Counter-transference reactions contributing to completed suicide.

Science.gov (United States)

Modestin, J

1987-12-01

Counter-transference reactions are frequently elicited while treating suicidal patients and they may contribute to the patient's committing suicide. Therapeutic constellations including the failure of the therapist to (1) cope with the patient's aggressiveness, (2) tolerate the patient's dependency, (3) handle the erotic transference adequately and (4) preserve loyalty towards the patient; they have all been identified as being responsible for a therapeutic impasse with fatal consequences. Knowledge of the therapeutic constellations especially prone to facilitate negative counter-transference reactions may help the therapist to master them effectively.

Probing cluster structures through sub-barrier transfer reactions

Directory of Open Access Journals (Sweden)

Rafferty D. C.

2016-01-01

Full Text Available Multinucleon transfer probabilities and excitation energy distributions have been measured in 16,18O, 19F + 208Pb at energies between 90% - 100% of the Coulomb barrier. A strong 2p2n enhancement is observed for all reactions, though most spectacularly in the 18O induced reaction. Results are interpreted in terms of the Semiclassical model, which seems to suggest α-cluster transfer in all studied systems. The relation to cluster-states in the projectile is discussed, with the experimental results consistent with previous structure studies. Dissipation of energy in the collisions of 18O is compared between different reaction modes, with cluster transfer associated with dissipation over a large number of internal states. Cluster transfer is shown to be a long range dissipation mechanism, which will inform the development of future models to treat these dynamic processes in reactions.

Neutron transfer reactions in the fp-shell region

Energy Technology Data Exchange (ETDEWEB)

Mahgoub, Mahmoud

2008-06-26

Neutron transfer reactions were used to study the stability of the magic number N=28 near {sup 56}Ni. On one hand the one-neutron pickup (d,p) reaction was used for precision spectroscopy of single-particle levels in {sup 55}Fe. On the other hand we investigated the two-neutron transfer mechanism into {sup 56}Ni using the pickup reaction {sup 58}Ni((vector)p,t){sup 56}Ni. In addition the reliability of inverse kinematics reactions at low energy to study exotic nuclei was tested by the neutron transfer reactions t({sup 40}Ar,p){sup 42}Ar and d({sup 54}Fe,p){sup 55}Fe using tritium and deuterium targets, respectively, and by comparing the results with those of the normal kinematics reactions. The experimental data, differential cross-section and analyzing powers, are compared to DWBA and coupled channel calculations utilizing the code CHUCK3. By performing the single-neutron stripping reaction ((vector)d,p) on {sup 54}Fe the 1f{sub 7/2} shell in the ground state configuration was found to be partly broken. The instability of the 1f{sub 7/2} shell and the magic number N=28 was confirmed once by observing a number of levels with J{sup {pi}} = 7/2{sup -} at low excitation energies, which should not be populated if {sup 54}Fe has a closed 1f{sub 7/2} shell, and also by comparing our high precision experimental data with a large scale shell model calculation using the ANTOINE code [5]. Calculations including a partly broken 1f{sub 7/2} shell show better agreement with the experiment. The instability of the 1f{sub 7/2} shell was confirmed also by performing the two-neutron pick-up reaction ((vector)p,t) on {sup 58}Ni to study {sup 56}Ni, where a considerable improvement in the DWBA calculation was observed after considering 1f{sub 7/2} as a broken shell. To prove the reliability of inverse kinematics transfer reactions at low energies ({proportional_to} 2 AMeV), the aforementioned single-neutron transfer reaction (d,p) was repeated using a beam of {sup 54}Fe ions and a

Nuclear structure effects in multi-nucleon transfer and sequential fission reactions

International Nuclear Information System (INIS)

Biswas, D.C.

2001-01-01

The role of the nuclear structure in multi-nucleon transfer and sequential fission reactions has been discussed. The recent results on multi-nucleon transfer and transfer induced fission reaction, have brought out many interesting features in understanding the reaction mechanism and collective dynamics of heavy ion reactions. The structure of the projectile nucleus has strong influence on the transfer of multi-nucleons and/or clusters from the projectile to the target. The mechanism of multi-nucleon transfer between two heavy nuclei is a complex process which has a strong dependence on the ground state Q-value of the reaction as well as on the number of transferred nucleons

Coherent and semi-coherent neutron transfer reactions

International Nuclear Information System (INIS)

Hagelstein, P.L.

1992-01-01

Neutron transfer reactions are proposed to account for anomalies reported in Pons-Fleischmann experiments. The prototypical reaction involves the transfer of a neutron (mediated by low frequency electric or magnetic fields) from a donor nucleus to virtual continuum states, followed by the capture of the virtual neutron by an acceptor nucleus. In this work we summarize basic principles, recent results and the ultimate goals of the theoretical effort

Coherent and semi-coherent neutron transfer reactions

International Nuclear Information System (INIS)

Hagelstein, P.L.

1993-01-01

Neutron transfer reactions are proposed to account for anomalies reported in Pons-Fleischmann experiments. The prototypical reaction involves the transfer of a neutron (mediated by low frequency electric or magnetic fields) from a donor nucleus to virtual continuum states, followed by the capture of the virtual neutron by an acceptor nucleus. In this work we summarize basic principles, recent results and the ultimate goals of the theoretical effort. (author)

On the theory of direct reactions with many particle final states

International Nuclear Information System (INIS)

Trautmann, D.; Baur, G.

1977-01-01

We study the theory of direct reactions with many particle final states. First, we concentrate on the DWBA formulation of the break-up of deuterons on heavy nuclei below the Coulomb barrier. Because there are no free parameters, this permits a clean test of the theory by comparing it to the experimental data. The agreement is very good. The theory is applied to the break-up of antideuteronic atoms. Then the effect of virtual deuteron break-up on Rutherford scattering is studied. It is small, but it seems to be measurable. Also the deuteron break-up above the Coulomb barrier can be well explained theoretically. In this context, small effects are studied briefly. A semiclassical theory of the break-up process is given, which results in an intuitive picture and a fast computational method. Our theory lends itself in a natural way to the study of stripping reactions to unbound states. The relation of stripping into the continuum to elastic scattering of the transferred particle on the same target nucleus is explained. Then the connection of stripping to bound and unbound states is established. Finally various examples of stripping of uncharged and charged particles into the continuum are given to illustrate the theory. Resonance wave functions describing the transferred particle are discussed. In a conclusion an outlook for possible future developments of experiment and theory is given. (author)

Tem holder for sample transfer under reaction conditions

DEFF Research Database (Denmark)

Damsgaard, Christian Danvad; Zandbergen, Henny W.; Wagner, Jakob Birkedal

Environmental transmission electron microscopy (ETEM) studies are usually performed using conventional sample holders in a dedicated ETEM [1] or in a traditional TEM by use of a dedicated high-pressure cell sample holder [2]. In both cases, the setup defines the conditions regarding gas, pressure......]. Furthermore, dedicated transfer holders have been used to transfer catalyst samples between reactor set-ups and TEM at room temperature in inert atmosphere [5]. To take the full advantage of complementary in situ techniques, transfer under reactions conditions is essential. This study introduces the in situ...... transfer concept by use of a dedicated TEM transfer holder capable of enclosing the sample in a gaseous environment at temperatures up to approx. 900C. By oxidation and reduction experiments of Cu nanoparticles it is shown possible to keep the reaction conditions during transfer outside the microscope...

Scattering and transfer reactions with heavy ions

International Nuclear Information System (INIS)

Hussein, M.S.

From the elastic scattering analysis the input parameters are found for the inelastic scattering analysis and the transfer reactions of the heavy ion reactions. The main theme reported is the likeness and conection among these processes. (L.C.) [pt

Charge transfer reactions in Xe plasma expansion

International Nuclear Information System (INIS)

Jiao, C. Q.; Garscadden, A.; Ganguly, B. N.

2007-01-01

Charge transfer reactions of fast Xe ions with hydrocarbons including methane (CH 4 ), ethene (C 2 H 4 ), and propane (C 3 H 8 ) are studied by adding these hydrocarbon gases into a cross flowing Xe plasma expansion. Branching ratios and relative reaction rates for the charge transfers of fast Xe + with each of the three hydrocarbon gases are measured under different rf powers of the inductively coupled Xe discharge. For CH 4 /Xe system, we find that fast Xe + reacts readily with CH 4 generating CH 4 + and CH 3 + in a ratio of 1:0.56, with an estimated rate coefficient of (2.3±0.3)x10 -10 cm 3 /s at 75 W rf power which slowly increases to (2.9±0.3)x10 -10 cm 3 /s at 250 W (error bars reflect only the uncertainties due to the unknown extent of the ion recombination that follows the charge transfer reaction). These observed charge transfer reactions are made possible by the kinetically excited Xe ions produced by free expansion of the plasma. For the C 2 H 4 /Xe system product ions C 2 H 4 + and C 2 H 2 + are observed, and for C 3 H 8 /Xe, C 2 H 4 + and C 2 H 5 + and minor product ions including C 2 H 2 + and C 3 H 7 + are observed

Final Report: The Impact of Carbonate on Surface Protonation, Electron Transfer and Crystallization Reactions in Iron Oxide Nanoparticles and Colloids

Energy Technology Data Exchange (ETDEWEB)

Dixon, David Adams [The University of Alabama

2013-07-02

This project addresses key issues of importance in the geochemical behavior of iron oxides and in the geochemical cycling of carbon and iron. For Fe, we are specifically studying the influence of carbonate on electron transfer reactions, solid phase transformations, and the binding of carbonate to reactive sites on the edges of particles. The emphasis on carbonate arises because it is widely present in the natural environment, is known to bind strongly to oxide surfaces, is reactive on the time scales of interest, and has a speciation driven by acid-base reactions. The geochemical behavior of carbonate strongly influences global climate change and CO{sub 2} sequestration technologies. Our goal is to answer key questions with regards to specific site binding, electron transfer reactions, and crystallization reactions of iron oxides that impact both the geochemical cycling of iron and CO{sub 2} species. Our work is focused on the molecular level description of carbonate chemistry in solution including the prediction of isotope fractionation factors. We have also done work on critical atmospheric species.

Mass transfer with complex reversible chemical reactions. II: Parallel reversible chemical reactions

NARCIS (Netherlands)

Versteeg, Geert; van Beckum, F.P.H.; Kuipers, J.A.M.; van Swaaij, Willibrordus Petrus Maria

1990-01-01

An absorption model has been developed which can be used to calculate rapidly absorption rates for the phenomenon mass transfer accompanied by multiple complex parallel reversible chemical reactions. This model can be applied for the calculation of the mass transfer rates, enhancement factors and

Mass transfer with complex reversible chemical reactions. II: parallel reversible chemical reactions

NARCIS (Netherlands)

Versteeg, G.F.; Kuipers, J.A.M.; Beckum, van F.P.H.; van Swaaij, W.P.M.

1990-01-01

An absorption model has been developed which can be used to calculate rapidly absorption rates for the phenomenon mass transfer accompanied by multiple complex parallel reversible chemical reactions. This model can be applied for the calculation of the mass transfer rates, enhancement factors and

Hydrogen-transfer and charge transfer in photochemical and high energy radiation induced reactions: effects of thiols. Final report, February 1, 1960-january 31, 1979

International Nuclear Information System (INIS)

Cohen, S.G.

1980-03-01

Absorption of ultraviolet or visible light, or high energy radiation, may lead to highly reactive free radicals. Thiols affect the reactions of these radicals in the following ways: (1) transfer of hydrogen from sulfur of the thiol to a substrate radical, converting the radical to a stable molecule, and the thiol to a reactive thiyl radical; and (2) transfer of hydrogen from a substrate radical or molecule to thiyl, regenerating thiol. The thiol is thus used repeatedly and a single molecule may affect the consequences of many quanta. Three effects may ensue, depending upon the system irradiated: (1) the substrate radicals may be converted by thiol-thiyl to the original molecules, and protection against radiation damage is afforded. (2) The radicals may be converted to molecules not identical with the starting materials, and in both cases damage caused by radical combination processes is prevented. (3) Product yields may be increased where the initial radicals might otherwise regenerate starting materials. It was shown that rates of reaction of excited species can be correlated with triplet energies and reduction potentials, and with ionization potentials, that amines are very reactive toward excited carbonyl compounds of all types, and that yields of products from these reactions can be increased by thiols, leading to increased efficiency in utilization of light

Computational Approach to Electron Charge Transfer Reactions

DEFF Research Database (Denmark)

Jónsson, Elvar Örn

-molecular mechanics scheme, and tools to analyse statistical data and generate relative free energies and free energy surfaces. The methodology is applied to several charge transfer species and reactions in chemical environments - chemical in the sense that solvent, counter ions and substrate surfaces are taken...... in to account - which directly influence the reactants and resulting reaction through both physical and chemical interactions. All methods are though general and can be applied to different types of chemistry. First, the basis of the various theoretical tools is presented and applied to several test systems...... and asymmetric charge transfer reactions between several first-row transition metals in water. The results are compared to experiments and rationalised with classical analytic expressions. Shortcomings of the methods are accounted for with clear steps towards improved accuracy. Later the analysis is extended...

Saponification reaction system: a detailed mass transfer coefficient determination.

Science.gov (United States)

Pečar, Darja; Goršek, Andreja

2015-01-01

The saponification of an aromatic ester with an aqueous sodium hydroxide was studied within a heterogeneous reaction medium in order to determine the overall kinetics of the selected system. The extended thermo-kinetic model was developed compared to the previously used simple one. The reaction rate within a heterogeneous liquid-liquid system incorporates a chemical kinetics term as well as mass transfer between both phases. Chemical rate constant was obtained from experiments within a homogeneous medium, whilst the mass-transfer coefficient was determined separately. The measured thermal profiles were then the bases for determining the overall reaction-rate. This study presents the development of an extended kinetic model for considering mass transfer regarding the saponification of ethyl benzoate with sodium hydroxide within a heterogeneous reaction medium. The time-dependences are presented for the mass transfer coefficient and the interfacial areas at different heterogeneous stages and temperatures. The results indicated an important role of reliable kinetic model, as significant difference in k(L)a product was obtained with extended and simple approach.

Polarization transfer in (d-vector,n-vector) reactions

International Nuclear Information System (INIS)

Walter, R.L.; Tornow, W.

1986-01-01

The status of the measurements and the role of polarization transfer coefficients for (d/sup →/,n/sup →/) reactions is reviewed. Emphasis is given to reactions, involving light-nuclei systems. The importance of (d/sup →/,n/sup →/) reactions as sources of polarized neutrons is pointed out

Electron transfer reactions involving porphyrins and chlorophyll a

International Nuclear Information System (INIS)

Neta, P.; Scherz, A.; Levanon, H.

1979-01-01

Electron transfer reactions involving porphyrins (P) and quinones (Q) have been studied by pulse radiolysis. The porphyrins used were tetraphenylporphyrin (H 2 TPP), its tetracarboxy derivative (H 2 TCPP), the sodium and zinc compounds (Na 2 TPP and ZnTPP), and chlorophyll a (Chl a). These compounds were found to be rapidly reduced by electron transfer from (CH 3 ) 2 CO - . Reduction by (CH 3 ) 2 COH was rapid in aqueous solutions but relatively slow in i-PrOH solutions. Transient spectra of the anion radicals were determined and, in the case of H 2 TCPP - ., a pK = 9.7 was derived for its protonation. Electron-transfer reactions from the anion radical of H 2 TCPP to benzoquinone, duroquinone, 9,10-anthraquinone 2-sulfonate, and methylviologen occur in aqueous solutions with rate constants approx. 10 7 -10 9 M -1 s -1 which depend on the pH and the quinone reduction potential. Reactions of Na 2 TPP - ., ZnTPP - ., and Chl a - . with anthraquinone in basic i-PrOH solutions occur with rate constants approx. 10 9 M -1 s -1 . The spectral changes associated with these electron-transfer reactions as observed over a period of approx. 1 ms indicated, in some cases, the formation of an intermediate complex [P...Q - .]. 8 figures, 2 tables

Final-state interactions and relativistic effects in the quasielastic (e,e') reaction

International Nuclear Information System (INIS)

Chinn, C.R.; Physics Division, Los Alamos National Laboratory, Los Alamos, New Mexico 87545); Picklesimer, A.; Van Orden, J.W.

1989-01-01

The longitudinal and transverse response functions for the inclusive quasielastic (e,e') reaction are analyzed in detail. A microscopic theoretical framework for the many-body reaction provides a clear conceptual (nonrelativistic) basis for treating final-state interactions and goes far beyond simple plane-wave or Hermitean potential models. The many-body physics of inelastic final-state channels as described by optical and multiple scattering theories is properly included by incorporating a full complex optical potential. Explicit nonrelativistic and relativistic momentum-space calculations quantitatively demonstrate the importance of such a treatment of final-state interactions for both the transverse and longitudinal response. Nonrelativistic calculations are performed using final-state interactions based on phenomenology, local density models, and microscopic multiple scattering theory. Relativistic calculations span a similar range of models and employ Dirac bound-state wave functions. The theoretical extension to relativistic dynamics is of course not clear, but is done in obvious parallel to elastic proton scattering. Extensive calculations are performed for 40 Ca at momentum transfers of 410, 550, and 700 MeV/c. A number of interesting physical effects are observed, including significant relativistic suppressions (especially for R L ), large off-shell and virtual pair effects, enhancement of the tails of the response by the final-state interactions, and large qualitative and even shape distinctions between the predictions of the various models of the final-state interactions. None of the models is found to be able to simultaneously predict the data for both response functions. This strongly suggests that additional physical mechanisms are of qualitative importance in inclusive quasielastic electron scattering

Mass transfer model for two-layer TBP oxidation reactions

International Nuclear Information System (INIS)

Laurinat, J.E.

1994-01-01

To prove that two-layer, TBP-nitric acid mixtures can be safely stored in the canyon evaporators, it must be demonstrated that a runaway reaction between TBP and nitric acid will not occur. Previous bench-scale experiments showed that, at typical evaporator temperatures, this reaction is endothermic and therefore cannot run away, due to the loss of heat from evaporation of water in the organic layer. However, the reaction would be exothermic and could run away if the small amount of water in the organic layer evaporates before the nitric acid in this layer is consumed by the reaction. Provided that there is enough water in the aqueous layer, this would occur if the organic layer is sufficiently thick so that the rate of loss of water by evaporation exceeds the rate of replenishment due to mixing with the aqueous layer. This report presents measurements of mass transfer rates for the mixing of water and butanol in two-layer, TBP-aqueous mixtures, where the top layer is primarily TBP and the bottom layer is comprised of water or aqueous salt solution. Mass transfer coefficients are derived for use in the modeling of two-layer TBP-nitric acid oxidation experiments. Three cases were investigated: (1) transfer of water into the TBP layer with sparging of both the aqueous and TBP layers, (2) transfer of water into the TBP layer with sparging of just the TBP layer, and (3) transfer of butanol into the aqueous layer with sparging of both layers. The TBP layer was comprised of 99% pure TBP (spiked with butanol for the butanol transfer experiments), and the aqueous layer was comprised of either water or an aluminum nitrate solution. The liquid layers were air sparged to simulate the mixing due to the evolution of gases generated by oxidation reactions. A plastic tube and a glass frit sparger were used to provide different size bubbles. Rates of mass transfer were measured using infrared spectrophotometers provided by SRTC/Analytical Development

Reaction kinetics in open reactors and serial transfers between closed reactors

Science.gov (United States)

Blokhuis, Alex; Lacoste, David; Gaspard, Pierre

2018-04-01

Kinetic theory and thermodynamics of reaction networks are extended to the out-of-equilibrium dynamics of continuous-flow stirred tank reactors (CSTR) and serial transfers. On the basis of their stoichiometry matrix, the conservation laws and the cycles of the network are determined for both dynamics. It is shown that the CSTR and serial transfer dynamics are equivalent in the limit where the time interval between the transfers tends to zero proportionally to the ratio of the fractions of fresh to transferred solutions. These results are illustrated with a finite cross-catalytic reaction network and an infinite reaction network describing mass exchange between polymers. Serial transfer dynamics is typically used in molecular evolution experiments in the context of research on the origins of life. The present study is shedding a new light on the role played by serial transfer parameters in these experiments.

Single-particle and collective states in transfer reactions

International Nuclear Information System (INIS)

Lhenry, I.; Suomijaervi, T.; Giai, N. van

1993-01-01

The possibility to excite collective states in transfer reactions induced by heavy ions is studied. Collective states are described within the Random Phase Approximation (RPA) and the collectivity is defined according to the number of configurations contributing to a given state. The particle transfer is described within the Distorted Wave Born Approximation (DWBA). Calculations are performed for two different stripping reactions: 207 Pb( 20 Ne, 19 Ne) 208 Pb and 59 Co( 20 Ne, 19 F) 60 Ni at 48 MeV/nucleon for which experimental data are available. The calculation shows that a sizeable fraction of collective strength can be excited in these reactions. The comparison with experiment shows that this parameter-free calculation qualitatively explains the data. (author) 19 refs.; 10 figs

Multi-nucleon transfer: a probe to investigate the reaction mechanism around the barrier

International Nuclear Information System (INIS)

Mandal, Samit K.

2014-01-01

The investigation of multi-nucleon transfer mechanism offers valuable information on the pairing interactions that enhance the transfer of nucleon pairs across heavy ions involved in the reaction. These reactions are also a useful tool to study exotic nuclei far from the stability line, which can be explored with the new generation radioactive beam facility. In this talk, multi-nucleon transfer reaction mechanisms between heavy ions and their effect on the reaction dynamics around the coulomb barrier energies have been discussed. Experimental results will be presented with a semi classical description of multi nucleon transfer reaction calculation. One and two nucleon transfer cross sections reproduced using a quantum mechanical coupled channel calculations will also be discussed. A feasibility of investigation of multi-nucleon transfer mechanism to explore the pairing correlation at moderate spin states with radioactive beams will be discussed. (author)

Carbene Transfer Reactions Catalysed by Dyes of the Metalloporphyrin Group

Directory of Open Access Journals (Sweden)

Mário M. Q. Simões

2018-03-01

Full Text Available Carbene transfer reactions are very important transformations in organic synthesis, allowing the generation of structurally challenging products by catalysed cyclopropanation, cyclopropenation, carbene C-H, N-H, O-H, S-H, and Si-H insertion, and olefination of carbonyl compounds. In particular, chiral and achiral metalloporphyrins have been successfully explored as biomimetic catalysts for these carbene transfer reactions under both homogeneous and heterogeneous conditions. In this work the use of synthetic metalloporphyrins (MPorph, M = Fe, Ru, Os, Co, Rh, Ir, Sn as homogeneous or heterogeneous catalysts for carbene transfer reactions in the last years is reviewed, almost exclusively focused on the literature since the year 2010, except when reference to older publications was deemed to be crucial.

Conformational dependence of a protein kinase phosphate transfer reaction

Science.gov (United States)

Labute, Montiago; Henkelman, Graeme; Tung, Chang-Shung; Fenimore, Paul; McMahon, Ben

2007-03-01

Atomic motions and energetics for a phosphate transfer reaction catalyzed by the cAMP-dependent protein kinase have been calculated using plane-wave density functional theory, starting from structures of proteins crystallized in both the reactant conformation (RC) and the transition-state conformation (TC). In TC, we calculate that the reactants and products are nearly isoenergetic with a 20-kJ/mol barrier, whereas phosphate transfer is unfavorable by 120 kJ/mol in the RC, with an even higher barrier. Our results demonstrate that the phosphate transfer reaction occurs rapidly and reversibly in a particular conformation of the protein, and that the reaction can be gated by changes of a few tenths of an angstrom in the catalytic site [1]. [1] G.H. Henkelman, M.X. LaBute, C.-S. Tung, P.W. Fenimore, B.H. McMahon, Proc. Natl. Acad. Sci. USA vol. 102, no. 43:15347-15351 (2005).

Transfer reactions with very heavy ions. Quarterly report 3. quarter 1987

International Nuclear Information System (INIS)

Juutinen, Sakari.

1988-03-01

This thesis deals with the reaction mechanism of the few-nucleon transfer reactions between the 58 Ni projectiles and the Dy targets. A series of transfer experiments utilizing the particle-γ coincidence technique was performed. Particle detection was used to give the scattering angles of two reaction products and the reaction channel was selected by the discrete γ-rays in the Ge detectors. Total γ-ray energy and multiplicity distributions were measured by the Spin Spectrometer. Total γ-ray energy and multiplicity distributions, γ-ray spectra obtained by the Ge and NaI detectors and angular distributions of the projectile-like ions are discussed. For one- and two-neutron transfer the experimental results provide direct evidence of a cold mechanism populating high-spin states near the yrast line. A schematic model for the transfer mechanism is proposed. This model accounts for the prominent features of one- and two-neutron pickup

Two-proton transfer reactions on even Ni and Zn isotopes

International Nuclear Information System (INIS)

Boucenna, A.; Kraus, L.; Linck, I.; Tsan Ung Chan

1988-01-01

Two-proton transfer reactions induced by 112 MeV 12 C ions on even Ni and Zn isotopes are found to be less selective than the analogous two-neutron transfer reactions induced on the same targets in a similar incident energy range. The additional collective aspects observed in the proton transfer are examined in view of a semiphenomenological model of two quasi-particles coupled to a triaxial asymmetric rotor. Tentative spin and parity assignments emerge from this comparison, from crude shell model calculations and from systematic trends

Polarization transfer in (p,n) reactions at 495 MeV

International Nuclear Information System (INIS)

Taddeucci, T.N.

1991-01-01

Polarization transfer observables have been measured with the NTOF facility at LAMPF for (p,n) reactions at 495 MeV. Measurements of the longitudinal polarization transfer parameter D LL for transitions to discrete states at 0 degrees show convincing evidence for tensor interaction effects. Complete sets of polarization transfer observables have been measured for quasifree (p,n) reactions on 2 H, 12 C, 40 Ca at a scattering angle of 18 degrees. These measurements show no evidence for an enhancement in the isovector spin longitudinal response. 19 refs., 10 figs

New Oxime Ligand with Potential for Proton-Coupled Electron-Transfer Reactions

DEFF Research Database (Denmark)

Deville, Claire; Sundberg, Jonas; McKenzie, Christine Joy

Proton-coupled electron-transfer (PCET) is found in a range of oxidation-reduction reactions in biology.1 This mechanism is of interest for applications in energy conversion processes. The PCET reaction has been shown to be facilitated when the proton is transferred to an intramolecular basic sit...

