that become important in state-to-state dynamics. WPs are propagated on each PES at total angular momentum values J ≤ 70, with CH in the two lowest vibrational states v0 and in the ground rotational state j0 = 1. Reaction probabilities are obtained for three possible final products (f): (dP) CH decay and C((3)P) + HD(X(1)Σ(+)) formation that occurs on the uncoupled ground PES, (dD) CH decay and C((1)D) + HD(X(1)Σ(+)) formation that depends on the RT-coupled singlet species, and (ex) exchange to CD(X(2)Π) + H((2)S) available adiabatically from the X̃(3)A″ PES and nonadiabatically from ã(1)A' and b̃(1)A″. Observable cross sections σf,v0j0 and rate constants kf,v0j0 in the temperature range T = 100-2000 K are obtained for (dP), (dD), and (ex) channels. Comparing BO with RT probabilities, we show that NA effects are important at high J values for the (ex) channel at v0 = 1. Real time mechanisms on the three PESs show that RT couplings are opened after some time and clearly point out the formation of the product channels. Both cross sections and rate constants present the same sequence, for example σex,11 > σdP,01 ∼ σex,01 > σdP,11 ≫ σdD,11 ≫ σdD,01, and the CH vibrational excitation enhances the total removal CH+D reactivity by a factor of ∼1.7, mainly due to the increase of the (ex) channel contribution from ∼47% at v0 = 0 to ∼76% at v0 = 1. This fact implies a considerable vibrational enhancement of combustion processes at high temperature. In agreement with the probability results, the ã(1)A'/b̃(1)A″ RT coupling increases both σex,11 and kex,11 up to ∼30%. Moreover, including the three PESs in the dynamics simulation of CH+D increase by far the (ex)/(dP) branching ratio with respect to the CH + H' reaction. Thus, at room temperature, kdP,01 changes from 10.8 × 10(-11) to 3.4 × 10(-11) cm(3) s(-1) substituting H atom by D.

Factors Influencing Ball-Player Impact Probability in Youth Baseball

PubMed Central

Matta, Philip A.; Myers, Joseph B.; Sawicki, Gregory S.

2015-01-01

Background: Altering the weight of baseballs for youth play has been studied out of concern for player safety. Research has shown that decreasing the weight of baseballs may limit the severity of both chronic arm and collision injuries. Unfortunately, reducing the weight of the ball also increases its exit velocity, leaving pitchers and nonpitchers with less time to defend themselves. The purpose of this study was to examine impact probability for pitchers and nonpitchers. Hypothesis: Reducing the available time to respond by 10% (expected from reducing ball weight from 142 g to 113 g) would increase impact probability for pitchers and nonpitchers, and players’ mean simple response time would be a primary predictor of impact probability for all participants. Study Design: Nineteen subjects between the ages of 9 and 13 years performed 3 experiments in a controlled laboratory setting: a simple response time test, an avoidance response time test, and a pitching response time test. Methods: Each subject performed these tests in order. The simple reaction time test tested the subjects’ mean simple response time, the avoidance reaction time test tested the subjects’ ability to avoid a simulated batted ball as a fielder, and the pitching reaction time test tested the subjects’ ability to avoid a simulated batted ball as a pitcher. Results: Reducing the weight of a standard baseball from 142 g to 113 g led to a less than 5% increase in impact probability for nonpitchers. However, the results indicate that the impact probability for pitchers could increase by more than 25%. Conclusion: Pitching may greatly increase the amount of time needed to react and defend oneself from a batted ball. Clinical Relevance: Impact injuries to youth baseball players may increase if a 113-g ball is used. PMID:25984261

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

PubMed

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

2017-08-02

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

Surface Interrogation Scanning Electrochemical Microscopy for a Photoelectrochemical Reaction: Water Oxidation on a Hematite Surface.

PubMed

Kim, Jae Young; Ahn, Hyun S; Bard, Allen J

2018-03-06

To understand the pathway of a photoelectrochemical (PEC) reaction, quantitative knowledge of reaction intermediates is important. We describe here surface interrogation scanning electrochemical microscopy for this purpose (PEC SI-SECM), where a light pulse to a photoactive semiconductor film at a given potential generates intermediates that are then analyzed by a tip generated titrant at known times after the light pulse. The improvements were demonstrated for photoelectrochemical water oxidation (oxygen evolution) reaction on a hematite surface. The density of photoactive sites, proposed to be Fe 4+ species, on a hematite surface was successfully quantified, and the photoelectrochemical water oxidation reaction dynamics were elucidated by time-dependent redox titration experiments. The new configuration of PEC SI-SECM should find expanded usage to understand and investigate more complicated PEC reactions with other materials.

Controlling Reaction Selectivity through the Surface Termination of Perovskite Catalysts

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

Polo-Garzon, Felipe; Yang, Shi-Ze; Fung, Victor

2017-07-19

Although perovskites have been widely used in catalysis, tuning their surface terminations to control reaction selectivities has not been well established. In this work, we employ multiple surface sensitive techniques to characterize the surface termination (one aspect of surface reconstruction) of SrTiO 3 (STO) after thermal pretreatment (Sr-enrichment) and chemical etching (Ti-enrichment). We show, using the conversion of 2-propanol as a probe reaction, that the surface termination of STO can be controlled to greatly tune catalytic acid/base properties and consequently the reaction selectivities in a wide range, which are inaccessible using single metal oxides, either SrO or TiO 2. Densitymore » functional theory (DFT) calculations well explain the selectivity tuning and reaction mechanism on different surface terminations of STO. Similar catalytic tunability is also observed on BaZrO 3, highlighting the generality of the finding from this work.« less

10 CFR 963.17 - Postclosure suitability criteria.

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2014-01-01

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10 CFR 963.17 - Postclosure suitability criteria.

Code of Federal Regulations, 2012 CFR

2012-01-01

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Code of Federal Regulations, 2010 CFR

2010-01-01

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2013-01-01

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2011-01-01

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Direct vs. indirect pathway for nitrobenzene reduction reaction on a Ni catalyst surface: a density functional study.

PubMed

Mahata, Arup; Rai, Rohit K; Choudhuri, Indrani; Singh, Sanjay K; Pathak, Biswarup

2014-12-21

Density functional theory (DFT) calculations are performed to understand and address the previous experimental results that showed the reduction of nitrobenzene to aniline prefers direct over indirect reaction pathways irrespective of the catalyst surface. Nitrobenzene to aniline conversion occurs via the hydroxyl amine intermediate (direct pathway) or via the azoxybenzene intermediate (indirect pathway). Through our computational study we calculated the spin polarized and dispersion corrected reaction energies and activation barriers corresponding to various reaction pathways for the reduction of nitrobenzene to aniline over a Ni catalyst surface. The adsorption behaviour of the substrate, nitrobenzene, on the catalyst surface was also considered and the energetically most preferable structural orientation was elucidated. Our study indicates that the parallel adsorption behaviour of the molecules over a catalyst surface is preferable over vertical adsorption behaviour. Based on the reaction energies and activation barrier of the various elementary steps involved in direct or indirect reaction pathways, we find that the direct reduction pathway of nitrobenzene over the Ni(111) catalyst surface is more favourable than the indirect reaction pathway.

Reaction Dynamics Following Ionization of Ammonia Dimer Adsorbed on Ice Surface.

PubMed

Tachikawa, Hiroto

2016-09-22

The ice surface provides an effective two-dimensional reaction field in interstellar space. However, how the ice surface affects the reaction mechanism is still unknown. In the present study, the reaction of an ammonia dimer cation adsorbed both on water ice and cluster surface was theoretically investigated using direct ab initio molecular dynamics (AIMD) combined with our own n-layered integrated molecular orbital and molecular mechanics (ONIOM) method, and the results were compared with reactions in the gas phase and on water clusters. A rapid proton transfer (PT) from NH3(+) to NH3 takes place after the ionization and the formation of intermediate complex NH2(NH4(+)) is found. The reaction rate of PT was significantly affected by the media connecting to the ammonia dimer. The time of PT was calculated to be 50 fs (in the gas phase), 38 fs (on ice), and 28-33 fs (on water clusters). The dissociation of NH2(NH4(+)) occurred on an ice surface. The reason behind the reaction acceleration on an ice surface is discussed.

Pulsed ion beam investigation of the kinetics of surface reactions

NASA Technical Reports Server (NTRS)

Horton, C. C.; Eck, T. G.; Hoffman, R. W.

1989-01-01

Pulsed ion beam measurements of the kinetics of surface reactions are discussed for the case where the width of the ion pulse is comparable to the measured reaction time, but short compared to the time between successive pulses. Theoretical expressions are derived for the time dependence of the ion-induced signals for linear surface reactions. Results are presented for CO emission from surface carbon and CF emission from Teflon induced by oxygen ion bombardment. The strengths and limitations of this technique are described.

Cumulative potential hydrologic impacts of surface coal mining in the eastern Powder River structural basin, northeastern Wyoming

USGS Publications Warehouse

Martin, L.J.; Naftz, D.L.; Lowham, H.W.; Rankl, J.G.

1988-01-01

There are 16 existing and six proposed surface coal mines in the eastern Powder River structural basin of northeastern Wyoming. Coal mining companies predict water level declines of 5 ft or more in the Wasatch aquifer to extend form about 1,000 to about 2,000 ft beyond the mine pits. The predicted 5 ft water level decline in the Wyodak coal aquifer generally extends 4-8 mi beyond the lease areas. About 3,000 wells are in the area of potential cumulative water level declines resulting from all anticipated mining. Of these 3,000 wells, about 1,200 are outside the areas of anticipated mining: about 1,000 wells supply water for domestic or livestock uses, and about 200 wells supply water for municipal, industrial, irrigation, and miscellaneous uses. The 1,800 remaining wells are used by coal mining companies. Future surface coal mining probably will result in postmining groundwater of similar quality to that currently present in the study area. By use of geochemical modeling techniques, the results of a hypothetical reaction path exercise indicate the potential for marked improvements in postmining water quality because of chemical reactions as postmining groundwater with a large dissolved solids concentration (3,540 mg/L) moves into a coal aquifer with relatively small dissolved solids concentrations (910 mg/L). Results of the modeling exercise also indicate geochemical conditions that are most ideal for large decreases in dissolved solids concentrations in coal aquifers receiving recharge from a spoil aquifer. (Lantz-PTT)

Adverse Effects of Iodine-derived Intravenous Radiopaque Contrast Media.

PubMed

Matthews, Eric P

2015-01-01

Although the advent of nonionic low-osmolar contrast agents has reduced the probability of a reaction to radiopaque contrast media derived from tri-iodinated benzoic acid, reactions still occur. Radiologic technologists must understand and know how to manage adverse effects of contrast media. Prompt attention to patients who exhibit the early signs of an adverse reaction can help to ensure the reaction does not progress to become severe or life-threatening.

Gain- and Loss-Related Brain Activation Are Associated with Information Search Differences in Risky Gambles: An fMRI and Eye-Tracking Study.

PubMed

Häusler, Alexander Niklas; Oroz Artigas, Sergio; Trautner, Peter; Weber, Bernd

2016-01-01

People differ in the way they approach and handle choices with unsure outcomes. In this study, we demonstrate that individual differences in the neural processing of gains and losses relates to attentional differences in the way individuals search for information in gambles. Fifty subjects participated in two independent experiments. Participants first completed an fMRI experiment involving financial gains and losses. Subsequently, they performed an eye-tracking experiment on binary choices between risky gambles, each displaying monetary outcomes and their respective probabilities. We find that individual differences in gain and loss processing relate to attention distribution. Individuals with a stronger reaction to gains in the ventromedial prefrontal cortex paid more attention to monetary amounts, while a stronger reaction in the ventral striatum to losses was correlated with an increased attention to probabilities. Reaction in the posterior cingulate cortex to losses was also found to correlate with an increased attention to probabilities. Our data show that individual differences in brain activity and differences in information search processes are closely linked.

Correlations between polarisation states of W particles in the reaction e - e +→ W - W + at LEP2 energies 189-209 GeV

NASA Astrophysics Data System (ADS)

Abdallah, J.; Abreu, P.; Adam, W.; Adzic, P.; Albrecht, T.; Alemany-Fernandez, R.; Allmendinger, T.; Allport, P. P.; Amaldi, U.; Amapane, N.; Amato, S.; Anashkin, E.; Andreazza, A.; Andringa, S.; Anjos, N.; Antilogus, P.; Apel, W.-D.; Arnoud, Y.; Ask, S.; Asman, B.; Augustin, J. E.; Augustinus, A.; Baillon, P.; Ballestrero, A.; Bambade, P.; Barbier, R.; Bardin, D.; Barker, G. J.; Baroncelli, A.; Battaglia, M.; Baubillier, M.; Becks, K.-H.; Begalli, M.; Behrmann, A.; Ben-Haim, E.; Benekos, N.; Benvenuti, A.; Berat, C.; Berggren, M.; Bertrand, D.; Besancon, M.; Besson, N.; Bloch, D.; Blom, M.; Bluj, M.; Bonesini, M.; Boonekamp, M.; Booth, P. S. L.; Borisov, G.; Botner, O.; Bouquet, B.; Bowcock, T. J. V.; Boyko, I.; Bracko, M.; Brenner, R.; Brodet, E.; Bruckman, P.; Brunet, J. M.; Buschbeck, B.; Buschmann, P.; Calvi, M.; Camporesi, T.; Canale, V.; Carena, F.; Castro, N.; Cavallo, F.; Chapkin, M.; Charpentier, Ph.; Checchia, P.; Chierici, R.; Chliapnikov, P.; Chudoba, J.; Chung, S. U.; Cieslik, K.; Collins, P.; Contri, R.; Cosme, G.; Cossutti, F.; Costa, M. J.; Crennell, D.; Cuevas, J.; D'Hondt, J.; da Silva, T.; da Silva, W.; Della Ricca, G.; de Angelis, A.; de Boer, W.; de Clercq, C.; de Lotto, B.; de Maria, N.; de Min, A.; de Paula, L.; di Ciaccio, L.; di Simone, A.; Doroba, K.; Drees, J.; Eigen, G.; Ekelof, T.; Ellert, M.; Elsing, M.; Espirito Santo, M. C.; Fanourakis, G.; Fassouliotis, D.; Feindt, M.; Fernandez, J.; Ferrer, A.; Ferro, F.; Flagmeyer, U.; Foeth, H.; Fokitis, E.; Fulda-Quenzer, F.; Fuster, J.; Gandelman, M.; Garcia, C.; Gavillet, Ph.; Gazis, E.; Gokieli, R.; Golob, B.; Gomez-Ceballos, G.; Goncalves, P.; Graziani, E.; Grosdidier, G.; Grzelak, K.; Guy, J.; Haag, C.; Hallgren, A.; Hamacher, K.; Hamilton, K.; Haug, S.; Hauler, F.; Hedberg, V.; Hennecke, M.; Hoffman, J.; Holmgren, S.-O.; Holt, P. J.; Houlden, M. A.; Jackson, J. N.; Jarlskog, G.; Jarry, P.; Jeans, D.; Johansson, E. K.; Jonsson, P.; Joram, C.; Jungermann, L.; Kapusta, F.; Katsanevas, S.; Katsoufis, E.; Kernel, G.; Kersevan, B. P.; Kerzel, U.; King, B. T.; Kjaer, N. J.; Kluit, P.; Kokkinias, P.; Kourkoumelis, C.; Kouznetsov, O.; Krumstein, Z.; Kucharczyk, M.; Lamsa, J.; Leder, G.; Ledroit, F.; Leinonen, L.; Leitner, R.; Lemonne, J.; Lepeltier, V.; Lesiak, T.; Liebig, W.; Liko, D.; Lipniacka, A.; Lopes, J. H.; Lopez, J. M.; Loukas, D.; Lutz, P.; Lyons, L.; MacNaughton, J.; Malek, A.; Maltezos, S.; Mandl, F.; Marco, J.; Marco, R.; Marechal, B.; Margoni, M.; Marin, J.-C.; Mariotti, C.; Markou, A.; Martinez-Rivero, C.; Masik, J.; Mastroyiannopoulos, N.; Matorras, F.; Matteuzzi, C.; Mazzucato, F.; Mazzucato, M.; McNulty, R.; Meroni, C.; Migliore, E.; Mitaroff, W.; Mjoernmark, U.; Moa, T.; Moch, M.; Moenig, K.; Monge, R.; Montenegro, J.; Moraes, D.; Moreno, S.; Morettini, P.; Mueller, U.; Muenich, K.; Mulders, M.; Mundim, L.; Murray, W.; Muryn, B.; Myatt, G.; Myklebust, T.; Nassiakou, M.; Navarria, F.; Nawrocki, K.; Nemecek, S.; Nicolaidou, R.; Nikolenko, M.; Oblakowska-Mucha, A.; Obraztsov, V.; Olshevski, A.; Onofre, A.; Orava, R.; Osterberg, K.; Ouraou, A.; Oyanguren, A.; Paganoni, M.; Paiano, S.; Palacios, J. P.; Palka, H.; Papadopoulou, Th. D.; Pape, L.; Parkes, C.; Parodi, F.; Parzefall, U.; Passeri, A.; Passon, O.; Peralta, L.; Perepelitsa, V.; Perrotta, A.; Petrolini, A.; Piedra, J.; Pieri, L.; Pierre, F.; Pimenta, M.; Piotto, E.; Podobnik, T.; Poireau, V.; Pol, M. E.; Polok, G.; Pozdniakov, V.; Pukhaeva, N.; Pullia, A.; Radojicic, D.; Rebecchi, P.; Rehn, J.; Reid, D.; Reinhardt, R.; Renton, P.; Richard, F.; Ridky, J.; Rivero, M.; Rodriguez, D.; Romero, A.; Ronchese, P.; Roudeau, P.; Rovelli, T.; Ruhlmann-Kleider, V.; Ryabtchikov, D.; Sadovsky, A.; Salmi, L.; Salt, J.; Sander, C.; Savoy-Navarro, A.; Schwickerath, U.; Sekulin, R.; Siebel, M.; Sisakian, A.; Smadja, G.; Smirnova, O.; Sokolov, A.; Sopczak, A.; Sosnowski, R.; Spassov, T.; Stanitzki, M.; Stocchi, A.; Strauss, J.; Stugu, B.; Szczekowski, M.; Szeptycka, M.; Szumlak, T.; Tabarelli, T.; Tegenfeldt, F.; Timmermans, J.; Tkatchev, L.; Tobin, M.; Todorovova, S.; Tome, B.; Tonazzo, A.; Tortosa, P.; Travnicek, P.; Treille, D.; Tristram, G.; Trochimczuk, M.; Troncon, C.; Turluer, M.-L.; Tyapkin, I. A.; Tyapkin, P.; Tzamarias, S.; Uvarov, V.; Valenti, G.; van Dam, P.; van Eldik, J.; van Remortel, N.; van Vulpen, I.; Vegni, G.; Veloso, F.; Venus, W.; Verdier, P.; Verzi, V.; Vilanova, D.; Vitale, L.; Vrba, V.; Wahlen, H.; Washbrook, A. J.; Weiser, C.; Wicke, D.; Wickens, J.; Wilkinson, G.; Winter, M.; Witek, M.; Yushchenko, O.; Zalewska, A.; Zalewski, P.; Zavrtanik, D.; Zhuravlov, V.; Zimin, N. I.; Zintchenko, A.; Zupan, M.

2009-10-01

In a study of the reaction e - e +→ W - W + with the DELPHI detector, the probabilities of the two W particles occurring in the joint polarisation states transverse-transverse ( TT), longitudinal-transverse plus transverse-longitudinal ( LT) and longitudinal-longitudinal ( LL) have been determined using the final states WW{rightarrow}lν qbar{q} ( l= e, μ). The two-particle joint polarisation probabilities, i.e. the spin density matrix elements ρ TT , ρ LT , ρ LL , are measured as functions of the W - production angle, θ _{W-}, at an average reaction energy of 198.2 GeV. Averaged over all \\cosθ_{W-}, the following joint probabilities are obtained: bar{ρ}_{TT}=(67±8)%, bar{ρ}_{LT}=(30±8)%, bar{ρ}_{LL}=(3±7)%. These results are in agreement with the Standard Model predictions of 63.0%, 28.9% and 8.1%, respectively. The related polarisation cross-sections σ TT , σ LT and σ LL are also presented.

Gain- and Loss-Related Brain Activation Are Associated with Information Search Differences in Risky Gambles: An fMRI and Eye-Tracking Study

PubMed Central

Trautner, Peter

2016-01-01

Abstract People differ in the way they approach and handle choices with unsure outcomes. In this study, we demonstrate that individual differences in the neural processing of gains and losses relates to attentional differences in the way individuals search for information in gambles. Fifty subjects participated in two independent experiments. Participants first completed an fMRI experiment involving financial gains and losses. Subsequently, they performed an eye-tracking experiment on binary choices between risky gambles, each displaying monetary outcomes and their respective probabilities. We find that individual differences in gain and loss processing relate to attention distribution. Individuals with a stronger reaction to gains in the ventromedial prefrontal cortex paid more attention to monetary amounts, while a stronger reaction in the ventral striatum to losses was correlated with an increased attention to probabilities. Reaction in the posterior cingulate cortex to losses was also found to correlate with an increased attention to probabilities. Our data show that individual differences in brain activity and differences in information search processes are closely linked. PMID:27679814

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

Chen, Hang, E-mail: hangchen@mit.edu; Thill, Peter; Cao, Jianshu

In biochemical systems, intrinsic noise may drive the system switch from one stable state to another. We investigate how kinetic switching between stable states in a bistable network is influenced by dynamic disorder, i.e., fluctuations in the rate coefficients. Using the geometric minimum action method, we first investigate the optimal transition paths and the corresponding minimum actions based on a genetic toggle switch model in which reaction coefficients draw from a discrete probability distribution. For the continuous probability distribution of the rate coefficient, we then consider two models of dynamic disorder in which reaction coefficients undergo different stochastic processes withmore » the same stationary distribution. In one, the kinetic parameters follow a discrete Markov process and in the other they follow continuous Langevin dynamics. We find that regulation of the parameters modulating the dynamic disorder, as has been demonstrated to occur through allosteric control in bistable networks in the immune system, can be crucial in shaping the statistics of optimal transition paths, transition probabilities, and the stationary probability distribution of the network.« less

Intraoperative radiotherapy in combined treatment of sinonasal malignant tumors

NASA Astrophysics Data System (ADS)

Novikov, V. A.; Gribova, O. V.; Vasiljev, R. V.; Choynzonov, E. L.; Shtin, V. I.; Shiianova, A. A.; Surkova, P. V.; Starceva, Zh. A.; Shilova, O. G.

2017-09-01

Obvious advantage of IORT (intraoperative radiotherapy) is that the radiation source is delivered directly to the bed of the tumor during surgery, thus avoiding the negative impact on the skin, subcutaneous tissue and reducing the risk of fibrosis. Sinonasal tumors—a convenient object for intraoperative radiotherapy application (surface location, relatively small size tumors, good operational access). The surface location and comparatively small size of neoplasms, good operational access provide an efficient and accurate transfer of the electron beam to the postoperative cavity to increase the irradiation dose in the areas of the most probable recurrence, which makes the tumors of this localization a convenient object for the use of the intraoperative radiation therapy. The treatment was conducted using a mobile compact betatron (MIB-6E), 10-12 Gy single dose. IORT session extends surgery period by 30 min. There were no pathological clinical and laboratory reactions on IORT in the early postoperative period. Carrying out the procedure is possible in various standard operating rooms. It does not require special security measures for the patients and the staff. IORT with the help of electron beam allows avoiding post-radiation reactions and achieving a 5-year—disease-free survival of 66% of the patients. IORT session is possible through a minimal incision during organ preservation surgeries. Evident economic feasibility provides the prospects of applying IORT in the clinical practice.

Bifurcation from stable holes to replicating holes in vibrated dense suspensions.

PubMed

Ebata, H; Sano, M

2013-11-01

In vertically vibrated starch suspensions, we observe bifurcations from stable holes to replicating holes. Above a certain acceleration, finite-amplitude deformations of the vibrated surface continue to grow until void penetrates fluid layers, and a hole forms. We studied experimentally and theoretically the parameter dependence of the holes and their stabilities. In suspensions of small dispersed particles, the circular shapes of the holes are stable. However, we find that larger particles or lower surface tension of water destabilize the circular shapes; this indicates the importance of capillary forces acting on the dispersed particles. Around the critical acceleration for bifurcation, holes show intermittent large deformations as a precursor to hole replication. We applied a phenomenological model for deformable domains, which is used in reaction-diffusion systems. The model can explain the basic dynamics of the holes, such as intermittent behavior, probability distribution functions of deformation, and time intervals of replication. Results from the phenomenological model match the linear growth rate below criticality that was estimated from experimental data.

Microimaging of transient guest profiles to monitor mass transfer in nanoporous materials

NASA Astrophysics Data System (ADS)

Kärger, Jörg; Binder, Tomas; Chmelik, Christian; Hibbe, Florian; Krautscheid, Harald; Krishna, Rajamani; Weitkamp, Jens

2014-04-01

The intense interactions of guest molecules with the pore walls of nanoporous materials is the subject of continued fundamental research. Stimulated by their thermal energy, the guest molecules in these materials are subject to a continuous, irregular motion, referred to as diffusion. Diffusion, which is omnipresent in nature, influences the efficacy of nanoporous materials in reaction and separation processes. The recently introduced techniques of microimaging by interference and infrared microscopy provide us with a wealth of information on diffusion, hitherto inaccessible from commonly used techniques. Examples include the determination of surface barriers and the sticking coefficient's analogue, namely the probability that, on colliding with the particle surface, a molecule may continue its diffusion path into the interior. Microimaging is further seen to open new vistas in multicomponent guest diffusion (including the detection of a reversal in the preferred diffusion pathways), in guest-induced phase transitions in nanoporous materials and in matching the results of diffusion studies under equilibrium and non-equilibrium conditions.

A permutationally invariant full-dimensional ab initio potential energy surface for the abstraction and exchange channels of the H + CH{sub 4} system

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

Li, Jun, E-mail: jli15@cqu.edu.cn, E-mail: zhangdh@dicp.ac.cn; Department of Chemistry and Chemical Biology, University of New Mexico, Albuquerque, New Mexico 87131; Chen, Jun

2015-05-28

We report a permutationally invariant global potential energy surface (PES) for the H + CH{sub 4} system based on ∼63 000 data points calculated at a high ab initio level (UCCSD(T)-F12a/AVTZ) using the recently proposed permutation invariant polynomial-neural network method. The small fitting error (5.1 meV) indicates a faithful representation of the ab initio points over a large configuration space. The rate coefficients calculated on the PES using tunneling corrected transition-state theory and quasi-classical trajectory are found to agree well with the available experimental and previous quantum dynamical results. The calculated total reaction probabilities (J{sub tot} = 0) including themore » abstraction and exchange channels using the new potential by a reduced dimensional quantum dynamic method are essentially the same as those on the Xu-Chen-Zhang PES [Chin. J. Chem. Phys. 27, 373 (2014)].« less

Anaphylactic deaths in asthmatic patients.