Observation of the one- to six-neutron transfer reactions at sub-barrier energies

Energy Technology Data Exchange (ETDEWEB)

Jiang, C.L.; Rehm, K.E.; Gehring, J. [and others

1995-08-01

It was suggested many years ago that when two heavy nuclei are in contact during a grazing collision, the transfer of several correlated neutron-pairs could occur. Despite considerable experimental effort, however, so far only cross sections for up to four-neutron transfers have been uniquely identified. The main difficulties in the study of multi-neutron transfer reactions are the small cross sections encountered at incident energies close to the barrier, and various experimental uncertainties which can complicate the analysis of these reactions. We have for the first time found evidence for multi-neutron transfer reactions covering the full sequence from one- to six-neutron transfer reactions at sub-barrier energies in the system {sup 58}Ni + {sup 100}Mo.

One-neutron transfer reaction: a toy model in one dimension

International Nuclear Information System (INIS)

G. Galilei, Padova, Italy INFN, Sezione di Padova, Padova (Italy))" data-affiliation=" (Dipartimento di Fisica e Astronomia G. Galilei, Padova, Italy INFN, Sezione di Padova, Padova (Italy))" >Moschini, L

2014-01-01

A simple 1D toy model to study one-neutron transfer reactions is developed. It is based on the solution of the time dependent Schroedinger equation for a particle initially bound by a fixed potential well, perturbed by a second moving potential, which accounts for the second partner of the reaction. At the end of the time evolution it is possible to evaluate the probability of the transfer of the particle from a potential to the other, as well as the transfer to continuum states in the case of weakly-bound systems. Although rather simple, the model accounts for most of the physical characteristics of these kind of reactions: such as the existence of an optimum Q-value and the dependence on the parameters defining the relative motion of the two potentials

Mass transfer with chemical reaction in multiphase systems

International Nuclear Information System (INIS)

Alper, E.

1983-01-01

These volumes deal with the phenomenon of 'mass transfer with chemical reaction' which is of industrial, biological and physiological importance. In process engineering, it is encountered both in separation processes and in reaction engineering and both aspects are covered here in four sections: introduction; gas-liquid system; liquid-liquid system; and gas-liquid-solid system

Dinuclear Tetrapyrazolyl Palladium Complexes Exhibiting Facile Tandem Transfer Hydrogenation/Suzuki Coupling Reaction of Fluoroarylketone

KAUST Repository

Dehury, Niranjan

2016-07-18

Herein, we report an unprecedented example of dinuclear pyrazolyl-based Pd complexes exhibiting facile tandem catalysis for fluoroarylketone: Tetrapyrazolyl di-palladium complexes with varying Pd-Pd distances efficiently catalyze the tandem reaction involving transfer hydrogenation of fluoroarylketone to the corresponding alcohol and Suzuki-Miyaura cross coupling reaction of the resulting fluoroarylalcohol under moderate reaction conditions, to biaryl alcohol. The complex with the shortest Pd-Pd distance exhibits the highest tandem activity among its di-metallic analogues, and exceeds in terms of activity and selectivity the analogous mononuclear compound. The kinetics of the reaction indicates clearly that reductive transformation of haloarylketone into haloaryalcohol is the rate determining step in the tandem reaction. Interestingly while fluoroarylketone undergoes the multistep tandem catalysis, the chloro- and bromo-arylketones undergo only a single step C-C coupling reaction resulting in biarylketone as the final product. Unlike the pyrazole based Pd compounds, the precursor PdCl2 and the phosphine based relevant complexes (PPh3)2PdCl2 and (PPh3)4Pd are found to be unable to exhibit the tandem catalysis.

Hydrogen transfer reactions of interstellar Complex Organic Molecules

Science.gov (United States)

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

2018-06-01

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

Investigation of transition metal-catalyzed nitrene transfer reactions in water.

Science.gov (United States)

Alderson, Juliet M; Corbin, Joshua R; Schomaker, Jennifer M

2018-04-11

Transition metal-catalyzed nitrene transfer is a powerful method for incorporating new CN bonds into relatively unfunctionalized scaffolds. In this communication, we report the first examples of site- and chemoselective CH bond amination reactions in aqueous media. The unexpected ability to employ water as the solvent in these reactions is advantageous in that it eliminates toxic solvent use and enables reactions to be run at increased concentrations with lower oxidant loadings. Using water as the reaction medium has potential to expand the scope of nitrene transfer to encompass a variety of biomolecules and highly polar substrates, as well as enable pH control over the site-selectivity of CH bond amination. Copyright © 2018 Elsevier Ltd. All rights reserved.

Selective population of high-j states via heavy-ion-induced transfer reactions

International Nuclear Information System (INIS)

Bond, P.D.

1982-01-01

One of the early hopes of heavy-ion-induced transfer reactions was to populate states not seen easily or at all by other means. To date, however, I believe it is fair to say that spectroscopic studies of previously unknown states have had, at best, limited success. Despite the early demonstration of selectivity with cluster transfer to high-lying states in light nuclei, the study of heavy-ion-induced transfer reactions has emphasized the reaction mechanism. The value of using two of these reactions for spectroscopy of high spin states is demonstrated: 143 Nd( 16 O, 15 O) 144 Nd and 170 Er( 16 O, 15 Oγ) 171 Er

Regge parametrization of angular distributions for heavy-ion transfer reactions

International Nuclear Information System (INIS)

Carlson, B.V.; McVoy, K.W.

1977-01-01

A two-pole one-zero Regge parametrization of the l-window for transfer reactions is employed in conjunction with a chi-squared search program to obtain high-quality fits to a wide variety of transfer data. The data employed include both direct and multi-step transfers. (Auth.)

Isotope effects for base-promoted, gas-phase proton transfer reactions

International Nuclear Information System (INIS)

Grabowski, J.J.; Cheng, Xueheng

1991-01-01

Proton transfer reactions are among the most basic, the most common and the most important of chemical transformations; despite their apparent simplicity, much is unknown about this most fundamental of all chemical processes. Active interest in understanding the underlying principles of organic proton transfer reactions continues because of efforts being made to develop the theory of elementary chemical processes, because of the resurgence of interest in mechanistic organic chemistry and because of the resurgence of interest in mechanistic organic chemistry processes, because of the resurgence of interest in mechanistic organic chemistry and because of the dynamic role played by proton transfers in biochemical transformations. As organic chemists, the authors have used the flowing afterglow technique to gain an appreciation of the fundamental issues involved in reaction mechanisms by examining such processes in a solvent-free environment under thermally-equilibrated (300 K) conditions. Recent characterization of the facile production of both acetate and the monoenolate anion from the interaction of hydroxide or fluoride with acetic acid reinforces the idea that much yet must be learned about proton transfers/proton abstractions in general. Earlier work by Riveros and co-workers on competitive H vs D abstraction from α-d 1 -toluenes and by Noest and Nibbering on competitive H vs D abstraction from α,α,α-d 3 -acetone, in combination with the acetic acid results, challenged the author's to assemble a comprehensive picture of the competitive nature of proton transfer reactions for anionic base-promoted processes

The (3He,α) reaction mechanism. A study of the angular momentum transfer

International Nuclear Information System (INIS)

Guttormsen, M.; Bergholt, L.; Ingebretsen, F.; Loevhoeiden, G.; Messelt, S.; Rekstad, J.; Tveter, T.S.; Helstrup, H.; Thorsteinsen, T.F.

1994-01-01

The γ-rays emitted after the 163 Dy( 3 He,αxn) reactions at E( 3 He) = 45 MeV have been measured. The transferred angular momentum in the reaction is deduced from the side-feeding γ-intensities of the ground bands in the residual 162-x Dy isotopes. With decreasing α-energy the average spin transfer increases from similar 5h to similar 11h. The ( 3 He,α) reaction at these energies is dominated by direct processes. Even at the highest spin transfer the contribution from the compound reaction channel is negligible. ((orig.))

Effect of electrostatic interactions on electron-transfer reactions

International Nuclear Information System (INIS)

Hickel, B.

1987-01-01

Fast reactions of electron transfer are studied by pulsed radiolysis. By this technique radicals and ionic radicals with high redox potentials are created homogeneously in the solution in about 10 -8 second. For solvated electron effect of electrostatic interaction on kinetics of reactions limited by diffusion is obtained with a good approximation by the Debye equation when ion mobility is known. Deviation from the theory occurs in ion pair formation, which is evidenced experimentally in reactions between anions when cations are complexed by a cryptate. Slow reactions k 8 M -1 s -1 are more sensitive to electrostatic interactions than reactions limited by diffusion. When there is no ion pair formation the velocity constant depends upon dielectric constant of the solvent and reaction distance. 17 refs

Parallel proton transfer pathways in aqueous acid-base reactions

NARCIS (Netherlands)

Cox, M.J.; Bakker, H.J.

2008-01-01

We study the mechanism of proton transfer (PT) between the photoacid 8-hydroxy-1,3, 6-pyrenetrisulfonic acid (HPTS) and the base chloroacetate in aqueous solution. We investigate both proton and deuteron transfer reactions in solutions with base concentrations ranging from 0.25M to 4M. Using

Study of charge transfer reactions in a microbial fuel cell

Energy Technology Data Exchange (ETDEWEB)

Martin, E.; Savadogo, O. [Ecole Polytechnique, Montreal, PQ (Canada). Dept. de Genie Chimique; National Research Council of Canada, Montreal, PQ (Canada). Biotechnology Research Inst.; Tartakovsky, B. [National Research Council of Canada, Montreal, PQ (Canada). Biotechnology Research Inst.

2008-07-01

Electron transfer reactions in a microbial fuel cell (MFC) were evaluated. The MFC was inoculated with anaerobic mesophilic sludge and operated with carbon felt, carbon cloth, and platinum (Pt) coated carbon cloth. The MFC was then fed with either acetate or glucose as a source of fuel and operated at a temperature of 25 degrees C and a pH of 7. Scanning electron microscopy (SEM) micrographs demonstrated that the micro-organisms colonized the anodes. Cyclic voltammetry and polarization tests were conducted using different fractions of the anodophilic biofilm in order to determine charge transfer routes. The study characterized the electron transfer mechanisms used by the exoelectrogenic micro-organisms to produce electricity. It was concluded that further research is needed to characterize reaction transfer routes. 2 refs., 1 fig.

An abnormally slow proton transfer reaction in a simple HBO derivative due to ultrafast intramolecular-charge transfer events.

Science.gov (United States)

Alarcos, Noemí; Gutierrez, Mario; Liras, Marta; Sánchez, Félix; Douhal, Abderrazzak

2015-07-07

We report on the steady-state, picosecond and femtosecond time-resolved studies of a charge and proton transfer dye 6-amino-2-(2'-hydroxyphenyl)benzoxazole (6A-HBO) and its methylated derivative 6-amino-2-(2'-methoxyphenyl)benzoxazole (6A-MBO), in different solvents. With femtosecond resolution and comparison with the photobehaviour of 6A-MBO, we demonstrate for 6A-HBO in solution, the photoproduction of an intramolecular charge-transfer (ICT) process at S1 taking place in ∼140 fs or shorter, followed by solvent relaxation in the charge transferred species. The generated structure (syn-enol charge transfer conformer) experiences an excited-state intramolecular proton-transfer (ESIPT) reaction to produce a keto-type tautomer. This subsequent proton motion occurs in 1.2 ps (n-heptane), 14 ps (DCM) and 35 ps (MeOH). In MeOH, it is assisted by the solvent molecules and occurs through tunneling for which we got a large kinetic isotope effect (KIE) of about 13. For the 6A-DBO (deuterated sample in CD3OD) the global proton-transfer reaction takes place in 200 ps, showing a remarkable slow KIE regime. The slow ESIPT reaction in DCM (14 ps), not through tunnelling as it is not sensitive to OH/OD exchange, has however to overcome an energy barrier using intramolecular as well as solvent coordinates. The rich ESIPT dynamics of 6A-HBO in the used solutions is governed by an ICT reaction, triggered by the amino group, and it is solvent dependent. Thus, the charge injection to a 6A-HBO molecular frame makes the ICT species more stable, and the phenol group less acidic, slowing down the subsequent ESIPT reaction. Our findings bring new insights into the coupling between ICT and ESIPT reactions on the potential-energy surfaces of several barriers.

Theory of nuclear heavy-ion direct transfer reactions

International Nuclear Information System (INIS)

Crowley, B.J.B.

1979-01-01

We review the distorted-wave approach to direct transfer reactions and draw attention to some of the shortcomings of current theories. We show that a reformulated form of the distorted-wave Born approximation (DWBA) for transfer can lead to important simplifications of the theory, which are valid for nuclear heavy-ion induced reactions at energies > or approx. =MeV/nucleon. In particular, in the semiclassical limit, it leads to a new and simple formula for the transfer t-matrix which includes all the essential physics while offering several important advantages over standard ''full-recoil finite-range'' DWBA. One such advantage is that the new formula is more transparent in that it is amendable to interpretation and analytical manipulation. At high-energy it is shown to reduce to one earlier deduced using eikonal-DWBA. The conditions for the validity of the new theory are discussed in detail. They are shown to be generally well satisfied for small-mass transfer between heavy-ions at energies at or above those particularly favour transfer (> or approx. =10 MeV/nucleon for transfer of valence nucleons). The restriction to small mass is not due to any recoil approximation; in fact, it is only a necessary restriction at certain energies. The theory treats recoil exactly. Consideration of the optimum dynamical conditions for transfer leads to a set of matching conditions. The presence of hitherto neglected absorption, arising from dynamical effects of poor matching, it suggested and qualitatively discussed. Condition under which such absorption may be neglected are derived. Results of numerical calculations are presented showing that the theory is capable of good agreement with standard full-recoil finite-range DWBA, and that it is capable of giving at least as good an account of experimental data for nucleon-transfer between heavy-ions at energies approx.10 MeV/nucleon

Nuclear transfer in peripheral heavy ion reactions

International Nuclear Information System (INIS)

Werner, K.

1984-01-01

The aim of the whole thesis is to understand the experimental results of N. Frascaria et al. (1980), namely structures in the cross section as function of the excitation energy for the reaction 40 Ca + 40 Ca at 400 MeV incident energy. We present therefore in chapter 1 a simple model of two identical potentials with only two energy levels. On the base of statistically independent T-L excitations and by fitting a two parameters to the experiments it succeeds to reproduce sufficiently the experimental results. The next step is a microscopical treatment of these parameters for the understanding and the foundation of the fitted values. For this we develop in chapter 2 a theory of collective variables in the framework of TDHF which allows to perform in chapter 3 in a very transparent way microscopical calculations and especially to understand the transfer behaviour in peripheral heavy ion reactions. This transfer behaviour will also be the key for the understanding of the experimental structures. (orig.) [de

Synthesis and Reactions of Five-Membered Heterocycles Using Phase Transfer Catalyst (PTC Techniques

Directory of Open Access Journals (Sweden)

Ahmed M. El-Sayed

2014-01-01

Full Text Available Phase transfer catalysts (PTCs have been widely used for the synthesis of organic compounds particularly in both liquid-liquid and solid-liquid heterogeneous reaction mixtures. They are known to accelerate reaction rates by facilitating formation of interphase transfer of species and making reactions between reagents in two immiscible phases possible. Application of PTC instead of traditional technologies for industrial processes of organic synthesis provides substantial benefits for the environment. On the basis of numerous reports it is evident that phase-transfer catalysis is the most efficient way for generation and reactions of many active intermediates. In this review we report various uses of PTC in syntheses and reactions of five-membered heterocycles compounds and their multifused rings.

Mass transfer model for two-layer TBP oxidation reactions: Revision 1

International Nuclear Information System (INIS)

Laurinat, J.E.

1994-01-01

To prove that two-layer, TBP-nitric acid mixtures can be safely stored in the Canyon evaporators, it must be demonstrated that a runaway reaction between TBP and nitric acid will not occur. Previous bench-scale experiments showed that, at typical evaporator temperatures, this reaction is endothermic and therefore cannot run away, due to the loss of heat from evaporation of water in the organic layer. However, the reaction would be exothermic and could run away if the small amount of water in the organic layer evaporates before the nitric acid in this layer is consumed by the reaction. Provided that there is enough water in the aqueous layer, this would occur if the organic layer is sufficiently thick so that the rate of loss of water by evaporation exceeds the rate of replenishment due to mixing with the aqueous layer. Bubbles containing reaction products enhance the rate of transfer of water from the aqueous layer to the organic layer. These bubbles are generated by the oxidation of TBP and its reaction products in the organic layer and by the oxidation of butanol in the aqueous layer. Butanol is formed by the hydrolysis of TBP in the organic layer. For aqueous-layer bubbling to occur, butanol must transfer into the aqueous layer. Consequently, the rate of oxidation and bubble generation in the aqueous layer strongly depends on the rate of transfer of butanol from the organic to the aqueous layer. This report presents measurements of mass transfer rates for the mixing of water and butanol in two-layer, TBP-aqueous mixtures, where the top layer is primarily TBP and the bottom layer is comprised of water or aqueous salt solution. Mass transfer coefficients are derived for use in the modeling of two-layer TBP-nitric acid oxidation experiments

Sub-Coulomb heavy ion neutron transfer reactions and neutron orbit sizes

International Nuclear Information System (INIS)

Phillips, W.R.

1976-01-01

Direct transfer reactions below the Coulomb barrier offer the best means of determining neutron densities near the nuclear surface. This paper describes how heavy ion sub-Coulomb transfer can be used to determine the rms radii of neutron orbits in certain nuclei. The theoretical background is outlined and problems associated with the comparison of experiment and theory are discussed. Experiments performed to calibrate sub-Coulomb heavy ion transfer reactions are presented, and some comments are made on the relative roles of light and heavy ion reactions. Preliminary values for the rms radii of neutron orbits and neutron excesses extracted from recent experiments are given, and some remarks are made concerning the implications of these results for the triton wave function and for the Coulomb energy difference anomaly. (author)

Production of neutron-rich nuclides in the vicinity of N = 126 shell closure in multinucleon transfer reactions

Directory of Open Access Journals (Sweden)

Karpov Alexander

2017-01-01

Full Text Available Multinucleon transfer in low-energy nucleus-nucleus collisions is widely discussed as a method of production of yet-unknown neutron-rich nuclei hardly accessible (or inaccessible by other methods. Modeling of complicated dynamics of nuclear reactions induced by heavy ions is done within a multidimensional dynamical model of nucleus-nucleus collisions based on the Langevin equations. The model gives a continuous description of the system evolution starting from the well-separated target and projectile in the entrance channel of the reaction up to the formation of final reaction products. In this paper, rather recent sets of experimental data for the 136Xe+198Pt,208Pb reactions are analyzed together with the production cross sections for neutron-rich nuclei in the vicinity of the N = 126 magic shell.

Mass transfer in porous media with heterogeneous chemical reaction

Directory of Open Access Journals (Sweden)

Souza S.M.A.G.Ulson de

2003-01-01

Full Text Available In this paper, the modeling of the mass transfer process in packed-bed reactors is presented and takes into account dispersion in the main fluid phase, internal diffusion of the reactant in the pores of the catalyst, and surface reaction inside the catalyst. The method of volume averaging is applied to obtain the governing equation for use on a small scale. The local mass equilibrium is assumed for obtaining the one-equation model for use on a large scale. The closure problems are developed subject to the length-scale constraints and the model of a spatially periodic porous medium. The expressions for effective diffusivity, hydrodynamic dispersion, total dispersion and the Darcy's law permeability tensors are presented. Solution of the set of final equations permits the variations of velocity and concentration of the chemical species along the packed-bed reactors to be obtained.

Three-nucleon transfer reactions and cluster structure in the A = 15 to A = 19 nuclei

International Nuclear Information System (INIS)

Martz, L.M.

1978-01-01

The ( 6 Li,t) and ( 6 Li, 3 He) reactions were studied on targets of 12 C, 13 C, 14 N, 15 N, and 16 O at E/sub Li/ approx. = 44 MeV and theta/sub lab/ approx. = 15 0 . A preferential population of final states was exhibited in spectra for the A = 15 to A = 19 nuclei. The strong forward peaking of angular distributions in the 13 C( 6 Li,t) 16 O and 13 C( 6 Li, 3 He) 16 N reactions can be reproduced by DWBA calculations but not by the Hauser-Feshbach model. Such indications of a primarily direct mechanism at forward angles suggest use of these three-nucleon-transfer reactions to identify candidates for 3p-nh states. A comparison with other multinucleon transfer data, e.g., those from ( 7 Li,α) and ( 7 Li,t) reactions on 13 C and 15 N targets, further tests dominant particle-hole configurations. The relationship between ( 6 Li,t) and ( 6 Li, 3 He) spectra reveals analog states, notably T = 1, T/sub z/ = 0 levels at high excitation in 16 O. Nuclear theory is used to investigate the role of triton clustering in such structure. The 2N + L = 6 band predicted by a folded-potential model of 18 O = 15 N + t shows an underlying correspondence to the experimental levels in triton-transfer data. Triton spectroscopic factors calculated from the SU(3) shell model further suggest the broad influence of clustering phenomena in this mass region. Experimental evidence of systematic behavior in the triton binding energies of proposed p/sup -n/(sd) 3 configurations was found

The electrodisintegration of the deuteron reaction at high four-momentum transfer

Science.gov (United States)

Ibrahim, Hassan F.

This dissertation presents the highest four-momentum transfer, Q2, quasielastic (xBj = 1) results from Experiment E01-020 which systematically explored the 2H(e, e'p)n reaction ("Electro-disintegration" of the deuteron) at three different four-momentum transfers, Q 2 = 0.8, 2.1, and 3.5 GeV2 and missing momenta, pmiss = 0, 100, 200, 300, 400, and 500 GeV including separations of the longitudinal-transverse interference response function, RLT, and extraction of the longitudinal-transverse asymmetry, ALT. This systematic approach will help to understand the reaction mechanism and the deuteron structure down to the short range part of the nucleon-nucleon interaction which is one of the fundamental missions of nuclear physics. By studying the very short distance structure of the deuteron, one may also determine whether or to what extent the description of nuclei in terms of nucleon/meson degrees of freedom must be supplemented by inclusion of explicit quark effects. The unique combination of energy, current, duty factor, and control of systematics for Hall A at Jefferson Lab made Jefferson Lab the only facility in the world where these systematic studies of the deuteron can be undertaken. This is especially true when we want to understand the short range structure of the deuteron where high energies and high luminosity/duty factor are needed. All these features of Jefferson Lab allow us to examine large missing momenta (short range scales) at kinematics where the effects of final state interactions (FSI), meson exchange currents (MEC), and isobar currents (IC) are minimal, making the extraction of the deuteron structure less model-dependent. Jefferson Lab also provides the kinematical flexibility to perform the separation of RLT over a broad range of missing momenta and momentum transfers. Experiment E01-020 used the standard Hall A equipment in coincidence configuration in addition to the cryogenic target system. The low and middle Q2 kinematics were completed in June

Studies on electron transfer reactions of Keggin-type mixed ...

Indian Academy of Sciences (India)

Administrator

(PV2) in aqueous phosphate buffer of pH 6 at ambient temperature. Electrochemical and optical studies show that the stoichiometry of the reaction is 1: 2 (NADH : HPA). EPR and optical studies show that HPA act as one electron acceptor and the products of electron transfer reactions are one elec- tron reduced heteropoly ...

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

Energy Technology Data Exchange (ETDEWEB)

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

1995-02-10

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

Single proton transfer reactions on odd-even nuclei

International Nuclear Information System (INIS)

Blasi, N.

1984-01-01

This thesis is devoted to the study of one proton transfer reactions, performed with the use of the magnetic spectrograph QMG/2 of the KVI, in two regions of the mass table. Stripping and pickup reactions on the odd-A target nuclei 193 Ir and 197 Au are described in the first part. The experimental spectroscopic factors obtained are used to test several collective models that are based on coupling between bosons (phonons) and fermions. In the second part, the proton stripping reactions on 113 In and 115 In are studied. Shell model calculations are performed and applied to the experimental results. (Auth.)

Definition and determination of the triplet-triplet energy transfer reaction coordinate.

Science.gov (United States)

Zapata, Felipe; Marazzi, Marco; Castaño, Obis; Acuña, A Ulises; Frutos, Luis Manuel

2014-01-21

A definition of the triplet-triplet energy transfer reaction coordinate within the very weak electronic coupling limit is proposed, and a novel theoretical formalism is developed for its quantitative determination in terms of internal coordinates The present formalism permits (i) the separation of donor and acceptor contributions to the reaction coordinate, (ii) the identification of the intrinsic role of donor and acceptor in the triplet energy transfer process, and (iii) the quantification of the effect of every internal coordinate on the transfer process. This formalism is general and can be applied to classical as well as to nonvertical triplet energy transfer processes. The utility of the novel formalism is demonstrated here by its application to the paradigm of nonvertical triplet-triplet energy transfer involving cis-stilbene as acceptor molecule. In this way the effect of each internal molecular coordinate in promoting the transfer rate, from triplet donors in the low and high-energy limit, could be analyzed in detail.

Flat Graphene-Enhanced Electron Transfer Involved in Redox Reactions.

Science.gov (United States)

Pan, Meilan; Zhang, Yanyang; Shan, Chao; Zhang, Xiaolin; Gao, Guandao; Pan, Bingcai

2017-08-01

Graphene is easily warped in the out-of-plane direction because of its high in-plane Young's modulus, and exploring the influence of wrinkled graphene on its properties is essential for the design of graphene-based materials for environmental applications. Herein, we prepared wrinkled graphene (WGN-1 and WGN-2) by thermal treatment and compared their electrochemical properties with those of flat graphene nanosheets (FGN). FGN exhibit activities that are much better than those of wrinkled graphene nanosheets (WGN), not only in the electrochemical oxidation of methylene blue (MB) but also in the electrochemical reduction of nitrobenzene (NB). Transformation ratios of MB and NB in FGN, WGN-1, and WGN-2 were 97.5, 80.1, and 57.9% and 94.6, 92.1, and 81.2%, respectively. Electrochemical impedance spectroscopy and the surface resistance of the graphene samples increased in the following order: FGN reaction charges transfer faster across the reaction interfaces and along the surface of FGN than that of WGN, and wrinkles restrict reaction charge transfer and reduce the reaction rates. This study reveals that the morphology of the graphene (flat or wrinkle) greatly affects redox reaction activities and may have important implications for the design of novel graphene-based nanostructures and for our understanding of graphene wrinkle-dependent redox reactions in environmental processes.

Thermodynamic chemical energy transfer mechanisms of non-equilibrium, quasi-equilibrium, and equilibrium chemical reactions

International Nuclear Information System (INIS)

Roh, Heui-Seol

2015-01-01

Chemical energy transfer mechanisms at finite temperature are explored by a chemical energy transfer theory which is capable of investigating various chemical mechanisms of non-equilibrium, quasi-equilibrium, and equilibrium. Gibbs energy fluxes are obtained as a function of chemical potential, time, and displacement. Diffusion, convection, internal convection, and internal equilibrium chemical energy fluxes are demonstrated. The theory reveals that there are chemical energy flux gaps and broken discrete symmetries at the activation chemical potential, time, and displacement. The statistical, thermodynamic theory is the unification of diffusion and internal convection chemical reactions which reduces to the non-equilibrium generalization beyond the quasi-equilibrium theories of migration and diffusion processes. The relationship between kinetic theories of chemical and electrochemical reactions is also explored. The theory is applied to explore non-equilibrium chemical reactions as an illustration. Three variable separation constants indicate particle number constants and play key roles in describing the distinct chemical reaction mechanisms. The kinetics of chemical energy transfer accounts for the four control mechanisms of chemical reactions such as activation, concentration, transition, and film chemical reactions. - Highlights: • Chemical energy transfer theory is proposed for non-, quasi-, and equilibrium. • Gibbs energy fluxes are expressed by chemical potential, time, and displacement. • Relationship between chemical and electrochemical reactions is discussed. • Theory is applied to explore nonequilibrium energy transfer in chemical reactions. • Kinetics of non-equilibrium chemical reactions shows the four control mechanisms

Transfer reactions at the neutron dripline with triton target

CERN Multimedia

Two-neutron transfer to $^{9}$Li will populate the ground state of $^{11}$Li as well as low-lying resonances in a way that is complementary to studies of these states performed at higher beam energies. We aim at detecting the charged particles from the transfer reactions as well as neutrons coming from the decay of possible $^{11}$Li resonances.

Transfer reactions at the neutron dripline with triton target

CERN Document Server

Borge, M J G; Fynbo, H O U; Gomez Camacho, J; Johansen, J; Johansson, H T; Jonson, B; Krücken, R; Kurcewicz, J; Martel, I; Moro, A; Mücher, D; Nilsson, T; Nyman, G; Raabe, R; Randisi, G; Riisager, K; Sambi, S; Sanchez-Benitez, AM; Tengblad, O

2012-01-01

Two-neutron transfer to $^{9}$Li will populate the ground state of $^{11}$Li as well as low-lying resonances in a way that is complementary to studies of these states performed at higher beam energies. We aim at detecting the charged particles from the transfer reactions as well as neutrons coming from the decay of possible $^{11}$Li resonances.

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

Science.gov (United States)

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

2014-09-18

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

Single particle transfer reactions: what can they tell us about vibrational states

International Nuclear Information System (INIS)

Hering, W.R.

1975-01-01

The topic discussed concerns single particle transfer reactions (SPTR) which are, in general, used to study SP states. However, good SP states are rare objects in nature and people who try to look for them have often to settle with something less than ideal. Indeed the picture of a pure SP state is physically not even reasonable. It means that a nucleon is moving around a core nucleus which stays in its ground state: a process which one could call equivalent to elastic scattering of a nucleon which is not free but rather in a bound state. However it is shown that inelastic scattering is a very strong competitor to elastic scattering if the nucleus possesses states of high collectivity. Thus one would expect inelastic scattering to happen also while the nucleon is bound. This is a very intuitive picture of what is called the fragmentation of SP states. A final state psi sub(B) is populated by the transfer reaction A + a → B + b where psi sub(B) = α 1 phi 1 phi sub(A)(0) + α 2 phi 2 phi sub(A)(lambda). Hence the population of psi sub(B) automatically involves the collective state phi sub(A)(lambda). A discussion of how one can get information about phi sub(A)(lambda) out of the experimental data is given. (Auth.)

Droplet heat transfer and chemical reactions during direct containment heating

International Nuclear Information System (INIS)

Baker, L. Jr.

1986-01-01

A simplified model of heat transfer and chemical reaction has been adapted to evaluate the expected behavior of droplets containing unreacted Zircaloy and stainless steel moving through the containment atmosphere during postulated accidents involving direct containment heating. The model includes internal and external diffusive resistances to reaction. The results indicate that reactions will be incomplete for many conditions characteristic of direct containment heating sequences

Cluster-transfer reactions with radioactive beams: a spectroscopic tool for neutron-rich nuclei

CERN Document Server

AUTHOR|(CDS)2086156; Raabe, Riccardo; Bracco, Angela

In this thesis work, an exploratory experiment to investigate cluster-transfer reactions with radioactive beams in inverse kinematics is presented. The aim of the experiment was to test the potential of cluster-transfer reactions at the Coulomb barrier, as a possible mean to perform $\\gamma$ spectroscopy studies of exotic neutron-rich nuclei at medium-high energies and spins. The experiment was performed at ISOLDE (CERN), employing the heavy-ion reaction $^{98}$Rb + $^{7}$Li at 2.85 MeV/A. Cluster-transfer reaction channels were studied through particle-$\\gamma$ coincidence measurements, using the MINIBALL Ge array coupled to the charged particle Si detectors T-REX. Sr, Y and Zr neutron-rich nuclei with A $\\approx$ 100 were populated by either triton- or $\\alpha$ transfer from $^{7}$Li to the beam nuclei and the emitted complementary charged fragment was detected in coincidence with the $\\gamma$ cascade of the residues, after few neutrons evaporation. The measured $\\gamma$ spectra were studied in detail and t...

Many-nucleon transfer reactions at the coulomb barrier

International Nuclear Information System (INIS)

Wegmann, H.

1974-01-01

The aim of the present work was to investigate the many-nucleon transfer with heavy ion radiation near the coulomb barrier. The neutron-rich targets 76 Ge, sup(92,94,96)Zr and 100 Mo were thus irradiated with 32 S and 34 S radiation. By measuring the activity of the back-scattered light reaction products in the transfer, total cross sections were determined for the 3p, 4p, 3pn, 4pn, 3n, 4n and 6n transfer. Excitation functions for the 3p, 4p, 3pn and 4pn transfer were measured for the target-projectile combination 96 Zr- 32 S. Differential cross sections could be determined with 96 Zr and 100 Mo. The results were compared with various theoretical calculations. (orig./LH) [de

High transfer cross sections from reactions with 254Es

International Nuclear Information System (INIS)

Schaedel, M.; Bruechle, W.; Bruegger, M.; Gaeggeler, H.; Moody, J.; Schardt, D.; Suemmerer, K.; Hulet, E.K.; Dougan, A.D.; Dougan, R.J.; Landrum, J.H.; Lougheed, R.W.; Wild, J.F.; O'Kelly, G.D.

1985-08-01

We report radiochemically determined cross sections for the heaviest known actinides produced in transfer reactions of 101 MeV 16 O, 98 MeV 18 O and 127 MeV 22 Ne with 254 Es as a target. A comparison with data for similar transfers from 248 Cm targets is made. Transfer cross sections are extrapolated for the production of unknown, neutron-rich isotopes of elements 101 through 105, and the unique potential of 254 Es as a target to make these exotic nuclei accessible is demonstrated. (orig.)

Nucleon transfer reactions to rotational states induced by 206,208PB projectiles

International Nuclear Information System (INIS)

Wollersheim, H.J.; DeBoer, F.W.N.; Emling, H.; Grein, H.; Grosse, E.; Spreng, W.; Eckert, G.; Elze, Th.W.; Stelzer, K.; Lauterbach, Ch.

1986-01-01

In a systematic study of nucleon transfer reactions accompanied by Coulomb excitation the authors bombarded 152 Sm, 160 Gd and 232 Th with 206, 208 Pb beams at incident energies close to the Coulomb barrier. Particle-gamma coincidence techniques were used to identify excited states of reaction products populated through inelastic scattering and in nucleon transfer reactions. Large cross sections were observed for one- and two-neutron pick-up from 232 Th at an incident energy of 6.4 MeV/μ. The results are analyzed in the framework of semiclassical models

Electrocatalysis of anodic oxygen-transfer reactions at modified lead dioxide electrodes

Energy Technology Data Exchange (ETDEWEB)

Hsiao, Yun-Lin.

1990-09-21

The electrocatalytic activities were compared for pure and chloride-doped beta-PbO{sub 2} (Cl-PbO{sub 2}) films on gold and platinum substrates. Rate constants were increased significantly for oxidations of Mn{sup 2+}, toluene, benzyl alcohol, dimethylsulphoxide (DMSO) and benzaldehyde in acidic media by the incorporation of Cl{sup {minus}} into the oxide films. These reactions are concluded to occur by the electrocatalytic transfer of oxygen from H{sub 2}O to the reaction products. Results of x-ray diffraction studies indicate the Cl-PbO{sub 2} film continues to have the slightly distorted rutile structure of pure beta-PbO{sub 2}. The observed electrocatalytic phenomena are concluded to be the beneficial consequence of surface defects generated when Cl{sup {minus}} serves for charge compensation within the surface matrix and, thereby, increases the number of surface sites capable of adsorbing hydroxyl radicals which are transferred in the electrocatalytic O-transfer reactions. 91 refs., 44 figs., 10 tabs.

7Li(d,p)8Li transfer reaction in the NCSM/RGM approach

Science.gov (United States)

Raimondi, F.; Hupin, G.; Navrátil, P.; Quaglioni, S.

2018-03-01

Recently, we applied an ab initio method, the no-core shell model combined with the resonating group method, to the transfer reactions with light p-shell nuclei as targets and deuteron as the projectile. In particular, we studied the elastic scattering of deuterium on 7Li and the 7Li(d,p)8Li transfer reaction starting from a realistic two-nucleon interaction. In this contribution, we review of our main results on the 7Li(d,p)8Li transfer reaction, and we extend the study of the relevant reaction channels, by showing the dominant resonant phase shifts of the scattering matrix. We assess also the impact of the polarization effects of the deuteron below the breakup on the positive-parity resonant states in the reaction. For this purpose, we perform an analysis of the convergence trend of the phase and eigenphase shifts, with respect to the number of deuteron pseudostates included in the model space.

Search for low spin superdeformed states by transfer reactions

Energy Technology Data Exchange (ETDEWEB)

Blons, J; Goutte, D; Lepretre, A; Lucas, R; Meot, V; Paya, D; Phan, X H [DAPNIA SPhN CE Saclay 91191 Gif sur Yvette (France); Barreau, G; Doan, T P; Pedemay, G [CENBG, 33175 Gradignan (France); Becker, J A; Stoyer, M A [LLNL, Livermore, CA (United States)

1992-08-01

We present a specific experimental technique aiming to observe superdeformed isomeric states. Preliminary results on two proton transfer reaction on platinum targets leading to {sup 194}Hg are shown. (author). 6 refs., 5 figs.

Nuclear rotational population patterns in heavy-ion scattering and transfer reactions

Energy Technology Data Exchange (ETDEWEB)

Rasmussen, J O; Stoyer, M A [Lawrence Berkeley Lab., CA (USA); Canto, L F; Donangelo, R [Universidade Federal do Rio de Janeiro, RJ (Brazil); Ring, P [Technische Univ. Muenchen, Garching (Germany, F.R.). Fakultaet fuer Physik

1991-05-01

A model of {sup 239}Pu with decoupled neutron is used for theoretical calculations of rotational population patterns in heavy ion inelastic scattering and one-neutron transfer reactions. The system treated in {sup 90}Zr on {sup 239}Pu at the near-barrier energy of 500 MeV and backscattering angles of 180deg and 140deg. The influence of the complex nuclear optical potential is seen to be very strong, and the Nilsson wave function of the odd neutron produces a distinctive pattern in the transfer reaction. (orig.).

Effects of electrostatic interactions on electron transfer reactions

International Nuclear Information System (INIS)

Hickel, B.

1987-01-01

The fast reactions of electron transfer are studied by pulse radiolysis. This technique allows the creation in about 10 -8 second radicals and radical ions with high redox potentials. For solvated electrons electrostatic interaction on the kinetics of reactions limited by diffusion is described by Debye's equation when ion mobility is known. Deviation from theory can occur in ion pairs formation. This is evidenced experimentally for anions by cation complexation with a cryptate. Relatively slow reactions are more sensitive to electrostatic interactions than limited by diffusion. If ion pairs are not formed kinetics constant depends on dielectric constant of solvent and reaction radius. Experimentally is studied the effect of electrostatic interaction on the rate constants of solvated electrons with anions and cations in water-ethanol mixtures where the dielectric constant change from 80 to 25 at room temperature. 17 refs

Mass transfer and slag-metal reaction in ladle refining : a CFD approach

OpenAIRE

Ramström, Eva

2009-01-01

  In order to optimise the ladle treatment mass transfer modelling of aluminium addition and homogenisation time was carried out. It was stressed that incorporating slag-metal reactions into the mass transfer modelling strongly would enhance the reliability and amount of information to be analyzed from the CFD calculations.   In the present work, a thermodynamic model taking all the involved slag metal reactions into consideration was incorporated into a 2-D fluid flow model of an argon stirr...

Excitation functions for quasielastic transfer reactions induced with heavy ions in bismuth

International Nuclear Information System (INIS)

Gardes, D.; Bimbot, R.; Maison, J.; de Reilhac, L.; Rivet, M.F.; Fleury, A.; Hubert, F.; Llabador, Y.

1978-01-01

The excitation functions for the production of 210 Bi, 210 Po, /sup 207-211/At, and 211 Rn through quasielastic transfer reactions induced with heavy ions in 209 Bi have been measured. The corresponding reactions involved the transfer of one neutron, one proton, two charges, and three charges from projectile to target. The projectiles used were 12 C, 14 N, 16 O, 19 F, 20 Ne, 40 Ar, 40 Ca, 56 Fe, and 63 Cu. The experimental techniques involved target irradiations and off-line α and γ activity measurements. Chemical separations were used to solve specific problems. Careful measuremnts of incident energies and cross sections were performed close to the reaction thresholds. All excitation functions exhibit the typical features of quasielastic transfer reactions: a sharp increase at low energy, and a constant value at high incident energy. The position of the thresholds are strongly influenced by the energetics of the reaction: High cross sections are observed under the strong interaction barrier if the energy balance at the minimum distance of approach is positive. This balance is equal to the difference between the interaction potentials in the entrance and exit channels, corrected for the mass balance. The constant cross sections observed for the high energy part of a given excitation function are consistent with the assumption that the curve P (R) which represents the transfer probability versus the distance between the nucleus centers does not vary with incident energy. This assumption implies the constancy of the optimum distance of approach R/sub opt/, of the R window ΔR for which P (R) is significant, and of the magnitude of P (R). Moreover the data show that the high energy cross sections for one-proton transfer are independent of the projectile, while odd-even effects of the projectile atomic number Z on the two-charge transfer cross sections are observed for the lightest incident ions 14 N to 20 Ne

Alpha-transfer reactions and the pairing-vibration model

International Nuclear Information System (INIS)

Betts, R.R.

1977-01-01

The pairing-vibration model with isospin is extended to include α-transfer reactions. Selection rules and expressions for transition strengths are derived and compared with experimental results for A = 40--66 nuclei. The selection rules are found to be followed quite well in the examples studied. The systematics of ground-state transition strengths are qualitatively quite well reproduced although the quantitative agreement is poor. When the changing nature of the pairing quanta is incorporated using two-particle transfer data the agreement becomes quantitatively good. Evidence is presented for clustering other than that due to pairing in 40 Ca and 44 Ti

Transfer reaction studies in the region of heavy and superheavy nuclei at SHIP

Energy Technology Data Exchange (ETDEWEB)

Heinz, S; Comas, V; Hofmann, S; Ackermann, D; Heredia, J; Hessberger, F P; Khuyagbaatar, J; Kindler, B; Lommel, B; Mann, R, E-mail: s.heinz@gsi.de [GSI Helmholtzzentrum fuer Schwerionenforschung GmbH, 64291 Darmstadt (Germany)

2011-02-01

We studied multi-nucleon transfer reactions in the region of heavy and superheavy nuclei. The goal was to investigate these reactions as possibility to create new superheavy neutron-rich isotopes, which cannot be produced in fusion reactions. The experiments have been performed at the velocity filter SHIP at GSI. At SHIP we can detect and identify the heavy, target-like, transfer products. Due to the low background at the focal plane detector and the isotope identification via radioactive decays, the setup allows to reach an upper cross-section limit of 10 pb/sr within one day of beamtime. We investigated the systems {sup 58,64}Ni + {sup 207}Pb and {sup 48}Ca + {sup 248}Cm at beam energies below and up to 20% above the Coulomb barrier. At all energies we observed a massive transfer of protons and neutrons, where transfer products with up to eight neutrons more than the target nucleus could be identified.

Impulse transfer and light particles emission during the reaction α + 232Th at 70 MeV/u

International Nuclear Information System (INIS)

Nguyen, M.S.

1988-02-01

We have measured during the reaction 4 He + 232 Th at 70 MeV/u the angular correlation of heavy fragments of fission, the inclusive energy spectra of light particles (p, d, t, 3 He and α) and triple coincidence between two fission fragments and a light ejectile. Energy spectra show an evaporation component at low energy, a component of projectile fragmentation at energy equivalent to beam velocity and an intermediate component attributed to pre-equilibrium emission. The analysis of the correlation between linear momentum transfer to the fissioning nucleus and the characteristics of the ejectile in coincidence shows a phenomenon of incomplete massive transfer. We run an Intra-Nuclear Cascade (INC) computation to reproduce ejectile energy spectra, but the agreement with experiment was very bad. We conclude to the impossibility to apply INC computation at intermediate energy of 70 MeV/u. We also applied Distorted Wave Born Approximation (DWBA) for direct transfer reaction extended to continuum states: but the agreement with experiment was again deceiving. Finally, we used an analysis by moving sources for which we propose a model of generalized fragmentation giving a continuous representation of the emission source phenomenon from low energy up to high energy [fr

Development of a high-density gas-jet target for nuclear astrophysics and reaction studies with rare isotope beams. Final Report

Energy Technology Data Exchange (ETDEWEB)

Uwe, Greife [Colorado School of Mines, Golden, CO (United States)

2014-08-12

The purpose of this project was to develop a high-density gas jet target that will enable a new program of transfer reaction studies with rare isotope beams and targets of hydrogen and helium that is not currently possible and will have an important impact on our understanding of stellar explosions and of the evolution of nuclear shell structure away from stability. This is the final closeout report for the project.

Development of a high-density gas-jet target for nuclear astrophysics and reaction studies with rare isotope beams. Final Report

International Nuclear Information System (INIS)

Uwe, Greife

2014-01-01

The purpose of this project was to develop a high-density gas jet target that will enable a new program of transfer reaction studies with rare isotope beams and targets of hydrogen and helium that is not currently possible and will have an important impact on our understanding of stellar explosions and of the evolution of nuclear shell structure away from stability. This is the final closeout report for the project.

Geometric phase and quantum interference in photosynthetic reaction center: Regulation of electron transfer

Energy Technology Data Exchange (ETDEWEB)

Sun, Yuming, E-mail: ymsun@ytu.edu.cn; Su, Yuehua; Dai, Zhenhong; Wang, WeiTian

2016-10-20

Photosynthesis is driven by electron transfer in reaction centers in which the functional unit is composed of several simple molecules C{sub 2}-symmetrically arranged into two branches. In view of quantum mechanism, both branches are possible pathways traversed by the transferred electron. Due to different evolution of spin state along two pathways in transmembrane electric potential (TEP), quantum state of the transferred electron at the bridged site acquires a geometric phase difference dependent on TEP, the most efficient electron transport takes place in a specific range of TEP beyond which electron transfer is dramatically suppressed. What’s more, reaction center acts like elaborately designed quantum device preparing polarized spin dependent on TEP for the transferred electron to regulate the reduction potential at bridged site. In brief, electron transfer generates the TEP, reversely, TEP modulates the efficiency of electron transfer. This may be an important approach to maintaining an appreciable pH environment in photosynthesis.

Role of transfer reactions in heavy-ion collisions at the Coulomb barrier

Directory of Open Access Journals (Sweden)

Pollarolo Giovanni

2011-10-01

Full Text Available One and two neutron transfer reactions are discussed in the semiclassical formalism. The twoneutrons transfer cross sections are calculated in the successive approximation. Comparisons with new experimental data below the Coulomb barrier are discussed in term of transfer probabilities as a function of the distance of closest approach for Coulomb scattering.

Light induced electron transfer reactions of metal complexes

International Nuclear Information System (INIS)

Sutin, N.; Creutz, C.

1980-01-01

Properties of the excited states of tris(2,2'-bipyridine) and tris(1,10-phenanthroline) complexes of chromium(III), iron(II), ruthenium(II), osmium(II), rhodium(III), and iridium(III) are described. The electron transfer reactions of the ground and excited states are discussed and interpreted in terms of the driving force for the reaction and the distortions of the excited states relative to the corresponding ground states. General considerations relevant to the conversion of light into chemical energy are presented and progress in the use of polypyridine complexes to effect the light decomposition of water into hydrogen and oxygen is reviewed

Heavy-ion induced multinucleon transfer reactions in the 2s--1d shell

International Nuclear Information System (INIS)

Olmer, C.

1975-01-01

In order to investigate whether new nuclear structure information can be obtained from studying the direct transfer of more than two nucleons using heavy-ion projectiles, we have investigated the 28 Si( 16 O, 12 C) 32 S and 12 C( 14 N,d) 24 Mg reactions as candidates for the direct transfer of four- and twelve-nucleons, respectively. The counter telescope-position sensitive detector kinematic coincidence method--both angular distributions (22 0 less than theta/sub L/ less than 95 0 , E/sub L/ = 55.54 MeV) and excitation functions (theta/sub L/ = 26 0 , 50 less than E/sub L/ less than 63 MeV) were obtained for strongly excited states below 10 MeV in excitation in the first reaction. For the 12 C + 14 N interaction, a measurement of the angular distributions (25 0 less than theta/sub L/ less than 140 0 , E/sub L/ = 20,25 MeV) for proton, deuteron and alpha-particle emission to many low-lying states sufficed for the present purposes. Comparison of Hauser-Feshbach statistical model calculations with these data indicated that the light-particle production from the 12 C + 14 N interaction as investigated here is predominantly compound nuclear in nature. The selectively strong population of a few states in 32 S by the 28 Si-( 16 O, 12 C) 32 S reaction is primarily direct. The structure of these states was deduced from available light-ion-induced transfer reaction studies and shell model calculations; the importance of shell model configurations is indicated, and an alpha-particle transfer model can not account for the observed selectivity. Calculations of the 28 Si( 16 O, 12 C) 32 S reaction with a microscopic multinucleon transfer code indicate selectivities consistent with the present results. Moreover, the calculations suggest the presence of other, unexpected selectivities, all of which may be understood on a physical basis, and some of which appear as an extension of a similar effect seen in two-nucleon transfer reactions

Comparison of dynamical aspects of nonadiabatic electron, proton, and proton-coupled electron transfer reactions

International Nuclear Information System (INIS)

Hatcher, Elizabeth; Soudackov, Alexander; Hammes-Schiffer, Sharon

2005-01-01

The dynamical aspects of a model proton-coupled electron transfer (PCET) reaction in solution are analyzed with molecular dynamics simulations. The rate for nonadiabatic PCET is expressed in terms of a time-dependent probability flux correlation function. The impact of the proton donor-acceptor and solvent dynamics on the probability flux is examined. The dynamical behavior of the probability flux correlation function is dominated by a solvent damping term that depends on the energy gap correlation function. The proton donor-acceptor motion does not impact the dynamical behavior of the probability flux correlation function but does influence the magnitude of the rate. The approximations previously invoked for the calculation of PCET rates are tested. The effects of solvent damping on the proton donor-acceptor vibrational motion are found to be negligible, and the short-time solvent approximation, in which only equilibrium fluctuations of the solvent are considered, is determined to be valid for these types of reactions. The analysis of PCET reactions is compared to previous analyses of single electron and proton transfer reactions. The dynamical behavior is qualitatively similar for all three types of reactions, but the time scale of the decay of the probability flux correlation function is significantly longer for single proton transfer than for PCET and single electron transfer due to a smaller solvent reorganization energy for proton transfer

Transfer reactions in inverse kinematics at REX-ISOLDE

CERN Document Server

Tengborn, E

Research on the structure of exotic nuclei is one of the most intriguing topics in present day nuclear physics. With the use of facilities for isotope separation on-line, such as ISOLDE at CERN, short-lived isotopes can be studied experimentally. Since 2002, the REX-ISOLDE facility enables radioactive ions produced by ISOLDE to be post-accelerated, increasing the energy of the ions enough to do nuclear transfer reactions in inverse kinematics. In this thesis, transfer reactions are used to study the structure of neutron-rich lithium isotopes through a series of experiments at REX-ISOLDE. The first experiment used a 9Li beam at 2.36 MeV/u impinging on a deuterated polyethylene target to study 10Li, 9Li and 8Li. For the (d,p)-channel the resonance ground state and a first excited state are observed and the results agree with theoretical calculations. The elastic channel agrees with Optical Model, OM, calculations. For the (d,t)-channel the shape of the angular distribution agrees with Distorted Wave Born Approx...

Deep-inelastic multinucleon transfer processes in the 16O+27Al reaction

Science.gov (United States)

Roy, B. J.; Sawant, Y.; Patwari, P.; Santra, S.; Pal, A.; Kundu, A.; Chattopadhyay, D.; Jha, V.; Pandit, S. K.; Parkar, V. V.; Ramachandran, K.; Mahata, K.; Nayak, B. K.; Saxena, A.; Kailas, S.; Nag, T. N.; Sahoo, R. N.; Singh, P. P.; Sekizawa, K.

2018-03-01

The reaction mechanism of deep-inelastic multinucleon transfer processes in the 16O+27Al reaction at an incident 16O energy (Elab=134 MeV) substantially above the Coulomb barrier has been studied both experimentally and theoretically. Elastic-scattering angular distribution, total kinetic energy loss spectra, and angular distributions for various transfer channels have been measured. The Q -value- and angle-integrated isotope production cross sections have been deduced. To obtain deeper insight into the underlying reaction mechanism, we have carried out a detailed analysis based on the time-dependent Hartree-Fock (TDHF) theory. A recently developed method, TDHF+GEMINI, has been applied to evaluate production cross sections for secondary products. From a comparison between the experimental and theoretical cross sections, we find that the theory qualitatively reproduces the experimental data. Significant effects of secondary light-particle emissions are demonstrated. Possible interplay among fusion-fission, deep-inelastic, multinucleon transfer, and particle evaporation processes is discussed.

Determination of S17(0) from transfer reactions

International Nuclear Information System (INIS)

Tribble, R.E.; Azhari, A.; Clark, H.L.; Gagliardi, C.A.; Lui, Y.; Mukhamedzhanov, A.M.; Sattarov, A.; Trache, L.; Burjan, V.; Cejpek, J.; Kroha, V.; Piskor, S.; Vincour, J.