PubMed

Settipane, G A

1989-01-01

We reviewed seven documented deaths to peanuts and two near deaths. We excluded hearsay undocumented deaths to peanuts. Peanut allergy is one of the most common food allergies and probably the most common cause of death by food anaphylaxis in the United States. About one-third of peanut-sensitive patients have severe reactions to peanuts. Asthmatics with peanut sensitivity appear more likely to develop fatal reactions probably because of the exquisite sensitivity that asthamatics have to chemical mediators of anaphylaxis. Severe reactions occur within a few minutes of ingestion and these patients must carry preloaded epinephrine syringes, antihistamines, and medic-alert bracelets. Treatment should include repeated doses of epinephrine, antihistamines and corticosteroids as well as availability of oxygen, mechanical methods to open airways, vasopressors, and intravenous fluids. Hidden sources of peanuts such as chili, egg rolls, cookies, candy, and pastry should be recognized and identified. Scratch/prick test to peanuts are highly diagnostic. Peanut is one of the most sensitive food allergens known requiring only a few milligrams to cause a reaction. In some individuals, even contact of peanut with unbroken skin can cause an immediate local reaction. Unfortunately, peanut reaction is not outgrown and remains a life-long threat.

The Initial Immune Reaction to a New Tumor Antigen Is Always Stimulatory and Probably Necessary for the Tumor's Growth

PubMed Central

Prehn, Richmond T.

2010-01-01

All nascent neoplasms probably elicit at least a weak immune reaction. However, the initial effect of the weak immune reaction on a nascent tumor is always stimulatory rather than inhibitory to tumor growth, assuming only that exposure to the tumor antigens did not antedate the initiation of the neoplasm (as may occur in some virally induced tumors). This conclusion derives from the observation that the relationship between the magnitude of an adaptive immune reaction and tumor growth is not linear but varies such that while large quantities of antitumor immune reactants tend to inhibit tumor growth, smaller quantities of the same reactants are, for unknown reasons, stimulatory. Any immune reaction must presumably be small before it can become large; hence the initial reaction to the first presentation of a tumor antigen must always be small and in the stimulatory portion of this nonlinear relationship. In mouse-skin carcinogenesis experiments it was found that premalignant papillomas were variously immunogenic, but that the carcinomas that arose in them were, presumably because of induced immune tolerance, nonimmunogenic in the animal of origin. PMID:20811480

Effect of nuclear-reaction mechanisms on the population of excited nuclear states and isomeric ratios

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

Skobelev, N. K., E-mail: skobelev@jinr.ru

2016-07-15

Experimental data on the cross sections for channels of fusion and transfer reactions induced by beams of radioactive halo nuclei and clustered and stable loosely bound nuclei were analyzed, and the results of this analysis were summarized. The interplay of the excitation of single-particle states in reaction-product nuclei and direct reaction channels was established for transfer reactions. Respective experiments were performed in stable ({sup 6}Li) and radioactive ({sup 6}He) beams of the DRIBs accelerator complex at the Flerov Laboratory of Nuclear Reactions, Joint Institute for Nuclear Research, and in deuteron and {sup 3}He beams of the U-120M cyclotron at themore » Nuclear Physics Institute, Academy Sciences of Czech Republic (Řež and Prague, Czech Republic). Data on subbarrier and near-barrier fusion reactions involving clustered and loosely bound light nuclei ({sup 6}Li and {sup 3}He) can be described quite reliably within simple evaporation models with allowance for different reaction Q-values and couple channels. In reactions involving halo nuclei, their structure manifests itself most strongly in the region of energies below the Coulomb barrier. Neutron transfer occurs with a high probability in the interactions of all loosely bound nuclei with light and heavy stable nuclei at positive Q-values. The cross sections for such reactions and the respective isomeric ratios differ drastically for nucleon stripping and nucleon pickup mechanisms. This is due to the difference in the population probabilities for excited single-particle states.« less

Structural characterization of bovine beta-lactoglobulin-galactose/tagatose Maillard complexes by electrophoretic, chromatographic, and spectroscopic methods.

PubMed

Corzo-Martínez, Marta; Moreno, F Javier; Olano, Agustín; Villamiel, Mar

2008-06-11

To investigate the influence of the type of carbonyl group of the sugar on the structural changes of proteins during glycation, an exhaustive structural characterization of glycated beta-lactoglobulin with galactose (aldose) and tagatose (ketose) has been carried out. Conjugates were prepared via Maillard reaction at 40 and 50 degrees C, pH 7, and a w = 0.44. The progress of the Maillard reaction was followed by indirect formation of Amadori and Heyns compounds, advanced glycation end products, and brown polymers. The structural characterization of glycoconjugates was conducted by using a number of analytical techniques such as RP-HPLC, isoelectric focusing, MALDI-ToF, SDS-PAGE, size exclusion chromatography, and spectrofluorimetry (tryptophan fluorescence). In addition, the surface hydrophobicity of the beta-lactoglobulin glycoconjugates was also assessed. The results showed a higher reactivity of galactose than tagatose to form the glycoconjugates, probably due to the higher electrophilicity of the aldehyde group. At 40 degrees C, more aggregation was produced when beta-lactoglobulin was conjugated with tagatose as compared to galactose. However, at 50 degrees C hardly any difference was observed in the aggregation produced by galactose and tagatose. These results afford more insight into the importance of the functional group of the carbohydrate moiety during the formation of protein-carbohydrate conjugates via Maillard reaction.

The role of fly-ash particulate material and oxide catalysts in stone degradation

NASA Astrophysics Data System (ADS)

Hutchinson, A. J.; Johnson, J. B.; Thompson, G. E.; Wood, G. C.; Sage, P. W.; Cooke, M. J.

Studies of fly-ash composition identified the presence of calcium and sulphur, indicating their potential role as sources of calcium sulphate. Residual acidity (particularly for oil fly ash) suggested the possibility of enhanced chemical reaction, and the presence of transition metals, probably as oxides, might accelerate the oxidation of SO 2 to SO 42-. Exposure tests in a laboratory-based rig simulating dry deposition on Portland and Monks Park limestone, either seeded or unseeded with fly-ash particulate material or transition metal oxide catalysts, were carried out using an SO 2-containing environment at 95% r.h. Enhanced sulphation of these seeded limestones due to the above factors was minimal; at high loadings of fly ash, there was even evidence of masking the limestone surface, reducing sulphation. However, pure CaCO 3 powder in the exposure rig showed increases in sulphation when seeded with metal oxide catalysts. Thus the limestones examined contained sufficient inherent catalysts for the oxidation of SO 2 to SO 42- to proceed at such a rate that external catalysts were superfluous. This implies that dissolution rate of SO 2 in moisture films controls the availability of species for reaction with these carbonate-based stones and that fly ash deposited from the atmosphere does not enhance the reaction.

Methanol partial oxidation on Ag(111) from first principles

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

Aljama, Hassan; Yoo, Jong Suk; Nørskov, Jens K.

In this work, we examine the thermochemistry and kinetics of the partial oxidation of methanol to formaldehyde on silver surfaces. Periodic density functional theory calculations employing the BEEF-vdW functional are used to identify the most stable phases of the silver surface under relevant reaction conditions and the reaction energetics are obtained on these surfaces. The calculated binding energies and transition state energies are used as input in a mean-field microkinetic model providing the reaction kinetics on silver surfaces under different reaction conditions. Our results show that, under conditions pertaining to methanol partial oxidation, oxygen is present at low concentrations andmore » it plays a critical role in the catalytic reaction. Surface oxygen promotes the reaction by activating the OH bond in methanol, thus forming a methoxy intermediate, which can react further to form formaldehyde. Finally, the dissociation of molecular oxygen is identified as the most critical step.« less

Methanol partial oxidation on Ag(111) from first principles

DOE PAGES

Aljama, Hassan; Yoo, Jong Suk; Nørskov, Jens K.; ...

2016-10-26

In this work, we examine the thermochemistry and kinetics of the partial oxidation of methanol to formaldehyde on silver surfaces. Periodic density functional theory calculations employing the BEEF-vdW functional are used to identify the most stable phases of the silver surface under relevant reaction conditions and the reaction energetics are obtained on these surfaces. The calculated binding energies and transition state energies are used as input in a mean-field microkinetic model providing the reaction kinetics on silver surfaces under different reaction conditions. Our results show that, under conditions pertaining to methanol partial oxidation, oxygen is present at low concentrations andmore » it plays a critical role in the catalytic reaction. Surface oxygen promotes the reaction by activating the OH bond in methanol, thus forming a methoxy intermediate, which can react further to form formaldehyde. Finally, the dissociation of molecular oxygen is identified as the most critical step.« less

Sub-barrier quasifission in heavy element formation reactions with deformed actinide target nuclei

NASA Astrophysics Data System (ADS)

Hinde, D. J.; Jeung, D. Y.; Prasad, E.; Wakhle, A.; Dasgupta, M.; Evers, M.; Luong, D. H.; du Rietz, R.; Simenel, C.; Simpson, E. C.; Williams, E.

2018-02-01

Background: The formation of superheavy elements (SHEs) by fusion of two massive nuclei is severely inhibited by the competing quasifission process. Low excitation energies favor SHE survival against fusion-fission competition. In "cold" fusion with spherical target nuclei near 208Pb, SHE yields are largest at beam energies significantly below the average capture barrier. In "hot" fusion with statically deformed actinide nuclei, this is not the case. Here the elongated deformation-aligned configurations in sub-barrier capture reactions inhibits fusion (formation of a compact compound nucleus), instead favoring rapid reseparation through quasifission. Purpose: To determine the probabilities of fast and slow quasifission in reactions with prolate statically deformed actinide nuclei, through measurement and quantitative analysis of the dependence of quasifission characteristics at beam energies spanning the average capture barrier energy. Methods: The Australian National University Heavy Ion Accelerator Facility and CUBE fission spectrometer have been used to measure fission and quasifission mass and angle distributions for reactions with projectiles from C to S, bombarding Th and U target nuclei. Results: Mass-asymmetric quasifission occurring on a fast time scale, associated with collisions with the tips of the prolate actinide nuclei, shows a rapid increase in probability with increasing projectile charge, the transition being centered around projectile atomic number ZP=14 . For mass-symmetric fission events, deviations of angular anisotropies from expectations for fusion fission, indicating a component of slower quasifission, suggest a similar transition, but centered around ZP˜8 . Conclusions: Collisions with the tips of statically deformed prolate actinide nuclei show evidence for two distinct quasifission processes of different time scales. Their probabilities both increase rapidly with the projectile charge. The probability of fusion can be severely suppressed by these two quasifission processes, since the sub-barrier heavy element yield is likely to be determined by the product of the probabilities of surviving each quasifission process.

Determination of kinetic data for soot oxidation: Modeling of competition between oxygen diffusion and reaction during thermogravimetric analysis

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

Gilot, P.; Bonnefoy, F.; Marcuccilli, F.

1993-10-01

Kinetic data concerning carbon black oxidation in the temperature range between 600 and 900 C have been obtained using thermogravimetric analysis. Modeling of diffusion in a boundary layer above the pan and inside the porous medium coupled to oxygen reaction with carbon black is necessary to obtain kinetic constants as a function of temperature. These calculations require the knowledge of the oxidation rate at a given constant temperature as a function of the initial mass loading m[sub o]. This oxidation rate, expressed in milligrams of soot consumed per second and per milligram of initial soot loading, decreases when m[sub o]more » increases, in agreement with a reaction in an intermediary regime where the kinetics and the oxygen diffusion operate. The equivalent diffusivity of oxygen inside the porous medium is evaluated assuming two degrees of porosity: between soot aggregates and inside each aggregate. Below 700 C an activation energy of about 103 kJ/mol can be related to a combustion reaction probably kinetically controlled. Beyond 700 C the activation energy of about 20 kJ/ mol corresponds to a reaction essentially controlled by oxygen diffusion leading to a constant density oxidation with oxygen consumption at or near the particle surface. To validate these data, they are used in the modeling of a Diesel particulate trap regeneration. In this particular case, the oxidizing flux is forced across the carbon black deposit, oxygen diffusion being insignificant. A good agreement between experimental results and model predictions is obtained, proving the rate constants validity.« less

Parallel replica dynamics with a heterogeneous distribution of barriers: Application to n-hexadecane pyrolysis

NASA Astrophysics Data System (ADS)

Kum, Oyeon; Dickson, Brad M.; Stuart, Steven J.; Uberuaga, Blas P.; Voter, Arthur F.

2004-11-01

Parallel replica dynamics simulation methods appropriate for the simulation of chemical reactions in molecular systems with many conformational degrees of freedom have been developed and applied to study the microsecond-scale pyrolysis of n-hexadecane in the temperature range of 2100-2500 K. The algorithm uses a transition detection scheme that is based on molecular topology, rather than energetic basins. This algorithm allows efficient parallelization of small systems even when using more processors than particles (in contrast to more traditional parallelization algorithms), and even when there are frequent conformational transitions (in contrast to previous implementations of the parallel replica algorithm). The parallel efficiency for pyrolysis initiation reactions was over 90% on 61 processors for this 50-atom system. The parallel replica dynamics technique results in reaction probabilities that are statistically indistinguishable from those obtained from direct molecular dynamics, under conditions where both are feasible, but allows simulations at temperatures as much as 1000 K lower than direct molecular dynamics simulations. The rate of initiation displayed Arrhenius behavior over the entire temperature range, with an activation energy and frequency factor of Ea=79.7 kcal/mol and log A/s-1=14.8, respectively, in reasonable agreement with experiment and empirical kinetic models. Several interesting unimolecular reaction mechanisms were observed in simulations of the chain propagation reactions above 2000 K, which are not included in most coarse-grained kinetic models. More studies are needed in order to determine whether these mechanisms are experimentally relevant, or specific to the potential energy surface used.

Spectral Rate Theory for Two-State Kinetics

NASA Astrophysics Data System (ADS)

Prinz, Jan-Hendrik; Chodera, John D.; Noé, Frank

2014-02-01

Classical rate theories often fail in cases where the observable(s) or order parameter(s) used is a poor reaction coordinate or the observed signal is deteriorated by noise, such that no clear separation between reactants and products is possible. Here, we present a general spectral two-state rate theory for ergodic dynamical systems in thermal equilibrium that explicitly takes into account how the system is observed. The theory allows the systematic estimation errors made by standard rate theories to be understood and quantified. We also elucidate the connection of spectral rate theory with the popular Markov state modeling approach for molecular simulation studies. An optimal rate estimator is formulated that gives robust and unbiased results even for poor reaction coordinates and can be applied to both computer simulations and single-molecule experiments. No definition of a dividing surface is required. Another result of the theory is a model-free definition of the reaction coordinate quality. The reaction coordinate quality can be bounded from below by the directly computable observation quality, thus providing a measure allowing the reaction coordinate quality to be optimized by tuning the experimental setup. Additionally, the respective partial probability distributions can be obtained for the reactant and product states along the observed order parameter, even when these strongly overlap. The effects of both filtering (averaging) and uncorrelated noise are also examined. The approach is demonstrated on numerical examples and experimental single-molecule force-probe data of the p5ab RNA hairpin and the apo-myoglobin protein at low pH, focusing here on the case of two-state kinetics.

Born-Oppenheimer and Renner-Teller coupled-channel quantum reaction dynamics of O((3)P) + H2(+)(X(2)Σg(+)) collisions.

PubMed

Gamallo, Pablo; Defazio, Paolo; González, Miguel; Paniagua, Miguel; Petrongolo, Carlo

2015-09-28

We present Born-Oppenheimer (BO) and Renner-Teller (RT) time dependent quantum dynamics studies of the reactions O((3)P) + H2(+)(X(2)Σg(+)) → OH(+)(X(3)Σ(-)) + H((2)S) and OH(X(2)Π) + H(+). We consider the OH2(+) X[combining tilde](2)A'' and Ã(2)A' electronic states that correlate with a linear (2)Π species. The electronic angular momenta operators L[combining circumflex] and L[combining circumflex](2) are considered in nonadiabatic coupled-channel calculations, where the associated RT effects are due to diagonal V(RT) potentials that add up to the PESs and to off-diagonal C(RT) couplings between the potential energy surfaces (PESs). Initial-state-resolved reaction probabilities PI, integral cross sections σI, and rate constants kI are obtained using recent ab initio PESs and couplings and the real wavepacket formalism. Because the PESs are strongly attractive, PI have no threshold energy and are large, σI decrease with collision energy, and kI depend little on the temperature. The X[combining tilde](2)A'' PES is up to three times more reactive than the Ã(2)A' PES and H2(+) rotational effects (j0 = 0, 1) are negligible. The diagonal V(RT) potentials are strongly repulsive at the collinearity and nearly halve all low-energy observables with respect to the BO ones. The off-diagonal C(RT) couplings are important at low partial waves, where they mix the X[combining tilde](2)A'' and Ã(2)A' states up to ∼20%. However, V(RT) effects predominate over the C(RT) ones that change at most by ∼19% the BO values of σI and kI. The reaction O((3)P) + H2(+)(X(2)Σg(+)) → OH(+)(X(3)Σ(-)) + H((2)S) is probably one of the most reactive atom + diatom collisions because its RT rate constant at room temperature is equal to 2.26 × 10(-10) cm(3) s(-1). Within the BO approximation, the present results agree rather well with recent quasiclassical and centrifugal-sudden data using the same PESs.

First-Principles Mechanistic Analysis of Dimethyl Ether Electro-Oxidation on Monometallic Single-Crystal Surfaces

DOE PAGES

Herron, Jeffrey A.; Ferrin, Peter; Mavrikakis, Manos

2014-08-27

Dimethyl ether is an attractive alternative to petroleum fuels due to its physical properties, comparable energy density to methanol and ethanol, and minimal deleterious environmental/toxicological effects. For direct fuel cells, it has a number of advantages over other prominent fuels, including easier storage with respect to hydrogen, lower toxicity and crossover when compared to methanol, and more facile complete oxidation as compared to ethanol (which includes a relatively difficult to break C–C bond). However, the dimethyl ether electro-oxidation reaction is poorly understood, hindering the development of improved electrocatalysts. Using periodic, self-consistent (PW91-GGA) density functional theory calculations, we evaluate the thermochemistrymore » of dimethyl ether (DME) electro-oxidation, at the elementary step level, on 12 model, closed-packed facets of pure transition metals: Au, Ag, Cu, Pt, Pd, Ni, Ir, Rh, Co, Os, Ru, and Re. From the calculated thermochemistry, we determine the most probable reaction paths on each of these surfaces, focusing on Pt as a model system. Our results predict two key electro-oxidation peaks. At lower potentials, there is a peak corresponding to partial oxidation of DME to CO (and other surface poisoning species) or complete oxidation to CO 2 via formic acid as a key intermediate. A second, higher-potential peak is due to complete oxidation of adsorbed CO (and other surface poisoning species) to CO 2. Assuming the catalysts remain in their metallic state during the DME electro-oxidation process, our results suggest that the onset potential of the surfaces increases in the order Cu < Ni < Os < Rh < Ir < Co < Ru < Pt < Ag < Pd < Re < Au. Using our results, we construct a theoretical phase diagram showing predicted catalyst activity based on two key reactivity descriptors, the free energies of adsorbed CO and OH. Here, we compare all results to methanol electro-oxidation to understand key mechanistic differences and their impacts on optimal catalyst design for direct DME fuel cells.« less

Cross sections of projectile-like fragments in the reaction {sup 19}F+{sup 66}Zn in the beam energy range of 3-6 MeV/nucleon

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

Tripathi, R.; Sudarshan, K.; Sodaye, S.

2009-06-15

Angular distributions of projectile-like fragments (PLFs) have been measured in the reaction {sup 19}F+{sup 66}Zn at E{sub lab}=61,82,92, and 109 MeV to understand their formation in the low energy domain (< or approx. 7 MeV nucleon). In this energy range, maximum angular momentum 'l{sub max}' in the reaction is lower than or close to the critical or limiting angular momentum for complete fusion 'l{sub lim}(CF).' The sum-rule model was modified to explain the cross sections of PLFs in the present study. For the first time, the modified sum-rule model, with a competition of incomplete fusion (ICF) reaction with complete fusionmore » below l{sub lim}(CF) reasonably reproduced the cross sections of PLFs in the beam energy range of the present study. It was observed that the cross sections of lighter PLFs fall more rapidly with decreasing beam energy compared to those of heavier PLFs, suggesting a change in the reaction mechanism from heavier to lighter PLFs. Transfer probabilities for peripheral collisions were calculated within the framework of a semiclassical formalism. The parameters of the nuclear potential required for the calculation of transfer probability were obtained by fitting the elastic scattering data measured in the present work. Calculated transfer probabilities were significantly lower compared to the corresponding experimental values, suggesting a significant overlap of the projectile and the target nuclei in incomplete fusion reactions. The present analysis showed that the overlap of the projectile and the target nuclei increases with increasing mass transfer at a given beam energy and for a given PLF, overlap increases with increasing beam energy.« less

Preparation of fluorinated Cr2O3 hexagonal prism and catalytic performance for the dehydrofluorination of 1,1-difluoroethane to vinyl fluoride

NASA Astrophysics Data System (ADS)

Han, Wenfeng; Li, Xiaojuan; Tang, Haodong; Wang, Zhikun; Xi, Miao; Li, Ying; Liu, Huazhang

2015-09-01

A Cr2O3 hexagonal prism structure synthesized via the reaction of aqueous CrCl3 solution with NaBH4 solution at room temperature followed by calcination of the precipitate in N2 atmosphere at 500 °C is investigated as an efficient catalyst for dehydrofluorination of 1,1-difluoroethane producing vinyl fluoride. With the assistance of scanning electron microscopy, transmission electron microscopy, and high-resolution transmission electron microscopy, experimental results revealed that the uniform hexagonal prism has a prism length of 285 ± 43 nm and width of 233 ± 33 nm. It is in the form of loose and net-like aggregation of nano-Cr2O3 with diameter less than 3-5 nm with polycrystalline structure. NH3 temperature programmed desorption and chlorodifluoromethane dismutation experiments confirm the existence of relatively abundant and strong acidic sites. As a catalyst for dehydrofluorination of 1,1-difluoroethane, compared with commercial Cr2O3, much higher activity and stability were observed due to the evolution of CrO x F y species and much higher surface area and mesoporous structure. No significant morphology changes or sintering of the catalyst are observed after 70-h reaction. Compared with the commercial Cr2O3, we suggest that the much smaller size of Cr2O3 crystalline which possesses higher surface energy, lower strength, and more abundant Lewis acidity and the formation of CrO x F y during reaction over hexagonal prism catalyst probably contributes to the activity and stability difference between these two catalysts.

Beyond Born-Oppenheimer theory for ab initio constructed diabatic potential energy surfaces of singlet H3+ to study reaction dynamics using coupled 3D time-dependent wave-packet approach.

PubMed

Ghosh, Sandip; Mukherjee, Saikat; Mukherjee, Bijit; Mandal, Souvik; Sharma, Rahul; Chaudhury, Pinaki; Adhikari, Satrajit

2017-08-21

The workability of beyond Born-Oppenheimer theory to construct diabatic potential energy surfaces (PESs) of a charge transfer atom-diatom collision process has been explored by performing scattering calculations to extract accurate integral cross sections (ICSs) and rate constants for comparison with most recent experimental quantities. We calculate non-adiabatic coupling terms among the lowest three singlet states of H 3 + system (1 1 A ' , 2 1 A ' , and 3 1 A ' ) using MRCI level of calculation and solve the adiabatic-diabatic transformation equation to formulate the diabatic Hamiltonian matrix of the same process [S. Mukherjee et al., J. Chem. Phys. 141, 204306 (2014)] for the entire region of nuclear configuration space. The nonadiabatic effects in the D + + H 2 reaction has been studied by implementing the coupled 3D time-dependent wave packet formalism in hyperspherical coordinates [S. Adhikari and A. J. C. Varandas, Comput. Phys. Commun. 184, 270 (2013)] with zero and non-zero total angular momentum (J) on such newly constructed accurate (ab initio) diabatic PESs of H 3 + . We have depicted the convergence profiles of reaction probabilities for the reactive non-charge transfer, non-reactive charge transfer, and reactive charge transfer processes for different collisional energies with respect to the helicity (K) and total angular momentum (J) quantum numbers. Finally, total and state-to-state ICSs are calculated as a function of collision energy for the initial rovibrational state (v = 0, j = 0) of the H 2 molecule, and consequently, those quantities are compared with previous theoretical and experimental results.

Protection of dopamine towards autoxidation reaction by encapsulation into non-coated- or chitosan- or thiolated chitosan-coated-liposomes.

PubMed

Trapani, A; Mandracchia, D; Tripodo, G; Cometa, S; Cellamare, S; De Giglio, E; Klepetsanis, P; Antimisiaris, S G

2018-05-26

The aim of this work is to evaluate the potential of non-coated-, chitosan-(CS)- or chitosan-glutathione conjugate- (CS-GSH)-coated liposomes to protect the neurotransmitter Dopamine (DA) from the autoxidation reaction in neutral/alkaline conditions. This may be of interest in the development of nanotechnology-based approaches to improve Parkinson's disease treatment because decreased ROS production and reduced DA associated neurotoxicity are expected. For the mentioned purposes, DA-loaded vesicles were prepared by the Dried Reconstituted Vesicles (DRV) method, and were subsequently coated using solutions of polycations. As for the mean diameters of liposomes so prepared, the CS-GSH coated liposomes showed a significant decrease in size compared to the corresponding non-coated and CS-coated vesicles. The surface charge of DA-loaded non-coated liposomes was -10.8 mV, whereas the CS or CS-GSH coated vesicles showed a slightly positive ζ-potential. The capability of the herein studied vesicles to prevent DA autoxidation was evaluated by visual inspection, monitoring DA/lipid ratio as such and under stressed conditions. The results suggest that liposome formulations partially protect the neurotransmitter from the autoxidation reaction. In particular, the CS-GSH coated liposomes were more stable than the corresponding CS-coated and non-coated ones against the oxidative damage and were found to deliver the neurotransmitter in a sustained manner. Probably, this is due to the localization of the neurotransmitter in the core of the vesicles as indicated by XPS which confirmed the absence of the neurotransmitter on the surface of these vesicles. Copyright © 2018 Elsevier B.V. All rights reserved.