1998-01-01

The S-factor for the direct capture reaction 7 Be(p,γ) 8 B can be found at astrophysical energies from the asymptotic normalization coefficients which provide the normalization of the tails of the overlap functions for 8 B→ 7 Be+p. Peripheral transfer reactions offer a technique to determine these asymptotic normalization coefficients. As a test of the technique, the 16 O( 3 He,d) 17 F reaction has been used to determine asymptotic normalization coefficients for transitions to the ground and first excited states of 17 F. The S-factors for 16 O(p,γ) 17 F calculated from these 17 F→ 16 O+p asymptotic normalization coefficients are found to be in very good agreement with recent measurements. Following the same technique, the 10 B( 7 Be, 8 B) 9 Be reaction has been used to measure the asymptotic normalization coefficient for 7 Be(p,γ) 8 B. This result provides an indirect determination of S 17 (0). copyright 1998 American Institute of Physics

Splendor and misery of the distorted wave method applied to heavy ions transfer reactions

International Nuclear Information System (INIS)

Mermaz, M.C.

1979-01-01

The success and failure of the Distorted Wave Method (DWM) applied to heavy ion transfer reactions are illustrated by few examples: one and multi-nucleon transfer reactions induced by 15 N and 18 O on 28 Si target nucleus performed on the vicinity of Coulomb barrier respectively at 44 and 56 MeV incident energy

Resonating group method as applied to the spectroscopy of α-transfer reactions

Science.gov (United States)

Subbotin, V. B.; Semjonov, V. M.; Gridnev, K. A.; Hefter, E. F.

1983-10-01

In the conventional approach to α-transfer reactions the finite- and/or zero-range distorted-wave Born approximation is used in liaison with a macroscopic description of the captured α particle in the residual nucleus. Here the specific example of 16O(6Li,d)20Ne reactions at different projectile energies is taken to present a microscopic resonating group method analysis of the α particle in the final nucleus (for the reaction part the simple zero-range distorted-wave Born approximation is employed). In the discussion of suitable nucleon-nucleon interactions, force number one of the effective interactions presented by Volkov is shown to be most appropriate for the system considered. Application of the continuous analog of Newton's method to the evaluation of the resonating group method equations yields an increased accuracy with respect to traditional methods. The resonating group method description induces only minor changes in the structures of the angular distributions, but it does serve its purpose in yielding reliable and consistent spectroscopic information. NUCLEAR STRUCTURE 16O(6Li,d)20Ne; E=20 to 32 MeV; calculated B(E2); reduced widths, dσdΩ extracted α-spectroscopic factors. ZRDWBA with microscope RGM description of residual α particle in 20Ne; application of continuous analog of Newton's method; tested and applied Volkov force No. 1; direct mechanism.

Golden rule kinetics of transfer reactions in condensed phase: The microscopic model of electron transfer reactions in disordered solid matrices

International Nuclear Information System (INIS)

Basilevsky, M. V.; Mitina, E. A.; Odinokov, A. V.; Titov, S. V.

2013-01-01

The algorithm for a theoretical calculation of transfer reaction rates for light quantum particles (i.e., the electron and H-atom transfers) in non-polar solid matrices is formulated and justified. The mechanism postulated involves a local mode (an either intra- or inter-molecular one) serving as a mediator which accomplishes the energy exchange between the reacting high-frequency quantum mode and the phonon modes belonging to the environment. This approach uses as a background the Fermi golden rule beyond the usually applied spin-boson approximation. The dynamical treatment rests on the one-dimensional version of the standard quantum relaxation equation for the reduced density matrix, which describes the frequency fluctuation spectrum for the local mode under consideration. The temperature dependence of a reaction rate is controlled by the dimensionless parameter ξ 0 =ℏω 0 /k B T where ω 0 is the frequency of the local mode and T is the temperature. The realization of the computational scheme is different for the high/intermediate (ξ 0 0 ≫ 1) temperature ranges. For the first (quasi-classical) kinetic regime, the Redfield approximation to the solution of the relaxation equation proved to be sufficient and efficient in practical applications. The study of the essentially quantum-mechanical low-temperature kinetic regime in its asymptotic limit requires the implementation of the exact relaxation equation. The coherent mechanism providing a non-vanishing reaction rate has been revealed when T→ 0. An accurate computational methodology for the cross-over kinetic regime needs a further elaboration. The original model of the hopping mechanism for electronic conduction in photosensitive organic materials is considered, based on the above techniques. The electron transfer (ET) in active centers of such systems proceeds via local intra- and intermolecular modes. The active modes, as a rule, operate beyond the kinetic regimes, which are usually postulated in the

Golden rule kinetics of transfer reactions in condensed phase: the microscopic model of electron transfer reactions in disordered solid matrices.

Science.gov (United States)

Basilevsky, M V; Odinokov, A V; Titov, S V; Mitina, E A

2013-12-21

The algorithm for a theoretical calculation of transfer reaction rates for light quantum particles (i.e., the electron and H-atom transfers) in non-polar solid matrices is formulated and justified. The mechanism postulated involves a local mode (an either intra- or inter-molecular one) serving as a mediator which accomplishes the energy exchange between the reacting high-frequency quantum mode and the phonon modes belonging to the environment. This approach uses as a background the Fermi golden rule beyond the usually applied spin-boson approximation. The dynamical treatment rests on the one-dimensional version of the standard quantum relaxation equation for the reduced density matrix, which describes the frequency fluctuation spectrum for the local mode under consideration. The temperature dependence of a reaction rate is controlled by the dimensionless parameter ξ0 = ℏω0/k(B)T where ω0 is the frequency of the local mode and T is the temperature. The realization of the computational scheme is different for the high/intermediate (ξ0 regime, the Redfield approximation to the solution of the relaxation equation proved to be sufficient and efficient in practical applications. The study of the essentially quantum-mechanical low-temperature kinetic regime in its asymptotic limit requires the implementation of the exact relaxation equation. The coherent mechanism providing a non-vanishing reaction rate has been revealed when T → 0. An accurate computational methodology for the cross-over kinetic regime needs a further elaboration. The original model of the hopping mechanism for electronic conduction in photosensitive organic materials is considered, based on the above techniques. The electron transfer (ET) in active centers of such systems proceeds via local intra- and intermolecular modes. The active modes, as a rule, operate beyond the kinetic regimes, which are usually postulated in the existing theories of the ET. Our alternative dynamic ET model for local

Mass transfer with complex reversible chemical reactions—II. parallel reversible chemical reactions

NARCIS (Netherlands)

Versteeg, G.F.; Kuipers, J.A.M.; Beckum, F.P.H. van; Swaaij, W.P.M. van

1990-01-01

An absorption model has been developed which can be used to calculate rapidly absorption rates for the phenomenon mass transfer accompanied by multiple complex parallel reversible chemical reactions. This model can be applied for the calculation of the mass transfer rates, enhancement factors and

Electron transfer reactions to probe the electrode/solution interface

Energy Technology Data Exchange (ETDEWEB)

Capitanio, F.; Guerrini, E.; Colombo, A.; Trasatti, S. [Milan Univ., Milan (Italy). Dept. of Physical Chemistry and Electrochemistry

2008-07-01

The reactions that occur at the interface between an electrode and an electrolyte were examined with particular reference to the interaction of different electrode surfaces with redox couples. A semi-integration or convolution technique was used to study the kinetics of electron transfer on different electrode materials with different hydrophilic behaviour, such as Boron-Doped-Diamond (BDD), Au and Pt. Standard reversible redox couples were also investigated, including (Fe3+/2+, Fe(CN)63-/4-, Ru(NH3)63+/2+, Co(NH3)63+/2+, Ir4+/3+, V4+/5+ and V3+/2+). The proposed method proved to be simple, straightforward and reliable since the obtained kinetic information was in good agreement with data in the literature. It was concluded that the kinetics of the electrode transfer reactions depend on the chemical nature of the redox couple and electrode material. The method should be further extended to irreversible couples and other electrode materials such as mixed oxide electrodes. 3 refs., 2 figs.

179Ta and 180Ta structure by transfer reactions

International Nuclear Information System (INIS)

Warde, Elias.

1979-01-01

Transfer reactions (α,t); ( 3 He,d); (p,t) and (p,d) have been used to study the nuclear spectroscopy of 179 Ta and 180 Ta. In 179 Ta, 5/2 - and 9/2 - states of the 1/2(541) configuration have been identified. The core-quasiproton interaction has to be taken into account in order to explain the two-nucleon transfer intensities in the 181 Ta(p,t) 179 Ta reaction. A level scheme has been proposed for 180 Ta for the first time. Especially the ground state is identified with the (1 + ,1) level of the [7/2 + (404)sub(p), 9/2 + (624)sub(n)] configuration and spin (9 - ,9) of the configuration [9/2 - (514)sub(p), 9/2 + (624)sub(n)] has been assigned to the long-lived isomer. From the observed configurations in 180 Ta, the matrix elements of the effective residual interaction vsub(np) have been deduced and compared to theoretical predictions [fr

Gamow-Teller transitions and neutron-proton-pair transfer reactions

Science.gov (United States)

Van Isacker, P.; Macchiavelli, A. O.

2018-05-01

We propose a schematic model of nucleons moving in spin-orbit partner levels, j = l ± 1/2, to explain Gamow-Teller and two-nucleon transfer data in N = Z nuclei above 40Ca. Use of the LS coupling scheme provides a more transparent approach to interpret the structure and reaction data. We apply the model to the analysis of charge-exchange, 42Ca(3He,t)42Sc, and np-transfer, 40Ca(3He,p)42Sc, reactions data to define the elementary modes of excitation in terms of both isovector and isoscalar pairs, whose properties can be determined by adjusting the parameters of the model (spin-orbit splitting, isovector pairing strength and quadrupole matrix element) to the available data. The overall agreement with experiment suggests that the approach captures the main physics ingredients and provides the basis for a boson approximation that can be extended to heavier nuclei. Our analysis also reveals that the SU(4)-symmetry limit is not realized in 42Sc.

Squids, supercurrents, and slope anomalies: Nuclear structure from heavy-ion transfer reactions

International Nuclear Information System (INIS)

Guidry, M.W.

1989-01-01

Within the past five years we have developed experimental techniques to study heavy-ion transfer reactions to high spin states in deformed nuclei. These methods have been turned into a quantitative tool to assess the influence of collective excitation on single-particle and pairing structure. I discuss some of the nuclear structure questions which are being answered in these experiments: How strong is ground state pairing? How does pairing change with angular momentum? Why is two-neutron transfer much stronger than expected at large radial separation? What is the evidence for a nuclear Josephson Effect? What is the evidence for a nuclear Berry phase effect (nuclear SQUID)? Why does one-neutron transfer populate much higher spins than would be naively expected? Conversely, why does two-neutron transfer populate much lower spins than anyone expected? The answer to each of these questions involves the influence of detailed nuclear structure on transfer reactions, and represents quantitative new information about the effect of angular momentum and excitation energy on many-body systems with a finite number of particles. 8 refs., 6 figs

Golden rule kinetics of transfer reactions in condensed phase: The microscopic model of electron transfer reactions in disordered solid matrices

Science.gov (United States)

Basilevsky, M. V.; Odinokov, A. V.; Titov, S. V.; Mitina, E. A.

2013-12-01

The algorithm for a theoretical calculation of transfer reaction rates for light quantum particles (i.e., the electron and H-atom transfers) in non-polar solid matrices is formulated and justified. The mechanism postulated involves a local mode (an either intra- or inter-molecular one) serving as a mediator which accomplishes the energy exchange between the reacting high-frequency quantum mode and the phonon modes belonging to the environment. This approach uses as a background the Fermi golden rule beyond the usually applied spin-boson approximation. The dynamical treatment rests on the one-dimensional version of the standard quantum relaxation equation for the reduced density matrix, which describes the frequency fluctuation spectrum for the local mode under consideration. The temperature dependence of a reaction rate is controlled by the dimensionless parameter ξ0 = ℏω0/kBT where ω0 is the frequency of the local mode and T is the temperature. The realization of the computational scheme is different for the high/intermediate (ξ0 conduction in photosensitive organic materials is considered, based on the above techniques. The electron transfer (ET) in active centers of such systems proceeds via local intra- and intermolecular modes. The active modes, as a rule, operate beyond the kinetic regimes, which are usually postulated in the existing theories of the ET. Our alternative dynamic ET model for local modes immersed in the continuum harmonic medium is formulated for both classical and quantum regimes, and accounts explicitly for the mode/medium interaction. The kinetics of the energy exchange between the local ET subsystem and the surrounding environment essentially determine the total ET rate. The efficient computer code for rate computations is elaborated on. The computations are available for a wide range of system parameters, such as the temperature, external field, local mode frequency, and characteristics of mode/medium interaction. The relation of the

Analysis of transfer reactions: determination of spectroscopic factors

Energy Technology Data Exchange (ETDEWEB)

Keeley, N. [CEA Saclay, Dept. d' Astrophysique, de Physique des Particules de Physique Nucleaire et de l' Instrumentation Associee (DSM/DAPNIA/SPhN), 91- Gif sur Yvette (France); The Andrzej So an Institute for Nuclear Studies, Dept. of Nuclear Reactions, Warsaw (Poland)

2007-07-01

An overview of the most popular models used for the analysis of direct reaction data is given, concentrating on practical aspects. The 4 following models (in order of increasing sophistication): the distorted wave born approximation (DWBA), the adiabatic model, the coupled channels born approximation, and the coupled reaction channels are briefly described. As a concrete example, the C{sup 12}(d,p)C{sup 13} reaction at an incident deuteron energy of 30 MeV is analysed with progressively more physically sophisticated models. The effect of the choice of the reaction model on the spectroscopic information extracted from the data is investigated and other sources of uncertainty in the derived spectroscopic factors are discussed. We have showed that the choice of the reaction model can significantly influence the nuclear structure information, particularly the spectroscopic factors or amplitudes but occasionally also the spin-parity, that we wish to extract from direct reaction data. We have also demonstrated that the DWBA can fail to give a satisfactory description of transfer data but when the tenets of the theory are fulfilled DWBA can work very well and will yield the same results as most sophisticated models. The use of global rather than fitted optical potentials can also lead to important differences in the extracted spectroscopic factors.

Study of transfer induced fission and fusion-fission reactions for 28 Si + 232 Th system at 340 MeV

International Nuclear Information System (INIS)

Prete, G.; Rizzi, V.; Fioretto, E.; Cinausero, M.; Shetty, D.V.; Pesente, S.; Brondi, A.; La Rana, G.; Moro, R.; Vardaci, E.; Boiano, A.; Ordine, A.; Gelli, N.; Lucarelli, F.; Bortignon, P.F.; Saxena, A.; Nayak, B.K.; Biswas, D.C.; Choudhury, R.K.; Kapoor, R.S.

2001-01-01

Full text: Fission induced by nucleons transfer has been investigated in the reaction 28 Si + 232 Th at 340 MeV. Looking at the projectile-like-fragments (PLF), the fission yield increases as the transfer increases, but a decreases is observed for transfers with DZ . Light charged particles in coincidence with PLF and Fission have been detected with large solid angle and show an increasing multiplicity as the Z of PLF is reduced and a constant value when fission is requested. The present results indicate inhibition of transfer induced fission reaction for higher Z transfer and increasing probability for decay through charged particle evaporation. Fission is the dominant decay process in heavy reactions involving fissile systems but the dynamical evolution of the composite system is largely governed by the formation and decay mechanisms. Important insight into the formation and the survival probability of the heavy composite nuclei formed in heavy ion collisions can be gained by simultaneously investigate the fission process and light particle emission over a continuous range of excitation energy, angular momentum and fissility. This can be achieved by studying fission induced by transfer of nucleons between the interacting projectile and the target nucleus. In the present work, we have carried out measurements on multinucleon transfer induced fission reactions in 28 Si + 232 Th system at Elab = 340 MeV. The experiment has been performed at the Laboratori Nazionale di Legnaro (LNL) using the 8pLP detector in its final configuration with 257 DE-E telescopes. The backward detectors were used to measure both light charged particles and fission fragments. The projectile-like fragments were detected using separate DE-E telescopes around the grazing angle. Two neutron detectors were placed at a distance of 115.5 cm from the target to measure neutrons emitted in coincidence with fission fragments. Here we present the results of the data analysis of transfer induced fission

Hydride Transfer versus Deprotonation Kinetics in the Isobutane–Propene Alkylation Reaction: A Computational Study

Science.gov (United States)

2017-01-01

The alkylation of isobutane with light alkenes plays an essential role in modern petrochemical processes for the production of high-octane gasoline. In this study we have employed periodic DFT calculations combined with microkinetic simulations to investigate the complex reaction mechanism of isobutane–propene alkylation catalyzed by zeolitic solid acids. Particular emphasis was given to addressing the selectivity of the alkylate formation versus alkene formation, which requires a high rate of hydride transfer in comparison to the competitive oligomerization and deprotonation reactions resulting in catalyst deactivation. Our calculations reveal that hydride transfer from isobutane to a carbenium ion occurs via a concerted C–C bond formation between a tert-butyl fragment and an additional olefin, or via deprotonation of the tert-butyl fragment to generate isobutene. A combination of high isobutane concentration and low propene concentration at the reaction center favor the selective alkylation. The key reaction step that has to be suppressed to increase the catalyst lifetime is the deprotonation of carbenium intermediates that are part of the hydride transfer reaction cycle. PMID:29226012

Hydride Transfer versus Deprotonation Kinetics in the Isobutane-Propene Alkylation Reaction: A Computational Study.

Science.gov (United States)

Liu, Chong; van Santen, Rutger A; Poursaeidesfahani, Ali; Vlugt, Thijs J H; Pidko, Evgeny A; Hensen, Emiel J M

2017-12-01

The alkylation of isobutane with light alkenes plays an essential role in modern petrochemical processes for the production of high-octane gasoline. In this study we have employed periodic DFT calculations combined with microkinetic simulations to investigate the complex reaction mechanism of isobutane-propene alkylation catalyzed by zeolitic solid acids. Particular emphasis was given to addressing the selectivity of the alkylate formation versus alkene formation, which requires a high rate of hydride transfer in comparison to the competitive oligomerization and deprotonation reactions resulting in catalyst deactivation. Our calculations reveal that hydride transfer from isobutane to a carbenium ion occurs via a concerted C-C bond formation between a tert -butyl fragment and an additional olefin, or via deprotonation of the tert -butyl fragment to generate isobutene. A combination of high isobutane concentration and low propene concentration at the reaction center favor the selective alkylation. The key reaction step that has to be suppressed to increase the catalyst lifetime is the deprotonation of carbenium intermediates that are part of the hydride transfer reaction cycle.

Excitation functions for quasi-elastic transfer reactions induced with heavy ions in bismuth

International Nuclear Information System (INIS)

Gardes, D.; Bimbot, R.; Maison, J.; Reilhac, L. de; Rivet, M.F.; Fleury, A.; Hubert, F.; Llabador, Y.

1977-01-01

The excitation functions for the production of 210 Bi, 210 Po, sup(207-211)At and 211 Rn through quasi-elastic transfer reactions induced with heavy ions in 209 Bi have been measured. The corresponding reactions involved the transfer of one neutron, one proton, two and three charges from projectile to target. The projectiles used were 12 C, 14 N, 16 O, 19 F, 20 Ne, 40 Ca, 56 Fe and 63 Cu. The experimental techniques involved target irradiations and off-line α and γ activity measurements. Chemical separations were used to solve specific problems. Careful measurements of incident energies and cross sections were performed close to the reaction thresholds

Synthesis of 3-Alkenyl-1-azaanthraquinones via Diels-Alder and Electron Transfer Reactions

Directory of Open Access Journals (Sweden)

Patrice Vanelle

2002-12-01

Full Text Available A convenient route to 3-alkenyl-1-azaanthraquinones via a hetero Diels-Alder reaction between an azadiene and naphthoquinone, a free radical chlorination and an electron transfer reaction is reported.

Quasielastic reactions

International Nuclear Information System (INIS)

Henning, W.

1979-01-01

Quasielastic reaction studies, because of their capability to microscopically probe nuclear structure, are still of considerable interest in heavy-ion reactions. The recent progress in understanding various aspects of the reaction mechanism make this aim appear closer. The relation between microscopic and macroscopic behavior, as suggested, for example, by the single proton transfer data to individual final states or averaged excitation energy intervals, needs to be explored. It seems particularly useful to extend measurements to higher incident energies, to explore and understand nuclear structure aspects up to the limit of the energy range where they are important

Transfer reactions in sup(32,36)S + sup(144,154)Sm

International Nuclear Information System (INIS)

Pacheco, A.J.; Tada, M. di; Fernandez Niello, J.; Testoni, J.E.

1990-01-01

The deformation of spherical nuclei in transfer reactions near to the coulomb barrier is studied. The sup(32,36)S + sup(144,154)Sm reactions were carried out using sup(32)S beams produced by TANDAR accelerator in Buenos Aires with energies of 148 MeV and 160 MeV and sup(36)S beams produced by tandem accelerator of Laboratorio Nazionale di Legnaro with energies of 142 MeV and 155 MeV. The angular distributions were measured for sup(32)S reaction using gas ionization chamber and position sensitive detector. The mass spectra of reaction products were obtained measuring time of flight between time detectors, in the sup(36)S reaction. (M.C.K.)

Mass transfer with complex chemical reactions in gas–liquid systems : two-step reversible reactions with unit stoichiometric and kinetic orders

NARCIS (Netherlands)

Vas Bhat, R.D.; Kuipers, J.A.M.; Versteeg, G.F.

2000-01-01

An absorption model to study gas–liquid mass transfer accompanied by reversible two-step reactions in the liquid phase has been presented. This model has been used to determine mass transfer rates, enhancement factors and concentration profiles over a wide range of process conditions. Although

Interplay of break-up and transfer processes in reactions involving weakly-bound systems

Science.gov (United States)

Vitturi, Andrea; Moschini, Laura

2018-02-01

In this note we illustrate some applications of a simple model which has been devised to clarify the reaction mechanism and the interplay of different reaction channels (elastic, inelastic, transfer, break-up) in heavy-ion collisions. The model involves two potential wells moving in one dimension and few active particles; in spite of its simplicity, it is supposed to maintain the main features, the properties and the physics of the full three-dimensional case. Special attention is given to the role of continuum states in reactions involving weakly-bound systems, and different approximation schemes (as first-order or coupled-channels) as well as different continuum discretization procedures are tested. In the case of two active particles the reaction mechanism associated with two-particle transfer and the effect of pairing intearction are investigated. Work done in collaboration with Antonio Moro and Kouichi Hagino

Theoretical study of chain transfer to solvent reactions of alkyl acrylates.

Science.gov (United States)

Moghadam, Nazanin; Srinivasan, Sriraj; Grady, Michael C; Rappe, Andrew M; Soroush, Masoud

2014-07-24

This computational and theoretical study deals with chain transfer to solvent (CTS) reactions of methyl acrylate (MA), ethyl acrylate (EA), and n-butyl acrylate (n-BA) self-initiated homopolymerization in solvents such as butanol (polar, protic), methyl ethyl ketone (MEK) (polar, aprotic), and p-xylene (nonpolar). The results indicate that abstraction of a hydrogen atom from the methylene group next to the oxygen atom in n-butanol, from the methylene group in MEK, and from a methyl group in p-xylene by a live polymer chain are the most likely mechanisms of CTS reactions in MA, EA, and n-BA. Energy barriers and molecular geometries of reactants, products, and transition states are predicted. The sensitivity of the predictions to three hybrid functionals (B3LYP, X3LYP, and M06-2X) and three different basis sets (6-31G(d,p), 6-311G(d), and 6-311G(d,p)) is investigated. Among n-butanol, sec-butanol, and tert-butanol, tert-butanol has the highest CTS energy barrier and the lowest rate constant. Although the application of the conductor-like screening model (COSMO) does not affect the predicted CTS kinetic parameter values, the application of the polarizable continuum model (PCM) results in higher CTS energy barriers. This increase in the predicted CTS energy barriers is larger for butanol and MEK than for p-xylene. The higher rate constants of chain transfer to n-butanol reactions compared to those of chain transfer to MEK and p-xylene reactions suggest the higher CTS reactivity of n-butanol.

Golden rule kinetics of transfer reactions in condensed phase: The microscopic model of electron transfer reactions in disordered solid matrices

Energy Technology Data Exchange (ETDEWEB)

Basilevsky, M. V.; Mitina, E. A. [Photochemistry Center, Russian Academy of Sciences, 7a, Novatorov ul., Moscow (Russian Federation); Odinokov, A. V. [Photochemistry Center, Russian Academy of Sciences, 7a, Novatorov ul., Moscow (Russian Federation); National Research Nuclear University “MEPhI,” 31, Kashirskoye shosse, Moscow (Russian Federation); Titov, S. V. [Karpov Institute of Physical Chemistry, 3-1/12, Building 6, Obuha pereulok, Moscow (Russian Federation)

2013-12-21

The algorithm for a theoretical calculation of transfer reaction rates for light quantum particles (i.e., the electron and H-atom transfers) in non-polar solid matrices is formulated and justified. The mechanism postulated involves a local mode (an either intra- or inter-molecular one) serving as a mediator which accomplishes the energy exchange between the reacting high-frequency quantum mode and the phonon modes belonging to the environment. This approach uses as a background the Fermi golden rule beyond the usually applied spin-boson approximation. The dynamical treatment rests on the one-dimensional version of the standard quantum relaxation equation for the reduced density matrix, which describes the frequency fluctuation spectrum for the local mode under consideration. The temperature dependence of a reaction rate is controlled by the dimensionless parameter ξ{sub 0}=ℏω{sub 0}/k{sub B}T where ω{sub 0} is the frequency of the local mode and T is the temperature. The realization of the computational scheme is different for the high/intermediate (ξ{sub 0} < 1 − 3) and for low (ξ{sub 0}≫ 1) temperature ranges. For the first (quasi-classical) kinetic regime, the Redfield approximation to the solution of the relaxation equation proved to be sufficient and efficient in practical applications. The study of the essentially quantum-mechanical low-temperature kinetic regime in its asymptotic limit requires the implementation of the exact relaxation equation. The coherent mechanism providing a non-vanishing reaction rate has been revealed when T→ 0. An accurate computational methodology for the cross-over kinetic regime needs a further elaboration. The original model of the hopping mechanism for electronic conduction in photosensitive organic materials is considered, based on the above techniques. The electron transfer (ET) in active centers of such systems proceeds via local intra- and intermolecular modes. The active modes, as a rule, operate beyond the

One-electron transfer reactions of the couple NAD./NADH

International Nuclear Information System (INIS)

Grodkowski, J.; Neta, P.; Carlson, B.W.; Miller, L.

1983-01-01

One-electron transfer reactions involving nicotinamide-adenine dinucleotide in its oxidized and reducd forms (NAD./NADH) were studied by pulse radiolysis in aqueous solutions. One-electron oxidation of NADH by various phenoxyl radicals and phenothiazine cation radicals was found to take place with rate constants in the range of 10 5 to 10 8 M -1 s -1 , depending on the redox potential of the oxidizing species. In all cases, NAD. is formed quantitatively with no indication for the existence of the protonated form (NADH + .). The spectrum of NAD., as well as the rates of oxidation of NADH by phenoxyl and by (chlorpromazine) + . were independent of pH between pH 4.5 and 13.5. Reaction of deuterated NADH indicated only a small kinetic isotope effect. All these findings point to an electron transfer mechanism. On the other hand, attempts to observe the reverse electron transfer, i.e., one-electron reduction of NAD. to NADH by radicals such as semiquinones, showed that k was less than 10 4 to 10 5 M -1 s -1 , so that it was unobservable. Consequently, it was not possible to achieve equilibrium conditions which would have permitted the direct measurement of the redox potential for NAD./NADH. One-electron reduction of NAD. appears to be an unlikely process. 1 table

Nobel Prize 1992: Rudolph A. Marcus: theory of electron transfer reactions in chemical systems

International Nuclear Information System (INIS)

Ulate Segura, Diego Guillermo

2011-01-01

A review of the theory developed by Rudolph A. Marcus is presented, who for his rating to the theory of electron transfer in chemical systems was awarded the Nobel Prize in Chemistry in 1992. Marcus theory has constituted not only a good extension of the use of a spectroscopic principle, but also has provided an energy balance and the application of energy conservation for electron transfer reactions. A better understanding of the reaction coordinate is exposed in terms energetic and establishing the principles that govern the transfer of electrons, protons and some labile small molecular groups as studied at present. Also, the postulates and equations described have established predictive models of reaction time, very useful for industrial environments, biological, metabolic, and others that involve redox processes. Marcus theory itself has also constituted a large contribution to the theory of complex transition [es

Spectroscopic study of nuclei of the 1f-2p layer by means of (16O,14C) and (16O,12C) transfer reactions

International Nuclear Information System (INIS)

Mallet-Lemaire, M.C.

1973-01-01

One-and two-nucleon transfer reactions induced by light projectiles have long been established as powerful spectroscopic tools to test one-and two-nucleon configurations of the wave functions describing the excited states of the residual nucleus A comparatively to the target nuclei A-1 and A-2. As soon as heavy ion beams became available, a further step was made in the experimental study of few-nucleon configurations by increasing the number of transferred particles as well as the variety of reactions leading to the same residual nucleus. It is well known that many theoretical models emphasize the role played by four-nucleon correlations in the microscopic description of deformed states. An experimental study of the reaction mechanism for ( 16 0, 12 C) and ( 16 0, 14 C) has been carried out by measuring angular distributions at several incident energies and excitation functions. A semi-classical description of the experimental results shows the strong influence of nuclear distortions on multi-nucleon-transfer reactions which appear with increasing incident energies. It will be noticed that spectroscopic information concerning the transferred nucleons can be achieved only through a complete finite range DWBA calculation including a microscopic nuclear structure form factor. The relative influence of the kinematic factors and nuclear structure factors on the DWBA cross-sections has been also investigated. The preliminary results on the DWBA analysis of the 54 Fe( 16 0, 12 C) 58 Ni and 48 Ca( 16 O, 14 C) 50 Ti angular distributions are discussed. Finally, ( 16 0, 14 C) and ( 16 0, 12 C) transfer reactions on different 1f-2p shell targets are described

Mass transfer with complex chemical reactions in gas-liquid systems: two-step reversible reactions with unit stoichiometric and kinetic orders

NARCIS (Netherlands)

Vas bhat, R.D.; Kuipers, J.A.M.; Versteeg, Geert

2000-01-01

An absorption model to study gas¿liquid mass transfer accompanied by reversible two-step reactions in the liquid phase has been presented. This model has been used to determine mass transfer rates, enhancement factors and concentration profiles over a wide range of process conditions. Although

Mass transfer with complex reversible chemical reactions—II. parallel reversible chemical reactions

OpenAIRE

Versteeg, G.F.; Kuipers, J.A.M.; Beckum, F.P.H. van; Swaaij, W.P.M. van

1990-01-01

An absorption model has been developed which can be used to calculate rapidly absorption rates for the phenomenon mass transfer accompanied by multiple complex parallel reversible chemical reactions. This model can be applied for the calculation of the mass transfer rates, enhancement factors and concentration profiles for a wide range of processes and conditions, for both film and penetration model. With the aid of this mass transfer model it is demonstrated that the absorption rates in syst...

The 2H(e, e' p)n reaction at large energy transfers

NARCIS (Netherlands)

Willering, Hendrik Willem

2003-01-01

At the ELSA accelerator facillity in Bonn, Germany, we have measured the deutron "breakup" reaction 2H(e,e' p)n at four-momentum transfers around Q2 = -0 .20(GeV/c)2 with an electron beam energy of E0 = 1.6 GeV. The cross section has been determined for energy transfers extending from the

Production of isomers in compound and transfer reactions with 4He ions

International Nuclear Information System (INIS)

Karamyan, S.A.; Aksenov, N.V.; Albin, Yu.A.; Bozhikov, G.A.; Dmitriev, S.N.; Starodub, G.Ya.; Vostokin, G.K.; Carroll, J.J.

2011-01-01

A well-known island of nuclear isomerism appears near A = 175-180 due to the deformation alignment of single-particle orbits at high angular momentum. This sometimes results in the formation of multi-quasiparticle states with record spin that are long-lived because of 'K-hindrance', i.e., symmetry rearrangement. Production methods and spectroscopic studies of these isomers remain a challenge for modern nuclear reaction and nuclear structure physics. Activities were produced by irradiation of 176 Yb(97.6%) enriched and nat Lu targets with 35-MeV 4 He ions from the internal beam of the U200 cyclotron. Induced activities were analyzed applying methods of radiochemistry and gamma spectroscopy. Yields of compound and nucleon-transfer reactions were measured and the isomer-to-ground state ratios were deduced. Calculated results were obtained using standard procedures to reproduce the (α, xn) cross sections, and the systematic behavior of the nucleon-transfer yields was established. The isomer-to-ground state ratios for direct reactions with 4 He ions were examined, resulting in a new characterization of the reaction mechanism

Coupled sensitizer-catalyst dyads: electron-transfer reactions in a perylene-polyoxometalate conjugate.

Science.gov (United States)

Odobel, Fabrice; Séverac, Marjorie; Pellegrin, Yann; Blart, Errol; Fosse, Céline; Cannizzo, Caroline; Mayer, Cédric R; Elliott, Kristopher J; Harriman, Anthony

2009-01-01

Ultrafast discharge of a single-electron capacitor: A variety of intramolecular electron-transfer reactions are apparent for polyoxometalates functionalized with covalently attached perylene monoimide chromophores, but these are restricted to single-electron events. (et=electron transfer, cr=charge recombination, csr=charge-shift reaction, PER=perylene, POM=polyoxometalate).A new strategy is introduced that permits covalent attachment of an organic chromophore to a polyoxometalate (POM) cluster. Two examples are reported that differ according to the nature of the anchoring group and the flexibility of the linker. Both POMs are functionalized with perylene monoimide units, which function as photon collectors and form a relatively long-lived charge-transfer state under illumination. They are reduced to a stable pi-radical anion by electrolysis or to a protonated dianion under photolysis in the presence of aqueous triethanolamine. The presence of the POM opens up an intramolecular electron-transfer route by which the charge-transfer state reduces the POM. The rate of this process depends on the molecular conformation and appears to involve through-space interactions. Prior reduction of the POM leads to efficient fluorescence quenching, again due to intramolecular electron transfer. In most cases, it is difficult to resolve the electron-transfer products because of relatively fast reverse charge shift that occurs within a closed conformer. Although the POM can store multiple electrons, it has not proved possible to use these systems as molecular-scale capacitors because of efficient electron transfer from the one-electron-reduced POM to the excited singlet state of the perylene monoimide.

Clinical survey on adverse reaction of contrast media, final report

International Nuclear Information System (INIS)

Katayama, Hitoshi; Ishida, Osamu; Osawa, Tadashi

1988-01-01

This report is a final analysis of adverse reactions to iodinated contrast media examined in 33,440 patients from 11 hospitals during the period from October 1983 through June 1986. Adverse reactions, such as nausea, exanthema and vomiting, to contrast media occurred in 2,523 patients (7.5 %), with the higher number occuring in patients aged 40 - 60, irrespective of sex. There were no significant alternations in vital signs. Patients positive for pretesting and having a history of allergy had higher incidences of adverse reactions (48 % and 52 %, respectively). A history of allergy is the most potential predictor for adverse reactions to contrast media. There was no definitive correlation between prior medication of contrast media and the occurrence of their adverse reactions. The relationship between the occurrence of adverse reactions and both kinds and dosage of contrast media was unknown. (Namekawa, K.)

Elastic scattering and cluster-transfer reactions of 98Rb on 7Li at REX-ISOLDE

CERN Document Server

Bouma, Jake

Exotic nuclei are nuclei with unusual proton to neutron ratios that exist far away from stability. Due to their instability, these nuclei are only available for nuclear reactions as radioactive ion beams. Experiments must therefore be performed in inverse kinematics at advanced radioactive isotope separation and acceleration facilities. REX-ISOLDE at CERN is one such facility, capable of producing post-accelerated radioactive ion beams with energies up to 2.85 MeV/u. Cluster-transfer reactions in inverse kinematics with a $^{7}$Li target are proposed as a tool for the study of exotic nuclei at REX-ISOLDE. In these reactions, either the $\\alpha$ or triton clusters that make up the weakly bound $^{7}$Li nucleus can be transfered to the beam nucleus. The remaining cluster that is not transferred can be detected, and identifies the particular transfer channel. Through this mechanism it is possible to populate states of very high spin, which is useful for $\\gamma$-spectroscopy in poorly known exotic regions. Speci...

Exciplex mediated photoinduced electron transfer reactions of phthalocyanine-fullerene dyads

NARCIS (Netherlands)

Niemi, Marja; Tkachenko, Nikolai V.; Efimov, Alexander; Lehtivuori, Heli; Ohkubo, Kei; Fukuzumi, Shunichi; Lemmetyinen, Helge

2008-01-01

Evidences of an intramolecular exciplex intermediate in a photoinduced electron transfer (ET) reaction of double-linked free-base and zinc phthalocyanine-C-60 dyads were found. This was the first time for a dyad with phthalocyanine donor. Excitation of the phthalocyanine moiety of the dyads results

Communication: Transfer Ionization in a Thermal Reaction of a Cation and Anion: Ar+ with Br and I (Postprint)

Science.gov (United States)

2016-01-29

AFRL-RV-PS- AFRL-RV-PS- TP-2015-0016 TP-2015-0016 COMMUNICATION: TRANSFER IONIZATION IN A THERMAL REACTION OF A CATION AND ANION: AR+ WITH BR...DATES COVERED (From - To) 01 Jun 2013 – 23 Sep 2013 4. TITLE AND SUBTITLE Communication: Transfer Ionization in a Thermal Reaction of a Cation and Anion...Rights. Communication: Transfer ionization in a thermal reaction of a cation and anion: Ar+ with Br− and I− Nicholas S. Shuman, Thomas M. Miller

Electron transfer reactions of macrocyclic compounds of cobalt

Energy Technology Data Exchange (ETDEWEB)

Heckman, R.A.

1978-08-01

The kinetics and mechanisms of reduction of H/sub 2/O/sub 2/, Br/sub 2/, and I/sub 2/ by various macrocyclic tetraaza complexes of cobalt(II), including Vitamin B/sub 12r/, were studied. The synthetic macrocycles studied were all 14-membered rings which varied in the degree of unsaturation,substitution of methyl groups on the periphery of the ring, and substitution within the ring itself. Scavenging experiments demonstrated that the reductions of H/sub 2/O/sub 2/ produce free hydroxyl radicals only in the case of Co((14)ane)/sup 2 +/ but with none of the others. In the latter instances apparently H/sub 2/O/sub 2/ simultaneously oxidizes the metal center and the ligand. The reductions of Br/sub 2/ and I/sub 2/ produce an aquohalocobalt(III) product for all reductants (except B/sub 12r/ + Br/sub 2/, which was complicated by bromination of the corrin ring). The mechanism of halogen reduction was found to involve rate-limiting inner-sphere electron transfer from cobalt to halogen to produce a dihalide anion coordinated to the cobalt center. This intermediate subsequently decomposes in rapid reactions to halocobalt(III) and halogen atom species or reacts with another cobalt(II) center to give two molecules of halocobalt(III). The reductions of halomethylcobaloximes and related compounds and diamminecobaloxime by Cr/sup 2 +/ were also studied. The reaction was found to be biphasic in all cases with the reaction products being halomethane (for the halomethylcobaloximes), Co/sup 2 +/ (in less than 100 percent yield), a Cr(III)-dimethylglyoxime species, a small amount of free dmgH/sub 2/, and a highly-charged species containing both cobalt and chromium. The first-stage reaction occurs with a stoichiometry of 1:1 producing an intermediate with an absorption maximum at 460 nm for all starting reagents. The results were interpreted in terms of inner-sphere coordination of the cobaloxime to the Cr(II) and electron transfer through the oxime N-O bond.

Promotion of multi-electron transfer for enhanced photocatalysis: A review focused on oxygen reduction reaction

Energy Technology Data Exchange (ETDEWEB)

Wang, Changhua [Centre for Advanced Optoelectronic Functional Materials Research, and Key Laboratory for UV-Emitting Materials and Technology of Ministry of Education, Northeast Normal University, Changchun 130024 (China); College of Chemistry and Biology, Beihua University, Jilin 132013 (China); Zhang, Xintong, E-mail: xtzhang@nenu.edu.cn [Centre for Advanced Optoelectronic Functional Materials Research, and Key Laboratory for UV-Emitting Materials and Technology of Ministry of Education, Northeast Normal University, Changchun 130024 (China); Liu, Yichun [Centre for Advanced Optoelectronic Functional Materials Research, and Key Laboratory for UV-Emitting Materials and Technology of Ministry of Education, Northeast Normal University, Changchun 130024 (China)

2015-12-15

Highlights: • Oxygen reduction reaction (ORR) in photocatalysis process is focused. • Multi-electron transfer ORR is reviewed. • This review provides a guide to access to enhanced photocatalysis via multi-electron transfer. - Abstract: Semiconductor photocatalysis has attracted significant interest for solar light induced environmental remediation and solar fuel generation. As is well known, photocatalytic performance is determined by three steps: photoexcitation, separation and transport of photogenerated charge carriers, and surface reactions. To achieve higher efficiency, significant efforts have been made on improvement of efficiency of above first two steps, which have been well documented in recent review articles. In contrast, this review intends to focus on strategies moving onto the third step of improvement for enhanced photocatalysis wherein active oxygen species including superoxide radical, hydrogen peroxide, hydroxyl radical are in situ detected. Particularly, surface electron-transfer reduction of oxygen over single component photocatalysts is reviewed and systems enabling multi-electron transfer induced oxygen reduction reaction (ORR) are highlighted. It is expected this review could provide a guideline for readers to better understand the critical role of ORR over photocatalyst in charge carrier separation and transfer and obtain reliable results for enhanced aerobic photocatalysis.

Studies of Silyl-Transfer Photochemical Reactions of N-[(Trimethylsilyl)alkyl]saccharins

Energy Technology Data Exchange (ETDEWEB)

Cho, Dae Won; Oh, Sun Wha; Park, Hea Jung; Yoon, Ung Chan [Pusan National University, Busan (Korea, Republic of); Kim, Dong Uk [Daegu National University of Education, Daegu (Korea, Republic of); Xue, Jin Ying [Harbin Normal University, Harbin (China); Mariano, Patrick S. [University of New Mexico, Albuquerque (United States)

2010-09-15

Photochemical studies of N-[(trimethylsilyl)alkyl]saccharins were carried out to investigate their photochemical behavior. Depending on the nature of the substrate and the solvent system employed, reactions of these substances can take place by either SET-promoted silyl migration from carbon to either the amide carbonyl or sulfonyl oxygen or by a N-S homolysis route. The results of the current studies show that an azomethine ylide, arising from a SET-promoted silyl migration pathway, is generated in photoreactions of N-[(trimethylsilyl)methyl]saccharin and this intermediate reacts to give various photoproducts depending on the conditions employed. In addition, irradiation of N-[(trimethylsily)ethyl]saccharin produces an excited state that reacts through two pathways, the relative importance is governed by solvent polarity and protic nature. Finally, photoirradiation of N-[(trimethylsilyl)propyl]saccharin in a highly polar solvent system comprised of 35% aqueous MeOH gives rise to formation of a tricyclic pyrrolizidine and saccharin that generated via competitive SET-promoted silyl transfer and γ-hydrogen abstraction pathways.

Studies of Silyl-Transfer Photochemical Reactions of N-[(Trimethylsilyl)alkyl]saccharins

International Nuclear Information System (INIS)

Cho, Dae Won; Oh, Sun Wha; Park, Hea Jung; Yoon, Ung Chan; Kim, Dong Uk; Xue, Jin Ying; Mariano, Patrick S.

2010-01-01

Photochemical studies of N-[(trimethylsilyl)alkyl]saccharins were carried out to investigate their photochemical behavior. Depending on the nature of the substrate and the solvent system employed, reactions of these substances can take place by either SET-promoted silyl migration from carbon to either the amide carbonyl or sulfonyl oxygen or by a N-S homolysis route. The results of the current studies show that an azomethine ylide, arising from a SET-promoted silyl migration pathway, is generated in photoreactions of N-[(trimethylsilyl)methyl]saccharin and this intermediate reacts to give various photoproducts depending on the conditions employed. In addition, irradiation of N-[(trimethylsily)ethyl]saccharin produces an excited state that reacts through two pathways, the relative importance is governed by solvent polarity and protic nature. Finally, photoirradiation of N-[(trimethylsilyl)propyl]saccharin in a highly polar solvent system comprised of 35% aqueous MeOH gives rise to formation of a tricyclic pyrrolizidine and saccharin that generated via competitive SET-promoted silyl transfer and γ-hydrogen abstraction pathways

Influence of zeolite pore structure on product selectivities for protolysis and hydride transfer reactions in the cracking of n-pentane.

Science.gov (United States)

Miyaji, Akimitsu; Iwase, Yasuyoshi; Nishitoba, Toshiki; Long, Nguyen Quang; Motokura, Ken; Baba, Toshihide

2015-02-21

The conversion of n-pentane was carried out to examine the effects of reaction conditions on changes in product selectivities at 823 K, using zeolites with 10- and 12-membered rings. We also investigated the influence of the pore structure of these zeolites on their catalytic activities for both protolysis and hydride transfer reactions. In the first half of this work, we examined the influence of acidic proton concentration and n-pentane pressure on the reaction rates for protolysis and hydride transfer reactions using ZSM-5 zeolites. The rates of hydride transfer reactions were more influenced by pentane pressure compared to protolysis reactions, and were proportional to the square of n-pentane pressure and the concentration of acidic protons. In the second half of this work, the influence of the zeolite pore structure on changes in product selectivities with n-pentane conversion and that on the rates of protolysis and the hydride transfer reactions were revealed using various zeolites with 10- and 12-membered rings. The catalytic activities of zeolites for the protolysis and hydride transfer reactions were influenced more by the spatial volume of the zeolite cavity than the acid strength of protons on the zeolite.

Understanding the two neutron transfer reaction mechanism in {sup 206}Pb({sup 18}O,{sup 16}O){sup 208}Pb

Energy Technology Data Exchange (ETDEWEB)

Parmar, A.; Sonika [Nuclear Physics Division, Bhabha Atomic Research Centre, Mumbai - 400 085 (India); Roy, B.J., E-mail: bjroy@barc.gov.in [Nuclear Physics Division, Bhabha Atomic Research Centre, Mumbai - 400 085 (India); Jha, V.; Pal, U.K. [Nuclear Physics Division, Bhabha Atomic Research Centre, Mumbai - 400 085 (India); Sinha, T. [High Energy Nuclear and Particle Physics Division, Saha Institute of Nuclear Physics, Kolkata - 700 064 (India); Pandit, S.K.; Parkar, V.V.; Ramachandran, K.; Mahata, K.; Santra, S.; Mohanty, A.K. [Nuclear Physics Division, Bhabha Atomic Research Centre, Mumbai - 400 085 (India)

2015-08-15

The absolute cross sections for elastic scattering and two-neutron transfer reaction for {sup 18}O + {sup 206}Pb system have been measured at an incident energy near the Coulomb barrier. Detailed coupled reaction channel calculations have been carried out for description of the measured angular distributions for the elastic scattering and transfer reactions simultaneously. The two-neutron transfer reaction {sup 206}Pb({sup 18}O, {sup 16}O){sup 208}Pb in the g.s. → g.s. transition is analyzed in (i) extreme cluster model assuming a di-neutron transfer, (ii) two-step successive transfer, and (iii) microscopic approach (independent coordinate scheme) of simultaneous transfer of two neutrons. The relative importance of one step simultaneous transfer versus two-step successive transfer has been studied. Present analysis suggests dominance of cluster transfer of a di-neutron. The contribution from the two-step sequential processes is less significant, however, the combined “two-step plus simultaneous (microscopic)” calculations give a reasonably good agreement with the measurement. The possibility of multi-step route via projectile and target excitations and contribution from such indirect transfer paths to the present two-neutron transfer cross section has been investigated.

Kinetic Monte Carlo modeling of chemical reactions coupled with heat transfer.

Science.gov (United States)

Castonguay, Thomas C; Wang, Feng

2008-03-28

In this paper, we describe two types of effective events for describing heat transfer in a kinetic Monte Carlo (KMC) simulation that may involve stochastic chemical reactions. Simulations employing these events are referred to as KMC-TBT and KMC-PHE. In KMC-TBT, heat transfer is modeled as the stochastic transfer of "thermal bits" between adjacent grid points. In KMC-PHE, heat transfer is modeled by integrating the Poisson heat equation for a short time. Either approach is capable of capturing the time dependent system behavior exactly. Both KMC-PHE and KMC-TBT are validated by simulating pure heat transfer in a rod and a square and modeling a heated desorption problem where exact numerical results are available. KMC-PHE is much faster than KMC-TBT and is used to study the endothermic desorption of a lattice gas. Interesting findings from this study are reported.

The effect of intramolecular quantum modes on free energy relationships for electron transfer reactions

DEFF Research Database (Denmark)

Ulstrup, Jens; Jortner, Joshua

1975-01-01

A general quantum mechanical description of exothermic electron transfer reactions is formulated by treating such reactions as the nonradiative decay of a ''supermolecule'' consisting of the electron donor, the electron acceptor, and the polar solvent. In particular, the role of the high-frequenc...

The measurement of cross sections of inelastic and transfer reactions with gamma-particle coincidence

International Nuclear Information System (INIS)

Zagatto, V.A.B.; Oliveira, J.R.B.; Pereira, D.; Allegro, P.R.P.; Chamon, L.C.; Cybulska, E.W.; Medina, N.H.; Ribas, R.V.; Rossi Junior, E.S.; Seale, W.A.; Silva, C.P.; Gasques, L.; Toufen, D.L.; Silveira, M.A.G.; Zahn, G.S.; Genezini, F.A.; Shorto, J.M.B.; Lubian, J.; Linares, R.

2011-01-01

Full text: The following work aims to obtain experimental reaction cross sections of inelastic excitation and transfer to excited states reactions (both measured by gamma-particle coincidences) and its comparison with theoretical predictions based in a new model based on the Sao Paulo Potential. The measurements were made at the Pelletron accelerator laboratory of the University of Sao Paulo with the Saci-Perere spectrometer, which consists of 4 a GeHP Compton suppressed gamma detectors and a 4 π charged particle ancillary system with 11ΔΕ - Ε plastic phoswich scintillators (further details about the experimental procedure may be found in: J.R.B. Oliveira et al., XVIII International School on Nuclear Physics, Neutron Physics and Applications (2009). Theoretical angular distribution calculations (using code GOSIA) were performed with a new model based on the Sao Paulo Potential, specifically developed for the inclusion of dissipative processes like deep-inelastic collisions (DIC) considering the Coulomb plus nuclear potential (with the aid of code FRESCO). The experimental cross sections were obtained such as described in J.R.B. Oliveira et al however, in this work, the particle-gamma angular correlations and the vacuum de-alignment effects (caused by hyperfine interaction) were finally added for the 110 Pd inelastic reaction and for the 112 Pd transfer reaction. For these purposes a new code has been developed to assist in the data analysis. We take into account the particle-gamma angular correlations using the scattering amplitudes given by FRESCO, considering the vacuum de-alignment effects as proposed by A. Abragam and R. V. Pound, Phys. Rev. 92, 943 (1953). The theoretical predictions still consider 2 different types of Sao Paulo Potential, the first one has a multiplying factor equals to 1.0 in the real part of the potential and the second considers this factor equals to 0.6, as proposed in D. Pereira, J. Lubian, J.R.B. Oliveira, D.P. de Sousa and L

Pentanidium-catalyzed enantioselective phase-transfer conjugate addition reactions

KAUST Repository

Ma, Ting

2011-03-09

A new chiral entity, pentanidium, has been shown to be an excellent chiral phase-transfer catalyst. The enantioselective Michael addition reactions of tert-butyl glycinate-benzophenone Schiff base with various α,β- unsaturated acceptors provide adducts with high enantioselectivities. A successful gram-scale experiment at a low catalyst loading of 0.05 mol % indicates the potential for practical applications of this methodology. Phosphoglycine ester analogues can also be utilized as the Michael donor, affording enantioenriched α-aminophosphonic acid derivatives and phosphonic analogues of (S)-proline. © 2011 American Chemical Society.

Molecular dynamics simulation of the first electron transfer step in the oxygen reduction reaction

NARCIS (Netherlands)

Hartnig, C.B.; Koper, M.T.M.

2002-01-01

We present a molecular dynamics simulation of solvent reorganization in the first electron transfer step in the oxygen reduction reaction, i.e. O2+e-¿O2-, modeled as taking place in the outer Helmholtz plane. The first electron transfer step is usually considered the rate-determining step from many

Transfer and breakup reactions in 16O + CsI at 16.4 MeV/n

Directory of Open Access Journals (Sweden)

M.J. Murphy

1983-01-01

Full Text Available A streamer-chamber particle-telescope system has been used to observe ejectile charge, energy, and associated charged particle multiplicity in the reaction of 16O + CsI at 16.4 MeV/n. The measurement provides relative probabilities for transfer and projectile breakup as a function of ejectile charge, and spectra for the heavy ejectiles from transfer and breakup events. The results show that the interaction energy of 16.4 MeV/n is near the threshold for breakup reactions in heavy-ion collisions.