Inference of reaction rate parameters based on summary statistics from experiments

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

Khalil, Mohammad; Chowdhary, Kamaljit Singh; Safta, Cosmin

Here, we present the results of an application of Bayesian inference and maximum entropy methods for the estimation of the joint probability density for the Arrhenius rate para meters of the rate coefficient of the H 2/O 2-mechanism chain branching reaction H + O 2 → OH + O. Available published data is in the form of summary statistics in terms of nominal values and error bars of the rate coefficient of this reaction at a number of temperature values obtained from shock-tube experiments. Our approach relies on generating data, in this case OH concentration profiles, consistent with the givenmore » summary statistics, using Approximate Bayesian Computation methods and a Markov Chain Monte Carlo procedure. The approach permits the forward propagation of parametric uncertainty through the computational model in a manner that is consistent with the published statistics. A consensus joint posterior on the parameters is obtained by pooling the posterior parameter densities given each consistent data set. To expedite this process, we construct efficient surrogates for the OH concentration using a combination of Pad'e and polynomial approximants. These surrogate models adequately represent forward model observables and their dependence on input parameters and are computationally efficient to allow their use in the Bayesian inference procedure. We also utilize Gauss-Hermite quadrature with Gaussian proposal probability density functions for moment computation resulting in orders of magnitude speedup in data likelihood evaluation. Despite the strong non-linearity in the model, the consistent data sets all res ult in nearly Gaussian conditional parameter probability density functions. The technique also accounts for nuisance parameters in the form of Arrhenius parameters of other rate coefficients with prescribed uncertainty. The resulting pooled parameter probability density function is propagated through stoichiometric hydrogen-air auto-ignition computations to illustrate the need to account for correlation among the Arrhenius rate parameters of one reaction and across rate parameters of different reactions.« less

Inference of reaction rate parameters based on summary statistics from experiments

DOE PAGES

Khalil, Mohammad; Chowdhary, Kamaljit Singh; Safta, Cosmin; ...

2016-10-15

Here, we present the results of an application of Bayesian inference and maximum entropy methods for the estimation of the joint probability density for the Arrhenius rate para meters of the rate coefficient of the H 2/O 2-mechanism chain branching reaction H + O 2 → OH + O. Available published data is in the form of summary statistics in terms of nominal values and error bars of the rate coefficient of this reaction at a number of temperature values obtained from shock-tube experiments. Our approach relies on generating data, in this case OH concentration profiles, consistent with the givenmore » summary statistics, using Approximate Bayesian Computation methods and a Markov Chain Monte Carlo procedure. The approach permits the forward propagation of parametric uncertainty through the computational model in a manner that is consistent with the published statistics. A consensus joint posterior on the parameters is obtained by pooling the posterior parameter densities given each consistent data set. To expedite this process, we construct efficient surrogates for the OH concentration using a combination of Pad'e and polynomial approximants. These surrogate models adequately represent forward model observables and their dependence on input parameters and are computationally efficient to allow their use in the Bayesian inference procedure. We also utilize Gauss-Hermite quadrature with Gaussian proposal probability density functions for moment computation resulting in orders of magnitude speedup in data likelihood evaluation. Despite the strong non-linearity in the model, the consistent data sets all res ult in nearly Gaussian conditional parameter probability density functions. The technique also accounts for nuisance parameters in the form of Arrhenius parameters of other rate coefficients with prescribed uncertainty. The resulting pooled parameter probability density function is propagated through stoichiometric hydrogen-air auto-ignition computations to illustrate the need to account for correlation among the Arrhenius rate parameters of one reaction and across rate parameters of different reactions.« less

Molecular-dynamics analysis of mobile helium cluster reactions near surfaces of plasma-exposed tungsten

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

Hu, Lin; Maroudas, Dimitrios, E-mail: maroudas@ecs.umass.edu; Hammond, Karl D.

We report the results of a systematic atomic-scale analysis of the reactions of small mobile helium clusters (He{sub n}, 4 ≤ n ≤ 7) near low-Miller-index tungsten (W) surfaces, aiming at a fundamental understanding of the near-surface dynamics of helium-carrying species in plasma-exposed tungsten. These small mobile helium clusters are attracted to the surface and migrate to the surface by Fickian diffusion and drift due to the thermodynamic driving force for surface segregation. As the clusters migrate toward the surface, trap mutation (TM) and cluster dissociation reactions are activated at rates higher than in the bulk. TM produces W adatoms and immobile complexes ofmore » helium clusters surrounding W vacancies located within the lattice planes at a short distance from the surface. These reactions are identified and characterized in detail based on the analysis of a large number of molecular-dynamics trajectories for each such mobile cluster near W(100), W(110), and W(111) surfaces. TM is found to be the dominant cluster reaction for all cluster and surface combinations, except for the He{sub 4} and He{sub 5} clusters near W(100) where cluster partial dissociation following TM dominates. We find that there exists a critical cluster size, n = 4 near W(100) and W(111) and n = 5 near W(110), beyond which the formation of multiple W adatoms and vacancies in the TM reactions is observed. The identified cluster reactions are responsible for important structural, morphological, and compositional features in the plasma-exposed tungsten, including surface adatom populations, near-surface immobile helium-vacancy complexes, and retained helium content, which are expected to influence the amount of hydrogen re-cycling and tritium retention in fusion tokamaks.« less

Reaction Heterogeneity in LiNi 0.8 Co 0.15 Al 0.05 O 2 Induced by Surface Layer

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

Grenier, Antonin; Liu, Hao; Wiaderek, Kamila M.

2017-08-15

Through operando synchrotron powder X-ray diffraction (XRD) analysis of layered transition metal oxide electrodes of composition LiNi0.8Co0.15Al0.05O2 (NCA), we decouple the intrinsic bulk reaction mechanism from surface-induced effects. For identically prepared and cycled electrodes stored in different environments, we demonstrate that the intrinsic bulk reaction for pristine NCA follows solid-solution mechanism, not a two-phase as suggested previously. By combining high resolution powder X-ray diffraction, diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) and surface sensitive X-ray photoelectron spectroscopy (XPS), we demonstrate that adventitious Li2CO3 forms on the electrode particle surface during exposure to air, through reaction with atmospheric CO2. This surfacemore » impedes ionic and electronic transport to the underlying electrode, with progressive erosion of this layer during cycling giving rise to different reaction states in particles with an intact vs an eroded Li2CO3 surface-coating. This reaction heterogeneity, with a bimodal distribution of reaction states, has previously been interpreted as a “two-phase” reaction mechanism for NCA, as an activation step that only occurs during the first cycle. Similar surface layers may impact the reaction mechanism observed in other electrode materials using bulk probes such as operando powder XRD.« less

Survival Mediated Heavy Element Capture Cross Sections

NASA Astrophysics Data System (ADS)

Loveland, Walter; Yao, Larry

2017-11-01

Formally, the cross section for producing a heavy evaporation residue, σEVR, in a fusion reaction can be written as where E is the center of mass energy, and T is the probability of the colliding nuclei to overcome the potential barrier in the entrance channel and reach the contact point. PCN is the probability that the projectile-target system will evolve from the contact point to the compound nucleus. Wsur is the probability that the compound nucleus will decay to produce an evaporation residue rather than fissioning. However, one must remember that the Wsur term effectively sets the allowed values of the spin, which in turn, restricts the values of the capture and fusion cross sections. We point out the implications of this fact for capture cross sections for heavy element formation reactions.

A multimodal optical and electrochemical device for monitoring surface reactions: redox active surfaces in porous silicon Rugate filters.

PubMed

Ciampi, Simone; Guan, Bin; Darwish, Nadim A; Zhu, Ying; Reece, Peter J; Gooding, J Justin

2012-12-21

Herein, mesoporous silicon (PSi) is configured as a single sensing device that has dual readouts; as a photonic crystal sensor in a Rugate filter configuration, and as a high surface area porous electrode. The as-prepared PSi is chemically modified to provide it with stability in aqueous media and to allow for the subsequent coupling of chemical species, such as via Cu(I)-catalyzed cycloaddition reactions between 1-alkynes and azides ("click" reactions). The utility of the bimodal capabilities of the PSi sensor for monitoring surface coupling procedures is demonstrated by the covalent coupling of a ferrocene derivative, as well as by demonstrating ligand-exchange reactions (LER) at the PSi surface. Both types of reactions were monitored through optical reflectivity measurements, as well as electrochemically via the oxidation/reduction of the surface tethered redox species.

Pathways for Ethanol Dehydrogenation and Dehydration Catalyzed by Ceria (111) and (100) Surfaces

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

Beste, Ariana; Steven Overbury

2015-01-08

We have performed computations to better understand how surface structure affects selectivity in dehydrogenation and dehydration reactions of alcohols. Ethanol reactions on the (111) and (100) ceria surfaces were studied starting from the dominant surface species, ethoxy. We used DFT (PBE+U) to explore reaction pathways leading to ethylene and acetaldehyde and calculated estimates of rate constants employing transition state theory. To assess pathway contributions, we carried out kinetic analysis. Our results show that intermediate and transition state structures are stabilized on the (100) surface compared to the (111) surface. Formation of acetaldehyde over ethylene is kinetically and thermodynamically preferred onmore » both surfaces. Our results are consistent with temperature programmed surface reaction and steady-state experiments, where acetaldehyde was found as the main product and evidence was presented that ethylene formation at higher temperature originates from changes in adsorbate and surface structure.« less

Surface contamination on LDEF exposed materials

NASA Technical Reports Server (NTRS)

Hemminger, Carol S.

1992-01-01

X-ray photoelectron spectroscopy (XPS) has been used to study the surface composition and chemistry of Long Duration Exposure Facility (LDEF) exposed materials including silvered Teflon (Ag/FEP), Kapton, S13GLO paint, quartz crystal monitors (QCM's), carbon fiber/organic matrix composites, and carbon fiber/Al Alloy composites. In each set of samples, silicones were the major contributors to the molecular film accumulated on the LDEF exposed surfaces. All surfaces analyzed have been contaminated with Si, O, and C; most have low levels (less than 1 atom percent) of N, S, and F. Occasionally observed contaminants included Cl, Na, K, P, and various metals. Orange/brown discoloration observed near vent slots in some Ag/FEP blankets were higher in carbon, sulfur, and nitrogen relative to other contamination types. The source of contamination has not been identified, but amine/amide functionalities were detected. It is probable that this same source of contamination account for the low levels of sulfur and nitrogen observed on most LDEF exposed surfaces. XPS, which probes 50 to 100 A in depth, detected the major sample components underneath the contaminant film in every analysis. This probably indicates that the contaminant overlayer is patchy, with significant areas covered by less that 100 A of molecular film. Energy dispersive x-ray spectroscopy (EDS) of LDEF exposed surfaces during secondary electron microscopy (SEM) of the samples confirmed contamination of the surfaces with Si and O. In general, particulates were not observed to develop from the contaminant overlayer on the exposed LDEF material surfaces. However, many SiO2 submicron particles were seen on a masked edge of an Ag/FEP blanket. In some cases such as the carbon fiber/organic matrix composites, interpretation of the contamination data was hindered by the lack of good laboratory controls. Examination of laboratory controls for the carbon fiber/Al alloy composites showed that preflight contamination was the most significant factor for all the contaminants generally detected at less than 1 atom percent, or detected only occasionally (i.e., all but Si, O, and C). Flight control surfaces, including sample backsides not exposed to space radiation or atomic oxygen flux, have accumulated some contamination on flight (compared to laboratory controls), but experimentally, the LDEF exposed surface contamination levels are generally higher for the contaminants Si and O. For most materials analyzed, Si contamination levels were higher on the leading edge surfaces than on the trailing edge surfaces. This was true even for the composite samples where considerable atomic oxygen erosion of the leading edge surfaces was observed by SEM. It is probable that the return flux associated with atmospheric backscatter resulted in enhanced deposition of silicones and other contaminants on the leading edge flight surfaces relative to the trailing edge. Although the Si concentration data suggested greater on-flight deposition of contaminants on the leading edge surfaces, the XPS analyses did not conclusively show different relative total thicknesses of flight deposited contamination for leading and trailing edge surfaces. It is possible that atomic oxygen reactions on the leading edge resulted in greater volatilization of the carbon component of the deposited silicones, effectively 'thinning' the leading edge deposited overlayer. Unlike other materials, exposed polymers such as Kapton and FEP-type Teflon had very low contamination on the leading edge surfaces. SEM evidence showed that undercutting of the contaminant overlayer and damaged polymer layers occurred during atomic oxygen erosion, which would enhance loss of material from the exposed surface.

Thruster residues on returned Mir solar panel

NASA Astrophysics Data System (ADS)

Harvey, Gale A.

2000-09-01

A solar panel with more than ten years space exposure was returned to Earth in January 1998. Several types of residues were deposited or transported onto the solar cell coverglasses during the space exposure. Self-contamination of SiOx films from the silicone potting compound was a major contamination of the coverglasses. A second type of contamination was thick, detergent-like residues of the order of a millimeter diameter on many, but not most of the coverglasses. A third, prevalent type of contamination was very thin irregular shaped films or patterns of a millimeter size which are readily visible in brilliant colors when the coverglasses are viewed with a 50x brightfield microscope. These prolific, overlapping, and almost ubiquitous patterns strongly suggest wetting on the surface. The probably cause of most of the wetted patterns on the returned Mir solar cell coverglasses is trace hydrazine nitrate in condensed water droplets produced as reaction products from Mir's and the Orbiters' hypergolic thrusters. This paper presents some of the wetted patterns, information regarding hypergolic reaction products, and type of thrusters associated with Mir operations.

Strong metal-support interactions

NASA Technical Reports Server (NTRS)

Vannice, M. Albert

1987-01-01

It has been demonstrated that synergistic metal-support effects can occur which markedly enhance specific activity and alter selectivity in certain reactions. Because of the presence of such effects in certain reactions conducted under reducing conditions (that is, under H2 pressure), but not others, the creation of unique sites at the metal-support interface seems to be the best model at the present time to explain this behavior. The postulation of these sites, which are specific for a certain reactant such as CO, provides an effective explanation for the higher methanation rates that have been reported over some catalysts. The creation of these sites in the adlineation zone is facilitated by hydrogen spillover from the metal surface, and this same process can also enhance the reduction of many oxide supports. Although oxygen spillover is much less probable due to its higher heat of adsorption, it is much less well understood and the possibility of rate enhancements in CO oxidation caused by special interface sites cannot be discounted at the present time. Consequently, this seems to be an important area of future research.

Electrochemical Studies of Redox Systems for Energy Storage

NASA Technical Reports Server (NTRS)

Wu, C. D.; Calvo, E. J.; Yeager, E.

1983-01-01

Particular attention was paid to the Cr(II)/Cr(III) redox couple in aqueous solutions in the presence of Cl(-) ions. The aim of this research has been to unravel the electrode kinetics of this redox couple and the effect of Cl(1) and electrode substrate. Gold and silver were studied as electrodes and the results show distinctive differences; this is probably due to the role Cl(-) ion may play as a mediator in the reaction and the difference in state of electrical charge on these two metals (difference in the potential of zero charge, pzc). The competition of hydrogen evolution with CrCl3 reduction on these surfaces was studied by means of the rotating ring disk electrode (RRDE). The ring downstream measures the flux of chromous ions from the disk and therefore separation of both Cr(III) and H2 generation can be achieved by analyzing ring and disk currents. The conditions for the quantitative detection of Cr(2+) at the ring electrode were established. Underpotential deposition of Pb on Ag and its effect on the electrokinetics of Cr(II)/Cr(III) reaction was studied.

Plasmon inducing effects for enhanced photoelectrochemical water splitting: X-ray absorption approach to electronic structures.

PubMed

Chen, Hao Ming; Chen, Chih Kai; Chen, Chih-Jung; Cheng, Liang-Chien; Wu, Pin Chieh; Cheng, Bo Han; Ho, You Zhe; Tseng, Ming Lun; Hsu, Ying-Ya; Chan, Ting-Shan; Lee, Jyh-Fu; Liu, Ru-Shi; Tsai, Din Ping

2012-08-28

Artificial photosynthesis using semiconductors has been investigated for more than three decades for the purpose of transferring solar energy into chemical fuels. Numerous studies have revealed that the introduction of plasmonic materials into photochemical reaction can substantially enhance the photo response to the solar splitting of water. Until recently, few systematic studies have provided clear evidence concerning how plasmon excitation and which factor dominates the solar splitting of water in photovoltaic devices. This work demonstrates the effects of plasmons upon an Au nanostructure-ZnO nanorods array as a photoanode. Several strategies have been successfully adopted to reveal the mutually independent contributions of various plasmonic effects under solar irradiation. These have clarified that the coupling of hot electrons that are formed by plasmons and the electromagnetic field can effectively increase the probability of a photochemical reaction in the splitting of water. These findings support a new approach to investigating localized plasmon-induced effects and charge separation in photoelectrochemical processes, and solar water splitting was used herein as platform to explore mechanisms of enhancement of surface plasmon resonance.

Modeling of metal thin film growth: Linking angstrom-scale molecular dynamics results to micron-scale film topographies

NASA Astrophysics Data System (ADS)

Hansen, U.; Rodgers, S.; Jensen, K. F.

2000-07-01

A general method for modeling ionized physical vapor deposition is presented. As an example, the method is applied to growth of an aluminum film in the presence of an ionized argon flux. Molecular dynamics techniques are used to examine the surface adsorption, reflection, and sputter reactions taking place during ionized physical vapor deposition. We predict their relative probabilities and discuss their dependence on energy and incident angle. Subsequently, we combine the information obtained from molecular dynamics with a line of sight transport model in a two-dimensional feature, incorporating all effects of reemission and resputtering. This provides a complete growth rate model that allows inclusion of energy- and angular-dependent reaction rates. Finally, a level-set approach is used to describe the morphology of the growing film. We thus arrive at a computationally highly efficient and accurate scheme to model the growth of thin films. We demonstrate the capabilities of the model predicting the major differences on Al film topographies between conventional and ionized sputter deposition techniques studying thin film growth under ionized physical vapor deposition conditions with different Ar fluxes.

Addition of oxygen to and distribution of oxides in tantalum alloy T-111 at low concentrations

NASA Technical Reports Server (NTRS)

Stecura, S.

1975-01-01

Oxygen was added at 820 and 990 C at an oxygen pressure of about .0003 torr. The technique permitted predetermined and reproducible oxygen doping of the tantalum alloy (T-111). Based on the temperature dependency of the doping reaction, it was concluded that the initial rates of oxygen pickup are probably controlled by solution of oxygen into the T-111 lattice. Although hafnium oxides are more stable than those of tantalum or tungsten, analyses of extracted residues indicate that the tantalum and tungsten oxides predominate in the as-doped specimens, presumably because of the higher concentrations of tantalum and tungsten in the alloy. However, high-temperature annealing promotes gettering of dissolved oxygen and oxygen from other oxides to form hafnium oxides. Small amounts of tantalum and tungsten oxides were still present after high temperature annealing. Tungsten oxide (WO3) volatilizes slightly from the surface of T-111 at 990 C but not at 820 C. The vaporization of WO3 has no apparent effect on the doping reaction.

Duration of skin photosensitivity and incidence of photosensitivity reactions after administration of verteporfin.

PubMed

Houle, Jean-Marie; Strong, H Andrew

2002-12-01

Verteporfin (Visudyne, Novartis AG) is a light-activated drug that reduces the risk of vision loss in patients with certain types of choroidal neovascularization (CNV). Because photosensitivity can occur with photosensitizers, it is important for ophthalmologists providing verteporfin therapy to understand its time course and duration, as well as the incidence of photosensitivity reactions. Data were obtained from three sources: 1) the time course of skin photosensitivity in 17 volunteers by measuring erythema/edema over time after verteporfin, using red light exposure; 2) the duration of skin photosensitivity in 30 patients with skin cancer by exposing skin to simulated solar light and calculating the daily minimal erythematous dose; and 3) the incidences of photosensitivity reactions as recorded in three phase III trials in patients with CNV secondary to age-related macular degeneration or pathologic myopia who received the regimen of verteporfin therapy currently approved by regulatory authorities (infusion of 6 mg/m(2) body surface area). 1) Skin photosensitivity was high at the first timepoint of 1.5 hours after dosing and decreased rapidly thereafter; 2) the duration of skin photosensitivity was dose dependent, ranging from 2.0 to 6.7 days at 6 to 20 mg/m(2), respectively (mean of 2 days at a dose of 6 mg/m(2)); and 3) photosensitivity reactions occurred in only 2.2% of patients in the phase III trials, including two severe events, one secondary to extravasation. All treatment-related reactions in the phase III trials occurred within the first 2 days after dosing, with the exception of two mild reactions and one moderate reaction that occurred 3 days after treatment. Verteporfin is associated with short-lived photosensitivity and a low incidence of photosensitivity reactions in clinical trials, most of which could probably have been avoided by adherence to protocol instructions for skin protection.

Monte Carlo Technique Used to Model the Degradation of Internal Spacecraft Surfaces by Atomic Oxygen

NASA Technical Reports Server (NTRS)

Banks, Bruce A.; Miller, Sharon K.

2004-01-01

Atomic oxygen is one of the predominant constituents of Earth's upper atmosphere. It is created by the photodissociation of molecular oxygen (O2) into single O atoms by ultraviolet radiation. It is chemically very reactive because a single O atom readily combines with another O atom or with other atoms or molecules that can form a stable oxide. The effects of atomic oxygen on the external surfaces of spacecraft in low Earth orbit can have dire consequences for spacecraft life, and this is a well-known and much studied problem. Much less information is known about the effects of atomic oxygen on the internal surfaces of spacecraft. This degradation can occur when openings in components of the spacecraft exterior exist that allow the entry of atomic oxygen into regions that may not have direct atomic oxygen attack but rather scattered attack. Openings can exist because of spacecraft venting, microwave cavities, and apertures for Earth viewing, Sun sensors, or star trackers. The effects of atomic oxygen erosion of polymers interior to an aperture on a spacecraft were simulated at the NASA Glenn Research Center by using Monte Carlo computational techniques. A two-dimensional model was used to provide quantitative indications of the attenuation of atomic oxygen flux as a function of the distance into a parallel-walled cavity. The model allows the atomic oxygen arrival direction, the Maxwell Boltzman temperature, and the ram energy to be varied along with the interaction parameters of the degree of recombination upon impact with polymer or nonreactive surfaces, the initial reaction probability, the reaction probability dependence upon energy and angle of attack, degree of specularity of scattering of reactive and nonreactive surfaces, and the degree of thermal accommodation upon impact with reactive and non-reactive surfaces to be varied to allow the model to produce atomic oxygen erosion geometries that replicate actual experimental results from space. The degree of erosion of various interior locations was compared with the erosion that would occur external to the spacecraft. Results of one cavity model indicate that, at depths into a two-dimensional cavity that are equal to 10 cavity widths, the erosion on the walls of the cavity is less than that on the top surface by over 2 orders of magnitude. Wall erosion near the surface of a cavity depends on which wall is receiving direct atomic oxygen attack. However, deep in the cavity little difference is present. Testing of various cavity models such as these gives spacecraft designers an indication of the level of threat to sensitive interior surfaces for different geometries. Even though the Monte Carlo model is two-dimensional, it can be used to provide qualitative information about spacecraft openings that are three-dimensional by offering reasonable insight as to the nature of the attenuation of damage that occurs within a spacecraft in low Earth orbit. As shown, there is more erosion on the side seeing direct atomic oxygen attack until a depth of approximately 5 times the width of the opening, where the erosion is the same on both sides.

Development of a reaction cell for in-situ/operando studies of surface of a catalyst under a reaction condition and during catalysis.

PubMed

Nguyen, Luan; Tao, Franklin Feng

2016-06-01

Tracking surface chemistry of a catalyst during catalysis is significant for fundamental understanding of catalytic performance of the catalyst since it allows for establishing an intrinsic correlation between surface chemistry of a catalyst at its working status and its corresponding catalytic performance. Ambient pressure X-ray photoelectron spectroscopy can be used for in-situ studies of surfaces of different materials or devices in a gas. To simulate the gaseous environment of a catalyst in a fixed-bed a flowing gaseous environment of reactants around the catalyst is necessary. Here, we report the development of a new flowing reaction cell for simulating in-situ study of a catalyst surface under a reaction condition in gas of one reactant or during catalysis in a mixture of reactants of a catalytic reaction. The homemade reaction cell is installed in a high vacuum (HV) or ultrahigh vacuum (UHV) environment of a chamber. The flowing gas in the reaction cell is separated from the HV or UHV environment through well sealings at three interfaces between the reaction cell and X-ray window, sample door and aperture of front cone of an energy analyzer. Catalyst in the cell is heated through infrared laser beam introduced through a fiber optics interfaced with the reaction cell through a homemade feedthrough. The highly localized heating on the sample holder and Au-passivated internal surface of the reaction cell effectively minimizes any unwanted reactions potentially catalyzed by the reaction cell. The incorporated laser heating allows a fast heating and a high thermal stability of the sample at a high temperature. With this cell, a catalyst at 800 °C in a flowing gas can be tracked readily.

The Atmosphere and Climate of Venus

NASA Astrophysics Data System (ADS)

Bullock, M. A.; Grinspoon, D. H.