Analysis of Native-Like Proteins and Protein Complexes Using Cation to Anion Proton Transfer Reactions (CAPTR)

Science.gov (United States)

Laszlo, Kenneth J.; Bush, Matthew F.

2015-12-01

Mass spectra of native-like protein complexes often exhibit narrow charge-state distributions, broad peaks, and contributions from multiple, coexisting species. These factors can make it challenging to interpret those spectra, particularly for mixtures with significant heterogeneity. Here we demonstrate the use of ion/ion proton transfer reactions to reduce the charge states of m/ z-selected, native-like ions of proteins and protein complexes, a technique that we refer to as cation to anion proton transfer reactions (CAPTR). We then demonstrate that CAPTR can increase the accuracy of charge state assignments and the resolution of interfering species in native mass spectrometry. The CAPTR product ion spectra for pyruvate kinase exhibit ~30 peaks and enable unambiguous determination of the charge state of each peak, whereas the corresponding precursor spectra exhibit ~6 peaks and the assigned charge states have an uncertainty of ±3%. 15+ bovine serum albumin and 21+ yeast enolase dimer both appear near m/ z 4450 and are completely unresolved in a mixture. After a single CAPTR event, the resulting product ions are baseline resolved. The separation of the product ions increases dramatically after each subsequent CAPTR event; 12 events resulted in a 3000-fold improvement in separation relative to the precursor ions. Finally, we introduce a framework for interpreting and predicting the figures of merit for CAPTR experiments. More generally, these results suggest that CAPTR strongly complements other mass spectrometry tools for analyzing proteins and protein complexes, particularly those in mixtures.

Reaction Coordinate, Free Energy, and Rate of Intramolecular Proton Transfer in Human Carbonic Anhydrase II.

Science.gov (United States)

Paul, Sanjib; Paul, Tanmoy Kumar; Taraphder, Srabani

2018-03-22

The role of structure and dynamics of an enzyme has been investigated at three different stages of its function including the chemical event it catalyzes. A one-pot computational method has been designed for each of these stages on the basis of classical and/or quantum mechanical-molecular mechanical molecular dynamics and transition path sampling simulations. For a pair of initial and final states A and B separated by a high free-energy barrier, using a two-stage selection process, several collective variables (CVs) are identified that can delineate A and B. However, these CVs are found to exhibit strong cross-coupling over the transition paths. A set of mutually orthogonal order parameters is then derived from these CVs and an optimal reaction coordinate, r, determined applying half-trajectory likelihood maximization along with a Bayesian information criterion. The transition paths are also used to project the multidimensional free energy surface and barrier crossing dynamics along r. The proposed scheme has been applied to the rate-determining intramolecular proton transfer reaction of the well-known enzyme human carbonic anhydrase II. The potential of mean force, F( r), in the absence of the chemical step is found to reproduce earlier results on the equilibrium population of two side-chain orientations of key residue His-64. Estimation of rate constants, k, from mean first passage times for the three different stages of catalysis shows that the rate-determining step of intramolecular proton transfer occurs with k ≃ 1.0 × 10 6 s -1 , in close agreement with known experimental results.

Long-range versus short-range correlations in the two-neutron transfer reaction 64Ni(18O,16O)66Ni

Science.gov (United States)

Paes, B.; Santagati, G.; Vsevolodovna, R. Magana; Cappuzzello, F.; Carbone, D.; Cardozo, E. N.; Cavallaro, M.; García-Tecocoatzi, H.; Gargano, A.; Ferreira, J. L.; Lenzi, S. M.; Linares, R.; Santopinto, E.; Vitturi, A.; Lubian, J.

2017-10-01

Recently, various two-neutron transfer studies using the (18O,16O) reaction were performed with a large success. This was achieved because of a combined use of the microscopic quantum description of the reaction mechanism and of the nuclear structure. In the present work we use this methodology to study the two-neutron transfer reaction of the 18O+64Ni system at 84 MeV incident energy, to the ground and first 2+ excited state of the residual 66Ni nucleus. All the experimental data were measured by the large acceptance MAGNEX spectrometer at the Instituto Nazionale di Fisica Nucleare -Laboratori Nazionali del Sud (Italy). We have performed exact finite range cross section calculations using the coupled channel Born approximation (CCBA) and coupled reaction channel (CRC) method for the sequential and direct two-neutron transfers, respectively. Moreover, this is the first time that the formalism of the microscopic interaction boson model (IBM-2) was applied to a two-neutron transfer reaction. From our results we conclude that for two-neutron transfer to the ground state of 66Ni, the direct transfer is the dominant reaction mechanism, whereas for the transfer to the first excited state of 66Ni, the sequential process dominates. A competition between long-range and short-range correlations is discussed, in particular, how the use of two different models (Shell model and IBM's) help to disentangle long- and short-range correlations.

The improvement of the heat transfer model for sodium-water reaction jet code

International Nuclear Information System (INIS)

Hashiguchi, Yoshirou; Yamamoto, Hajime; Kamoshida, Norio; Murata, Shuuichi

2001-02-01

For confirming the reasonable DBL (Design Base Leak) on steam generator (SG), it is necessary to evaluate phenomena of sodium-water reaction (SWR) in an actual steam generator realistically. The improvement of a heat transfer model on sodium-water reaction (SWR) jet code (LEAP-JET ver.1.40) and application analysis to the water injection tests for confirmation of propriety for the code were performed. On the improvement of the code, the heat transfer model between a inside fluid and a tube wall was introduced instead of the prior model which was heat capacity model including both heat capacity of the tube wall and inside fluid. And it was considered that the fluid of inside the heat exchange tube was able to treat as water or sodium and typical heat transfer equations used in SG design were also introduced in the new heat transfer model. Further additional work was carried out in order to improve the stability of the calculation for long calculation time. The test calculation using the improved code (LEAP-JET ver.1.50) were carried out with conditions of the SWAT-IR·Run-HT-2 test. It was confirmed that the SWR jet behavior on the result and the influence to the result of the heat transfer model were reasonable. And also on the improved code (LEAP-JET ver.1.50), user's manual was revised with additional I/O manual and explanation of the heat transfer model and new variable name. (author)

Polymerization of Acetonitrile via a Hydrogen Transfer Reaction from CH3 to CN under Extreme Conditions.

Science.gov (United States)

Zheng, Haiyan; Li, Kuo; Cody, George D; Tulk, Christopher A; Dong, Xiao; Gao, Guoying; Molaison, Jamie J; Liu, Zhenxian; Feygenson, Mikhail; Yang, Wenge; Ivanov, Ilia N; Basile, Leonardo; Idrobo, Juan-Carlos; Guthrie, Malcolm; Mao, Ho-Kwang

2016-09-19

Acetonitrile (CH3 CN) is the simplest and one of the most stable nitriles. Reactions usually occur on the C≡N triple bond, while the C-H bond is very inert and can only be activated by a very strong base or a metal catalyst. It is demonstrated that C-H bonds can be activated by the cyano group under high pressure, but at room temperature. The hydrogen atom transfers from the CH3 to CN along the CH⋅⋅⋅N hydrogen bond, which produces an amino group and initiates polymerization to form a dimer, 1D chain, and 2D nanoribbon with mixed sp(2) and sp(3) bonded carbon. Finally, it transforms into a graphitic polymer by eliminating ammonia. This study shows that applying pressure can induce a distinctive reaction which is guided by the structure of the molecular crystal. It highlights the fact that very inert C-H can be activated by high pressure, even at room temperature and without a catalyst. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Spin transfer in reactions between heavy ions

International Nuclear Information System (INIS)

Dong Pil Min.

1980-06-01

The model presented affords a better understanding of the manner in which the orbital angular moment can be converted into an intrinsic spin in the collision between two heavy ions. After referring to the vector fields and the collective energy of a spheroidal nucleus, the calculation of the exchange of nucleons is described and the dissipation function is constructed. The spin transfer and the reorientation of the spin during the reaction are then examined (effect of friction and vibration). The estimated calculations are compared with the results of the 63 Cu+ 197 Au and 86 Kr+ 209 Bi experiments. The sensitivity of the calculation to the parameters of the model is discussed (nuclear potential, vibrational inertial parameter) [fr

Membrane introduction proton-transfer-reaction mass spectrometry

International Nuclear Information System (INIS)

Alexander, M.; Boscaini, E.; Maerk, T.; Lindinger, W.

2002-01-01

Proton-transfer-reaction mass spectrometry (PTR-MS) is a rapidly expanding field with multiple applications in ion physics, atmospheric chemistry, food chemistry, volatile organic compounds monitoring and biology. Initial studies that combine PTR-MS and membrane introduction mass spectrometry (MIMS) were researched and outlined. First using PTR-MS, certain fundamental physical properties of a poly-dimethylsiloxane (PDMS) membrane including solubilities and diffusion coefficients were measured. Second, it was shown how the chemical selectivity of the (PDMS) can be used to extend the capabilities of the PTR-MS instrument by eliminating certain isobaric interferences and excluding water from volatile organic compounds (VOCs). Experiments with mixtures of several VOCs (toluene, benzene, acetone, propanal, methanol) are presented. (nevyjel)

Momentum transfer in relativistic heavy ion charge-exchange reactions

Science.gov (United States)

Townsend, L. W.; Wilson, J. W.; Khan, F.; Khandelwal, G. S.

1991-01-01

Relativistic heavy ion charge-exchange reactions yield fragments (Delta-Z = + 1) whose longitudinal momentum distributions are downshifted by larger values than those associated with the remaining fragments (Delta-Z = 1, -2,...). Kinematics alone cannot account for the observed downshifts; therefore, an additional contribution from collision dynamics must be included. In this work, an optical model description of collision momentum transfer is used to estimate the additional dynamical momentum downshift. Good agreement between theoretical estimates and experimental data is obtained.

Studies of transfer reactions of photosensitized electrons involving complexes of transition metals in view of solar energy storage

International Nuclear Information System (INIS)

Takakubo, Masaaki

1984-01-01

This research thesis addresses electron transfer reactions occurring during photosynthesis, for example, photosensitized reaction in which chlorophyll is the sensitizer. More specifically, the author studied experimentally electron photo-transfers with type D sensitizers (riboflavin, phenoxazine and porphyrin), and various complexes of transition metals. After a presentation of these experiments, the author describes the photosensitisation process (photo-physics of riboflavin, oxygen deactivation, sensitized photo-oxidation and photo-reduction). The theoretical aspect of electron transfer is then addressed: generalities, deactivation of the riboflavin triplet, initial efficiency of electron transfer. Experimental results on three basic processes (non-radiative deactivation, energy transfer, electron transfer) are interpreted in a unified way by using the non-radiative transfer theory. Some applications are described: photo-electrochemical batteries, photo-oxidation and photo-reduction of the cobalt ion

Densities of accessible final states for multi-step compound reactions

International Nuclear Information System (INIS)

Maoming De; Guo Hua

1993-01-01

The densities of accessible final states for calculations of multi-step compound reactions are derived. The Pauli exclusion principle is taken into account in the calculations. The results are compared with a previous author's results and the effect of the Pauli exclusion principle is investigated. (Author)

Study of neutron-proton pairing in N=Z unstable nuclei through transfer reactions

International Nuclear Information System (INIS)

Le Crom, B.

2016-01-01

A nucleus is described as a set of independent neutrons and protons linked by a mean-field potential. However, in order to have a better description one needs to take into account some residual interactions such as pairing. Neutron-neutron and proton-proton pairings are well-studied but neutron-proton pairing is not well-known. np pairing can be isovector pairing such as nn and pp pairing or isoscalar which is yet unknown. Over-binding of N=Z nuclei could be a manifestation of np pairing. We have studied np pairing through transfer reactions. In this case, the cross-section of np pair transfer is expected to be enhanced in the presence of important np pairing. np pairing is expected to be important in N=Z nuclei with high J orbitals. Since the development of radioactive beam facilities, such beams are only available. The experiment was performed at GANIL with an efficient set-up so as to detect products from the (p, 3 He) transfer reaction. This reaction is affected by isovector and isoscalar np pairing. We used 56 Ni and 52 Fe beams so as to see the effect of the occupancy of 0f 7/2 shell on the np pairing. First, we analysed the data from the 56 Ni(p,d) 55 Ni reaction and we compared the results with the literature to validate analysis procedure. After analysing data from the 56 Ni(p, 3 He) 54 Co reaction and extracting the population of the various states of 54 Co, we obtained information about the relative intensity between isoscalar and isovector np pairing in 56 Ni showing the predominance of isovector np pairing in this nucleus. Moreover, in the framework of developing a new charged particle detector, research on the discrimination of light nuclei using pulse shape analysis was performed and is also presented. (author)

Pore to core scale simulation of the mass transfer with mineral reaction in porous media

International Nuclear Information System (INIS)

Bekri, S.; Renard, S.; Delprat-Jannaud, F.

2015-01-01

Pore Network Model (PNM) is used to simulate mass transfer with mineral reaction in a single phase flow through porous medium which is here a sandstone sample from the reservoir formation of the Pakoslaw gas field. The void space of the porous medium is represented by an idealized geometry of pore-bodies joined by pore-throats. Parameters defining the pore-bodies and the pore-throats distribution are determined by an optimization process aiming to match the experimental Mercury Intrusion Capillary Pressure (MICP) curve and petrophysical properties of the rock such as intrinsic permeability and formation factor. The generated network is used first to simulate the multiphase flow by solving Kirchhoff's laws. The capillary pressure and relative permeability curves are derived. Then, reactive transport is addressed under asymptotic regime where the solute concentration undergoes an exponential evolution with time. The porosity/ permeability relationship and the three phenomenological coefficients of transport, namely the solute velocity, the dispersion and the mean reaction rate are determined as functions of Peclet and Peclet-Damkohler dimensionless numbers. Finally, the role of the dimensionless numbers on the reactive flow properties is highlighted. (authors)

Stereochemistry of 1,2-elimination and proton-transfer reactions: toward a unified understanding.

Science.gov (United States)

Mohrig, Jerry R

2013-07-16

Many mechanistic and stereochemical studies have focused on the breaking of the C-H bond through base-catalyzed elimination reactions. When we began our research, however, chemists knew almost nothing about the stereospecificity of addition-elimination reactions involving conjugated acyclic carbonyl compounds, even though the carbonyl group is a pivotal functional group in organic chemistry. Over the last 25 years, we have studied the addition-elimination reactions of β-substituted acyclic esters, thioesters, and ketones in order to reach a comprehensive understanding of how electronic effects influence their stereochemistry. This Account brings together our understanding of the stereochemistry of 1,2-elimination and proton-transfer reactions, describing how each study has built upon previous work and contributed to our understanding of this field. When we began, chemists thought that anti stereospecificity in base-catalyzed 1,2-elimination reactions occurred via concerted E2 mechanisms, which provide a smooth path for anti elimination. Unexpectedly, we discovered that some E1cBirrev reactions produce the same anti stereospecificity as E2 reactions even though they proceed through diffusionally equilibrated, "free" enolate-anion intermediates. This result calls into question the conventional wisdom that anti stereochemistry must result from a concerted mechanism. While carrying out our research, we developed insights ranging from the role of historical contingency in the evolution of hydratase-dehydratase enzymes to the influence of buffers on the stereochemistry of H/D exchange in D2O. Negative hyperconjugation is the most important concept for understanding our results. This idea provides a unifying view for the largely anti stereochemistry in E1cBirrev elimination reactions and a basis for understanding the stereoelectronic influence of electron-withdrawing β-substituents on proton-transfer reactions.

Microporous hollow fibre membrane modules as gas-liquid contactors. Part 2. Mass transfer with chemical reaction

NARCIS (Netherlands)

Kreulen, H.; Versteeg, G.F.; Swaaij, W.P.M. van

1993-01-01

Absorption determined by mass transfer in the liquid is described well with the Graetz-Lévèque equation adapted from heat transfer. The influence of a chemical reaction on the mass transfer was simulated with a numerical model and tested on the absorption of CO2 in a hydroxide solution. Absorption

Proton transfer reaction time-of-flight mass spectrometry advancement in detection of hazardous substances

International Nuclear Information System (INIS)

Agarwal, B.

2012-01-01

Proton Transfer Reaction Mass Spectrometry (PTR-MS) is a mass spectrometric technique based on chemical ionization, which provides very rapid measurements (within seconds) of volatile organic compounds in air, usually without special sample preparation, and with a very low detection limit. The detection and study of product ion patterns of threat agents such as explosives and drugs and some major environmental pollutants (isocyanates and polychlorinated biphenyls (PCBs)) is explored in detail here using PTR-MS, specifically Proton Transfer Reaction Time-of-Flight Mass Spectrometry (PTR-TOF-MS). The proton transfer reaction (PTR) principle works on the detection of the compound in the vapor phase. For some compounds, which have extremely low vapor pressures, both sample and inlet line heating were needed. Generally, the protonated parent molecule (MH+) is found to be the dominant product ion, which therefore provides us with a higher level of confidence in the assignment of a trace compound. However, for several compounds, dissociative proton transfer can occur at various degrees resulting in other product ions. Analysis of other compounds, such as the presence of taggants and impurities were carried out, and in certain compounds unusual E/N anomalies were discovered (E/N is an instrumental set of parameters, where E is the electric field strength and N is the number density). Head space measurements above four different drinks (plain water, tea, red wine and white wine) spiked with four different 'date rape' drugs were also conducted. (author)

Enantioselective H-atom transfer reaction: a strategy to synthesize formaldehyde aldol products.

Science.gov (United States)

Sibi, Mukund P; Patil, Kalyani

2005-04-14

[reaction: see text] Enantioselective radical alkylation of Baylis-Hillman adducts furnished aldol products in good yield and selectivity. The results illustrate that the selectivity in the hydrogen atom transfer is dependent on the size of the ester substituent, with smaller substituents providing better enantioselectivity.

Analysis of trace gases at ppb levels by proton transfer reaction mass spectrometry (PTR-MS)

International Nuclear Information System (INIS)

Lindinger, W.; Hansel, A.

1996-01-01

A proton transfer reaction mass spectrometry (PTR-MS) system has been developed which allows for on-line measurements of trace gas components with concentrations as low as 1 ppb. The method is based on reactions of H 3 O + ions, which perform non-dissociative proton transfer to most of the common organic trace constituents but do not react with any of the components present in clean air. Examples of medical information obtained by means of breath analysis, of environmental trace analysis, and examples in the field of food chemistry demonstrate the wide applicability of the method. (Authors)

Electronic shift register memory based on molecular electron-transfer reactions

Science.gov (United States)

Hopfield, J. J.; Onuchic, Jose Nelson; Beratan, David N.

1989-01-01

The design of a shift register memory at the molecular level is described in detail. The memory elements are based on a chain of electron-transfer molecules incorporated on a very large scale integrated (VLSI) substrate, and the information is shifted by photoinduced electron-transfer reactions. The design requirements for such a system are discussed, and several realistic strategies for synthesizing these systems are presented. The immediate advantage of such a hybrid molecular/VLSI device would arise from the possible information storage density. The prospect of considerable savings of energy per bit processed also exists. This molecular shift register memory element design solves the conceptual problems associated with integrating molecular size components with larger (micron) size features on a chip.

A dynamical theory of incomplete fusion reactions: The breakup-fusion reaction approach

International Nuclear Information System (INIS)

Udagawa, T.

1984-01-01

A dynamical theory of partial fusion reactions is presented, which may fill the gap between direct and compound nuclear reaction theories. With the new theory one can calculate partial fusion taking place in three-body (and many more) channels reached via direct reactions, e.g., breakup and knockout reactions. The authors present first the results for the cross section for such reactions, taking as an example breakup followed by fusion. They then discuss a physical picture which emerges from their theory, namely that the partial fusion reactions, particularly of the massive-transfer type, take place in a so-called deep peripheral region. It is also shown that the deep peripheral character of such processes diminishes as the mass of the fused system decreases, so that the reactions essentially evolve to the usual peripheral character. Finally, comparisons are made of results of numerical calculations with experimental data, taking as an example the /sup 159/Tb(/sup 14/N,α) reaction with E/sub lab/ = 95 MeV

Study of actinides fission induced by multi-nucleon transfer reactions in inverse kinematics

International Nuclear Information System (INIS)

Derkx, X.

2010-10-01

The study of actinide fission encounters two major issues. On one hand, measurements of the fission fragment distributions and the fission probabilities allow a better understanding of the fission process itself and the discrimination among the models of nuclear structure and dynamics. On the other hand, new measurements are required to improve nuclear data bases, which are a key component for the design of new generation reactors and radio-toxic waste incinerators. This thesis is in line with different French and American experimental projects using the surrogate method, i.e. transfer reactions leading to the same compound nuclei as in neutron irradiation, allowing the study of fission of actinides which are inaccessible by conventional techniques, whereas they are important for applications. The experiment is based on multi-nucleon transfer reactions between a 238 U beam and a 12 C target, using the inverse kinematics technique to measure, for each transfer channel, the complete isotopic distributions of the fission fragments with the VAMOS spectrometer. The work presented in this dissertation is focused on the identification of the transfer channels and their properties, as their angular distributions and the distributions of the associated excitation energy, using the SPIDER telescope to identify the target recoil nuclei. This work of an exploratory nature aims to generalize the surrogate method to heavy transfers and to measure, for the first time, the fission probabilities in inverse kinematics. The obtained results are compared with available direct kinematics and neutron irradiation measurements. (author)

Moving triangle singularities: the possibilities for observation in deuteron reactions

International Nuclear Information System (INIS)

Kolybasov, V.M.

1996-01-01

If the amplitude of direct reaction is dominated by the triangle graph then it can be identified observing the picture corresponding to so-called moving triangle singularity: the form of the distribution with respect to the invariant mass of several final particles must change with momentum transferred from initial fast particle to final one. The possibilities for observation are discussed using two reactions, namely deuteron break up and η-meson production pd → pdη [ru

Post-prior equivalence for transfer reactions with complex potentials

Science.gov (United States)

Lei, Jin; Moro, Antonio M.

2018-01-01

In this paper, we address the problem of the post-prior equivalence in the calculation of inclusive breakup and transfer cross sections. For that, we employ the model proposed by Ichimura et al. [Phys. Rev. C 32, 431 (1985), 10.1103/PhysRevC.32.431], conveniently generalized to include the part of the cross section corresponding the transfer to bound states. We pay particular attention to the case in which the unobserved particle is left in a bound state of the residual nucleus, in which case the theory prescribes the use of a complex potential, responsible for the spreading width of the populated single-particle states. We see that the introduction of this complex potential gives rise to an additional term in the prior cross-section formula, not present in the usual case of real binding potentials. The equivalence is numerically tested for the 58Ni(d ,p X ) reaction.

Search for proton emission in {sup 54}Ni and multi-nucleon transfer reactions in the actinide region

Energy Technology Data Exchange (ETDEWEB)

Geibel, Kerstin

2012-06-15

The first part of the thesis presents the investigation of fusion-evaporation reactions in order to verify one-proton emission from the isomeric 10{sup +} state in the proton rich nucleus {sup 54}Ni. Between the years 2006 and 2009 a series of experimental studies were performed at the Tandem accelerator in the Institut fuer Kernphysik (IKP), University of Cologne. These experiments used fusion-evaporation reactions to populate {sup 54}Ni via the two-neutron-evaporation channel of the compound nucleus {sup 56}Ni. The cross section for the population of the ground state of {sup 54}Ni was predicted to be in orders of microbarn. This required special care with respect to the sensitivity of the experimental setup, which consisted of a double-sided silicon-strip detector (DSSSD), a neutron-detector array and HPGe detectors. In two experiments the excitation functions of the reactions ({sup 32}S+{sup 24}Mg) and ({sup 28}Si+{sup 28}Si) were determined to find the optimal experimental conditions for the population of {sup 54}Ni. A final experiment employed a {sup 28}Si beam at an energy of 70 MeV, impinging on a {sup 28}Si target. With a complex analysis it is possible to obtain a background-free energy spectrum of the DSSSD. An upper cross section limit for the population of the 10{sup +} state in {sup 54}Ni is established at σ({sup 54}Ni(10{sup +})) ≤ (13.9 ± 7.8) nbarn. In the second part of the thesis the population of actinide nuclei by multi-nucleon transfer reactions is investigated. Two experiments, performed in 2007 and 2008 at the CLARA-PRISMA setup at the Laboratori Nazionali di Legnaro, are analyzed with respect to the target-like reaction products. In both experiments {sup 238}U was used as target. A {sup 70}Zn beam with 460 MeV and a {sup 136}Xe beam with 926 MeV, respectively, impinged on the target, inducing transfer reactions. Kinematic correlations between the reaction partners are used to obtain information on the unobserved target-like reaction

Mass transfer with complex reversible chemical reactions—I. Single reversible chemical reaction

NARCIS (Netherlands)

Versteeg, G.F.; Kuipers, J.A.M.; Beckum, F.P.H. van; Swaaij, W.P.M. van

1989-01-01

An improved numerical technique was used in order to develop an absorption model with which it is possible to calculate rapidly absorption rates for the phenomenon of mass transfer accompanied by a complex reversible chemical reaction. This model can be applied for the calculation of the mass

Charge-exchange breakup of the deuteron with the production of two protons and spin structure of the amplitude of the nucleon charge transfer reaction

International Nuclear Information System (INIS)

Glagolev, V.V.; Lyuboshits, V.L.; Lyuboshits, V.V.; Piskunov, N.M.

1999-01-01

In the framework of the impulse approximation, the relation between the effective cross section of the charge-exchange breakup of a fast deuteron d + a → (pp) + b and the effective cross section of the charge transfer process n + a → p + b is discussed. In doing so, the effects of the proton identity (Fermi-statistics) and of the Coulomb and strong interactions of protons in the final state are taken into account. The distribution over relative momenta of the protons, produced in the charge-exchange process d + p → (pp) + n in the forward direction, is investigated. At the transfer momenta being close to zero the effective cross section of the charge-exchange breakup of a fast deuteron, colliding with the proton target, is determined only by the spin-flip part of the amplitude of the charge transfer reaction n + p → p + n at the zero angle. It is shown that the study of the process d + p → (pp) + n in a beam of the polarized (aligned) deuterons allows one, in principle, to separate two spin-dependent terms in the amplitude of the charge transfer reaction n + p → p + n, one of which does not conserve and the other one conserves the projection of the nucleon spin onto the direction of momentum at the transition of the neutron into the proton

A molecular dynamics study of intramolecular proton transfer reaction of malonaldehyde in solution based upon a mixed quantum-classical approximation. II. Proton transfer reaction in non-polar solvent

Science.gov (United States)

Kojima, H.; Yamada, A.; Okazaki, S.

2015-05-01

The intramolecular proton transfer reaction of malonaldehyde in neon solvent has been investigated by mixed quantum-classical molecular dynamics (QCMD) calculations and fully classical molecular dynamics (FCMD) calculations. Comparing these calculated results with those for malonaldehyde in water reported in Part I [A. Yamada, H. Kojima, and S. Okazaki, J. Chem. Phys. 141, 084509 (2014)], the solvent dependence of the reaction rate, the reaction mechanism involved, and the quantum effect therein have been investigated. With FCMD, the reaction rate in weakly interacting neon is lower than that in strongly interacting water. However, with QCMD, the order of the reaction rates is reversed. To investigate the mechanisms in detail, the reactions were categorized into three mechanisms: tunneling, thermal activation, and barrier vanishing. Then, the quantum and solvent effects were analyzed from the viewpoint of the reaction mechanism focusing on the shape of potential energy curve and its fluctuations. The higher reaction rate that was found for neon in QCMD compared with that found for water solvent arises from the tunneling reactions because of the nearly symmetric double-well shape of the potential curve in neon. The thermal activation and barrier vanishing reactions were also accelerated by the zero-point energy. The number of reactions based on these two mechanisms in water was greater than that in neon in both QCMD and FCMD because these reactions are dominated by the strength of solute-solvent interactions.

Fragmentation and direct transfer reactions for 40Ar incident beam on 27Al target at 1760 MeV

International Nuclear Information System (INIS)

Cisse, Ousmane

1985-01-01

Peripheral collision studies performed with 40 Ar projectiles at 44 MeV/A and 27 Al target show that both fragmentation and transfer reactions can be discerned in this type of interaction. The experimental observation of fragments with masses charges and velocities close to those of the incident beam are the signature of transfer reactions and a detailed analysis of the energy spectra of such fragments has been carried out and interpreted in terms of a direct diffraction transfer model. On the other hand, for large mass transfer reactions, abrasion is the suitable mechanism. Inclusive fragment measurement together with the appropriate residual nuclei-fragment coincidence results then provides experimental data in good agreement with the theoretical predictions obtained from a participant spectator model. These investigations also indicate that the separation energies of the participant from the spectator nucleus, at least within the framework of the above model, can be interpreted in terms of a friction force which becomes more efficient as the projectile energy decreases. (author) [fr

Radiolytic and electron-transfer reactions in supercritical CO2

International Nuclear Information System (INIS)

Bartels, D. M.; Dimitrijevic, N. M.; Jonah, C. D.; Takahashi, K.

2000-01-01

Using supercritical fluids as solvents is useful for both practical and theoretical reasons. It has been proposed to use supercritical CO 2 as a solvent for synthesis because it eliminates the air pollution arising from other solvents. The properties of supercritical fluids can be easily varied with only modest changes in temperature and density, so they provide a way of testing theories of chemical reactions. It has also been proposed to use supercritical fluids for the treatment of hazardous mixed waste. For these reasons the authors have studied the production of radiolytic species in supercritical CO 2 and have measured their reactivity as a function of density. They have shown that the C 2 O 4 + is formed. They also have shown that the electron transfer reactions of dimethylaniline to C 2 O 4 + and CO 2 (e - ) to benzoquinone are diffusion controlled over a considerable density range

Study of multi-nucleon transfer reactions in {sup 58,} {sup 64}Ni + {sup 207}Pb collisions at the velocity filter SHIP

Energy Technology Data Exchange (ETDEWEB)

Comas, V.F.; Heinz, S.; Ackermann, D.; Heredia, J.A.; Hessberger, F.P.; Khuyagbaatar, J.; Kindler, B.; Lommel, B.; Mann, R. [GSI Helmholtzzentrum fuer Schwerionenforschung GmbH, Darmstadt (Germany); Hofmann, S. [GSI Helmholtzzentrum fuer Schwerionenforschung GmbH, Darmstadt (Germany); Goethe-Universitaet Frankfurt, Institut fuer Physik, Frankfurt (Germany)

2013-09-15

We investigated multi-nucleon transfer reactions in collisions of {sup 58}Ni + {sup 207}Pb and {sup 64}Ni + {sup 207}Pb at Coulomb barrier energies. The new aspect is that we used a velocity filter (SHIP at GSI) for the separation of the heavy target-like transfer products from background events. The isotopic identification was performed via the {alpha} decay properties of the reaction products. The goal of the experiment was to study the characteristics of multi-nucleon transfer reactions in the region of heavy nuclei and the applicability of existing separation and detection techniques, which are usually used for identification of heavy fusion-evaporation residues, to heavy transfer products. This was motivated by recent theoretical results from macroscopic-microscopic models which suggest deep inelastic transfer reactions in heavy systems as a means to produce new neutron-rich isotopes in the region of N = 126 and in the region of superheavy nuclei. In this paper we present the isotopic yields, the excitation functions and the excitation energies of the heavy transfer products with Z > 82 as well as the influence of shell effects on the reaction products. The influence of the different neutron numbers of the projectiles is also discussed. (orig.)

Electron-transfer reactions of extremely small AgI colloids

International Nuclear Information System (INIS)

Vucemilovic, M.I.; Micic, O.I.

1988-01-01

Small colloidal AgI particles (particle diameter 20-50 A) have been prepared in water and acetonitrile, and optical effects due to size quantization have been observed. Electron transfer reactions involving electron donors and electron acceptors with AgI have been studied by pulse radiolysis techniques. Both reduction and oxidation of the colloids led to transient bleaching of semiconductor absorption. The recovery of the bleaching has been attributed to corrosion processes. Electrons injected into AgI colloids produce metallic silver and hydrogen. Hydrogen evolution is catalyzed by metallic silver formation. (author)

Four- and six-charge transfer reactions induced by 52Cr, 56Fe, 63Cu in rare-earths

International Nuclear Information System (INIS)

Mouchaty, G.

1977-01-01

The cross sections for transfer reactions in which 4 and 6 charges are gained by Sm and Nd targets have been measured, the projectiles being 52 Cr and 56 Fe at 343 and 377 MeV. These energies correspond to 1.5B, B being the interaction barrier. The results obtained indicate that the cross section increases when the number of charges transferred and the mass of the projectile are increased. The angular distributions and recoil ranges at each angle of 151 Dy produced through 52 Cr+ 148 Sm, 52 Cr+ 144 Nd, 56 Fe+ 144 Nd, 63 Cu+ 144 Nd reactions were determined for incident energies equivalent to 1.5B. After transformation into the c.m. system, the angular distributions exhibit a maximum close to 155 0 and a tail at small angles. The position of the maximum is independent of the incident ion and of the number of transferred charges. The analysis of the energy distributions indicate that the observed reactions can be explained by a two-step process: a transfer of nucleons followed by an evaporation step. The number of nucleons transferred in the 1st step and the associated excitation energies are higher for the events corresponding to the tail than for those corresponding to the maximum [fr

Photo- and radiation chemical studies of intermediates involved in excited-state electron-transfer reactions

International Nuclear Information System (INIS)

Hoffman, M.Z.

1985-01-01

Excited-state inter- and intramolecular electron-transfer reactions lie at the heart of the most photochemical solar energy conversion schemes. The authors research, which has utilized the techniques of continuous and pulsed photolysis and radiolysis, has focused on three general aspects of these reactions involving transition metal coordination complexes and electron donor-acceptor complexes: i) the effect of solution medium on the properties and quenching of the excited states; ii) the control of the quantum yields of formation of redox products; iii) the mechanism by which reduced species interact with water to yield H 2 homogeneously and heterogeneously. EDTA is among the most popular sacrificial electron donors used in model systems. Its role is to scavenge the oxidized form of the photosensitizer in order to prevent its rapid reaction with the reduced form of the electron relay species that results from the electron-transfer quenching of the excited photosensitizer. In systems involving MV 2+ , the radicals resulting from the oxidation of EDTA can eventually lead to the generation of a second equivalent of MV + ; the reducing agent is believed to be a radical localized on the carbon atom alpha to the carboxylate group. The reaction of radiolytically-generated OH/H with EDTA produces this radical directly via H-abstraction or indirectly via deprotonation of the carbon atom adjacent to the nitrogen radical site in the oxidized amine moiety; it reduces MV 2+ with rate constants of 2.8 x 10 9 , 7.6 x 10 9 , and 8.5 x 10 6 M -1 s -1 at pH 12.5, 8.3, and 4.7, respectively. Degradative decarboxylation of EDTA-radicals and their back electron-transfer reactions are enhanced in acidic solution causing the yield of MV + to be severely diminished

Electron transfer reactions, cyanide and O2 binding of truncated hemoglobin from Bacillus subtilis

International Nuclear Information System (INIS)

Fernandez, Esther; Larsson, Jonas T.; McLean, Kirsty J.; Munro, Andrew W.; Gorton, Lo; Wachenfeldt, Claes von; Ferapontova, Elena E.

2013-01-01

The truncated hemoglobin from Bacillus subtilis (trHb-Bs) possesses a surprisingly high affinity for oxygen and resistance to (auto)oxidation; its physiological role in the bacterium is not understood and may be connected with its very special redox and ligand binding reactions. Electron transfer reactions of trHb-Bs were electrochemically studied in solution and at graphite electrodes. Spectrophotometrical potentiometric titration and direct electrochemical measurements gave a heme iron redox potential of −103 ± 4 mV and −108 ± 2 mV vs. NHE, at pH 7, respectively. The redox potential of the heme in trHb-Bs shifted −59 mV per pH unit at pH higher than 7, consistently with a 1e − /1 H + – transfer reaction. The heterogeneous rate constant k s for a quasi-reversible 1e − – 1H + – transfer reaction between graphite and trHb-Bs was 10.1 ± 2.3 s −1 . Upon reversible cyanide binding the k s doubled, while the redox potential of heme shifted 21 mV negatively, presumably reflecting changes in redox activity and in vivo signaling functions of trHb-Bs associated with ligand binding. Bioelectrocatalytic reduction of O 2 catalyzed by trHb-Bs was one of the most efficient hitherto reported for Hbs, with an apparent catalytic rate constant, k cat , of 56 ± 6 s −1 . The results obtained are of particular interest for applications of trHb in environmental biosensing and toxicity screening

Electron transfer reactions induced by the triplet state of thiacarbocyanine dimers

International Nuclear Information System (INIS)

Chibisov, Alexander K.; Slavnova, Tatyana D.; Goerner, Helmut

2004-01-01

The photoinduced electron transfer between either cationic 5,5 ' -dichloro-3,3 ' ,9-triethylthiacarbocyanine (1) or a structurally similar anionic dye (2) and appropriate donors, e.g. ascorbic acid, and acceptors, e.g. methyl viologen, was studied by ns-laser photolysis. In aqueous solution the dyes in the ground state are present as an equilibrated mixture of dimers and monomers, whereas the triplet state is mainly populated from dimers. The triplet states of both dimers and monomers are quenched by electron donors or acceptors and the rate constant for quenching is generally 2-4 times higher for dimers than for monomers. The kinetics of triplet decay and radical formation and decay as a result of primary and secondary electron transfer were analyzed. While the one-electron reduced dimer decays due to back reactions, the one-electron oxidized dimer rapidly dissociates into the monomer and the monomeric dye radical. For the dimeric dye/donor/acceptor systems the primary photoinduced electron transfer occurs either from the donor or to the acceptor yielding the dimeric dye radicals. The one-electron reduced dimer can be efficiently oxidized by acceptors, e.g. the rate constant for reaction of the dimeric dye radical of 1 with methyl viologen (photoreductive pathway of sensitization) is 1.6x10 9 M -1 s -1 . The photooxidative pathway of sensitization is more complicated; after dissociation of the dimeric dye radical, the monomeric dye radical is reduced in a secondary electron transfer from ascorbic acid, e.g. with a rate constant of 1x10 9 M -1 s -1 for 2, yielding the monomer. On increasing the donor concentration the photooxidative pathway of sensitization is switched to a photoreductive one

The (p→,t) reaction on 58Ni and 56Fe at 24.6 MeV

International Nuclear Information System (INIS)

Polane, J.H.; Feix, W.F.; Hall, P.J. van; Klein, S.S.; Nijgh, G.J.; Poppema, O.J.; Wassenaar, S.D.

1989-01-01

The (p, t) reactions on 56 Fe and 58 Ni initiated by 24.6 MeV polarised protons has been investigated. The reaction process is described in terms of simultaneous and sequential neutron transfer. For all five final states studied the sequential process competes strongly with simultaneous transfer of a neutron pair. Theoretical values for the spectroscopic amplitudes were derived from shell-model wavefunctions; these seem to give a reliable description of the reaction process. (author)

Coupled-channels analyses for 9,11Li + 208Pb fusion reactions with multi-neutron transfer couplings

Science.gov (United States)

Choi, Ki-Seok; Cheoun, Myung-Ki; So, W. Y.; Hagino, K.; Kim, K. S.

2018-05-01

We discuss the role of two-neutron transfer processes in the fusion reaction of the 9,11Li + 208Pb systems. We first analyze the 9Li + 208Pb reaction by taking into account the coupling to the 7Li + 210Pb channel. To this end, we assume that two neutrons are directly transferred to a single effective channel in 210Pb and solve the coupled-channels equations with the two channels. By adjusting the coupling strength and the effective Q-value, we successfully reproduce the experimental fusion cross sections for this system. We then analyze the 11Li + 208Pb reaction in a similar manner, that is, by taking into account three effective channels with 11Li + 208Pb, 9Li + 210Pb, and 7Li + 212Pb partitions. In order to take into account the halo structure of the 11Li nucleus, we construct the potential between 11Li and 208Pb with a double folding procedure, while we employ a Woods-Saxon type potential with the global Akyüz-Winther parameters for the other channels. Our calculation indicates that the multiple two-neutron transfer process plays a crucial role in the 11Li + 208Pb fusion reaction at energies around the Coulomb barrier.

Calculation of rate coefficients of some proton-transfer ion-molecule reactions in weakly ionized gases

International Nuclear Information System (INIS)

Stiller, W.

1985-01-01

A classical collision theory is used to describe thermal bimolecular rate coefficeints for reaction between positive and negative ions and polar molecules in a carrier gas. Special attention is paid to ion-molecule reaction in which proton transfer occurs. These reactions play an important role in terrestrial plasma devices, in ionosphere, in planetary atmospheres and in interstellar matter. The equilibrium rate coefficients of the reactions are calculated based on a microscopic reactive cross section derived from a long distance polar molecule-ion potential. The results are compared with experimental values of afterglow measurements. (D.Gy.)

Evaporation rates and surface profiles on heterogeneous surfaces with mass transfer and surface reaction

Energy Technology Data Exchange (ETDEWEB)

Flytzani-Stephanopoulos, M; Schmidt, L D

1979-01-01

Simple models incorporating surface reaction and diffusion of volatile products through a boundary layer are developed to calculate effective rates of evaporation and local surface profiles on surfaces having active and inactive regions. The coupling between surface heterogeneities with respect to a particular reaction and external mass transfer may provide a mechanism for the surface rearrangement and metal loss encountered in several catalytic systems of practical interest. Calculated transport rates for the volatilization of platinum in oxidizing environments and the rearrangement of this metal during the ammonia oxidation reaction agree well with published experimental data.

Mechanism of the Primary Charge Transfer Reaction in the Cytochrome bc1 Complex

DEFF Research Database (Denmark)

Barragan, Angela M; Schulten, Klaus; Solov'yov, Ilia A

2016-01-01

, the quinol-protein interaction, which initiates the Q-cycle, has not yet been completely described. Furthermore, the initial charge transfer reactions of the Q-cycle lack a physical description. The present investigation utilizes classical molecular dynamics simulations in tandem with quantum density...

An annular ionization detector for quasi-elastic and transfer reaction studies

CERN Document Server

Dinesh, B V; Nayak, B K; Biswas, D C; Saxena, A; Pant, L M; Sahu, P K; Choudhury, R K

2000-01-01

An annular ionization chamber detector has been developed to study quasi-elastic and transfer reactions in heavy-ion collisions at near-barrier and sub-barrier energies. The important feature of the detector is that it has a near 2 pi coverage in the azimuthal angle phi for the particles entering in the detector at a given theta direction. This feature makes the detector very useful for measurement of the differential cross-sections at backward angles with respect to the beam direction, involving low cross-section reaction channels. The split anode configuration of the detector makes it capable of both particle identification and energy measurement for heavy ions and fission fragments. The detector has been tested using heavy-ion beams from the 14 MV-pelletron accelerator at Mumbai. Results on quasi-elastic excitation function measurements and barrier distribution studies in many heavy-ion reactions using this detector setup are discussed.

One nucleon transfer reactions around $^{68}$Ni at REX-ISOLDE

CERN Multimedia

Blazhev, A A; Kruecken, R; Mertzimekis, T; Darby, I G; Lagogiannis, A; Habs, D; Diriken, J V J; Patronis, N

2008-01-01

We intend to investigate the single particle properties of the neutron-rich Ni isotopes in the mass region around $^{68}$Ni and at a later stage towards the doubly-magic $^{78}$Ni. As a first experiment we propose to study the single particle character of the ground and first excited states of $^{67}$Ni. This nucleus will be the projectile-like reaction product for the one-neutron transfer reaction. A $^{66}$Ni beam at 3A MeV delivered from REX-ISOLDE will be directed on a CD$_{2}$ target. Protons produced from the (d,p) reaction will be detected either in singles or in coincidence with ${\\gamma}$-rays recorded by the MINIBALL array. The particles will be detected by the newly-built Si position-sensitive barrel configuration. The objectives of this work are the unambiguous determination of the spins and parities of the first excited states of $^{67}$Ni and measurement of the relative spectroscopic factors of those states as well as of the ground state. The experimental results will be compared with those from...

Exciplex mediated photoinduced electron transfer reactions of phthalocyanine-fullerene dyads.

Science.gov (United States)

Niemi, Marja; Tkachenko, Nikolai V; Efimov, Alexander; Lehtivuori, Heli; Ohkubo, Kei; Fukuzumi, Shunichi; Lemmetyinen, Helge

2008-07-31

Evidences of an intramolecular exciplex intermediate in a photoinduced electron transfer (ET) reaction of double-linked free-base and zinc phthalocyanine-C60 dyads were found. This was the first time for a dyad with phthalocyanine donor. Excitation of the phthalocyanine moiety of the dyads results in rapid ET from phthalocyanine to fullerene via an exciplex state in both polar and nonpolar solvents. Relaxation of the charge-separated (CS) state Pc(*+)-C60(*-) in a polar solvent occurs directly to the ground state in 30-70 ps. In a nonpolar solvent, roughly 20% of the molecules undergo transition from the CS state to phthalocyanine triplet state (3)Pc*-C60 before relaxation to the ground state. Formation of the CS state was confirmed with electron spin resonance measurements at low temperature in both polar and nonpolar solvent. Reaction schemes for the photoinduced ET reactions of the dyads were completed with rate constants obtained from the time-resolved absorption and emission measurements and with state energies obtained from the fluorescence, phosphorescence, and voltammetric measurements.

Tunable differentiation of tertiary C-H bonds in intramolecular transition metal-catalyzed nitrene transfer reactions.

Science.gov (United States)

Corbin, Joshua R; Schomaker, Jennifer M

2017-04-13

Metal-catalyzed nitrene transfer reactions are an appealing and efficient strategy for accessing tetrasubstituted amines through the direct amination of tertiary C-H bonds. Traditional catalysts for these reactions rely on substrate control to achieve site-selectivity in the C-H amination event; thus, tunability is challenging when competing C-H bonds have similar steric or electronic features. One consequence of this fact is that the impact of catalyst identity on the selectivity in the competitive amination of tertiary C-H bonds has not been well-explored, despite the potential for progress towards predictable and catalyst-controlled C-N bond formation. In this communication, we report investigations into tunable and site-selective nitrene transfers between tertiary C(sp 3 )-H bonds using a combination of transition metal catalysts, including complexes based on Ag, Mn, Rh and Ru. Particularly striking was the ability to reverse the selectivity of nitrene transfer by a simple change in the identity of the N-donor ligand supporting the Ag(i) complex. The combination of our Ag(i) catalysts with known Rh 2 (ii) complexes expands the scope of successful catalyst-controlled intramolecular nitrene transfer and represents a promising springboard for the future development of intermolecular C-H N-group transfer methods.

Crossed beam study of He+-O2 charge transfer reactions in the collision energy range 0.5-200 eV

International Nuclear Information System (INIS)

Bischof, G.; Linder, F.

1986-01-01

Energy spectra and angular distributions of the O + and O 2 + product ions resulting from the He + -O 2 charge transfer reaction have been measured in the collision energy range 0.5-200 eV using the crossed-beam method. The O 2 + ions represent only a minor fraction of the reaction products (0.2-0.6% over the energy range measured). In the dissociative charge transfer reaction, four main processes are identified leading to O+O + reaction products in different electronic states. Two different mechanisms can be distinguished, each being responsible for two of the observed processes: (i) a long-distance energy-resonant charge transfer process involving the c 4 Σsub(u) - (upsilon'=0) state of O 2 + and (ii) a slightly exothermic charge transfer process via the (III) 2 PIsub(u) state of O 2 + (with the exothermicity depending on the collision energy). Angle-integrated branching ratios and partial cross sections (in absolute units) have been determined. The branching ratios of the individual processes show a pronounced dependence on the collision energy. At low energies, the O + product ions are preferentially formed in the 2 P 0 and 2 D 0 excited states. The angular distributions of the O + product ions show an anisotropic behaviour indicating an orientation-dependent charge transfer probability in the He + -O 2 reaction. (orig.)

Proton transfers in the Strecker reaction revealed by DFT calculations

Directory of Open Access Journals (Sweden)

Shinichi Yamabe

2014-08-01

Full Text Available The Strecker reaction of acetaldehyde, NH3, and HCN to afford alanine was studied by DFT calculations for the first time, which involves two reaction stages. In the first reaction stage, the aminonitrile was formed. The rate-determining step is the deprotonation of the NH3+ group in MeCH(OH-NH3+ to form 1-aminoethanol, which occurs with an activation energy barrier (ΔE≠ of 9.6 kcal/mol. The stereochemistry (R or S of the aminonitrile product is determined at the NH3 addition step to the carbonyl carbon of the aldehyde. While the addition of CN− to the carbon atom of the protonated imine 7 appears to scramble the stereochemistry, the water cluster above the imine plane reinforces the CN− to attack the imine group below the plane. The enforcement hinders the scrambling. In the second stage, the aminonitrile transforms to alanine, where an amide Me-CH(NH2-C(=O-NH2 is the key intermediate. The rate-determining step is the hydrolysis of the cyano group of N(amino-protonated aminonitrile which occurs with an ΔE≠ value of 34.7 kcal/mol. In the Strecker reaction, the proton transfer along the hydrogen bonds plays a crucial role.

Influence of Proton Acceptors on the Proton-Coupled Electron Transfer Reaction Kinetics of a Ruthenium-Tyrosine Complex.

Science.gov (United States)

Lennox, J Christian; Dempsey, Jillian L

2017-11-22

A polypyridyl ruthenium complex with fluorinated bipyridine ligands and a covalently bound tyrosine moiety was synthesized, and its photo-induced proton-coupled electron transfer (PCET) reactivity in acetonitrile was investigated with transient absorption spectroscopy. Using flash-quench methodology with methyl viologen as an oxidative quencher, a Ru 3+ species is generated that is capable of initiating the intramolecular PCET oxidation of the tyrosine moiety. Using a series of substituted pyridine bases, the reaction kinetics were found to vary as a function of proton acceptor concentration and identity, with no significant H/D kinetic isotope effect. Through analysis of the kinetics traces and comparison to a control complex without the tyrosine moiety, PCET reactivity was found to proceed through an equilibrium electron transfer followed by proton transfer (ET-PT) pathway in which irreversible deprotonation of the tyrosine radical cation shifts the ET equilibrium, conferring a base dependence on the reaction. Comprehensive kinetics modeling allowed for deconvolution of complex kinetics and determination of rate constants for each elementary step. Across the five pyridine bases explored, spanning a range of 4.2 pK a units, a linear free-energy relationship was found for the proton transfer rate constant with a slope of 0.32. These findings highlight the influence that proton transfer driving force exerts on PCET reaction kinetics.

Effect of vibrational excitation on the dynamics of ion-molecule reactions

International Nuclear Information System (INIS)

Anderson, S.L.