Venus lies just sunward of the inner edge of the Sun's habitable zone. Liquid water is not stable. Like Earth and Mars, Venus probably accreted at least an ocean's worth of water, although there are alternative scenarios. The loss of this water led to the massive, dry CO2 atmosphere, extensive H2SO4 clouds (at least some of the time), and an intense CO2 greenhouse effect. This chapter describes the current understanding of Venus' atmosphere, established from the data of dozens of spacecraft and atmospheric probe missions since 1962, and by telescopic observations since the nineteenth century. Theoretical work to model the temperature, chemistry, and circulation of Venus' atmosphere is largely based on analogous models developed in the Earth sciences. We discuss the data and modeling used to understand the temperature structure of the atmosphere, as well as its composition, cloud structure, and general circulation. We address what is known and theorized about the origin and early evolution of Venus' atmosphere. It is widely understood that Venus' dense CO2 atmosphere is the ultimate result of the loss of an ocean to space, but the timing of major transitions in Venus' climate is very poorly constrained by the available data. At present, the bright clouds allow only 20% of the sunlight to drive the energy balance and therefore determine conditions at Venus' surface. Like Earth and Mars, differential heating between the equator and poles drives the atmospheric circulation. Condensable species in the atmosphere create clouds and hazes that drive feedbacks that alter radiative forcing. Also in common with Earth and Mars, the loss of light, volatile elements to space produces long-term changes in composition and chemistry. As on Earth, geologic processes are most likely modifying the atmosphere and clouds by injecting gases from volcanos as well as directly through chemical reactions with the surface. The sensitivity of Venus' atmospheric energy balance is quantified in this chapter in terms of the initial forcing due to a perturbation, radiative response, and indirect responses, which are feedbacks — either positive or negative. When applied to one Venus climate model, we found that the albedo-radiative feedback is more important than greenhouse forcing for small changes in atmospheric H2O and SO2. An increase in these gases cools the planet by making the clouds brighter. On geologic timescales the reaction of some atmospheric species (SO2, CO, OCS, S, H2O, H2S, HCl, HF) with surface minerals could cause significant changes in atmospheric composition. Laboratory data and thermochemical modeling have been important for showing that atmospheric SO2 would be depleted in ~10 m.y. if carbonates are available at the surface. Without replenishment, the clouds would disappear. Alternatively, the oxidation of pyrite could add SO2 to the atmosphere while producing stable Fe oxides at the surface. The correlation of near-infrared high emissivity (dark) surface features with three young, large volcanos on Venus is strong evidence for recent volcanic activity at these sites, certainly over the timescale necessary to support the clouds. We address the nature of heterogeneous reactions with the surface and the implications for climate change on Venus. Chemical and mineralogical signatures of past climates must exist at the surface and below, so in situ experiments on the composition of surface layers are vital for reconstructing Venus' past climate. Many of the most Earth-like planets found around other stars will probably resemble Venus or a younger version of Venus. We finish the chapter with discussing what Venus can tell us about life in the universe, since it is an example of a planetary climate rendered uninhabitable. It also resembles our world's likely future. As with the climate history of Venus, however, the timing of predictable climate transitions on the Earth is poorly constrained by the data.

Space-weathering processes and products on volatile-rich asteroids

NASA Astrophysics Data System (ADS)

Britt, D.; Schelling, P.; Consolmagno, G.; Bradley, T.

2014-07-01

Space weathering is a generic term for the effects on atmosphereless solid bodies in the solar system from a range of processes associated with direct exposure to the space environment. These include impact processes (shock, vaporization, fragmentation, heating, melting, and ejecta formation), radiation damage (from galactic and solar cosmic rays), solar-wind effects (irradiation, ion implantation, and sputtering), and the chemical reactions driven by these processes. The classic example of space weathering is the formation of the lunar spectral red slope associated with the production of nanophase Fe (npFe0) in the dusty lunar regolith (C.R. Chapman, 2004, Annual Review of Earth & Planet. Sci. 32, C.M. Pieters, 2000, MAPS 35). Similar npFe0 has been recovered from asteroid (25143) Itokawa and some asteroid classes do exhibit modest spectral red slopes (T. Noguchi, 2011, Science 333). Space weathering can be thought of as driven by a combination of the chemical environment of space (hard vacuum, low oxygen fugacity, solar-wind implantation of hydrogen) along with thermal energy supplied by micrometeorite impacts. The forward modeling of space weathering as thermodynamically-driven decomposition of common rock-forming minerals suggests the production of a range of daughter products: (1) The silicate products typically lose oxygen, other volatile elements (i.e., sulfur and sodium), and metallic cations, producing minerals that are typically more disordered and less optically active than the original parent materials. (2) The decomposed metallic cations form in nano-sized blebs including npFe0, on the surfaces or in condensing rims of mineral grains. This creates a powerful optical component as seen in the lunar red slope. Surfaces with exposed npFe0 are an ideal environment for catalyzing further reactions. (3) The liberated volatile elements and gases (O, S, Na) may form an observable exosphere (e.g., Moon and Mercury) and can either escape from the body or recombine with available solar-wind-implanted hydrogen to form trace amounts of water and OH. Mineral decomposition can be thought of as the first stage of space weathering. It produces weathered surfaces somewhat depleted in volatile elements, creates a predictable set of minor or trace minerals, and leaves the surfaces with catalytic species, primarily npFe0. However, a second stage of further reactions and weathering depends upon the presence of ''feed-stock'' components that can participate in catalyzed chemical reactions on exposed surfaces. For volatile-rich small bodies, the available materials are not only silicates, but a volatile feedstock that can include water, carbon monoxide, ammonia, to name a few. Thermodynamically-driven decomposition of silicates will produce trace amounts of npFe0 which are ideal sites for Fischer-Tropsch type (FTT) catalytic reactions that can produce organics in situ on the asteroids including alkanes, polyaromatic hydrocarbons, and amino acids (J.E. Elsila, 2012, MAPS 47). The mix and range of products depends on the composition and morphology of the mineral surface, energy inputs produced by the micrometeorite impacts or other processes, and the composition of the input volatile feedstock. FFT reactions generate long-chain carbon compounds and amino acids. Secondary reactions that generate more complex carbon compounds and amino acids are likely to occur as the organic material matures. Weathering maturity can be thought of as a function of the abundance and diversity of the weathering products. Since the npFe0 is not destroyed in the reaction, continued micrometeorite bombardment would result in continuing processing and recombination of the existing organic feedstock. More weathering would result in progressively longer-chain carbon compounds as well as more complex and diverse amino acids, and eventually the kerogen-like insoluble-organic matter that forms a large fraction of carbonaceous meteorites. This insight has several major implications for our planetary science and, potentially, the formation of the precursors of life. First, the range of weathering products seen in remotely-sensed data, meteorites, and returned samples are not random, but the predictable outcome of the source region's mineral kinetics and chemical feedstock. Weathering products do not have to be optically active like the npFe0 that produces the lunar red slope; on the contrary, probably most weathering products are spectrally neutral or even suppress an object's near-IR reflectance spectrum. In the case of volatile-rich parent bodies, a major weathering product is a range of carbon-rich compounds. But an additional result of considerable interest is the generation of pre-biotic compounds as a routine and predictable byproduct of common space-weathering processes. Any atmosphereless body around any star with mafic silicate mineral compositions and volatile feedstocks should create amino acids as a standard byproduct of space weathering. The precursors of life are probably abundant in any space-weathered asteroid belt, in any solar system, and only wait being accreted to a hospitable environment.

Effect of surface curvature on diffusion-limited reactions on a curved surface

NASA Astrophysics Data System (ADS)

Eun, Changsun

2017-11-01

To investigate how the curvature of a reactive surface can affect reaction kinetics, we use a simple model in which a diffusion-limited bimolecular reaction occurs on a curved surface that is hollowed inward, flat, or extended outward while keeping the reactive area on the surface constant. By numerically solving the diffusion equation for this model using the finite element method, we find that the rate constant is a non-linear function of the surface curvature and that there is an optimal curvature providing the maximum value of the rate constant, which indicates that a spherical reactant whose entire surface is reactive (a uniformly reactive sphere) is not the most reactive species for a given reactive surface area. We discuss how this result arises from the interplay between two opposing effects: the exposedness of the reactive area to its partner reactants, which causes the rate constant to increase as the curvature increases, and the competition occurring on the reactive surface, which decreases the rate constant. This study helps us to understand the role of curvature in surface reactions and allows us to rationally design reactants that provide a high reaction rate.

PHOTOTROPISM OF GERMINATING MYCELIA OF SOME PARASITIC FUNGI

DTIC Science & Technology

uredinales on young wheat plants; Distribution and significance of the phototropism of germinating mycelia -- confirmation of older data, examination of...eight additional uredinales, probable meaning of negative phototropism for the occurrence of infection; Analysis of the stimulus physiology of the...reaction -- the minimum effective illumination intensity, the effective special region, inversion of the phototropic reaction in liquid paraffin, the negative light- growth reaction, the light-sensitive zone.

Driving Chemical Reactions in Plasmonic Nanogaps with Electrohydrodynamic Flow.

PubMed

Thrift, William J; Nguyen, Cuong Q; Darvishzadeh-Varcheie, Mahsa; Zare, Siavash; Sharac, Nicholas; Sanderson, Robert N; Dupper, Torin J; Hochbaum, Allon I; Capolino, Filippo; Abdolhosseini Qomi, Mohammad Javad; Ragan, Regina

2017-11-28

Nanoparticles from colloidal solution-with controlled composition, size, and shape-serve as excellent building blocks for plasmonic devices and metasurfaces. However, understanding hierarchical driving forces affecting the geometry of oligomers and interparticle gap spacings is still needed to fabricate high-density architectures over large areas. Here, electrohydrodynamic (EHD) flow is used as a long-range driving force to enable carbodiimide cross-linking between nanospheres and produces oligomers exhibiting sub-nanometer gap spacing over mm 2 areas. Anhydride linkers between nanospheres are observed via surface-enhanced Raman scattering (SERS) spectroscopy. The anhydride linkers are cleavable via nucleophilic substitution and enable placement of nucleophilic molecules in electromagnetic hotspots. Atomistic simulations elucidate that the transient attractive force provided by EHD flow is needed to provide a sufficient residence time for anhydride cross-linking to overcome slow reaction kinetics. This synergistic analysis shows assembly involves an interplay between long-range driving forces increasing nanoparticle-nanoparticle interactions and probability that ligands are in proximity to overcome activation energy barriers associated with short-range chemical reactions. Absorption spectroscopy and electromagnetic full-wave simulations show that variations in nanogap spacing have a greater influence on optical response than variations in close-packed oligomer geometry. The EHD flow-anhydride cross-linking assembly method enables close-packed oligomers with uniform gap spacings that produce uniform SERS enhancement factors. These results demonstrate the efficacy of colloidal driving forces to selectively enable chemical reactions leading to future assembly platforms for large-area nanodevices.

Mass spectrometric study of the negative and positive secondary ions emitted from ethanol microdroplets by MeV-energy heavy ion impact

NASA Astrophysics Data System (ADS)

Kitajima, Kensei; Majima, Takuya; Nishio, Tatsuya; Oonishi, Yoshiki; Mizutani, Shiori; Kohno, Jun-ya; Saito, Manabu; Tsuchida, Hidetsugu

2018-06-01

We have investigated the negative and positive secondary ions emitted from ethanol droplets by 4.0-MeV C3+ impact to reveal the characteristic features of the reaction processes induced by fast heavy ions at the liquid ethanol surface. Analysis of the secondary ions was performed by time-of-flight mass spectrometry for microdroplet targets in a high vacuum environment. Fragment ions, deprotonated cluster ions, and trace amounts of the reaction product ions are observed in the negative secondary ions. The main fragment anions are C2HmO- (m = 1, 3, and 5) and C2H- generated by loss of hydrogen and oxygen atoms. The reaction product anions include deprotonated glycols, larger alcohols, and their dehydrated and dehydrogenated forms generated by secondary reactions between fragments and radicals. Furthermore, C3Hm- (m = 0-2) and C4Hm- (m = 0 and 1) are observed, which could be produced through a plasma state generated in the heavy ion track. Deprotonated ethanol cluster ions, [(EtOH)n - H]-, are observed up to about n = 25. [(EtOH)n - H]- have smaller kinetic energies than the protonated cluster ions (EtOH)nH+. This probably represents the effect of the positive Coulomb potential transiently formed in the ion track. We also discuss the size distributions and structures of the water- and CH2OH-radical-attached ethanol cluster ions.

Surface Defect Passivation and Reaction of c-Si in H2S.

PubMed

Liu, Hsiang-Yu; Das, Ujjwal K; Birkmire, Robert W

2017-12-26

A unique passivation process of Si surface dangling bonds through reaction with hydrogen sulfide (H 2 S) is demonstrated in this paper. A high-level passivation quality with an effective minority carrier lifetime (τ eff ) of >2000 μs corresponding to a surface recombination velocity of <3 cm/s is achieved at a temperature range of 550-650 °C. X-ray photoelectron spectroscopy (XPS) confirmed the bonding states of Si and S and provides insights into the reaction pathway of Si with H 2 S and other impurity elements both during and after the reaction. Quantitative analysis of XPS spectra showed that the τ eff increases with an increase in the surface S content up to ∼3.5% and stabilizes thereafter, indicative of surface passivation by monolayer coverage of S on the Si surface. However, S passivation of the Si surface is highly unstable because of thermodynamically favorable reaction with atmospheric H 2 O and O 2 . This instability can be eliminated by capping the S-passivated Si surface with a protective thin film such as low-temperature-deposited amorphous silicon nitride.

Mechanochemical Association Reaction of Interfacial Molecules Driven by Shear.

PubMed

Khajeh, Arash; He, Xin; Yeon, Jejoon; Kim, Seong H; Martini, Ashlie

2018-05-29

Shear-driven chemical reaction mechanisms are poorly understood because the relevant reactions are often hidden between two solid surfaces moving in relative motion. Here, this phenomenon is explored by characterizing shear-induced polymerization reactions that occur during vapor phase lubrication of α-pinene between sliding hydroxylated and dehydroxylated silica surfaces, complemented by reactive molecular dynamics simulations. The results suggest that oxidative chemisorption of the α-pinene molecules at reactive surface sites, which transfers oxygen atoms from the surface to the adsorbate molecule, is the critical activation step. Such activation takes place more readily on the dehydroxylated surface. During this activation, the most strained part of the α-pinene molecules undergoes a partial distortion from its equilibrium geometry, which appears to be related to the critical activation volume for mechanical activation. Once α-pinene molecules are activated, association reactions occur between the newly attached oxygen and one of the carbon atoms in another molecule, forming ether bonds. These findings have general implications for mechanochemistry because they reveal that shear-driven reactions may occur through reaction pathways very different from their thermally induced counterparts and specifically the critical role of molecular distortion in such reactions.

Low Earth orbit atomic oxygen simulation for durability evaluation of solar reflector surfaces

NASA Technical Reports Server (NTRS)

Degroh, Kim K.; Banks, Bruce A.

1992-01-01

To evaluate the performance and durability of solar reflector surfaces in the atomic oxygen environment typical of low Earth orbit (LEO), one must expose the reflector surface either directly to LEO or to ground-laboratory atomic oxygen environments. Although actual LEO exposures are most desired, such opportunities are typically scarce, expensive, and of limited duration. As a result, ground-laboratory exposures must be relied upon as the most practical long-term durability evaluation technique. Plasma ashers are widely used as LEO simulation facilities by producing atomic oxygen environments for durability evaluation of potential spacecraft materials. Atomic oxygen arrival differs between ground and space exposure in that plasma asher exposure produces isotropic arrival and space solar tracking produces sweeping arrival. Differences in initial impact reaction probability occur, dependent upon the energy and species existing in these environments. Due to the variations in ground-laboratory and space atomic oxygen, quantification of in-space performance based on plasma asher testing is not straightforward. The various atomic oxygen interactions that can occur with reflector surfaces, such as undercutting in organic substrates at protective coating defect sites, ground-laboratory techniques recommended for evaluating the atomic oxygen durability of reflectors based on asher exposures, and computational techniques which make use of ground-laboratory atomic oxygen exposure to predict in-space LEO durability are addressed.

Facile Synthesis of Thick Films of Poly(methyl methacrylate), Poly(styrene), and Poly(vinyl pyridine) from Au Surfaces

PubMed Central

Saha, Sampa

2011-01-01

Atom transfer radical polymerization (ATRP) is commonly used to grow polymer brushes from Au surfaces, but the resulting film thicknesses are usually significantly less than with ATRP from SiO2 substrates. On Au, growth of poly(methyl methacrylate) (PMMA) blocks from poly(tert-butyl acrylate) brushes occurs more rapidly than growth of PMMA from initiator monolayers, suggesting that the disparity between growth rates from Au and SiO2 stems from the Au surface. Radical quenching by electron transfer from Au is probably not the termination mechanism because polymerization from thin, cross-linked initiators gives film thicknesses that are essentially the same as the thicknesses of films grown from SiO2 under the same polymerization conditions. However, this result is consistent with termination through desorption of thiols from non-cross-linked films, and reaction of these thiols with growing polymer chains. The enhanced stability of cross-linked initiators allows ATRP at temperatures up to ~100 °C and enables the growth of thick films of PMMA (350 nm), polystyrene (120 nm) and poly(vinyl pyridine) (200 nm) from Au surfaces in 1 hour. At temperatures >100 °C, the polymer brush layers delaminate as large area films. PMID:21728374

Model polymer etching and surface modification by a time modulated RF plasma jet: role of atomic oxygen and water vapor

NASA Astrophysics Data System (ADS)

Luan, P.; Knoll, A. J.; Wang, H.; Kondeti, V. S. S. K.; Bruggeman, P. J.; Oehrlein, G. S.

2017-01-01

The surface interaction of a well-characterized time modulated radio frequency (RF) plasma jet with polystyrene, poly(methyl methacrylate) and poly(vinyl alcohol) as model polymers is investigated. The RF plasma jet shows fast polymer etching but mild chemical modification with a characteristic carbonate ester and NO formation on the etched surface. By varying the plasma treatment conditions including feed gas composition, environment gaseous composition, and treatment distance, we find that short lived species, especially atomic O for Ar/1% O2 and 1% air plasma and OH for Ar/1% H2O plasma, play an essential role for polymer etching. For O2 containing plasma, we find that atomic O initiates polymer etching and the etching depth mirrors the measured decay of O atoms in the gas phase as the nozzle-surface distance increases. The etching reaction probability of an O atom ranging from 10-4 to 10-3 is consistent with low pressure plasma research. We also find that adding O2 and H2O simultaneously into Ar feed gas quenches polymer etching compared to adding them separately which suggests the reduction of O and OH density in Ar/O2/H2O plasma.

Reversible and irreversible reactions of three oxygen precursors on InAs(0 0 1)-(4 × 2)/ c(8 × 2)

NASA Astrophysics Data System (ADS)

Clemens, Jonathon B.; Droopad, Ravi; Kummel, Andrew C.

2010-10-01

The substrate reactions of three common oxygen sources for gate oxide deposition on the group III rich InAs(0 0 1)-(4 × 2)/ c(8 × 2) surface are compared: water, hydrogen peroxide (HOOH), and isopropyl alcohol (IPA). Scanning tunneling microscopy reveals that surface atom displacement occurs in all cases, but via different mechanisms for each oxygen precursor. The reactions are examined as a function of post-deposition annealing temperature. Water reaction shows displacement of surface As atoms, but it does not fully oxidize the As; the reaction is reversed by high temperature (450 °C) annealing. Exposure to IPA and subsequent low-temperature annealing (100 °C) show the preferential reaction on the row features of InAs(0 0 1)-(4 × 2)/ c(8 × 2), but higher temperature anneals result in permanent surface atom displacement/etching. Etching of the substrate is observed with HOOH exposure for all annealing temperatures. While nearly all oxidation reactions on group IV semiconductors are irreversible, the group III rich surface of InAs(0 0 1) shows that oxidation displacement reactions can be reversible at low temperature, thereby providing a mechanism of self-healing during oxidation reactions.

Computed potential energy surfaces for chemical reactions

NASA Technical Reports Server (NTRS)

Walch, Stephen P.

1994-01-01

Quantum mechanical methods have been used to compute potential energy surfaces for chemical reactions. The reactions studied were among those believed to be important to the NASP and HSR programs and included the recombination of two H atoms with several different third bodies; the reactions in the thermal Zeldovich mechanism; the reactions of H atom with O2, N2, and NO; reactions involved in the thermal De-NO(x) process; and the reaction of CH(squared Pi) with N2 (leading to 'prompt NO'). These potential energy surfaces have been used to compute reaction rate constants and rates of unimolecular decomposition. An additional application was the calculation of transport properties of gases using a semiclassical approximation (and in the case of interactions involving hydrogen inclusion of quantum mechanical effects).

Polymerase Chain Reaction for Detection of Systemic Plant Pathogens

USDA-ARS?s Scientific Manuscript database

This chapter outlines the advances and application of the polymerase chain reaction (PCR) since its development in 1984 and its enhancements and applications to detection of viruses, viroids and phytoplasma in pome and stone fruits. PCR is probably the most rapidly and widely adopted technology eve...

Construction of super - hydrophobic copper alloy surface by one - step mixed solution immersion method

NASA Astrophysics Data System (ADS)

Gu, Qiang; Chen, Ying; Chen, Dong; Zhang, Zeting

2018-01-01

This paper presents a method for preparing a super hydrophobic surface with a fast, simple, low-cost, one-step reaction by immersing copper alloy in an ethanol solution containing silver nitrate and myristic acid. The effects of reaction time, reaction temperature, reactant concentration and reaction time on the wettability of the material were studied. The surface wettability, appearance, chemical composition, durability and chemical stability of the prepared samples was measured by water contact angle (CA), scanning electron microscopy (SEM), energy dispersive spectrometer (EDS), X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FTIR). The results show that when the reaction time is only 10min, the surface WCA of the prepared material can reach 154.9. This study provides an effective method for the rapid preparation of stable super hydrophobic surfaces.

Surface chemistry of rare-earth oxide surfaces at ambient conditions: reactions with water and hydrocarbons

NASA Astrophysics Data System (ADS)

Külah, Elçin; Marot, Laurent; Steiner, Roland; Romanyuk, Andriy; Jung, Thomas A.; Wäckerlin, Aneliia; Meyer, Ernst

2017-03-01

Rare-earth (RE) oxide surfaces are of significant importance for catalysis and were recently reported to possess intrinsic hydrophobicity. The surface chemistry of these oxides in the low temperature regime, however, remains to a large extent unexplored. The reactions occurring at RE surfaces at room temperature (RT) in real air environment, in particular, in presence of polycyclic aromatic hydrocarbons (PAHs), were not addressed until now. Discovering these reactions would shed light onto intermediate steps occurring in automotive exhaust catalysts before reaching the final high operational temperature and full conversion of organics. Here we first address physical properties of the RE oxide, nitride and fluoride surfaces modified by exposure to ambient air and then we report a room temperature reaction between PAH and RE oxide surfaces, exemplified by tetracene (C18H12) on a Gd2O3. Our study evidences a novel effect - oxidation of higher hydrocarbons at significantly lower temperatures (~300 K) than previously reported (>500 K). The evolution of the surface chemical composition of RE compounds in ambient air is investigated and correlated with the surface wetting. Our surprising results reveal the complex behavior of RE surfaces and motivate follow-up studies of reactions between PAH and catalytic surfaces at the single molecule level.

Bayesian inversion analysis of nonlinear dynamics in surface heterogeneous reactions.

PubMed

Omori, Toshiaki; Kuwatani, Tatsu; Okamoto, Atsushi; Hukushima, Koji

2016-09-01

It is essential to extract nonlinear dynamics from time-series data as an inverse problem in natural sciences. We propose a Bayesian statistical framework for extracting nonlinear dynamics of surface heterogeneous reactions from sparse and noisy observable data. Surface heterogeneous reactions are chemical reactions with conjugation of multiple phases, and they have the intrinsic nonlinearity of their dynamics caused by the effect of surface-area between different phases. We adapt a belief propagation method and an expectation-maximization (EM) algorithm to partial observation problem, in order to simultaneously estimate the time course of hidden variables and the kinetic parameters underlying dynamics. The proposed belief propagation method is performed by using sequential Monte Carlo algorithm in order to estimate nonlinear dynamical system. Using our proposed method, we show that the rate constants of dissolution and precipitation reactions, which are typical examples of surface heterogeneous reactions, as well as the temporal changes of solid reactants and products, were successfully estimated only from the observable temporal changes in the concentration of the dissolved intermediate product.

Chemisorption studies of Pt/SnO2 catalysts

NASA Technical Reports Server (NTRS)

Brown, Kenneth G.; Ohorodnik, Susan K.; Vannorman, John D.; Schryer, Jacqueline; Upchurch, Billy T.; Schryer, David R.

1990-01-01

The low temperature CO oxidation catalysts that are being developed and tested at NASA-Langley are fairly unique in their ability to efficiently oxidize CO at low temperatures (approx. 303 K). The bulk of the reaction data that has been collected in the laboratory has been determined using plug flow reactors with a low mass of Pt/SnO2/SiO2 catalyst (approx. 0.1 g) and a modest flow rate (5 to 10 sc sm). The researchers have previously characterized the surface solely in terms of N2 BET surface areas. These surface areas have not been that indicative of reaction rate. Indeed, some of the formulations with high BET surface area have yielded lower reaction rates than those with lower BET surface areas. As a result researchers began a program of determining the chemisorption of the various species involved in the reaction; CO, O2 and CO2. Such a determination of will lead to a better understanding of the mechanism and overall kinetics of the reaction. The pulsed-reactor technique, initially described by Freel, is used to determine the amount of a particular molecule that is adsorbed on the catalyst. Since there is some reaction of CO with the surface to produce CO2, the pulsed reactor had to be coupled with a gas chromatograph in order to distinguish between the loss of CO that is due to adsorption by the surface and the loss that is due to reaction with the surface.

Weaker soil carbon-climate feedbacks resulting from microbial and abiotic interactions

NASA Astrophysics Data System (ADS)

Tang, Jinyun; Riley, William J.

2015-01-01

The large uncertainty in soil carbon-climate feedback predictions has been attributed to the incorrect parameterization of decomposition temperature sensitivity (Q10; ref. ) and microbial carbon use efficiency. Empirical experiments have found that these parameters vary spatiotemporally, but such variability is not included in current ecosystem models. Here we use a thermodynamically based decomposition model to test the hypothesis that this observed variability arises from interactions between temperature, microbial biogeochemistry, and mineral surface sorptive reactions. We show that because mineral surfaces interact with substrates, enzymes and microbes, both Q10 and microbial carbon use efficiency are hysteretic (so that neither can be represented by a single static function) and the conventional labile and recalcitrant substrate characterization with static temperature sensitivity is flawed. In a 4-K temperature perturbation experiment, our fully dynamic model predicted more variable but weaker soil carbon-climate feedbacks than did the static Q10 and static carbon use efficiency model when forced with yearly, daily and hourly variable temperatures. These results imply that current Earth system models probably overestimate the response of soil carbon stocks to global warming. Future ecosystem models should therefore consider the dynamic interactions between sorptive mineral surfaces, substrates and microbial processes.

Impact of stratospheric aircraft on calculations of nitric acid trihydrate cloud surface area densities using NMC temperatures and 2D model constituent distributions

NASA Technical Reports Server (NTRS)

Considine, David B.; Douglass, Anne R.

1994-01-01

A parameterization of NAT (nitric acid trihydrate) clouds is developed for use in 2D models of the stratosphere. The parameterization uses model distributions of HNO3 and H2O to determine critical temperatures for NAT formation as a function of latitude and pressure. National Meteorological Center temperature fields are then used to determine monthly temperature frequency distributions, also as a function of latitude and pressure. The fractions of these distributions which fall below the critical temperatures for NAT formation are then used to determine the NAT cloud surface area density for each location in the model grid. By specifying heterogeneous reaction rates as functions of the surface area density, it is then possible to assess the effects of the NAT clouds on model constituent distributions. We also consider the increase in the NAT cloud formation in the presence of a fleet of stratospheric aircraft. The stratospheric aircraft NO(x) and H2O perturbations result in increased HNO3 as well as H2O. This increases the probability of NAT formation substantially, especially if it is assumed that the aircraft perturbations are confined to a corridor region.

SURFACE CHEMKIN-III: A Fortran package for analyzing heterogeneous chemical kinetics at a solid-surface - gas-phase interface

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

Coltrin, M.E.; Kee, R.J.; Rupley, F.M.

1996-05-01

This document is the user`s manual for the SURFACE CHEMKIN-III package. Together with CHEMKIN-III, this software facilitates the formation, solution, and interpretation of problems involving elementary heterogeneous and gas-phase chemical kinetics in the presence of a solid surface. The package consists of two major software components: an Interpreter and a Surface Subroutine Library. The Interpreter is a program that reads a symbolic description of a user-specified chemical reaction mechanism. One output from the Interpreter is a data file that forms a link to the Surface Subroutine Library, which is a collection of about seventy modular Fortran subroutines that may bemore » called from a user`s application code to return information on chemical production rates and thermodynamic properties. This version of SURFACE CHEMKIN-III includes many modifications to allow treatment of multi-fluid plasma systems, for example modeling the reactions of highly energetic ionic species with a surface. Optional rate expressions allow reaction rates to depend upon ion energy rather than a single thermodynamic temperature. In addition, subroutines treat temperature as an array, allowing an application code to define a different temperature for each species. This version of SURFACE CHEMKIN-III allows use of real (non-integer) stoichiometric coefficients; the reaction order with respect to species concentrations can also be specified independent of the reaction`s stoichiometric coefficients. Several different reaction mechanisms can be specified in the Interpreter input file through the new construct of multiple materials.« less

On-Surface Pseudo-High-Dilution Synthesis of Macrocycles: Principle and Mechanism.

PubMed

Fan, Qitang; Wang, Tao; Dai, Jingya; Kuttner, Julian; Hilt, Gerhard; Gottfried, J Michael; Zhu, Junfa

2017-05-23

Macrocycles have attracted much attention due to their specific "endless" topology, which results in extraordinary properties compared to related linear (open-chain) molecules. However, challenges still remain in their controlled synthesis with well-defined constitution and geometry. Here, we report the successful application of the (pseudo-)high-dilution method to the conditions of on-surface synthesis in ultrahigh vacuum. This approach leads to high yields (up to 84%) of cyclic hyperbenzene ([18]-honeycombene) via an Ullmann-type reaction from 4,4″-dibromo-meta-terphenyl (DMTP) as precursor on a Ag(111) surface. The mechanism of macrocycle formation was explored in detail using scanning tunneling microscopy and X-ray photoemission spectroscopy. We propose that the dominant pathway for hyperbenzene (MTP) 6 formation is the stepwise desilverization of an organometallic (MTP-Ag) 6 macrocycle, which forms via cyclization of (MTP-Ag) 6 chains under pseudo-high-dilution conditions. The high probability of cyclization on the stage of the organometallic phase results from the reversibility of the C-Ag bond. The case is different from that in solution, in which cyclization typically occurs on the stage of a covalently bonded open-chain precursor. This difference in the cyclization mechanism on a surface compared to that in solution stems mainly from the 2D confinement exerted by the surface template, which hinders the flipping of chain segments necessary for cyclization.

Preparation of Water-Repellent Glass by Sol-Gel Process Using Perfluoroalkylsilane and Tetraethoxysilane.

PubMed

Jeong, Hye-Jeong; Kim, Dong-Kwon; Lee, Soo-Bok; Kwon, Soo-Han; Kadono, Kohei

2001-03-01

Coating films on glass substrate were prepared by sol-gel process using alkoxide solutions containing perfluoroalkylsilane (PFAS) and tetraethoxysilane (TEOS). The physical properties of the coating films were characterized by SEM, FT-IR, and XRD. And their surface properties were investigated by measuring contact angles and atomic compositions. Transparent coating films with smooth surface and uniform thickness could be obtained. The contact angles of the coating films for water and methylene iodide are extremely high, at 118 degrees and 97 degrees, respectively, and their surface free energies are about 9.7 dyn/cm. It was found that the water-repellent glass prepared is very hydrophobic and exhibits excellent water-repellency. Hydrophobic perfluoroalkyl groups are preferentially enriched to the outermost layer at the coating film-air interface, and two layers probably exist in the coating film. The upper layer oriented toward the air is composed of mainly perfluoroalkyl groups originating from PFAS, and the lower layer is composed of mainly -OSiO- groups originating from TEOS. The heat treatment after drying step cannot influence the surface enrichment of the perfluoroalkyl group. The hydrolysis reaction should be more completely done before the dip coating step to obtain lower surface free energy. The burning temperature should be less than 300 degrees C because the perfluoroalkyl group begins to decompose from this temperature. Copyright 2001 Academic Press.

Vibrations At Surfaces During Heterogeneous Catalytic Reactions

NASA Astrophysics Data System (ADS)

Aragno, A.; Basini, Luca; Marchionna, M.; Raffaelli, A.

1989-12-01

FTIR spectroscopies can be used in a wide range of temperature and pressure conditions to investigate on the chemistry and the physics of heterogeneous catalytic reactions. In this paper we have shortly discussed the spectroscopic results obtained during the study of two different reactions; the skeletal isomerization of 1-butene to obtain 2-methylpropene and the surface aggregation and fragmentation of rhodium carbonyl complexes during thermal treatments in N2, H2, CO, CH4 atmospheres. In the first case high temperature proton tran-sfer reactions are proposed to be responsible for the skeletal isomerization reaction. In the second case our experiments have shown a partial reversibility of the nucleation processes at the surfaces and revealed a low temperature reactivity of methane on rhodium car-bonyl surface complexes.

Chemical Separation of Fe-Ni Particles after Impact

NASA Astrophysics Data System (ADS)

Miura, Y.; Fukuyama, S.; Kedves, M. A.; Yamori, A.; Okamoto, M.; Gucsik, A.

Tiny grains of Fe-Ni system originated from planetesimals or meteoroids can remain under solid (or melt)-solid impact reactions even after impact process, probably together with high pressure form of Fe phase. Impact fragment with major Fe-Si (-Ni) system can be formed under vapor condition of impact reaction from terrestrial and artificial impact craters and spherules, and those with Ni-Cl (-S) system in composi- tion are formed under vapor condition of artificial impact experiments on the Barringer iron meteorite. These impact grains of Fe-bearing composition or high pressure form of iron-rich phases will be found probably on the asteroids in future exploration

Plasticity in probabilistic reaction norms for maturation in a salmonid fish.

PubMed

Morita, Kentaro; Tsuboi, Jun-ichi; Nagasawa, Toru

2009-10-23

The relationship between body size and the probability of maturing, often referred to as the probabilistic maturation reaction norm (PMRN), has been increasingly used to infer genetic variation in maturation schedule. Despite this trend, few studies have directly evaluated plasticity in the PMRN. A transplant experiment using white-spotted charr demonstrated that the PMRN for precocious males exhibited plasticity. A smaller threshold size at maturity occurred in charr inhabiting narrow streams where more refuges are probably available for small charr, which in turn might enhance the reproductive success of sneaker precocious males. Our findings suggested that plastic effects should clearly be included in investigations of variation in PMRNs.

The influence of surface properties on the plasma dynamics in radio-frequency driven oxygen plasmas: Measurements and simulations

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

Greb, Arthur; Niemi, Kari; O'Connell, Deborah

2013-12-09

Plasma parameters and dynamics in capacitively coupled oxygen plasmas are investigated for different surface conditions. Metastable species concentration, electronegativity, spatial distribution of particle densities as well as the ionization dynamics are significantly influenced by the surface loss probability of metastable singlet delta oxygen (SDO). Simulated surface conditions are compared to experiments in the plasma-surface interface region using phase resolved optical emission spectroscopy. It is demonstrated how in-situ measurements of excitation features can be used to determine SDO surface loss probabilities for different surface materials.

Biodiesel production from waste frying oil using waste animal bone and solar heat.

PubMed

Corro, Grisel; Sánchez, Nallely; Pal, Umapada; Bañuelos, Fortino

2016-01-01

A two-step catalytic process for the production of biodiesel from waste frying oil (WFO) at low cost, utilizing waste animal-bone as catalyst and solar radiation as heat source is reported in this work. In the first step, the free fatty acids (FFA) in WFO were esterified with methanol by a catalytic process using calcined waste animal-bone as catalyst, which remains active even after 10 esterification runs. The trans-esterification step was catalyzed by NaOH through thermal activation process. Produced biodiesel fulfills all the international requirements for its utilization as a fuel. A probable reaction mechanism for the esterification process is proposed considering the presence of hydroxyapatite at the surface of calcined animal bones. Copyright © 2015 Elsevier Ltd. All rights reserved.

THE INDUCED SUSCEPTIBILITY OF THE GUINEA-PIG TO THE TOXIC ACTION OF THE BLOOD SERUM OF THE HORSE.

PubMed

Lewis, P A

1908-01-01

Following the divisions before used, the results presented in the preceding pages may be briefly stated. I. The particular method of sensitization and the place where the test injection is made have an important bearing on the results obtained by various workers. Comparing the results obtained by the various methods, we may conclude that the incubation period of the hypersensitive reaction is not sharply limited, but that there is a progressive increase in sensitiveness from the sixth day, and presumably before that, extending over a period of several weeks. It seems very probable that the degree of hypersensitiveness attained where the sensitizing dose consists of a mixture of diphtheria toxin and serum is greater than when a single dose of the same small quantity of serum is given alone. II. Our early experiments, the first in this field, are in thorough agreement with those first reported by Otto, and shortly after him by Rosenau and Anderson. III. This hypersensitive reaction is transmissible from mother to offspring. The transmission is probably not equally effective in all cases, and individual young guinea-pigs probably vary greatly in the rate with which they lose their ability to react. As a result not all of the young of a hypersensitive mother react to a subcutaneous dose of five cubic centimeters of serum given when they are four or five weeks old. The reaction in the young animals differs quite markedly from that in those actively sensitized. These differences are such as to indicate that in the mother there is a considerable localization of the reaction in tissues and organs whose destruction does not cause sudden death. This local reaction is a protective factor and is not transmitted to the same degree as the factors involved in the fatal acute reaction. IV. The hypersensitive reaction to horse serum depends on the development of a special anti-body during the incubation period, which anti-body may be passively transferred to a fresh animal. If the dose of hypersensitive serum be sufficient, and the intoxicating injection be given directly into the circulation, this passive hypersensitiveness may be enough so that the animal will die when tested. There is also in the serum of hypersensitive guinea-pigs an uneliminated horse serum element or "rest," which is distinct from this antibody, and probably without influence on the course of the acute reaction. V. The anti-body on which the hypersensitive reaction depends may be entirely neutralized by horse serum without causing symptoms. The gradual introduction of increasing doses over a total period of twenty-four hours suffices for this. The animal is then, properly speaking, neither immune nor refractory, but is essentially in the condition of a normal animal which has recently had a large dose of horse serum. This rapid neutralization is made possible by the great binding power which the subcutaneous and other relatively unimportant tissues have for the toxic element of the serum. The so-called "Phenomenon of Arthus" is probably the same reaction for the rabbit that we have here dealt with in the guinea-pig. The fact that the manifestation is more prominently a local one depends on racial differences. I have encountered cases in the guinea-pig in which the conditions in the rabbit are closely simulated.

Effect of Molecule–Surface Reaction Mechanism on the Electronic Characteristics and Photovoltaic Performance of Molecularly Modified Si

PubMed Central

2013-01-01

We report on the passivation properties of molecularly modified, oxide-free Si(111) surfaces. The reaction of 1-alcohol with the H-passivated Si(111) surface can follow two possible paths, nucleophilic substitution (SN) and radical chain reaction (RCR), depending on adsorption conditions. Moderate heating leads to the SN reaction, whereas with UV irradiation RCR dominates, with SN as a secondary path. We show that the site-sensitive SN reaction leads to better electrical passivation, as indicated by smaller surface band bending and a longer lifetime of minority carriers. However, the surface-insensitive RCR reaction leads to more dense monolayers and, therefore, to much better chemical stability, with lasting protection of the Si surface against oxidation. Thus, our study reveals an inherent dissonance between electrical and chemical passivation. Alkoxy monolayers, formed under UV irradiation, benefit, though, from both chemical and electronic passivation because under these conditions both SN and RCR occur. This is reflected in longer minority carrier lifetimes, lower reverse currents in the dark, and improved photovoltaic performance, over what is obtained if only one of the mechanisms operates. These results show how chemical kinetics and reaction paths impact electronic properties at the device level. It further suggests an approach for effective passivation of other semiconductors. PMID:24205409

Catalytic reaction processes revealed by scanning probe microscopy. [corrected].

PubMed

Jiang, Peng; Bao, Xinhe; Salmeron, Miquel

2015-05-19

Heterogeneous catalysis is of great importance for modern society. About 80% of the chemicals are produced by catalytic reactions. Green energy production and utilization as well as environmental protection also need efficient catalysts. Understanding the reaction mechanisms is crucial to improve the existing catalysts and develop new ones with better activity, selectivity, and stability. Three components are involved in one catalytic reaction: reactant, product, and catalyst. The catalytic reaction process consists of a series of elementary steps: adsorption, diffusion, reaction, and desorption. During reaction, the catalyst surface can change at the atomic level, with roughening, sintering, and segregation processes occurring dynamically in response to the reaction conditions. Therefore, it is imperative to obtain atomic-scale information for understanding catalytic reactions. Scanning probe microscopy (SPM) is a very appropriate tool for catalytic research at the atomic scale because of its unique atomic-resolution capability. A distinguishing feature of SPM, compared to other surface characterization techniques, such as X-ray photoelectron spectroscopy, is that there is no intrinsic limitation for SPM to work under realistic reaction conditions (usually high temperature and high pressure). Therefore, since it was introduced in 1981, scanning tunneling microscopy (STM) has been widely used to investigate the adsorption, diffusion, reaction, and desorption processes on solid catalyst surfaces at the atomic level. STM can also monitor dynamic changes of catalyst surfaces during reactions. These invaluable microscopic insights have not only deepened the understanding of catalytic processes, but also provided important guidance for the development of new catalysts. This Account will focus on elementary reaction processes revealed by SPM. First, we will demonstrate the power of SPM to investigate the adsorption and diffusion process of reactants on catalyst surfaces at the atomic level. Then the dynamic processes, including surface reconstruction, roughening, sintering, and phase separation, studied by SPM will be discussed. Furthermore, SPM provides valuable insights toward identifying the active sites and understanding the reaction mechanisms. We also illustrate here how both ultrahigh vacuum STM and high pressure STM provide valuable information, expanding the understanding provided by traditional surface science. We conclude with highlighting remarkable recent progress in noncontact atomic force microscopy (NC-AFM) and inelastic electron tunneling spectroscopy (IETS), and their impact on single-chemical-bond level characterization for catalytic reaction processes in the future.

Methylene migration and coupling on a non-reducible metal oxide: The reaction of dichloromethane on stoichiometric α-Cr 2O 3(0001)

DOE PAGES

Dong, Yujung; Brooks, John D.; Chen, Tsung-Liang; ...

2014-09-17

The reaction of CH 2Cl 2 over the nearly-stoichiometric α-Cr 2O 3(0001) surface produces gas phase ethylene, methane and surface chlorine adatoms. The reaction is initiated by the decomposition of CH 2Cl 2 into surface methylene and chlorine. Photoemission indicates that surface cations are the preferred binding sites for both methylene and chlorine adatoms. Two reaction channels are observed for methylene coupling to ethylene in temperature-programmed desorption (TPD). A desorption-limited, low-temperature route is attributed to two methylenes bound at a single site. The majority of ethylene is produced by a reaction-limited process involving surface migration (diffusion) of methylene as themore » rate-limiting step. DFT calculations indicate the surface diffusion mechanism is mediated by surface oxygen anions. The source of hydrogen for methane formation is adsorbed background water. Chlorine adatoms produced by the dissociation of CH 2Cl 2 deactivate the surface by simple site-blocking of surface Cr 3+ sites. Finally, a comparison of experiment and theory shows that DFT provides a better description of the surface chemistry of the carbene intermediate than DFT+U using reported parameters for a best representation of the bulk electronic properties of α-Cr 2O 3.« less

Catalytic combustion of hydrogen-air mixtures in stagnation flows

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

Ikeda, H.; Libby, P.A.; Williams, F.A.

1993-04-01

The interaction between heterogeneous and homogeneous reactions arising when a mixture of hydrogen and air impinges on a platinum plate at elevated temperature is studied. A reasonably complete description of the kinetic mechanism for homogeneous reactions is employed along with a simplified model for heterogeneous reactions. Four regimes are identified depending on the temperature of the plate, on the rate of strain imposed on the flow adjacent to the plate and on the composition and temperature of the reactant stream: (1) surface reaction alone; (2) surface reaction inhibiting homogeneous reaction; (3) homogeneous reaction inhibiting surface reaction; and (4) homogeneous reactionmore » alone. These regimes are related to those found earlier for other chemical systems and form the basis of future experimental investigation of the chemical system considered in the present study.« less

Elapsed decision time affects the weighting of prior probability in a perceptual decision task

PubMed Central

Hanks, Timothy D.; Mazurek, Mark E.; Kiani, Roozbeh; Hopp, Elizabeth; Shadlen, Michael N.

2012-01-01

Decisions are often based on a combination of new evidence with prior knowledge of the probable best choice. Optimal combination requires knowledge about the reliability of evidence, but in many realistic situations, this is unknown. Here we propose and test a novel theory: the brain exploits elapsed time during decision formation to combine sensory evidence with prior probability. Elapsed time is useful because (i) decisions that linger tend to arise from less reliable evidence, and (ii) the expected accuracy at a given decision time depends on the reliability of the evidence gathered up to that point. These regularities allow the brain to combine prior information with sensory evidence by weighting the latter in accordance with reliability. To test this theory, we manipulated the prior probability of the rewarded choice while subjects performed a reaction-time discrimination of motion direction using a range of stimulus reliabilities that varied from trial to trial. The theory explains the effect of prior probability on choice and reaction time over a wide range of stimulus strengths. We found that prior probability was incorporated into the decision process as a dynamic bias signal that increases as a function of decision time. This bias signal depends on the speed-accuracy setting of human subjects, and it is reflected in the firing rates of neurons in the lateral intraparietal cortex (LIP) of rhesus monkeys performing this task. PMID:21525274

Elapsed decision time affects the weighting of prior probability in a perceptual decision task.

PubMed

Hanks, Timothy D; Mazurek, Mark E; Kiani, Roozbeh; Hopp, Elisabeth; Shadlen, Michael N

2011-04-27

Decisions are often based on a combination of new evidence with prior knowledge of the probable best choice. Optimal combination requires knowledge about the reliability of evidence, but in many realistic situations, this is unknown. Here we propose and test a novel theory: the brain exploits elapsed time during decision formation to combine sensory evidence with prior probability. Elapsed time is useful because (1) decisions that linger tend to arise from less reliable evidence, and (2) the expected accuracy at a given decision time depends on the reliability of the evidence gathered up to that point. These regularities allow the brain to combine prior information with sensory evidence by weighting the latter in accordance with reliability. To test this theory, we manipulated the prior probability of the rewarded choice while subjects performed a reaction-time discrimination of motion direction using a range of stimulus reliabilities that varied from trial to trial. The theory explains the effect of prior probability on choice and reaction time over a wide range of stimulus strengths. We found that prior probability was incorporated into the decision process as a dynamic bias signal that increases as a function of decision time. This bias signal depends on the speed-accuracy setting of human subjects, and it is reflected in the firing rates of neurons in the lateral intraparietal area (LIP) of rhesus monkeys performing this task.

Matrix photochemistry of small molecules: Influencing reaction dynamics on electronically excited hypersurfaces

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

Laursen, S.L.

Investigations of chemical reactions on electronically excited reaction surfaces are presented. The role of excited-surface multiplicity is of particular interest, as are chemical reactivity and energy transfer in systems in which photochemistry is initiated through a metal atom sensitizer.'' Two approaches are employed: A heavy-atom matrix affords access to forbidden triplet reaction surfaces, eliminating the need for a potentially reactive sensitizer. Later, the role of the metal atom in the photosensitization process is examined directly.

Hydrothermal performance of catalyst supports

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

Elam, Jeffrey W.; Marshall, Christopher L.; Libera, Joseph A.

A high surface area catalyst with a mesoporous support structure and a thin conformal coating over the surface of the support structure. The high surface area catalyst support is adapted for carrying out a reaction in a reaction environment where the thin conformal coating protects the support structure within the reaction environment. In various embodiments, the support structure is a mesoporous silica catalytic support and the thin conformal coating comprises a layer of metal oxide resistant to the reaction environment which may be a hydrothermal environment.

Cyclic Square Wave Voltammetry of Surface-Confined Quasireversible Electron Transfer Reactions.

PubMed

Mann, Megan A; Bottomley, Lawrence A

2015-09-01

The theory for cyclic square wave voltammetry of surface-confined quasireversible electrode reactions is presented and experimentally verified. Theoretical voltammograms were calculated following systematic variation of empirical parameters to assess their impact on the shape of the voltammogram. From the trends obtained, diagnostic criteria for this mechanism were deduced. These criteria were experimentally confirmed using two well-established surface-confined analytes. When properly applied, these criteria will enable non-experts in voltammetry to assign the electrode reaction mechanism and accurately measure electrode reaction kinetics.

Vibrational and rotational excitation effects of the N(2D) + D2(X1Σg +) → ND(X3Σ+) + D(2S) reaction

NASA Astrophysics Data System (ADS)

Zhu, Ziliang; Wang, Haijie; Wang, Xiquan; Shi, Yanying

2018-05-01

The effects of the rovibrational excitation of reactants in the N(2D) + D2(X1Σg+) → ND(X3Σ+) + D(2S) reaction are calculated in a collision energy range from the threshold to 1.0 eV using the time-dependent wave packet approach and a second-order split operator. The reaction probability, integral cross-section, differential cross-section and rate constant of the title reaction are calculated. The integral cross-section and rate constant of the initial states v = 0, j = 0, 1, are in good agreement with experimental data available in the literature. The rotational excitation of the D2 molecule has little effect on reaction probability, integral cross-section and the rate constant, but it increased the sideways and forward scattering signals. The vibrational excitation of the D2 molecule reduced the threshold and broke up the forward-backward symmetry of the differential cross-section; it also increased the forward scattering signals. This may be because the vibrational excitation of the D2 molecule reduced the lifetime of the intermediate complex.

Mechanisms of stochastic focusing and defocusing in biological reaction networks: insight from accurate chemical master equation (ACME) solutions.

PubMed

Gursoy, Gamze; Terebus, Anna; Youfang Cao; Jie Liang

2016-08-01

Stochasticity plays important roles in regulation of biochemical reaction networks when the copy numbers of molecular species are small. Studies based on Stochastic Simulation Algorithm (SSA) has shown that a basic reaction system can display stochastic focusing (SF) by increasing the sensitivity of the network as a result of the signal noise. Although SSA has been widely used to study stochastic networks, it is ineffective in examining rare events and this becomes a significant issue when the tails of probability distributions are relevant as is the case of SF. Here we use the ACME method to solve the exact solution of the discrete Chemical Master Equations and to study a network where SF was reported. We showed that the level of SF depends on the degree of the fluctuations of signal molecule. We discovered that signaling noise under certain conditions in the same reaction network can lead to a decrease in the system sensitivities, thus the network can experience stochastic defocusing. These results highlight the fundamental role of stochasticity in biological reaction networks and the need for exact computation of probability landscape of the molecules in the system.

Thermodynamic and kinetic analysis of the reaction between biological catecholamines and chlorinated methylperoxy radicals

NASA Astrophysics Data System (ADS)

Dimić, Dušan S.; Milenković, Dejan A.; Marković, Jasmina M. Dimitrić; Marković, Zoran S.

2018-05-01

The antiradical potency of catecholamines (dopamine, epinephrine, norepinephrine, L-DOPA), metabolites of dopamine (homovanillic acid, 3-methoxytyramine and 3,4-dihydroxyphenylacetic acid) and catechol towards substituted methylperoxy radicals is investigated. The thermodynamic parameters, together with the kinetic approach, are used to determine the most probable mechanism of action. The natural bond orbital and quantum theory of atoms in molecules are utilised to explain the highest reactivity of trichloromethylperoxy radical. The preferred mechanism is dependent both on the thermodynamic and kinetic parameters . The number of chlorine atoms on radical, the presence of intra-molecular hydrogen bond and number of hydroxy groups attached to the aromatic ring significantly influence the mechanism. The results suggest that sequential proton loss electron transfer (SPLET) is the most probable for reaction with methylperoxy and hydrogen atom transfer (HAT) for reaction with trichloromethylperoxy radicals, with a gradual transition between SPLET and HAT for other two radicals. Due to the significant deprotonation of molecules containing the carboxyl group, the respective anions are also investigated. The HAT and SPLET mechanisms are highly competitive in reaction with MP radical, while the dominant mechanism towards chlorinated radicals is HAT. The reactions in methanol and benzene are also discussed.

Comparison of preparation methods for ceria catalyst and the effect of surface and bulk sulfates on its activity toward NH3-SCR.

PubMed

Chang, Huazhen; Ma, Lei; Yang, Shijian; Li, Junhua; Chen, Liang; Wang, Wei; Hao, Jiming

2013-11-15

A series of CeO2 catalysts prepared with sulfate (S) and nitrate (N) precursors by hydrothermal (H) and precipitation (P) methods were investigated in selective catalytic reduction of NOx by NH3 (NH3-SCR). The catalytic activity of CeO2 was significantly affected by the preparation methods and the precursor type. CeO2-SH, which was prepared by hydrothermal method with cerium (IV) sulfate as a precursor, showed excellent SCR activity and high N2 selectivity in the temperature range of 230-450 °C. Based on the results obtained by temperature-programmed reduction (H2-TPR), transmission infrared spectra (IR) and thermal gravimetric analysis (TGA), the excellent performance of CeO2-SH was correlated with the surface sulfate species formed in the hydrothermal reaction. These results indicated that sulfate species bind with Ce(4+) on the CeO2-SH catalyst, and the specific sulfate species, such as Ce(SO4)2 or CeOSO4, were formed. The adsorption of NH3 was promoted by these sulfate species, and the probability of immediate oxidation of NH3 to N2O on Ce(4+) was reduced. Accordingly, the selective oxidation of NH3 was enhanced, which contributed to the high N2 selectivity in the SCR reaction. However, the location of sulfate on the CeO2-SP catalyst was different. Plenty of sulfate species were likely deposited on CeO2-SP surface, covering the active sites for NO oxidation, which resulted in poor SCR activity in the test temperature range. Moreover, the resistance to alkali metals, such as Na and K, was improved over the CeO2-SH catalyst. Copyright © 2013 Elsevier B.V. All rights reserved.

Spectroscopic study of gold nanoparticle formation through high intensity laser irradiation of solution

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

Nakamura, Takahiro, E-mail: nakamu@tagen.tohoku.ac.jp; Sato, Shunichi; Herbani, Yuliati

A spectroscopic study of the gold nanoparticle (NP) formation by high-intensity femtosecond laser irradiation of a gold ion solution was reported. The effect of varying energy density of the laser on the formation of gold NPs was also investigated. The surface plasmon resonance (SPR) peak of the gold nanocolloid in real-time UV-visible absorption spectra during laser irradiation showed a distinctive progress; the SPR absorption peak intensity increased after a certain irradiation time, reached a maximum and then gradually decreased. During this absorption variation, at the same time, the peak wavelength changed from 530 to 507 nm. According to an empiricalmore » equation derived from a large volume of experimental data, the estimated mean size of the gold NPs varied from 43.4 to 3.2 nm during the laser irradiation. The mean size of gold NPs formed at specific irradiation times by transmission electron microscopy showed the similar trend as that obtained in the spectroscopic analysis. From these observations, the formation mechanism of gold NPs during laser irradiation was considered to have two steps. The first is a reduction of gold ions by reactive species produced through a non-linear reaction during high intensity laser irradiation of the solution; the second is the laser fragmentation of produced gold particles into smaller pieces. The gold nanocolloid produced after the fragmentation by excess irradiation showed high stability for at least a week without the addition of any dispersant because of the negative charge on the surface of the nanoparticles probably due to the surface oxidation of gold nanoparticles. A higher laser intensity resulted in a higher efficiency of gold NPs fabrication, which was attributed to a larger effective volume of the reaction.« less

Spontaneous grafting of diazonium salts: chemical mechanism on metallic surfaces.

PubMed

Mesnage, Alice; Lefèvre, Xavier; Jégou, Pascale; Deniau, Guy; Palacin, Serge

2012-08-14

The spontaneous reaction of diazonium salts on various substrates has been widely employed since it consists of a simple immersion of the substrate in the diazonium salt solution. As electrochemical processes involving the same diazonium salts, the spontaneous grafting is assumed to give covalently poly(phenylene)-like bonded films. Resistance to solvents and to ultrasonication is commonly accepted as indirect proof of the existence of a covalent bond. However, the most relevant attempts to demonstrate a metal-C interface bond have been obtained by an XPS investigation of spontaneously grafted films on copper. Similarly, our experiments give evidence of such a bond in spontaneously grafted films on nickel substrates in acetonitrile. In the case of gold substrates, the formation of a spontaneous film was unexpected but reported in the literature in parallel to our observations. Even if no interfacial bond was observed, formation of the films was explained by grafting of aryl cations or radicals on the surface arising from dediazoniation, the film growing later by azo coupling, radical addition, or cationic addition on the grafted phenyl layer. Nevertheless, none of these mechanisms fits our experimental results showing the presence of an Au-N bond. In this work, we present a fine spectroscopic analysis of the coatings obtained on gold and nickel substrates that allow us to propose a chemical structure of such films, in particular, their interface with the substrates. After testing the most probable mechanisms, we have concluded in favor of the involvement of two complementary mechanisms which are the direct reaction of diazonium salts with the gold surface that accounts for the observed Au-N interfacial bonds as well as the formation of aryl cations able to graft on the substrate through Au-C linkages.

[Enzymatic conversion of tetradecanol in heterogenous phase by yeast-alcohol dehydrogenase].

PubMed

Rothe, U; Schöpp, W; Aurich, H

1976-01-01

Alcohol dehydrogenase from yeast converts long-chain primary alcohols not only in the dissolved state, but also at the surface of undissolved particles. Tetradecanol beads with a defined surface can be produced and employed as model substrate. The reaction rate was determined by the proton release accomplished in the reaction. The initial reaction rate depends on the enzyme concentration. The relation is nonlinear (vi = k-[e]0,4); the numerical value of the exponent (n = 0.4) argues in favour of a reaction occurring at the interface. The Lineweaver-Burk plots become linear if the substrate concentrations are based on the molar surface concentrations of the particles. The pH optimum for the reaction at the surface is displaced by 0.25 pH units towards the alkaline region (compared with ethanol as substrate). The activation energy of the reaction with tetradecanol beads as substrate is 30% lower than that for the ethanol oxydation.

The role of surface nonuniformity in controlling the initiation of a galvanic replacement reaction.

PubMed

Cobley, Claire M; Zhang, Qiang; Song, Wilbur; Xia, Younan

2011-06-06

The use of silver nanocrystals--asymmetrically truncated octahedrons and nanobars--characterized by a nonuniform surface as substrates for a galvanic replacement reaction was investigated. As the surfaces of these nanocrystals contain facets with a variety of different areas, shapes, and atomic arrangements, we were able to examine the roles of these parameters in different stages of the galvanic replacement reaction with HAuCl(4) (e.g., pitting, hollowing, pit closing, and pore formation), and thus obtain a deeper understanding of the reaction mechanism than is possible with silver nanocubes. We found that the most important of these parameters was the atomic arrangement, that is, whether the surface was capped by a {100} or {111} facet, and that the area and shape of the facet had essentially no effect on the initiation of the reaction. Interestingly, through the reaction with asymmetrically truncated octahedrons, we were also able to demonstrate that even when pitting occurred over a large area, this region would be sealed through a combination of atomic diffusion and deposition during the intermediate stages of the reaction. Consequently, even if pitting occurred across a large percentage of the nanocrystal surface, it was still possible to maintain the morphology of the template throughout the reaction. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Usefulness of antigen-specific IgE probability curves derived from the 3gAllergy assay in diagnosing egg, cow's milk, and wheat allergies.

PubMed

Sato, Sakura; Ogura, Kiyotake; Takahashi, Kyohei; Sato, Yasunori; Yanagida, Noriyuki; Ebisawa, Motohiro

2017-04-01

Specific IgE (sIgE) antibody detection using the Siemens IMMULITE ® 3gAllergy™ (3gAllergy) assay have not been sufficiently examined for the diagnosis of food allergy. The aim of this study was to evaluate the utility of measuring sIgE levels using the 3gAllergy assay to diagnose allergic reactions to egg, milk, and wheat. This retrospective study was conducted on patients with diagnosed or suspected allergies to egg, milk and wheat. Patients were divided into two groups according to their clinical reactivity to these allergens based on oral food challenge outcomes and/or convincing histories of immediate reaction to causative food(s). The sIgE levels were measured using 3gAllergy and ImmunoCAP. Predicted probability curves were estimated using logistic regression analysis. We analyzed 1561 patients, ages 0-19 y (egg = 436, milk = 499, wheat = 626). The sIgE levels determined using 3gAllergy correlated with those of ImmunoCAP, classifying 355 patients as symptomatic: egg = 149, milk = 123, wheat = 83. 3gAllergy sIgE levels were significantly higher in symptomatic than in asymptomatic patients (P < 0.0001). Predictive probability for positive food allergy was significantly increased and correlated with increased sIgE levels. The cut-offs for allergic reaction with 95% predictive probability as determined by the 3gAllergy probability curves were different from those of ImmunoCAP. Measurements of sIgE against egg, milk, and wheat as determined by 3gAllergy may be used as a tool to facilitate the diagnosis of food allergy in subjects with suspected food allergies. However, these probability curves should not be applied interchangeably between different assays. Copyright © 2016 Japanese Society of Allergology. Production and hosting by Elsevier B.V. All rights reserved.

Six-dimensional quantum dynamics study for the dissociative adsorption of DCl on Au(111) surface

NASA Astrophysics Data System (ADS)

Liu, Tianhui; Fu, Bina; Zhang, Dong H.

2014-04-01

We carried out six-dimensional quantum dynamics calculations for the dissociative adsorption of deuterium chloride (DCl) on Au(111) surface using the initial state-selected time-dependent wave packet approach. The four-dimensional dissociation probabilities are also obtained with the center of mass of DCl fixed at various sites. These calculations were all performed based on an accurate potential energy surface recently constructed by neural network fitting to density function theory energy points. The origin of the extremely small dissociation probability for DCl/HCl (v = 0, j = 0) fixed at the top site compared to other fixed sites is elucidated in this study. The influence of vibrational excitation and rotational orientation of DCl on the reactivity was investigated by calculating six-dimensional dissociation probabilities. The vibrational excitation of DCl enhances the reactivity substantially and the helicopter orientation yields higher dissociation probability than the cartwheel orientation. The site-averaged dissociation probability over 25 fixed sites obtained from four-dimensional quantum dynamics calculations can accurately reproduce the six-dimensional dissociation probability.

Six-dimensional quantum dynamics study for the dissociative adsorption of DCl on Au(111) surface

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

Liu, Tianhui; Fu, Bina, E-mail: bina@dicp.ac.cn, E-mail: zhangdh@dicp.ac.cn; Zhang, Dong H., E-mail: bina@dicp.ac.cn, E-mail: zhangdh@dicp.ac.cn

We carried out six-dimensional quantum dynamics calculations for the dissociative adsorption of deuterium chloride (DCl) on Au(111) surface using the initial state-selected time-dependent wave packet approach. The four-dimensional dissociation probabilities are also obtained with the center of mass of DCl fixed at various sites. These calculations were all performed based on an accurate potential energy surface recently constructed by neural network fitting to density function theory energy points. The origin of the extremely small dissociation probability for DCl/HCl (v = 0, j = 0) fixed at the top site compared to other fixed sites is elucidated in this study. The influence of vibrational excitationmore » and rotational orientation of DCl on the reactivity was investigated by calculating six-dimensional dissociation probabilities. The vibrational excitation of DCl enhances the reactivity substantially and the helicopter orientation yields higher dissociation probability than the cartwheel orientation. The site-averaged dissociation probability over 25 fixed sites obtained from four-dimensional quantum dynamics calculations can accurately reproduce the six-dimensional dissociation probability.« less

Influence of surface heterogeneity in electroosmotic flows—Implications in chromatography, fluid mixing, and chemical reactions in microdevices

NASA Astrophysics Data System (ADS)

Adrover, Alessandra; Giona, Massimiliano; Pagnanelli, Francesca; Toro, Luigi

2007-04-01

We analyze the influence of surface heterogeneity, inducing a random ζ-potential at the walls in electroosmotic incompressible flows. Specifically, we focus on how surface heterogeneity modifies the physico-chemical processes (transport, chemical reaction, mixing) occurring in microchannel and microreactors. While the macroscopic short-time features associated with solute transport (e.g. chromatographic patterns) do not depend significantly on ζ-potential heterogeneity, spatial randomness in the surface ζ-potential modifies the spectral properties of the advection-diffusion operator, determining different long-term properties of transport/reaction phenomena compared to the homogeneous case. Examples of physical relevance (chromatography, infinitely fast reactions) are addressed.

The mineralogic evolution of the Martian surface through time: Implications from chemical reaction path modeling studies

NASA Technical Reports Server (NTRS)

Plumlee, G. S.; Ridley, W. I.; Debraal, J. D.; Reed, M. H.

1993-01-01

Chemical reaction path calculations were used to model the minerals that might have formed at or near the Martian surface as a result of volcano or meteorite impact driven hydrothermal systems; weathering at the Martian surface during an early warm, wet climate; and near-zero or sub-zero C brine-regolith reactions in the current cold climate. Although the chemical reaction path calculations carried out do not define the exact mineralogical evolution of the Martian surface over time, they do place valuable geochemical constraints on the types of minerals that formed from an aqueous phase under various surficial and geochemically complex conditions.

Producing the deuteron in stars: anthropic limits on fundamental constants

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

Barnes, Luke A.; Lewis, Geraint F., E-mail: luke.barnes@sydney.edu.au, E-mail: gfl@physics.usyd.edu.au

2017-07-01

Stellar nucleosynthesis proceeds via the deuteron (D), but only a small change in the fundamental constants of nature is required to unbind it. Here, we investigate the effect of altering the binding energy of the deuteron on proton burning in stars. We find that the most definitive boundary in parameter space that divides probably life-permitting universes from probably life-prohibiting ones is between a bound and unbound deuteron. Due to neutrino losses, a ball of gas will undergo rapid cooling or stabilization by electron degeneracy pressure before it can form a stable, nuclear reaction-sustaining star. We also consider a less-bound deuteron,more » which changes the energetics of the pp and pep reactions. The transition to endothermic pp and pep reactions, and the resulting beta-decay instability of the deuteron, do not seem to present catastrophic problems for life.« less

Consideration of probability of bacterial growth for Jovian planets and their satellites

NASA Technical Reports Server (NTRS)

Taylor, D. M.; Berkman, R. M.; Divine, N.

1974-01-01

Environmental parameters affecting growth of bacteria are compared with current atmospheric models for Jupiter and Saturn, and with the available physical data for their satellites. Different zones of relative probability of growth are identified for Jupiter and Saturn. Of the more than two dozen satellites, only the largest (Io, Europa, Ganymede, Callisto, and Titan) are found to be interesting biologically. Titan's atmosphere may produce a substantial greenhouse effect providing increased surface temperatures. Models predicting a dense atmosphere are compatible with microbial growth for a range of pressures at Titan's surface. For Titan's surface the probability of growth would be enhanced if: (1) the surface is entirely or partially liquid; (2) volcanism is present; or (3) access to internal heat sources is significant.

Investigation of the reaction of 5Al-2.5Sn titanium with hydrogen at subzero temperature

NASA Technical Reports Server (NTRS)

Williams, D. N.; Wood, R. A.

1972-01-01

An investigation of the effect of temperature on the surface hydriding reaction of 5Al-2.5Sn titanium exposed to hydrogen at 250 psig was made. The temperature range studied extended from 160 F to -160 F. Reaction conditions were controlled so as to expose a vacuum-cleaned, oxide-free alloy surface to an ultrapure hydrogen atmosphere. Reaction times up to 1458 hours were studied. The hydriding reaction was extremely sensitive to experimental variables and the reproducibility of reaction behavior was poor. However, it was demonstrated that the reaction proceeded quite rapidly at 160 F; as much as 1 mil surface hydriding being observed after exposure for 162 hours. The amount of hydriding appeared to decrease with decreasing temperature at 75 F, -36 F, and -76 F. No surface hydriding was detected either by vacuum fusion analysis or by metallographic examination after exposure for 1458 hours at -110 F or -160 F. Tensile properties were unaffected by surface hydriding of the severity developed in this program (up to 1 mil thick) as determined by slow strain rate testing of hydrided sheet tensile samples.

Optimizing Chemical Reactions with Deep Reinforcement Learning.

PubMed

Zhou, Zhenpeng; Li, Xiaocheng; Zare, Richard N

2017-12-27

Deep reinforcement learning was employed to optimize chemical reactions. Our model iteratively records the results of a chemical reaction and chooses new experimental conditions to improve the reaction outcome. This model outperformed a state-of-the-art blackbox optimization algorithm by using 71% fewer steps on both simulations and real reactions. Furthermore, we introduced an efficient exploration strategy by drawing the reaction conditions from certain probability distributions, which resulted in an improvement on regret from 0.062 to 0.039 compared with a deterministic policy. Combining the efficient exploration policy with accelerated microdroplet reactions, optimal reaction conditions were determined in 30 min for the four reactions considered, and a better understanding of the factors that control microdroplet reactions was reached. Moreover, our model showed a better performance after training on reactions with similar or even dissimilar underlying mechanisms, which demonstrates its learning ability.

Supersonic molecular beam experiments on surface chemical reactions.

PubMed

Okada, Michio

2014-10-01

The interaction of a molecule and a surface is important in various fields, and in particular in complex systems like biomaterials and their related chemistry. However, the detailed understanding of the elementary steps in the surface chemistry, for example, stereodynamics, is still insufficient even for simple model systems. In this Personal Account, I review our recent studies of chemical reactions on single-crystalline Cu and Si surfaces induced by hyperthermal oxygen molecular beams and by oriented molecular beams, respectively. Studies of oxide formation on Cu induced by hyperthermal molecular beams demonstrate a significant role of the translational energy of the incident molecules. The use of hyperthermal molecular beams enables us to open up new chemical reaction paths specific for the hyperthermal energy region, and to develop new methods for the fabrication of thin films. On the other hand, oriented molecular beams also demonstrate the possibility of understanding surface chemical reactions in detail by varying the orientation of the incident molecules. The steric effects found on Si surfaces hint at new ways of material fabrication on Si surfaces. Controlling the initial conditions of incoming molecules is a powerful tool for finely monitoring the elementary step of the surface chemical reactions and creating new materials on surfaces. Copyright © 2014 The Chemical Society of Japan and Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Covalent-Bond Formation via On-Surface Chemistry.

PubMed

Held, Philipp Alexander; Fuchs, Harald; Studer, Armido

2017-05-02

In this Review article pioneering work and recent achievements in the emerging research area of on-surface chemistry is discussed. On-surface chemistry, sometimes also called two-dimensional chemistry, shows great potential for bottom-up preparation of defined nanostructures. In contrast to traditional organic synthesis, where reactions are generally conducted in well-defined reaction flasks in solution, on-surface chemistry is performed in the cavity of a scanning probe microscope on a metal crystal under ultrahigh vacuum conditions. The metal first acts as a platform for self-assembly of the organic building blocks and in many cases it also acts as a catalyst for the given chemical transformation. Products and hence success of the reaction are directly analyzed by scanning probe microscopy. This Review provides a general overview of this chemistry highlighting advantages and disadvantages as compared to traditional reaction setups. The second part of the Review then focuses on reactions that have been successfully conducted as on-surface processes. On-surface Ullmann and Glaser couplings are addressed. In addition, cyclodehydrogenation reactions and cycloadditions are discussed and reactions involving the carbonyl functionality are highlighted. Finally, the first examples of sequential on-surface chemistry are considered in which two different functionalities are chemoselectively addressed. The Review gives an overview for experts working in the area but also offers a starting point to non-experts to enter into this exciting new interdisciplinary research field. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

The Role of Electronic Excitations on Chemical Reaction Dynamics at Metal, Semiconductor and Nanoparticle Surfaces

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

Tully, John C.

Chemical reactions are often facilitated and steered when carried out on solid surfaces, essential for applications such as heterogeneous catalysis, solar energy conversion, corrosion, materials processing, and many others. A critical factor that can determine the rates and pathways of chemical reactions at surfaces is the efficiency and specificity of energy transfer; how fast does energy move around and where does it go? For reactions on insulator surfaces energy transfer generally moves in and out of vibrations of the adsorbed molecule and the underlying substrate. By contrast, on metal surfaces, metallic nanoparticles and semiconductors, another pathway for energy flow opensmore » up, excitation and de-excitation of electrons. This so-called “nonadiabatic” mechanism often dominates the transfer of energy and can directly impact the course of a chemical reaction. Conventional computational methods such as molecular dynamics simulation do not account for this nonadiabatic behavior. The current DOE-BES funded project has focused on developing the underlying theoretical foundation and the computational methodology for the prediction of nonadiabatic chemical reaction dynamics at surfaces. The research has successfully opened up new methodology and new applications for molecular simulation. In particular, over the last three years, the “Electronic Friction” theory, pioneered by the PI, has now been developed into a stable and accurate computational method that is sufficiently practical to allow first principles “on-the-fly” simulation of chemical reaction dynamics at metal surfaces.« less

Serpentinization of Olivine by Seawater: A Flow-Through Experiment

NASA Astrophysics Data System (ADS)

Gouze, P.; Luquot, L.; Andreani, M.; Godard, M.; Gibert, B.

2011-12-01

The mantle exposed at slow spreading ridges is pervasively serpentinized, down to ca. 5km according to geophysical data. The onset and durability of this hydration process require efficient penetration and renewal of fluids at the mineral-fluid interface. However, the mechanisms of fluid penetration are still poorly understood. Moreover, serpentinization is exovolumic, if a mass-conservative system is assumed, or chemical elements are leached out to conserve rock volume. Thus, the extent of serpentinization depends of the system capacity to create space and/or to drive mass transfers. In order to investigate these hydrodynamic and chemical mechanisms, we did a laboratory experiment during which seawater was injected in a sintered San Carlos olivine sample at conditions representative of low temperature ultramafic hydrothermal systems. The percolation-reaction experiment was carried out at 19 MPa and 190°C; the initial water flow was set at 0.2 mL/h then decreased down to 0.06 mL/h after 8 days. During the experiment (23 days), permeability decreased continuously. The composition of the outlet fluid varied strongly during the first 24h of the experiment, then reached equilibrium values. The high Si concentrations in outlet fluids indicated steady olivine dissolution, while their low Fe and Mg concentrations suggested precipitation of Fe- and Mg-rich mineral phases. The reacted sample acquired a reddish brown color, indicating oxidation reactions occurred. Optical observation and SEM imaging revealed the presence of a soft white material filling the pores of the reacted sample. It was identified as a poorly crystallized serpentine type material by AEM/TEM analyses. This proto-serpentine is intimately associated to <100 nm Fe-oxide patches (probably hematite) growing on the olivine surface. We interpret the precipitation of this proto-serpentine together with Fe-oxides throughout the sample as marking the early stages of serpentinization. The fluid composition not being modified by changes in fluid flow, we posit that olivine serpentinization is not controlled by elemental transport and/or by chemical kinetics, but takes place at-equilibrium; the reaction velocity is very fast and independent on the changes in the reaction surface area. Indeed, mass balance calculations indicate that more than 15 wt. % olivine was dissolved while the same mass of proto-serpentine was formed; concurrently, porosity decreased from ˜ 12% to 5 %. We infer that the structure of the newly formed proto-serpentine resulted in the clogging of fluid paths and explain the decrease of permeability during experiments. Yet the loose structure of the proto-serpentine allows maintaining a connected pore structure ensuring the perennial renewing (diffusion and/or advection) of the reactants at the reaction surfaces. These experimental results are used to constrain numerical reactive transport models and better understand the scale and efficiency of serpentinization reactions (effective reaction rates in porous/fractured media) at the scale of spreading ridges.

Computed potential energy surfaces for chemical reactions

NASA Technical Reports Server (NTRS)

Walch, Stephen P.

1990-01-01

The objective was to obtain accurate potential energy surfaces (PES's) for a number of reactions which are important in the H/N/O combustion process. The interest in this is centered around the design of the SCRAM jet engine for the National Aerospace Plane (NASP), which was envisioned as an air-breathing hydrogen-burning vehicle capable of reaching velocities as large as Mach 25. Preliminary studies indicated that the supersonic flow in the combustor region of the scram jet engine required accurate reaction rate data for reactions in the H/N/O system, some of which was not readily available from experiment. The most important class of combustion reactions from the standpoint of the NASP project are radical recombinaton reactions, since these reactions result in most of the heat release in the combustion process. Theoretical characterizations of the potential energy surfaces for these reactions are presented and discussed.

Surface treatment process of Al-Mg alloy powder by BTSPS

NASA Astrophysics Data System (ADS)

Zhao, Ran; Gao, Xinbao; Lu, Yanling; Du, Fengzhen; Zhang, Li; Liu, Dazhi; Chen, Xuefang

2018-04-01

The surface of Al-Mg alloy powder was treated by BTSPS(bis(triethoxysilylpropyl)tetrasulfide) in order to avoid easy oxidation in air. The pH value, reaction temperature, reaction time, and reaction concentration were used as test conditions. The results show that the BTSPS can form a protected film on the surface of Al-Mg alloy powder. Select the best test solution by orthogonal test. The study found that the reaction time and reaction temperature have the biggest influence on the two indexes of the orthogonal test (melting enthalpy of heat and enthalpy of oxidation). The optimal conditions were as follows: pH value is 8, reaction concentration is 2%, reaction temperature is 25 °C, reaction time is 2 h. The oxidation weight gain of the alloy reached 74.45% and the decomposition temperature of silane film is 181.8 °C.

An unexpected cause of an acute hypersensitivity reaction during recovery from anaesthesia.

PubMed

Thong, C L; Lambros, M; Stewart, M G; Kam, P C A

2005-08-01

Acute hypersensitivity reactions to chlorhexidine in the operating room are probably more likely to occur during the early phases of anaesthesia because chlorhexidine is often used for cleaning the surgical field or during placement of indwelling catheters. We report a case of an acute hypersensitivity reaction that occurred in the post anaesthetic care unit. Subsequent skin testing suggested sensitivity to chlorhexidine, which had been applied over the vaginal mucosa at the end of surgery. Relevant issues in the investigation of acute hypersensitivity reactions in the post anaesthetic period are discussed.

SQERTSS: Dynamic rank based throttling of transition probabilities in kinetic Monte Carlo simulations

DOE PAGES

Danielson, Thomas; Sutton, Jonathan E.; Hin, Céline; ...

2017-06-09

Lattice based Kinetic Monte Carlo (KMC) simulations offer a powerful simulation technique for investigating large reaction networks while retaining spatial configuration information, unlike ordinary differential equations. However, large chemical reaction networks can contain reaction processes with rates spanning multiple orders of magnitude. This can lead to the problem of “KMC stiffness” (similar to stiffness in differential equations), where the computational expense has the potential to be overwhelmed by very short time-steps during KMC simulations, with the simulation spending an inordinate amount of KMC steps / cpu-time simulating fast frivolous processes (FFPs) without progressing the system (reaction network). In order tomore » achieve simulation times that are experimentally relevant or desired for predictions, a dynamic throttling algorithm involving separation of the processes into speed-ranks based on event frequencies has been designed and implemented with the intent of decreasing the probability of FFP events, and increasing the probability of slow process events -- allowing rate limiting events to become more likely to be observed in KMC simulations. This Staggered Quasi-Equilibrium Rank-based Throttling for Steady-state (SQERTSS) algorithm designed for use in achieving and simulating steady-state conditions in KMC simulations. Lastly, as shown in this work, the SQERTSS algorithm also works for transient conditions: the correct configuration space and final state will still be achieved if the required assumptions are not violated, with the caveat that the sizes of the time-steps may be distorted during the transient period.« less

SQERTSS: Dynamic rank based throttling of transition probabilities in kinetic Monte Carlo simulations

NASA Astrophysics Data System (ADS)

Danielson, Thomas; Sutton, Jonathan E.; Hin, Céline; Savara, Aditya

2017-10-01

Lattice based Kinetic Monte Carlo (KMC) simulations offer a powerful simulation technique for investigating large reaction networks while retaining spatial configuration information, unlike ordinary differential equations. However, large chemical reaction networks can contain reaction processes with rates spanning multiple orders of magnitude. This can lead to the problem of "KMC stiffness" (similar to stiffness in differential equations), where the computational expense has the potential to be overwhelmed by very short time-steps during KMC simulations, with the simulation spending an inordinate amount of KMC steps/CPU time simulating fast frivolous processes (FFPs) without progressing the system (reaction network). In order to achieve simulation times that are experimentally relevant or desired for predictions, a dynamic throttling algorithm involving separation of the processes into speed-ranks based on event frequencies has been designed and implemented with the intent of decreasing the probability of FFP events, and increasing the probability of slow process events-allowing rate limiting events to become more likely to be observed in KMC simulations. This Staggered Quasi-Equilibrium Rank-based Throttling for Steady-state (SQERTSS) algorithm is designed for use in achieving and simulating steady-state conditions in KMC simulations. As shown in this work, the SQERTSS algorithm also works for transient conditions: the correct configuration space and final state will still be achieved if the required assumptions are not violated, with the caveat that the sizes of the time-steps may be distorted during the transient period.

Surface chemistry reactions of alpha-terpineol [(R)-2-(4-methyl-3-cyclohexenyl)isopropanol] with ozone and air on a glass and a vinyl tile.

PubMed

Ham, J E; Wells, J R

2008-10-01

The surface-phase reaction products of alpha-terpineol [(R)-2-(4-methyl-3-cyclohexenyl)isopropanol] with ozone (O(3)), air or nitrogen (N(2)) on both a glass and vinyl flooring tile were investigated using the recently published FLEC Automation and Control System (FACS). The FACS was used to deliver O(3) (100 ppb), air or N(2) to the surface at a specified flow rate (300 ml/min) and relative humidity (50%) after application of a 1.6%alpha-terpineol solution in methanol. Oxidation products were detected using the derivatization agents: O-(2,3,4,5,6-pentafluorobenzyl) hydroxylamine and N,O-bis(trimethysilyl)trifluoroacetamide. The positively identified reaction products were glyoxal, methylglyoxal and 4-oxopentanal. The proposed oxidation products based on previously published VOC/O(3) reaction mechanisms were: 4-methylcyclohex-3-en-1-one, 6-hydroxyhept-en-2-one, 3-(1-hydroxy-1-methylethyl)-6-methylcyclohex-2-en-1-one) and one surface-enhanced reaction product: 5-(1-hydroxy-1-methylethyl)-2-methylcyclohex-2-en-1-one. Though similar products were observed in gas-phase alpha-terpineol/O(3) reactions, the ratio of the reaction products were different suggesting stabilization of larger molecular weight species by the surface. Emission profiles of these oxidation products over 72 h are also reported. Volatile organic compounds (VOCs) can interact with indoor initiators [such as hydroxyl radicals (OH*), ozone and nitrate radicals (NO(3)*)] to form a number of oxygenated by-products in the gas-phase. However, when VOCs are applied to or are present on the surface, heterogeneous chemistry with indoor initiators can also occur. The surface can influence the reaction mechanism to produce new surface reaction products. The work, described here, shows the interaction of alpha-terpineol (major component of pine oil) with ozone and air on both glass and vinyl flooring. These results demonstrated emissions of oxygenated organic compounds as a result of reaction and that further investigations of this chemistry are required to accurately estimate indoor occupant exposures.

Children as an Evocative Influence on Adults' Reactions to Terrorism

ERIC Educational Resources Information Center

Phillips, Deborah; Featherman, David L.; Liu, Jinyun

2004-01-01

This longitudinal study involving repeated telephone interviews of a national probability sample assessed parents' and other adults' own psychological vulnerability, as well as any observed reactions of coresident and other children, immediately after September 11th, 2001 (N = 752) and again 1 year later (N = 484). For a significant minority of…

Evaluating photo-degradation of COD and TOC in petroleum refinery wastewater by using TiO2/ZnO photo-catalyst.

PubMed

Aljuboury, Dheeaa Al Deen Atallah; Palaniandy, Puganeshwary; Abdul Aziz, Hamidi Bin; Feroz, Shaik; Abu Amr, Salem S

2016-09-01

The aim of this study is to investigate the performance of combined solar photo-catalyst of titanium oxide/zinc oxide (TiO 2 /ZnO) with aeration processes to treat petroleum wastewater. Central composite design with response surface methodology was used to evaluate the relationships between operating variables for TiO 2 dosage, ZnO dosage, air flow, pH, and reaction time to identify the optimum operating conditions. Quadratic models for chemical oxygen demand (COD) and total organic carbon (TOC) removals prove to be significant with low probabilities (<0.0001). The obtained optimum conditions included a reaction time of 170 min, TiO 2 dosage (0.5 g/L), ZnO dosage (0.54 g/L), air flow (4.3 L/min), and pH 6.8 COD and TOC removal rates of 99% and 74%, respectively. The TOC and COD removal rates correspond well with the predicted models. The maximum removal rate for TOC and COD was 99.3% and 76%, respectively at optimum operational conditions of TiO 2 dosage (0.5 g/L), ZnO dosage (0.54 g/L), air flow (4.3 L/min), reaction time (170 min) and pH (6.8). The new treatment process achieved higher degradation efficiencies for TOC and COD and reduced the treatment time comparing with other related processes.

Characterization of LaRhO3 perovskites for dry (CO2) reforming of methane (DRM)

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

Johansson, Ted; Pakhare, Devendra; Haynes, Daniel

2014-01-01

Abstract This work reports on the characterization of LaRhO3 perovskite as a catalyst for dry reforming of methane. The catalyst was studied using CH4-temperature programmed reduction (TPR), H2-TPR, and temperature programmed surface reaction (TPSR), and the changes in the crystal structure of the catalyst due to these treatments were studied by X-ray diffraction (XRD). XRD pattern of the freshly calcined perovskites showed the formation of highly crystalline LaRhO3 and La2O3 phases. H2-TPR of the fresh calcined catalyst showed a shoulder at 342°C and a broad peak at 448°C, suggesting that the reduction of Rh in perovskite occurs in multiple steps.more » XRD pattern of the reduced catalyst suggests complete reduction of the LaRhO3 phase and the formation of metallic Rh and minor amounts of La(OH)3. The CH4-TPR data show qualitatively similar results as H2-TPR, with a shoulder and a broad peak in the same temperature range. Following the H2-TPR up to 950°C, the same batch of catalyst was oxidized by flowing 5 vol. % O2/He up to 500°C and a second H2-TPR (also up to 950°C) was conducted. This second H2-TPR differed significantly from that of the fresh calcined catalyst. The single sharp peak at 163°C in the second H2-TPR suggests a significant change in the catalyst, probably causedby the transformation of about 90 % of the perovskite into Rh/La2O3. This was confirmed by the XRD studies of the catalyst reduced after the oxidation at 500°C. TPSR of the dry reforming reaction on the fresh calcined catalyst showed CO and H2 formation starting at 400°C, with complete consumption of the reactants at 650°C. The uneven consumption of reactants between 400°C and 650°C suggests that reactions other than DRM occur, including reverse water gas shift (RWGS) and the Boudouard reaction (BR), probably as a result of in-situ changes in the catalyst, consistent with the H2-TPR results. TPSR, after a H2-TPR up to 950°C, showed that the dry reforming reaction did not light off until 570°C, which is much higher temperature than the one observed using fresh calcined catalyst. This shows that the uniform sites produced during the 950°C H2-TPR are catalytically less active than those of the fresh calcined catalyst, and that no significant side reactions such as RWGS or the Boudouard reaction occur. This suggests that reduction leads to the formation of a single type of sites which do not catalyze simultaneous side reactions.« less

Stratified turbulent Bunsen flames: flame surface analysis and flame surface density modelling

NASA Astrophysics Data System (ADS)

Ramaekers, W. J. S.; van Oijen, J. A.; de Goey, L. P. H.

2012-12-01

In this paper it is investigated whether the Flame Surface Density (FSD) model, developed for turbulent premixed combustion, is also applicable to stratified flames. Direct Numerical Simulations (DNS) of turbulent stratified Bunsen flames have been carried out, using the Flamelet Generated Manifold (FGM) reduction method for reaction kinetics. Before examining the suitability of the FSD model, flame surfaces are characterized in terms of thickness, curvature and stratification. All flames are in the Thin Reaction Zones regime, and the maximum equivalence ratio range covers 0.1⩽φ⩽1.3. For all flames, local flame thicknesses correspond very well to those observed in stretchless, steady premixed flamelets. Extracted curvature radii and mixing length scales are significantly larger than the flame thickness, implying that the stratified flames all burn in a premixed mode. The remaining challenge is accounting for the large variation in (subfilter) mass burning rate. In this contribution, the FSD model is proven to be applicable for Large Eddy Simulations (LES) of stratified flames for the equivalence ratio range 0.1⩽φ⩽1.3. Subfilter mass burning rate variations are taken into account by a subfilter Probability Density Function (PDF) for the mixture fraction, on which the mass burning rate directly depends. A priori analysis point out that for small stratifications (0.4⩽φ⩽1.0), the replacement of the subfilter PDF (obtained from DNS data) by the corresponding Dirac function is appropriate. Integration of the Dirac function with the mass burning rate m=m(φ), can then adequately model the filtered mass burning rate obtained from filtered DNS data. For a larger stratification (0.1⩽φ⩽1.3), and filter widths up to ten flame thicknesses, a β-function for the subfilter PDF yields substantially better predictions than a Dirac function. Finally, inclusion of a simple algebraic model for the FSD resulted only in small additional deviations from DNS data, thereby rendering this approach promising for application in LES.

Diffuse reflection from a stochastically bounded, semi-infinite medium

NASA Technical Reports Server (NTRS)

Lumme, K.; Peltoniemi, J. I.; Irvine, W. M.

1990-01-01

In order to determine the diffuse reflection from a medium bounded by a rough surface, the problem of radiative transfer in a boundary layer characterized by a statistical distribution of heights is considered. For the case that the surface is defined by a multivariate normal probability density, the propagation probability for rays traversing the boundary layer is derived and, from that probability, a corresponding radiative transfer equation. A solution of the Eddington (two stream) type is found explicitly, and examples are given. The results should be applicable to reflection from the regoliths of solar system bodies, as well as from a rough ocean surface.

Controlling Reaction Selectivity through the Surface Termination of Perovskite Catalysts

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

Polo-Garzon, Felipe; Yang, Shi-Ze; Fung, Victor

2017-07-19

Although well known in the material science field, surface reconstruction of perovskites has not been implemented in heterogeneous catalysis. In this work, we employ multiple surface sensitive techniques to characterize the surface reconstruction of SrTiO3 (STO) after thermal pretreatment (Sr-enrichment) and chemical etching (Ti-enrichment). We show, using the conversion of 2-propanol as a probe reaction, that the surface reconstruction of STO can be controlled to greatly tune catalytic acid/base properties and consequently the reaction selectivities in a wide range, which are inaccessible using single metal oxides, either SrO or TiO2. Density functional theory (DFT) calculations well explain the selectivity tuningmore » and reaction mechanism on differently reconstructed surfaces of STO. Similar catalytic tunability is also observed on BaZrO3, highlighting the generality of the finding from this work.« less

Review of literature surface tension data for molten silicon

NASA Technical Reports Server (NTRS)

Hardy, S.

1981-01-01

Measurements of the surface tension of molten silicon are reported. For marangoni flow, the important parameter is the variation of surface tension with temperature, not the absolute value of the surface tension. It is not possible to calculate temperature coefficients using surface tension measurements from different experiments because the systematic errors are usually larger than the changes in surface tension because of temperature variations. The lack of good surface tension data for liquid silicon is probably due to its extreme chemical reactivity. A material which resists attack by molten silicon is not found. It is suggested that all of the sessile drip surface tension measurements are probably for silicon which is contaminated by the substrate materials.

Covalent Surface Modification of Silicon Oxides with Alcohols in Polar Aprotic Solvents.

PubMed

Lee, Austin W H; Gates, Byron D

2017-09-05

Alcohol-based monolayers were successfully formed on the surfaces of silicon oxides through reactions performed in polar aprotic solvents. Monolayers prepared from alcohol-based reagents have been previously introduced as an alternative approach to covalently modify the surfaces of silicon oxides. These reagents are readily available, widely distributed, and are minimally susceptible to side reactions with ambient moisture. A limitation of using alcohol-based compounds is that previous reactions required relatively high temperatures in neat solutions, which can degrade some alcohol compounds or could lead to other unwanted side reactions during the formation of the monolayers. To overcome these challenges, we investigate the condensation reaction of alcohols on silicon oxides carried out in polar aprotic solvents. In particular, propylene carbonate has been identified as a polar aprotic solvent that is relatively nontoxic, readily accessible, and can facilitate the formation of alcohol-based monolayers. We have successfully demonstrated this approach for tuning the surface chemistry of silicon oxide surfaces with a variety of alcohol containing compounds. The strategy introduced in this research can be utilized to create silicon oxide surfaces with hydrophobic, oleophobic, or charged functionalities.

Real-space characterization of reactivity towards water at the B i 2 T e 3 (111) surface

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

Zhang, Kai-Wen; Ding, Ding; Yang, Chao-Long

2016-06-01

Surface reactivity is important in modifying the physical and chemical properties of surface-sensitive materials, such as the topological insulators. Even though many studies addressing the reactivity of topological insulators towards external gases have been reported, it is still under heavy debate whether and how the topological insulators react with H2O. Here, we employ scanning tunneling microscopy to directly probe the surface reaction of Bi2Te3 towards H2O. Surprisingly, it is found that only the top quintuple layer is reactive to H2O, resulting in a hydrated Bi bilayer as well as some Bi islands, which passivate the surface and prevent subsequent reaction.more » A reaction mechanism is proposed with H2Te and hydrated Bi as the products. Unexpectedly, our study indicates that the reaction with water is intrinsic and not dependent on any surface defects. Since water inevitably exists, these findings provide key information when considering the reactions of Bi2Te3 with residual gases or atmosphere.« less

Plasticity in probabilistic reaction norms for maturation in a salmonid fish

PubMed Central

Morita, Kentaro; Tsuboi, Jun-ichi; Nagasawa, Toru

2009-01-01

The relationship between body size and the probability of maturing, often referred to as the probabilistic maturation reaction norm (PMRN), has been increasingly used to infer genetic variation in maturation schedule. Despite this trend, few studies have directly evaluated plasticity in the PMRN. A transplant experiment using white-spotted charr demonstrated that the PMRN for precocious males exhibited plasticity. A smaller threshold size at maturity occurred in charr inhabiting narrow streams where more refuges are probably available for small charr, which in turn might enhance the reproductive success of sneaker precocious males. Our findings suggested that plastic effects should clearly be included in investigations of variation in PMRNs. PMID:19493875

Thin film growth by 3D multi-particle diffusion limited aggregation model: Anomalous roughening and fractal analysis

NASA Astrophysics Data System (ADS)

Nasehnejad, Maryam; Nabiyouni, G.; Gholipour Shahraki, Mehran

2018-03-01

In this study a 3D multi-particle diffusion limited aggregation method is employed to simulate growth of rough surfaces with fractal behavior in electrodeposition process. A deposition model is used in which the radial motion of the particles with probability P, competes with random motions with probability 1 - P. Thin films growth is simulated for different values of probability P (related to the electric field) and thickness of the layer(related to the number of deposited particles). The influence of these parameters on morphology, kinetic of roughening and the fractal dimension of the simulated surfaces has been investigated. The results show that the surface roughness increases with increasing the deposition time and scaling exponents exhibit a complex behavior which is called as anomalous scaling. It seems that in electrodeposition process, radial motion of the particles toward the growing seeds may be an important mechanism leading to anomalous scaling. The results also indicate that the larger values of probability P, results in smoother topography with more densely packed structure. We have suggested a dynamic scaling ansatz for interface width has a function of deposition time, scan length and probability. Two different methods are employed to evaluate the fractal dimension of the simulated surfaces which are "cube counting" and "roughness" methods. The results of both methods show that by increasing the probability P or decreasing the deposition time, the fractal dimension of the simulated surfaces is increased. All gained values for fractal dimensions are close to 2.5 in the diffusion limited aggregation model.

Reactive solid surface morphology variation via ionic diffusion.

PubMed

Sun, Zhenchao; Zhou, Qiang; Fan, Liang-Shih

2012-08-14

In gas-solid reactions, one of the most important factors that determine the overall reaction rate is the solid morphology, which can be characterized by a combination of smooth, convex and concave structures. Generally, the solid surface structure varies in the course of reactions, which is classically noted as being attributed to one or more of the following three mechanisms: mechanical interaction, molar volume change, and sintering. Here we show that if a gas-solid reaction involves the outward ionic diffusion of a solid-phase reactant then this outward ionic diffusion could eventually smooth the surface with an initial concave and/or convex structure. Specifically, the concave surface is filled via a larger outward diffusing surface pointing to the concave valley, whereas the height of the convex surface decreases via a lower outward diffusion flux in the vertical direction. A quantitative 2-D continuum diffusion model is established to analyze these two morphological variation processes, which shows consistent results with the experiments. This surface morphology variation by solid-phase ionic diffusion serves to provide a fourth mechanism that supplements the traditionally acknowledged solid morphology variation or, in general, porosity variation mechanisms in gas-solid reactions.

Leaching characteristics of ash from the May 18, 1980, eruption of Mount St. Helens Volcano, Washington

USGS Publications Warehouse

Smith, David Burl; Zielinski, Robert A.; Taylor, Howard E.

1982-01-01

Leaching of freshly erupted air-fall ash, unaffected by rain, from the May 18, 1.980,eruption of Mount St. Helens volcano, Washington, shows that Ca 2+, Na+, Mg+, SO4 2-, and Cl- are the predominant chemical species released on first exposure of the ash to water. Extremely high correlation of Ca with SO4 and Na with Cl in water leachates suggests the presence of CaSO4 and NaCl salts on the ash. The amount of water soluble material on ash increases with distance from source and with the weight fraction of small (less than 63 micrometers) ash particles of high-surface area. This suggests that surface reactions such as adsorption are responsible for concentrating the soluble material. CaSO4, NaCl, and other salts are probably formed as microscopic crystals in the high-temperature core of the eruption column and are then adsorbed by silicate ash particles. The environmentally important elements Zn, Cu, Cd, F, Pb, and Ba are released by a water leach in concentrations which could pose short-term hazards to some forms of aquatic life. However, calculated concentrations are based on a water-to-ash ratio of 4:1 or less, which is probably an underestimation of the regionally operative ratio. A subsequent leach of ash by warm alkaline solution shows dramatic increases in the amount of dissolved SiO2, U, and V, which are probably caused by increased dissolution of the glassy component of ash. Glass dissolution by alkaline ground water is a mechanism for providing these three elements to sedimentary traps where they may co-accumulate as uraniferous silica or U-V minerals. Leaching characteristics of ash from Mount St. Helens are comparable to characteristics of ash of similar composition from volcanoes in Guatemala. Ashes from each locality show similar ions predominating for a given leachate and similar fractions of a particular element in the ash removed on contact with the leach solution.

Stochastic surface walking reaction sampling for resolving heterogeneous catalytic reaction network: A revisit to the mechanism of water-gas shift reaction on Cu

NASA Astrophysics Data System (ADS)

Zhang, Xiao-Jie; Shang, Cheng; Liu, Zhi-Pan

2017-10-01

Heterogeneous catalytic reactions on surface and interfaces are renowned for ample intermediate adsorbates and complex reaction networks. The common practice to reveal the reaction mechanism is via theoretical computation, which locates all likely transition states based on the pre-guessed reaction mechanism. Here we develop a new theoretical method, namely, stochastic surface walking (SSW)-Cat method, to resolve the lowest energy reaction pathway of heterogeneous catalytic reactions, which combines our recently developed SSW global structure optimization and SSW reaction sampling. The SSW-Cat is automated and massively parallel, taking a rough reaction pattern as input to guide reaction search. We present the detailed algorithm, discuss the key features, and demonstrate the efficiency in a model catalytic reaction, water-gas shift reaction on Cu(111) (CO + H2O → CO2 + H2). The SSW-Cat simulation shows that water dissociation is the rate-determining step and formic acid (HCOOH) is the kinetically favorable product, instead of the observed final products, CO2 and H2. It implies that CO2 and H2 are secondary products from further decomposition of HCOOH at high temperatures. Being a general purpose tool for reaction prediction, the SSW-Cat may be utilized for rational catalyst design via large-scale computations.

Low Energy Nuclear Reaction Products at Surfaces

NASA Astrophysics Data System (ADS)

Nagel, David J.

2008-03-01

This paper examines the evidence for LENR occurring on or very near to the surface of materials. Several types of experimental indications for LENR surface reactions have been reported and will be reviewed. LENR result in two types of products, energy and the appearance of new elements. The level of instantaneous power production can be written as the product of four factors: (1) the total area of the surface on which the reactions can occur, (2) the fraction of the area that is active at any time, (3) the reaction rate, that is, the number of reactions per unit active area per second, and (4) the energy produced per reaction. Each of these factors, and their limits, are reviewed. A graphical means of relating these four factors over their wide variations has been devised. The instantaneous generation of atoms of new elements can also be written as the product of the first three factors and the new elemental mass produced per reaction. Again, a graphical means of presenting the factors and their results over many orders of magnitude has been developed.

Mechanistic understanding of surface plasmon assisted catalysis on a single particle: cyclic redox of 4-aminothiophenol

DOE PAGES

Xu, Ping; Kang, Leilei; Mack, Nathan H.; ...

2013-10-21

We investigate surface plasmon assisted catalysis (SPAC) reactions of 4-aminothiophenol (4ATP) to and back from 4,4'-dimercaptoazobenzene (DMAB) by single particle surface enhanced Raman spectroscopy, using a self-designed gas flow cell to control the reductive/oxidative environment over the reactions. Conversion of 4ATP into DMAB is induced by energy transfer (plasmonic heating) from surface plasmon resonance to 4ATP, where O 2 (as an electron acceptor) is essential and H 2O (as a base) can accelerate the reaction. In contrast, hot electron (from surface plasmon decay) induction drives the reverse reaction of DMAB to 4ATP, where H 2O (or H 2) acts asmore » the hydrogen source. More interestingly, the cyclic redox between 4ATP and DMAB by SPAC approach has been demonstrated. Finally, this SPAC methodology presents a unique platform for studying chemical reactions that are not possible under standard synthetic conditions.« less

Theory of the reaction dynamics of small molecules on metal surfaces

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

Jackson, Bret

The objective of this project has been to develop realistic theoretical models for gas-surface interactions, with a focus on processes important in heterogeneous catalysis. The dissociative chemisorption of a molecule on a metal is a key step in many catalyzed reactions, and is often the rate-limiting step. We have explored the dissociative chemisorption of H 2, H 2O and CH 4 on a variety of metal surfaces. Most recently, our extensive studies of methane dissociation on Ni and Pt surfaces have fully elucidated its dependence on translational energy, vibrational state and surface temperature, providing the first accurate comparisons with experimentalmore » data. We have explored Eley-Rideal and hot atom reactions of H atoms with H- and C-covered metal surfaces. H atom interactions with graphite have also been explored, including both sticking and Eley-Rideal recombination processes. Again, our methods made it possible to explain several experiments studying these reactions. The sticking of atoms on metal surfaces has also been studied. To help elucidate the experiments that study these processes, we examine how the reaction dynamics depend upon the nature of the molecule-metal interaction, as well as experimental variables such as substrate temperature, beam energy, angle of impact, and the internal states of the molecules. Electronic structure methods based on Density Functional Theory are used to compute each molecule-metal potential energy surface. Both time-dependent quantum scattering techniques and quasi-classical methods are used to examine the reaction or scattering dynamics. Much of our effort has been directed towards developing improved quantum methods that can accurately describe reactions, as well as include the effects of substrate temperature (lattice vibration).« less

Biogeochemical Reactions Under Simulated Europa Ocean Conditions

NASA Astrophysics Data System (ADS)

Amashukeli, X.; Connon, S. A.; Gleeson, D. F.; Kowalczyk, R. S.; Pappalardo, R. T.

2007-12-01

Galileo data have demonstrated the probable presence of a liquid water ocean on Europa, and existence of salts and carbon dioxide in the satellite's surface ice (e.g., Carr et al., 1998; McCord et al., 1999, Pappalardo et al., 1999; Kivelson et al., 2000). Subsequently, the discovery of chemical signatures of extinct or extant life in Europa's ocean and on its surface became a distinct possibility. Moreover, understanding of Europa's potential habitability is now one of the major goals of the Europa Orbiter Flagship mission. It is likely, that in the early stages of Europa's ocean formation, moderately alkaline oceanic sulfate-carbonate species and a magnetite-silicate mantel could have participated in low-temperature biogeochemical sulfur, iron and carbon cycles facilitated by primitive organisms (Zolotov and Shock, 2004). If periodic supplies of fresh rock and sulfate-carbonate ions are available in Europa's ocean, then an exciting prospect exists that life may be present in Europa's ocean today. In our laboratory, we began the study of the plausible biogeochemical reactions under conditions appropriate to Europa's ocean using barophilic psychrophilic organisms that thrive under anaerobic conditions. In the near absence of abiotic synthetic pathways due to low Europa's temperatures, the biotic synthesis may present a viable opportunity for the formation of the organic and inorganic compounds under these extreme conditions. This work is independent of assumptions regarding hydrothermal vents at Europa's ocean floor or surface-derived oxidant sources. For our studies, we have fabricated a high-pressure (5,000 psi) reaction vessel that simulates aqueous conditions on Europa. We were also successful at reviving barophilic psychrophilic strains of Shewanella bacterium, which serve as test organisms in this investigation. Currently, facultative barophilic psychrophilic stains of Shewanella are grown in the presence of ferric food source; the strains exhibiting iron reduction capability will be later selected and used to facilitate biogeochemical reduction of iron under simulated temperature and pressure of Europa's ocean. The results of this work will enable us to ascertain whether Europa's cold, high-pressure ocean is capable of supporting life. In addition, the data from this study will help in generating a list of organic and inorganic target molecules for future remote sensing and in situ exploration missions.

Optimizing Chemical Reactions with Deep Reinforcement Learning

PubMed Central

2017-01-01

Deep reinforcement learning was employed to optimize chemical reactions. Our model iteratively records the results of a chemical reaction and chooses new experimental conditions to improve the reaction outcome. This model outperformed a state-of-the-art blackbox optimization algorithm by using 71% fewer steps on both simulations and real reactions. Furthermore, we introduced an efficient exploration strategy by drawing the reaction conditions from certain probability distributions, which resulted in an improvement on regret from 0.062 to 0.039 compared with a deterministic policy. Combining the efficient exploration policy with accelerated microdroplet reactions, optimal reaction conditions were determined in 30 min for the four reactions considered, and a better understanding of the factors that control microdroplet reactions was reached. Moreover, our model showed a better performance after training on reactions with similar or even dissimilar underlying mechanisms, which demonstrates its learning ability. PMID:29296675

Tuning Catalytic Performance through a Single or Sequential Post-Synthesis Reaction(s) in a Gas Phase

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

Shan, Junjun; Zhang, Shiran; Choksi, Tej

2016-12-05

Catalytic performance of a bimetallic catalyst is determined by geometric structure and electronic state of the surface or even the near-surface region of the catalyst. Here we report that single and sequential postsynthesis reactions of an as-synthesized bimetallic nanoparticle catalyst in one or more gas phases can tailor surface chemistry and structure of the catalyst in a gas phase, by which catalytic performance of this bimetallic catalyst can be tuned. Pt–Cu regular nanocube (Pt–Cu RNC) and concave nanocube (Pt–Cu CNC) are chosen as models of bimetallic catalysts. Surface chemistry and catalyst structure under different reaction conditions and during catalysis weremore » explored in gas phase of one or two reactants with ambient-pressure X-ray photoelectron spectroscopy (AP-XPS) and extended X-ray absorption fine structure (EXAFS) spectroscopy. The newly formed surface structures of Pt–Cu RNC and Pt–Cu CNC catalysts strongly depend on the reactive gas(es) used in the postsynthesis reaction(s). A reaction of Pt–Cu RNC-as synthesized with H2 at 200 °C generates a near-surface alloy consisting of a Pt skin layer, a Cu-rich subsurface, and a Pt-rich deep layer. This near-surface alloy of Pt–Cu RNC-as synthesized-H2 exhibits a much higher catalytic activity in CO oxidation in terms of a low activation barrier of 39 ± 4 kJ/mol in contrast to 128 ± 7 kJ/mol of Pt–Cu RNC-as synthesized. Here the significant decrease of activation barrier demonstrates a method to tune catalytic performances of as-synthesized bimetallic catalysts. A further reaction of Pt–Cu RNC-as synthesized-H2 with CO forms a Pt–Cu alloy surface, which exhibits quite different catalytic performance in CO oxidation. It suggests the capability of generating a different surface by using another gas. The capability of tuning surface chemistry and structure of bimetallic catalysts was also demonstrated in restructuring of Pt–Cu CNC-as synthesized.« less

Stereodynamics of the reactions: F + H2/HD/HT→FH + H/D/T

NASA Astrophysics Data System (ADS)

Chi, Xiao-Lin; Zhao, Jin-Feng; Zhang, Yong-Jia; Ma, Feng-Cai; Li, Yong-Qing

2015-05-01

Among many kinds of ways to study the properties of atom and molecule collision, the quasi-classical trajectory (QCT) method is an effective one to investigate the molecular reaction dynamics. QCT calculations have been carried out to investigate the stereodynamics of the reactions F + H2/HD/HT→FH + H/D/T, which proceed on the lowest-lying electronic states of the FH2 system based on the potential energy surface (PES) of the 12A’ FH2 ground state. Although the QCT method cannot describe all quantum effects in the process of the reaction, it has unique advantages when facing a three-atoms system or complicated polyatomic systems. Differential cross sections (DCSs) and three angle distribution functions P(θr), P(ϕr), P(θr, ϕr) on the PES at the collision of 2.74 kcal/mol have been investigated. The isotope effect becomes more obvious with the reagent molecule H2 turning into HD and HT. P(θr, ϕr), as the joint probability density function of both polar angles θr and ϕr, can reflect the properties of three-dimensional dynamic more intuitively. Project supported by the National Natural Science Foundation of China (Grant No. 11474141), the Scientific Research Foundation for the Returned Overseas Chinese Scholars (Grant No. 2014-1685), the Scientific Research Foundation for the Doctor of Liaoning University, the Special Fund Based Research New Technology of Methanol Conversion and Coal Instead of Oil, and the China Postdoctoral Science Foundation (Grant No. 2014M550158).

Product energy distributions and energy partitioning in O atom reactions on surfaces

NASA Technical Reports Server (NTRS)

Halpern, Bret; Kori, Moris

1987-01-01

Surface reactions involving O atoms are likely to be highly exoergic, with different consequences if energy is channeled mostly to product molecules or surface modes. Thus the surface may become a source of excited species which can react elsewhere, or a sink for localized heat deposition which may disrupt the surface. The vibrational energy distribution of the product molecule contains strong clues about the flow of released energy. Two instructive examples of energy partitioning at surfaces are the Pt catalyzed oxidations: (1) C(ads) + O(ads) yields CO* (T is greater than 1000 K); and (2) CO(ads) + O(gas) yields CO2* (T is approx. 300 K). The infrared emission spectra of the excited product molecules were recorded and the vibrational population distributions were determined. In reaction 1, energy appeared to be statistically partitioned between the product CO and several Pt atoms. In reaction 2, partitioning was non-statistical; the CO2 asymmetric stretch distribution was inverted. In gas reactions these results would indicate a long lived and short lived activated complex. The requirement that Pt be heated in O atoms to promote reaction of atomic O and CO at room temperature is specifically addressed. Finally, the fraction of released energy that is deposited in the catalyst is estimated.

THE INFLUENCE OF MINERAL REACTIONS ON THE ENVIRONMENTAL FATE OF METALS IN SOILS AND SEDIMENTS

EPA Science Inventory

Significant progress has been made in elucidating sorption reactions that control the partitioning of metals from solution to mineral surfaces in contaminated soil/sediment systems. Surface complexation models have been developed to quantify the forward reaction, however, these ...

Classical Trajectory Study of Collision Energy Transfer between Ne and C2H2 on a Full Dimensional Accurate Potential Energy Surface.

PubMed

Liu, Yang; Huang, Yin; Ma, Jianyi; Li, Jun

2018-02-15

Collision energy transfer plays an important role in gas phase reaction kinetics and relaxation of excited molecules. However, empirical treatments are generally adopted for the collisional energy transfer in the master equation based approach. In this work, classical trajectory approach is employed to investigate the collision energy transfer dynamics in the C 2 H 2 -Ne system. The entire potential energy surface is described as the sum of the C 2 H 2 potential and interaction potential between C 2 H 2 and Ne. It is highlighted that both parts of the entire potential are highly accurate. In particular, the interaction potential is fit to ∼41 300 configurations determined at the level of CCSD(T)-F12a/cc-pCVTZ-F12 with the counterpoise correction. Collision energy transfer dynamics are then carried out on this benchmark potential and the widely used Lennard-Jones and Buckingham interaction potentials. Energy transfers and related probability densities at different collisional energies are reported and discussed.

Nickel-Aluminum Layered Double Hydroxide Coating on the Surface of Conductive Substrates by Liquid Phase Deposition.

PubMed

Maki, Hideshi; Takigawa, Masashi; Mizuhata, Minoru

2015-08-12

The direct synthesis of the adhered Ni-Al LDH thin film onto the surface of electrically conductive substrates by the liquid phase deposition (LPD) reaction is carried out for the development of the positive electrode. The complexation and solution equilibria of the dissolved species in the LPD reaction have been clarified by a theoretical approach, and the LPD reaction conditions for the Ni-Al LDH depositions are shown to be optimized by controlling the fluoride ion concentration and the pH of the LPD reaction solutions. The yields of metal oxides and hydroxides by the LPD method are very sensitive to the supersaturation state of the hydroxide in the reaction solution. The surfaces of conductive substrates are completely covered by the minute mesh-like Ni-Al LDH thin film; furthermore, there is no gap between the surfaces of conductive substrates and the deposited Ni-Al LDH thin film. The active material layer thickness was able to be controlled within the range from 100 nm to 1 μm by the LPD reaction time. The high-crystallinity and the arbitrary-thickness thin films on the conductive substrate surface will be beneficial for the interface control of charge transfer reaction fields and the internal resistance reduction of various secondary batteries.

Numerical simulation of two-dimensional flow over a heated carbon surface with coupled heterogeneous and homogeneous reactions

NASA Astrophysics Data System (ADS)

Johnson, Ryan Federick; Chelliah, Harsha Kumar

2017-01-01

For a range of flow and chemical timescales, numerical simulations of two-dimensional laminar flow over a reacting carbon surface were performed to understand further the complex coupling between heterogeneous and homogeneous reactions. An open-source computational package (OpenFOAM®) was used with previously developed lumped heterogeneous reaction models for carbon surfaces and a detailed homogeneous reaction model for CO oxidation. The influence of finite-rate chemical kinetics was explored by varying the surface temperatures from 1800 to 2600 K, while flow residence time effects were explored by varying the free-stream velocity up to 50 m/s. The reacting boundary layer structure dependence on the residence time was analysed by extracting the ratio of chemical source and species diffusion terms. The important contributions of radical species reactions on overall carbon removal rate, which is often neglected in multi-dimensional simulations, are highlighted. The results provide a framework for future development and validation of lumped heterogeneous reaction models based on multi-dimensional reacting flow configurations.

Quadrupole type mass spectrometric study of the abstraction reaction between hydrogen atoms and ethane.

PubMed

Bayrakçeken, Fuat

2008-02-01

The reactions of photochemically generated deuterium atoms of selected initial translational energy with ethane have been investigated. At each initial energy the relative probability of the atoms undergoing reaction or energy loss on collision with ethane was investigated, and the phenomenological threshold energy was measured as 30+/-5kJmol(-1) for the abstraction from the secondary C-H bonds. The ratio of relative yields per bond, secondary:primary was approximately 3 at the higher energies studied. The correlation of threshold energies with bond dissociation energies, heats of reaction and activation energies is discussed for abstraction reactions with several hydrocarbons.

Silica, Alumina and Clay Catalyzed Peptide Bond Formation: Enhanced Efficiency of Alumina Catalyst

NASA Astrophysics Data System (ADS)

Bujdák, Juraj; Rode, Bernd M.

1999-10-01

Catalytic efficiencies of clay (hectorite), silica and alumina were tested in peptide bond formation reactions of glycine (Gly), alanine (Ala), proline (Pro), valine (Val) and leucine (Leu). The reactions were performed as drying/wetting (hectorite) and temperature fluctuation (silica and alumina) experiments at 85 °C. The reactivity of amino acids decreased in order Gly > Ala > Pro ~ Val ~ Leu. The highest catalytic efficiency was observed for alumina, the only catalyst producing oligopeptides in all investigated reaction systems. The peptide bond formation on alumina is probably catalyzed by the same sites and via similar reaction mechanisms as some alumina-catalyzed dehydration reactions used in industrial chemistry.

Multifunctional silicon surfaces: reaction of dichlorocarbene generated from Seyferth reagent with hydrogen-terminated silicon (111) surfaces.

PubMed

Liu, Wenjun; Sharp, Ian D; Tilley, T Don

2014-01-14

Insertion of dichlorocarbene (:CCl2), generated by decomposition of the Seyferth reagent PhHgCCl2Br, into the Si-H bond of a tertiary silane to form a Si-CCl2H group is an efficient homogeneous, molecular transformation. A heterogeneous version of this reaction, between PhHgCCl2Br and a silicon (111) surface terminated by tertiary Si-H bonds, was studied using a combination of surface-sensitive infrared and X-ray photoelectron spectroscopies. The insertion of dichlorocarbene into surface Si-H bonds parallels the corresponding reaction of silanes in solution, to produce surface-bound dichloromethyl groups (Si-CCl2H) covering ∼25% of the silicon surface sites. A significant fraction of the remaining Si-H bonds on the surface was converted to Si-Cl/Br groups during the same reaction, with PhHgCCl2Br serving as a halogen atom source. The presence of two distinct environments for the chlorine atoms (Si-CCl2H and Si-Cl) and one type of bromine atom (Si-Br) was confirmed by Cl 2p, Br 3d, and C 1s X-ray photoelectron spectroscopy. The formation of reactive, halogen-terminated atop silicon sites was also verified by reaction with sodium azide or the Grignard reagent (CH3MgBr), to produce Si-N3 or Si-Me functionalities, respectively. Thus, reaction of a hydrogen-terminated silicon (111) surface with PhHgCCl2Br provides a facile route to multifunctional surfaces possessing both stable silicon-carbon and labile silicon-halogen sites, in a single pot synthesis. The reactive silicon-halogen groups can be utilized for subsequent transformations and, potentially, the construction of more complex organic-silicon hybrid systems.

Prevalence of Dog Erythrocyte Antigens 1, 4, and 7 in Podenco Ibicenco (Ibizan Hounds) from Ibiza Island

PubMed Central

Proverbio, Daniela; Viñals Flórez, Luis Miguel; Serra Gómez de la Serna, Blanca; del Rosario Perlado Chamizo, Maria; Baggiani, Luciana; Perego, Roberta

2016-01-01

The aims of this study were to evaluate the prevalence of Dog Erythrocyte Antigens (DEA) 1, 4, and 7 in Ibizan hounds, to compare the results with the prevalence of DEA in Spanish greyhounds, and to determine the risk of sensitization following the first transfusion of blood not typed for DEA 1 and the probability of an acute hemolytic reaction following a second incompatible transfusion using untyped DEA 1 blood. DEA 1, 4, and 7 status was determined in 92 Ibizan hounds. Results were compared with the previously reported prevalence in Spanish greyhounds. The risks of sensitization and of a hemolytic transfusion reaction were determined amongst Ibizan hounds and between Ibizan hounds and Spanish greyhounds. The prevalence of DEA 1, 4, and 7 was 75%, 98.9%, and 25%, respectively. There was a significantly higher expression of DEA 1 and 7 in Ibizan hounds than in Spanish greyhounds. The probability of sensitization of a recipient dog to DEA 1 with transfusions amongst Ibizan hounds was 18.5% and between Ibizan hounds and Spanish greyhounds was 13.7%. The probability of an acute hemolytic reaction in each group was 3.5% and 1.9%, respectively. There is a higher prevalence of DEA 1 and 7 in Ibizan hounds than in other sighthounds. PMID:27034890

The use of sensory perception indicators for improving the characterization and modelling of total petroleum hydrocarbon (TPH) grade in soils.

PubMed

Roxo, Sónia; de Almeida, José António; Matias, Filipa Vieira; Mata-Lima, Herlander; Barbosa, Sofia

2016-03-01

This paper proposes a multistep approach for creating a 3D stochastic model of total petroleum hydrocarbon (TPH) grade in potentially polluted soils of a deactivated oil storage site by using chemical analysis results as primary or hard data and classes of sensory perception variables as secondary or soft data. First, the statistical relationship between the sensory perception variables (e.g. colour, odour and oil-water reaction) and TPH grade is analysed, after which the sensory perception variable exhibiting the highest correlation is selected (oil-water reaction in this case study). The probabilities of cells belonging to classes of oil-water reaction are then estimated for the entire soil volume using indicator kriging. Next, local histograms of TPH grade for each grid cell are computed, combining the probabilities of belonging to a specific sensory perception indicator class and conditional to the simulated values of TPH grade. Finally, simulated images of TPH grade are generated by using the P-field simulation algorithm, utilising the local histograms of TPH grade for each grid cell. The set of simulated TPH values allows several calculations to be performed, such as average values, local uncertainties and the probability of the TPH grade of the soil exceeding a specific threshold value.

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.

Vertical changes in the probability distribution of downward irradiance within the near-surface ocean under sunny conditions

NASA Astrophysics Data System (ADS)

Gernez, Pierre; Stramski, Dariusz; Darecki, Miroslaw

2011-07-01

Time series measurements of fluctuations in underwater downward irradiance, Ed, within the green spectral band (532 nm) show that the probability distribution of instantaneous irradiance varies greatly as a function of depth within the near-surface ocean under sunny conditions. Because of intense light flashes caused by surface wave focusing, the near-surface probability distributions are highly skewed to the right and are heavy tailed. The coefficients of skewness and excess kurtosis at depths smaller than 1 m can exceed 3 and 20, respectively. We tested several probability models, such as lognormal, Gumbel, Fréchet, log-logistic, and Pareto, which are potentially suited to describe the highly skewed heavy-tailed distributions. We found that the models cannot approximate with consistently good accuracy the high irradiance values within the right tail of the experimental distribution where the probability of these values is less than 10%. This portion of the distribution corresponds approximately to light flashes with Ed > 1.5?, where ? is the time-averaged downward irradiance. However, the remaining part of the probability distribution covering all irradiance values smaller than the 90th percentile can be described with a reasonable accuracy (i.e., within 20%) with a lognormal model for all 86 measurements from the top 10 m of the ocean included in this analysis. As the intensity of irradiance fluctuations decreases with depth, the probability distribution tends toward a function symmetrical around the mean like the normal distribution. For the examined data set, the skewness and excess kurtosis assumed values very close to zero at a depth of about 10 m.

On the sputter alteration of regoliths of outer solar system bodies

NASA Technical Reports Server (NTRS)

Hapke, Bruce

1987-01-01

Several processes that are expected to occur when the porous regoliths of outer solar system bodies (without atmospheres) are subjected to energetic ion bombardment are discussed. The conclusions reached in much of the literature addressing sputtering are quantitatively or qualitatively incorrect because effects of soil porosity have been neglected. It is shown theoretically and experimentally that porosity reduces the effective sputtering yield of a soil by more than an order of magnitude. Between 90 and 97% of the sputtered atoms are trapped within the regolith, where they are factionated by differential desorption. Experiments indicate that more volatile species have higher desorption probabilities. This process is the most important way in which alteration of chemical and optical properties occurs when a regolith is sputtered. When a basic silicate soil is irradiated these effects lead to sputter-deposited films enriched in metallic iron, while O, Na and K are preferentially lost. The Na and K are present in the atmosphere above the sputtered silicate in quantities much greater than their abundances in the regolith. Icy regoliths of SO2 should be enriched in elemental S and/or S2O. This prediction is supported by the probable identification of S2O and polysulfur oxide bands in the IR spectra of H-sputtered SO2 reported by Moore. When porous mixtures of water, ammonia and methane frosts are sputtered, the loss of H and surface reactions of C, N and O in the deposits should produce complex hydrocarbons and carbohydrates, some of which may be quite dark. Such reactions may have played a role in the formation of the matrix material of carbonaceous chondrites prior to agglomeration.

Potential energy surfaces and reaction dynamics of polyatomic molecules

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

Chang, Yan-Tyng

A simple empirical valence bond (EVB) model approach is suggested for constructing global potential energy surfaces for reactions of polyatomic molecular systems. This approach produces smooth and continuous potential surfaces which can be directly utilized in a dynamical study. Two types of reactions are of special interest, the unimolecular dissociation and the unimolecular isomerization. For the first type, the molecular dissociation dynamics of formaldehyde on the ground electronic surface is investigated through classical trajectory calculations on EVB surfaces. The product state distributions and vector correlations obtained from this study suggest very similar behaviors seen in the experiments. The intramolecular hydrogenmore » atom transfer in the formic acid dimer is an example of the isomerization reaction. High level ab initio quantum chemistry calculations are performed to obtain optimized equilibrium and transition state dimer geometries and also the harmonic frequencies.« less

Surface Protonics Promotes Catalysis

PubMed Central

Manabe, R.; Okada, S.; Inagaki, R.; Oshima, K.; Ogo, S.; Sekine, Y.

2016-01-01

Catalytic steam reforming of methane for hydrogen production proceeds even at 473 K over 1 wt% Pd/CeO2 catalyst in an electric field, thanks to the surface protonics. Kinetic analyses demonstrated the synergetic effect between catalytic reaction and electric field, revealing strengthened water pressure dependence of the reaction rate when applying an electric field, with one-third the apparent activation energy at the lower reaction temperature range. Operando–IR measurements revealed that proton conduction via adsorbed water on the catalyst surface occurred during electric field application. Methane was activated by proton collision at the Pd–CeO2 interface, based on the inverse kinetic isotope effect. Proton conduction on the catalyst surface plays an important role in methane activation at low temperature. This report is the first describing promotion of the catalytic reaction by surface protonics. PMID:27905505

Effect of dipolar fields, surface termination, and surface orientation on photochemical reactions on transition metal oxides

NASA Astrophysics Data System (ADS)

Giocondi, Jennifer Lynn

Experiments have been conducted to determine the effects of dipolar fields, surface termination, and surface orientation on the photochemical reactivity of several transition metal oxides. These compounds include BaTiO3, SrTiO3, BaTi4O9, Sr2Nb2O 7, and Sr2Ta2O7 which were studied as polycrystalline ceramics, single crystals, micron-sized faceted particles, or some combination of these forms. The reduction of Ag+ from an aqueous AgNO3 solution (Ag0 product) and the oxidation of Pb2+ from an aqueous lead acetate solution (PbO 2 product) were selected as probe reactions because they leave insoluble products on the oxide surfaces. The reactivity of ferroelectric BaTiO3 was dominated by the effect of dipolar fields on the transport of photogenerated charge carriers. Silver was reduced on domains with a positive surface charge while lead was oxidized on domains with a negative surface charge. This reactivity implies that the dipolar field in individual domains drives photogenerated charge carriers to oppositely charged surfaces. This reaction mechanism results in a physical separation of the photogenerated charge carriers and the locations of the oxidation and reduction half reactions on the catalyst surface. Experiments performed on polycrystalline ceramics, single crystals, and micron-sized particles all showed this domain specific reactivity. SrTiO3 has the ideal cubic perovskite structure from which the tetragonally distorted ferroelectric BaTiO3 phase is derived. Polished and annealed surfaces of randomly oriented grain surfaces were bound by some combination of the following three planes: {110}, {111}, and a complex facet inclined approximately 24° from {100}. Surfaces with the complex {100} facet were found to be the most active for Ag reduction. Single crystal studies also showed that the nonpolar (100) surface is the most reactive and that the composition of the termination layer does not influence this reaction. However, the polar (111) and (110) surfaces had a non-uniform distribution of reaction products. For these orientations, the location of the reduction and oxidation reactions is determined by the chemical and charge terminations of the different terraces or facets. The reactivity for silver reduction on the faceted particles is ranked as (100) > (111) > (110) while the (100) surface was least reactive for lead oxidation. Overall, these results show that the photochemical reactivity of SrTiO3 is anisotropic and that on polar surfaces, dipolar fields arising from charged surface domains influence the transport of photogenerated charge carriers and promote spatially selective oxidation and reduction reactions. (Abstract shortened by UMI.)

Reflectance-difference spectroscopy of GaAs crystal growth by OMCVD

NASA Astrophysics Data System (ADS)

Colas, Etienne G.; Aspnes, David E.; Bhat, Rajaram J.; Studna, A. A.; Koza, M. A.; Keramidas, Vassilis G.

1990-02-01

This paper summarizes results of our investigations of growth on (001) and (110) GaAs by atmospheric-pressure organometallic chemical vapor deposition (OMCVD). We follow evolutions of surface species to a sensitivity of 0.01 monolayer (ML) on a time scale of 0.1 s under alternating flows of trimethylgallium (TMG) and arsine (AsH3) as functions of partial pressure, sample temperature, and surface orienta-tion. The reaction of TMG with an AsH3-saturated (001) surface is rate-limited by com-petition between desorption and decomposition of TMG molecules chemisorbed to surface lattice sites via an excluded-volume mechanism, while the reaction of AsH3 with the TMG-saturated (001) surface is essentially instantaneous. In contrast, TMG reacts essentially instantaneously with the AsH3 -saturated (110) surface while the AsH3 reaction with the TMG-saturated (110) surface is the rate-limiting step. However, the latter rate is not intrinsic to the AsH3-surface reaction but appears to be determined by desorption of adsorbed species that block active sites.

Pulse electrochemical meso/micro/nano ultraprecision machining technology.

PubMed

Lee, Jeong Min; Kim, Young Bin; Park, Jeong Woo

2013-11-01

This study demonstrated meso/micro/nano-ultraprecision machining through electrochemical reactions using intermittent DC pulses. The experiment focused on two machining methods: (1) pulse electrochemical polishing (PECP) of stainless steel, and (2) pulse electrochemical nano-patterning (PECNP) on a silicon (Si) surface, using atomic force microscopy (AFM) for fabrication. The dissolution reaction at the stainless steel surface following PECP produced a very clean, smooth workpiece. The advantages of the PECP process included improvements in corrosion resistance, deburring of the sample surface, and removal of hydrogen from the stainless steel surface as verified by time-of-flight secondary-ion mass spectrometry (TOF-SIMS). In PECNP, the electrochemical reaction generated within water molecules produced nanoscale oxide textures on a Si surface. Scanning probe microscopy (SPM) was used to evaluate nanoscale-pattern processing on a Si wafer surface produced by AFM-PECNP For both processes using pulse electrochemical reactions, three-dimensional (3-D) measurements and AFM were used to investigate the changes on the machined surfaces. Preliminary results indicated the potential for advancing surface polishing techniques and localized micro/nano-texturing technology using PECP and PECNP processes.

Transfer products from the reactions of heavy ions with heavy nuclei. [394 to 1156 MeV

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

Thomas, K.E. III

1979-11-01

Production of nuclides heavier than the target from /sup 86/Kr- and /sup 136/Xe-induced reactions with /sup 181/Ta and /sup 238/U was investigated. Attempts were made to produce new neutron-excess Np and Pu isotopes by the deep inelastic mechanism. No evidence was found for /sup 242/Np or /sup 247/Pu. Estimates were made for the production of /sup 242/Np, /sup 247/Pu, and /sup 248/Am from heavy-ion reactions with uranium targets. Comparisons of reactions of /sup 86/Kr and /sup 136/Xe ions with thick /sup 181/Ta targets and /sup 86/Kr, /sup 136/Xe and /sup 238/U ions with thick /sup 238/U targets indicate that themore » most probable products are not dependent on the projectile. The most probable products can be predicted by the equation Z - Z/sub target/ = 0.43 (A - A/sub target/) + 1.0. The major effect of the projectile is the magnitude of the production cross section of the heavy products. Based on these results, estimates are made of the most probable mass of element 114 produced from heavy-ion reactions with /sup 248/Cm and /sup 254/Es targets. These estimates give the mass number of element 114 as approx. 287 if produced in heavy-ion reactions with these very heavy targets. Excitation functions of gold and bismuth isotopes arising from /sup 86/Kr- and /sup 136/Xe-induced reactions with thin /sup 181/Ta targets were measured. These results indicate that the shape and location (in Z and A above the target) of the isotopic distributions are not strongly dependent on the projectile incident energy. Also, the nuclidic cross sections are found to increase with an increase in projectile energy to a maximum at approximately 1.4 to 1.5 times the Coulomb barrier. Above this maximum, the nuclidic cross sections are found to decrease with an increase in projectile energy. This decrease in cross section is believed to be due to fission of the heavy products caused by high excitation energy and angular momentum. 111 references, 39 figures, 34 tables.« less