1981-11-01

A new experimental technique for the study of vibrational effects on ion-molecule reaction cross sections is described. Vibrational and collision energy dependent cross sections are presented for proton and H atom transfer, charge transfer and collision induced dissociation reactions in various isotopic H 2 + + H 2 systems. Charge and proton transfer cross sections are presented for the reactions of H 2 + and D 2 + with Ar, N 2 , CO, and O 2 . All the reactions are shown to be highly influenced by avoided crossings between the ground and first excited potential energy surfaces. Because of the nature of the crossings, vibrational motion of the systems can cause both adiabatic and non-adiabatic behavior of the system. This makes the vibrational dependences of the various cross sections a very sensitive probe of the dynamics of the collisions particularly, their behavior in the region of the crossings. Evidence is seen for charge transfer between reagents as they approach each other, transition to and in some cases reactions on excited potential energy surfaces, competition between different channels, and strong coupling of proton and charge transfer channels which occurs only for two of the systems studied (H 2 + + Ar, N 2 ). Oscillatory structure is observed in the collision energy dependence of the endoergic H 2 + (v = 0) + Ar charge transfer reaction for the first time, and a simple model which is commonly used for atom-atom charge transfer is used to fit the peaks. Finally a simple model is used to assess the importance of energy resonance and Franck-Condon effects on molecular charge transfer

Chaotic scattering in heavy-ion reactions with mass transfer

International Nuclear Information System (INIS)

Rodriguez Padron, Emilio; Guzman Martinez, Fernando

1998-01-01

The role of the mass transfer in heavy ion collisions is analyzed in the framework of a simple semi phenomenological model searching for chaotic scattering effects. The model couples the relative motion of the ions to a collective degree of freedom. The collective degree of freedom is identified by the mass asymmetry of the system. A Saxon-Woods potential is used for nucleus-nucleus interaction whiles a harmonic potential rules the temporal behaviour of the collective degree of freedom. This model shows chaotic scattering which could be an explanation for certain types of cross-section fluctuations observed in this kind of reactions

Experiments on multi-nucleon transfer reactions with the systems {sup 58,64}Ni+{sup 207}Pb at SHIP

Energy Technology Data Exchange (ETDEWEB)

Fernandovich Comas Lijachev, Victor

2012-07-01

This work presents experimental results on multi-nucleon transfer reactions in the collision systems {sup 58}Ni+{sup 207}Pb and {sup 64}Ni+{sup 207}Pb which were measured at the velocity filter SHIP at GSI. The reactions were performed at beam energies below and up to 10% above the Coulomb barrier. The work was motivated by theoretical predictions to apply multi-nucleon transfer reactions in heavy systems to synthesize new neutron-rich isotopes in the region of superheavy nuclei with Z>100 and in the region of the closed neutron shell N=126. The expected cross-sections for the production of these nuclei in transfer reactions are small and reach typically nanobarn and below. Therefore, efficient separation techniques have to be applied and the detection system must allow for the identification of single nuclei. A dedicated experimental setup to study such rare transfer products does not exist presently. But already existing facilities which are used for the synthesis of superheavy fusion products meet the requirements for the detection of rare reaction products. In this context, the velocity filter SHIP offers the possibility to separate heavy target-like transfer products from projectiles and projectile-like reaction products before they reach the detection system where the particles are identified by their alpha-decay properties. At SHIP, a cross-section limit of 10 pb can be reached at usual beam intensities. In the present work on collisions of {sup 58,64}Ni+{sup 207}Pb the influence of the projectile neutron number on the cross-sections, isotopic distributions and excitation energies of the transfer products was studied. Especially with the more neutron-rich {sup 64}Ni projectiles a transfer of up to seven protons and eight neutrons to the target nucleus was observed. The largest cross-sections for the most neutron-rich isotopes were reached at the beam energies around the Coulomb barrier. The transfer was accompanied by the full dissipation of the available

Study of photo-activated electron transfer reactions in the first excited singlet state by picosecond and nanosecond laser spectroscopy

International Nuclear Information System (INIS)

Doizi, Denis

1983-01-01

Picosecond laser spectroscopy has been used to study two photo-activated electron transfer reactions: - a bimolecular electron transfer reaction between a sensitizer, DODCI, and an electron acceptor, methylviologen. The two radical ions created with an electron transfer efficiency γ ≅ 0.07 have been identified in picosecond and nanosecond laser absorption spectroscopy by adding selective solutes such as para-benzoquinone (an electron acceptor) or L(+) ascorbic acid (an electron donor). - an intramolecular electron transfer reaction in a triad molecule consisting of a tetra-aryl-porphyrin covalently linked to both a carotenoid and a quinone. The photoinduced charge separation occurs within 30 ps and leads, with a yield of 25 pc, to the formation of a zwitterion whose half-life is 2.5 μs. The experimental results obtained in these two studies show an effective decrease in the recombination rate of the two radical ions created in the encounter pair. (author) [fr

pH-dependent electron transfer reaction and direct bioelectrocatalysis of the quinohemoprotein pyranose dehydrogenase

Energy Technology Data Exchange (ETDEWEB)

Takeda, Kouta [Department of Biotechnology and Life Science, Tokyo University of Agriculture and Technology, Koganei, Tokyo 184-8588 (Japan); Matsumura, Hirotoshi; Ishida, Takuya [Department of Biomaterial Sciences, Graduate School of Agriculture and Life Sciences, The University of Tokyo, Bunkyo-ku, Tokyo 113-8657 (Japan); Yoshida, Makoto [Department of Environmental and Natural Resource Science, Tokyo University of Agriculture and Technology, Fuchu, Tokyo 183-8509 (Japan); Igarashi, Kiyohiko; Samejima, Masahiro [Department of Biomaterial Sciences, Graduate School of Agriculture and Life Sciences, The University of Tokyo, Bunkyo-ku, Tokyo 113-8657 (Japan); Ohno, Hiroyuki [Department of Biotechnology and Life Science, Tokyo University of Agriculture and Technology, Koganei, Tokyo 184-8588 (Japan); Nakamura, Nobuhumi, E-mail: nobu1@cc.tuat.ac.jp [Department of Biotechnology and Life Science, Tokyo University of Agriculture and Technology, Koganei, Tokyo 184-8588 (Japan)

2016-08-26

A pyranose dehydrogenase from Coprinopsis cinerea (CcPDH) is an extracellular quinohemoeprotein, which consists a b-type cytochrome domain, a pyrroloquinoline-quinone (PQQ) domain, and a family 1-type carbohydrate-binding module. The electron transfer reaction of CcPDH was studied using some electron acceptors and a carbon electrode at various pH levels. Phenazine methosulfate (PMS) reacted directly at the PQQ domain, whereas cytochrome c (cyt c) reacted via the cytochrome domain of intact CcPDH. Thus, electrons are transferred from reduced PQQ in the catalytic domain of CcPDH to heme b in the N-terminal cytochrome domain, which acts as a built-in mediator and transfers electron to a heterogenous electron transfer protein. The optimal pH values of the PMS reduction (pH 6.5) and the cyt c reduction (pH 8.5) differ. The catalytic currents for the oxidation of L-fucose were observed within a range of pH 4.5 to 11. Bioelectrocatalysis of CcPDH based on direct electron transfer demonstrated that the pH profile of the biocatalytic current was similar to the reduction activity of cyt c characters. - Highlights: • pH dependencies of activity were different for the reduction of cyt c and DCPIP. • DET-based bioelectrocatalysis of CcPDH was observed. • The similar pH-dependent profile was found with cyt c and electrode. • The present results suggested that IET reaction of CcPDH shows pH dependence.

Nucleon transfer reactions in D.W.B.A; Les reactions de transfert d'un nucleon dans la D.W.B.A

Energy Technology Data Exchange (ETDEWEB)

Giraud, B; Picard, J [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires

1968-08-01

The DWBA for one nucleon transfer reaction is described as simply and completely as possible to show the possibilities and limits of this method. The extraction of spectroscopic factors is described in the appendix. (authors) [French] Le formalisme de la DWBA est decrit d'une maniere aussi simple et complete que possible pour mettre en evidence les possibilites et les limites de cette methode d'analyse des reactions de transfert. L'extraction des facteurs spectroscopiques est exposee en appendice. (auteurs)

Charged-particle transfer reactions and nuclear astrophysics problems

International Nuclear Information System (INIS)

Artemov, S.V.; Yarmukhamedov, R.; Yuldashev, B.S.; Burtebaev, N.; Duysebaev, A.; Kadyrzhanov, K.K.

2002-01-01

In the report a review of the recent results of calculation of the astrophysical S-factors S(E) for the D(α, γ) 6 Li, 3 He(α, γ) 7 Be, 7 Be(p, γ) 8 Be, 12,13 C(p, γ) 13, 14 N and 12 C(p,γ) 16 O* reactions at extremely low energies E, including value E=0 , performed within the framework of a new method taking into account the additional information about the nuclear vertex constant (Nc) (or the respective asymptotic normalization coefficient) are presented. The required values of Nc can be obtained from an analysis of measured differential cross-sections of proton and α-particle transfer reactions (for example A( 3 He,d)B, 6 Li(d, 6 Li)d, 6 Li(α, 6 Li)α, 12 C( 6 Li, d) 16 O* etc.). A comparative analysis between the results obtained by different authors is also done. Taking into account an important role of the NVC's values for the nuclear astrophysical A(p, γ)B and A(α, γ)B reactions, a possibility of obtaining the reliable NVC values for the virtual decay B→A+p and B→A+α from the analysis of differential cross sections both sub- and above-barrier A( 3 He, d) and A( 6,7 Li, 2,3 H)B reactions is discussed in detail. In this line the use the isochronous cyclotron U-150 M, the 'DC-60' heavy ion machine and electrostatic charge-exchanging accelerator UKP-2-1 of Institute of Nuclear Physics of National Nuclear Center of the Republic of Kazakhstan for carrying out the needed experiments is considered and the possibility of the obtained data application for the astrophysical interest is also discussed

Heavy ion transfer reactions

Indian Academy of Sciences (India)

array (CLARA), extensive investigations of nuclear structure and reaction dynamics have been carried out. In the present paper aspects of these studies will be presented, focussing more closely on the reaction mechanism, in particular on the ...

Disentangling the transfer and breakup contributions for the inclusive 8 Li + 208 Pb reaction

International Nuclear Information System (INIS)

Moro, A.M.; Crespo, R.; Garcia M, H.; Aguilera, E.F.; Martinez Q, E.; Gomez C, J.; Nunes, F.M.

2003-01-01

An analysis of the 8 Li + 208 Pb reaction at energies around the Coulomb barrier is presented. The study is focused on the elastic and one-neutron removal channels. For the elastic scattering, an optical model analysis of the experimental data is performed. The observed 7 Li is interpreted as the superposition of the one-neutron transfer reaction, 208 Pb ( 8 Li, 7 Li) 209 Pb, and the breakup reaction. The separate contribution of each one of these processes has been calculated within the DWBA formalism. The sum of both contributions explains adequately the experimental angular distribution of 7 Li. (Author)

Room Temperature, Hybrid Sodium-Based Flow Batteries with Multi-Electron Transfer Redox Reactions

Science.gov (United States)

Shamie, Jack S.; Liu, Caihong; Shaw, Leon L.; Sprenkle, Vincent L.

2015-01-01

We introduce a new concept of hybrid Na-based flow batteries (HNFBs) with a molten Na alloy anode in conjunction with a flowing catholyte separated by a solid Na-ion exchange membrane for grid-scale energy storage. Such HNFBs can operate at ambient temperature, allow catholytes to have multiple electron transfer redox reactions per active ion, offer wide selection of catholyte chemistries with multiple active ions to couple with the highly negative Na alloy anode, and enable the use of both aqueous and non-aqueous catholytes. Further, the molten Na alloy anode permits the decoupled design of power and energy since a large volume of the molten Na alloy can be used with a limited ion-exchange membrane size. In this proof-of-concept study, the feasibility of multi-electron transfer redox reactions per active ion and multiple active ions for catholytes has been demonstrated. The critical barriers to mature this new HNFBs have also been explored. PMID:26063629

Hydrogen-transfer and charge-transfer in photochemical and radiation induced reactions. Progress report, November 1, 1975--October 31, 1976

International Nuclear Information System (INIS)

Cohen, S.G.

1976-10-01

The relative importance of light absorption, quenching of triplet, and hydrogen transfer repair has been examined in retardation by mercaptans of photoreduction of aromatic ketones by alcohols. In the reduction of benzophenone by 2-propanol, retardation is efficient and, after correction for the first two effects, is due entirely to hydrogen-transfer repair, as indicated by deuterium labeling. In reduction of acetophenone by α-methylbenzyl alcohol, repair by hydrogen transfer is also operative. In reduction of benzophenone by benzhydrol, retardation is less efficient and is due to quenching, as the ketyl radical does not abstract hydrogen from mercaptan rapidly in competition with coupling. Deuterium isotope effects are discussed in terms of competitive reactions. Photoreduction of benzophenone by 2-butylamine and by triethylamine is retarded by aromatic mercaptans and disulfides. Of the retardation not due to light absorption and triplet quenching by the sulfur compounds, half is due to hydrogen-transfer repair, as indicated by racemization and deuterium labeling. The remainder is attributed to quenching by the sulfur compound of the charge-transfer-complex intermediate. Photoreduction by primary and secondary amines, but not by tertiary amines, is accelerated by aliphatic mercaptans. The acceleration is attributed to catalysis of hydrogen transfer by the mercaptan in the charge-transfer complex. The effect is large in hydrocarbon solvent, less in polar organic solvents and absent in water

Energy, Electron Transfer and Photocatalytic Reactions of Visible Light Absorbing Transition Metal Complexes

Energy Technology Data Exchange (ETDEWEB)

Schmehl, Russell H. [Tulane Univ., New Orleans, LA (United States)

2016-03-02

This is the final technical report for a project carried out at Tulane University of New Orleans that describes the development of light induced (solar) reactions geared toward decomposing water into its component elements : hydrogen and oxygen. Much of the work involved optimizing systems for absorbing visible light and undergoing light promoted reactions to generate very strong reducing agents that are capable of reacting with water to produce hydrogen. Additional portions of the research were collaborative efforts to put the strong reducing agents to work in reaction with hydrogen generation catalysts prepared elsewhere. Time resolved laser spectroscopic methods were used to evaluate the light induced reactions and characterize very reactive intermediate substances formed during the reactions.

Final stage of high energy hadron-nucleus nuclear collision reactions

International Nuclear Information System (INIS)

Strugal'ski, Z.; Jedrzejec, H.; Strugalska-Gola, E.; Mulas, E.

1996-01-01

The final or 'slow' stage of the hadron-nucleus collision reactions at high energy is considered on the basis of the collision mechanism prompted experimentally. The transmutation process of the damaged target nucleus into nucleons and stable nuclear fragments is discussed. Relations between intensities or multiplicities n p of the emitted fast protons and the mean intensities or multiplicities b > of the evaporated nucleons and nuclear fragments are presented. 14 refs

Possibilities of production of neutron-rich Md isotopes in multi-nucleon transfer reactions

Energy Technology Data Exchange (ETDEWEB)

Mun, Myeong-Hwan; Lee, Young-Ouk [Korea Atomic Energy Research Institue, Daejeon (Korea, Republic of); Adamian, G.G.; Antonenko, N.V. [Joint Institute for Nuclear Research, Dubna (Russian Federation)

2016-12-15

The possibilities of production of yet unknown neutron-rich isotopes of Md are explored in several multi-nucleon transfer reactions with actinide targets and stable and radioactive beams. The projectile-target combinations and bombarding energies are suggested to produce new neutron-rich isotopes of Md in future experiments. (orig.)

Functional LH1 antenna complexes influence electron transfer in bacterial photosynthetic reaction centers

NARCIS (Netherlands)

Visschers, R.W.; Vulto, S.I.E.; Jones, M.R.; van Grondelle, R.; Kraayenhof, R.

1999-01-01

The effect of the light harvesting 1 (LH1) antenna complex on the driving force for light-driven electron transfer in the Rhodobacter sphaeroides reaction center has been examined. Equilibrium redox titrations show that the presence of the LH1 antenna complex influences the free energy change for

Functional LH1 antenna complexes influence electron transfer in bacterial photosynthetic reaction centers.

NARCIS (Netherlands)

Visschers, R.W.; Vulto, S.I.E.; Jones, M.R.; van Grondelle, R.; Kraayenhof, R.

1999-01-01

The effect of the light harvesting 1 (LH1) antenna complex on the driving force for light-driven electron transfer in the Rhodobacter sphaeroides reaction center has been examined. Equilibrium redox titrations show that the presence of the LH1 antenna complex influences the free energy change for

Charge separation in photoinitiated electron transfer reactions induced by a polyelectrolyte

International Nuclear Information System (INIS)

Meyerstein, D.; Rabani, J.; Matheson, M.S.; Meisel, D.

1978-01-01

When uncharged molecules quench the luminescence of Ru(bpy) 3 /sup 2+*/ by electron transfer to the quencher, the addition of poly(vinyl sulfate) (PVS) may, through its potential field, affect the rate of quenching, enhance the net separated charge yield, and slow the back reaction of the separated photoredox products. In all such cases that we have studied the quenching rate in the presence of PVS was reduced to about 60% of the rate measured in the absence of PVS. For two neutral species, iron(III) nitrilotriacetate (FeNTA) and cobalt(III) acetylacetonate (Co(acac) 3 ), photoreduction of the quencher was observed, and the redox yield escaping geminate recombination was substantially increased by added PVS. In the case of FeNTA the rate of the bulk back reaction was not changed appreciably by the presence of PVS owing to the rapid neutralization of Fe(NTA) - by protonation. For Co(acac) 3 the rate of the bulk back reaction was decreased by several orders of magnitude and the back reaction was shown to occur via the enolate form of the ligand which is released to the bulk solution. 4 figures, 4 tables

Quasi-elastic transfer and charge-exchange reactions in collisions of 48Ti on 42Ca and 26Mg

International Nuclear Information System (INIS)

Brendel, C.

1985-01-01

At the GSI magnetic spectrometer quasi-elastic transfer and charge-exchange reactions of the system 48 Ti + 42 Ca at incident energies E lab = 240, 300, and 385 MeV and additionally at the higher projectile energy the system 48 Ti + 26 Mg were studied each in the excitation energy range up to E x ≅ 80 MeV. The transition strength was for each particle-hole configuration of the final system calculated by means of the DWBA and subsequently folded with a Breit-Wigner distribution. The localization of the strength of the cross section and the specific structure of the energy spectra were at incident energies between 6 and 8 MeV/amu for all angles well reproduced. By an extension of the core-excitation model to many-stage reactions the charge-exchange reaction 48 Ti + 42 Ca → 48 Sc + 42 Sc could be described as sequential two-stage process. In the two-neutron stripping reaction 48 Ti + 42 Ca → 46 Ti + 44 Ca a surprisingly narrow line with a width of the experimental resolution and an excitation energy of E x = 17.8 MeV was measured at angles smaller than the grazing angle. In the 48 Ti + 26 Mg system the corresponding 46 Ti spectra show also under forward angles structures at excitation energies between 8 and 16 MeV. These lines can be explained as two-neutron states with high spin. (orig./HSI) [de

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

Science.gov (United States)

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

2015-02-21

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

Optically Controlled Electron-Transfer Reaction Kinetics and Solvation Dynamics : Effect of Franck-Condon States

NARCIS (Netherlands)

Gupta, Kriti; Patra, Aniket; Dhole, Kajal; Samanta, Alok Kumar; Ghosh, Swapan K.

2017-01-01

Experimental results for optically controlled electron-transfer reaction kinetics (ETRK) and nonequilibrium solvation dynamics (NESD) of Coumarin 480 in DMPC vesicle show their dependence on excitation wavelength λex. However, the celebrated Marcus theory and linear-response-theory-based approaches

Kinetics and mechanisms of photoinduced electron-transfer reaction of zinc myoglobin

International Nuclear Information System (INIS)

Tsukahara, Keiichi; Asami, Satoko; Okada, Mihoko; Sakurai, Takeshi.

1994-01-01

Photoinduced electron transfer (ET) between zinc myoglobin (ZnPPMb) and a variety of quenchers, such as hexacyanoferrate(III)([Fe(CN) 6 ] 3- ) and hexaammineruthenium(III)(Ru(NH 3 ) 6 ] 3+ ions, cationic viologens, copper(II) protein (stellacyanin), and metmyoglobins, has been studied in aqueous degassed solutions. The excited triplet state of ZnPPMb( * ZnPPMb) was quenched by [Fe(CN) 6 ] 3- in a self-associated complex. Both quenching rate constant and formation constant of the self-associated complex decrease with increasing ionic strengths. The thermal backward ET reaction for this system was not observed; it is most likely that the backward ET step is much faster than the quenching reaction. All of the cationic quenchers examined in this work did not form a self-associated complex with * ZnPPMb, and the intermolecular quenching occurred. The thermal backward ET reaction was observed for these cationic quenchers. Not only photoinduced ET but also thermal backward ET reactions were insensitive to the driving force of the reactions, suggesting that the reactions are controlled by conformational changes in ZnPPMb. The quenching rate constants increase with increasing ionic strength for the cationic quenchers. The effects of poly-L-lysine hydrochloride, sodium poly-L-glutamate, and sodium cyclo-hexaphosphate were also examined. The active site of the * ZnPPMb toward both anionic and cationic quenchers is assumed to be the positively charged site near the heme pocket. (author)

Collective charge and mass transfer in heavy ion reactions

International Nuclear Information System (INIS)

Hahn, J.

1982-01-01

In this thesis the dynamics of the charge and mass asymmetry degree of freedom was studied in the framework of the fragmentation theory by means of a time-dependent Schroedinger equation. New is the introduction of a friction potential which describes the coupling of these collective degrees of freedom to the not explicitely treated other collective respectively internal degrees of freedom. Thereby it was shown that the measured widths of the isobaric charge distributions in the 86 Kr+sup(92,98)Mo reaction can be explained mainly by the quantum mechanical uncertainty in the charge asymmetry degree of freedom. The charge equilibration occurring at the begin of a deep inelastic collision can therefore by considered as a quantum mechanical, collective, damped motion which is connected with the excitation of the isovector giant dipole resonance of the nucleus-nucleus system. The study of the mass transfer in the reactions 132 Xe+ 120 Sn and 86 Kr+ 166 Er shows, how important at the begin of a deep inelastic collision shell structures and their conservation are for a large part of the reaction, even if the elemental distribution show no maxima in the region of magic shell closures. The experimental width are up to 10 MeV/A well described under conservation of the shell structure. (orig./HSI) [de

Nuclear transfer reaction measurements at the ESR—for the investigation of the astrophysical 15O(α,γ)19Ne reaction

International Nuclear Information System (INIS)

Doherty, D T; Woods, P J; Davinson, T; Estrade, A; Lotay, G; Litvinov, Yu A; Brandau, C; Dillmann, I; Egelhof, P; Evdokimov, A; Gumberidze, A; Heil, M; Litvinov, S A; Kiselev, O; Najafi, M Ali; Bagchi, S; Kalantar-Nayestanaki, N; Bishop, S; Bo, M; Lederer, C

2015-01-01

Astrophysical x-ray bursts are thought to be a result of thermonuclear explosions on the atmosphere of an accreting neutron star. Between these bursts, energy is thought to be generated by the hot CNO cycles. The 15 O(α,γ) 19 Ne reaction is one reaction that allows breakout from these CNO cycles and into the rp-process to fuel outbursts. The reaction is expected to be dominated by a single 3/2 + resonance at 4.033 MeV in 19 Ne, however, limited information is available on this key state. This work reports on a pioneering study of the 20 Ne(p,d) 19 Ne reaction, performed in inverse kinematics at the experimental storage ring (ESR) as a means of accessing the astrophysically important 4.033 MeV state in 19 Ne. The unique, background free, high luminosity conditions of the storage ring were utilized for this, the first transfer reaction performed at the ESR. The results of this pioneering test experiment are presented along with suggestions for future measurements at storage ring facilities. (paper)

Deeply inelastic transfer reactions induced by heavy ions in rare earth targets. II. Interpretation of experimental data

International Nuclear Information System (INIS)

Rivet, M.F.; Bimbot, R.; Ngo, C.

1979-01-01

The experimental angular distributions and cross sections for a series of deeply inelastic transfer reactions induced by various projectiles in rare earth targets have been interpreted using a model which includes a dynamical coupling between relative motion and mass asymmetry and treats statistical fluctuations. As the transfer reactions considered correspond to an increase of the potential energy of the composite system their observation is mainly due to fluctuations. The calculation reproduces correctly the angular distributions, but the cross sections are underestimated. Several effects are discussed which may increase these cross sections and are neglected in the calculation

Nucleon transfer reactions in D.W.B.A; Les reactions de transfert d'un nucleon dans la D.W.B.A

Energy Technology Data Exchange (ETDEWEB)

Giraud, B.; Picard, J. [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires

1968-08-01

The DWBA for one nucleon transfer reaction is described as simply and completely as possible to show the possibilities and limits of this method. The extraction of spectroscopic factors is described in the appendix. (authors) [French] Le formalisme de la DWBA est decrit d'une maniere aussi simple et complete que possible pour mettre en evidence les possibilites et les limites de cette methode d'analyse des reactions de transfert. L'extraction des facteurs spectroscopiques est exposee en appendice. (auteurs)

Isotopic resolution of fission fragments from 238U + 12C transfer and fusion reactions

International Nuclear Information System (INIS)

Caamano, M.; Rejmund, F.; Derkx, X.; Schmidt, K. H.; Andouin, L.; Bacri, C. O.; Barreau, G.; Benlliure, J.; Casarejos, E.; Fernandez-Dominguez, B.; Gaudefroy, L.; Golabek, C.; Jurado, B.; Lemasson, A.; Navin, A.; Rejmund, M.; Roger, T.; Shrivastava, A.; Schmitt, C.; Taieb, J.

2010-01-01

Recent results from an experiment at GANIL, performed to investigate the main properties of fission-fragment yields and energy distributions in different fissioning nuclei as a function of the excitation energy, in a neutron-rich region of actinides, are presented. Transfer reactions in inverse kinematics between a 238 U beam and a 12 C target produced different actinides, within a range of excitation energy below 30 MeV. These fissioning nuclei are identified by detecting the target-like recoil, and their kinetic and excitation energy are determined from the reconstruction of the transfer reaction. The large-acceptance spectrometer VAMOS was used to identify the mass, atomic number and charge state of the fission fragments in flight. As a result, the characteristics of the fission-fragment isotopic distributions of a variety of neutron-rich actinides are observed for the first time over the complete range of fission fragments. (authors)

Reaction between aminoalkyl radicals and akyl halides: Dehalogenation by electron transfer?

Science.gov (United States)

Lalevée, J.; Fouassier, J. P.; Blanchard, N.; Ingold, K. U.

2011-07-01

Aminoalkyl radicals, such as Et2NCrad HCH3, have low oxidation potentials and are therefore powerful reducing agents. We have found that Et2NCrad HCH3 reacts with CCl4 and CBr4 in di-tert-butyl peroxide with bimolecular rate constants (measured by LFP) close, or equal, to the diffusion-controlled limit. For the less reactive halide, CH2Br2, the reaction rate is increased substantially by the addition of acetonitrile as a co-solvent. It is tentatively concluded that these reactions occur by electron-transfer from the aminoalkyl to the organohalide with formation of the iminium ion, Et2N+dbnd CHCH3 (NMR detection), halide ion and a halomethyl radical, e.g., rad CCl3 and rad CHCl2 (ESR, spin-trapping detection).

Two-Dimensional Resonance Raman Signatures of Vibronic Coherence Transfer in Chemical Reactions.

Science.gov (United States)

Guo, Zhenkun; Molesky, Brian P; Cheshire, Thomas P; Moran, Andrew M

2017-11-02

Two-dimensional resonance Raman (2DRR) spectroscopy has been developed for studies of photochemical reaction mechanisms and structural heterogeneity in condensed phase systems. 2DRR spectroscopy is motivated by knowledge of non-equilibrium effects that cannot be detected with traditional resonance Raman spectroscopy. For example, 2DRR spectra may reveal correlated distributions of reactant and product geometries in systems that undergo chemical reactions on the femtosecond time scale. Structural heterogeneity in an ensemble may also be reflected in the 2D spectroscopic line shapes of both reactive and non-reactive systems. In this chapter, these capabilities of 2DRR spectroscopy are discussed in the context of recent applications to the photodissociation reactions of triiodide. We show that signatures of "vibronic coherence transfer" in the photodissociation process can be targeted with particular 2DRR pulse sequences. Key differences between the signal generation mechanisms for 2DRR and off-resonant 2D Raman spectroscopy techniques are also addressed. Overall, recent experimental developments and applications of the 2DRR method suggest that it will be a valuable tool for elucidating ultrafast chemical reaction mechanisms.

Continuous Flow Chemistry: Reaction of Diphenyldiazomethane with p-Nitrobenzoic Acid.

Science.gov (United States)

Aw, Alex; Fritz, Marshall; Napoline, Jonathan W; Pollet, Pamela; Liotta, Charles L

2017-11-15

Continuous flow technology has been identified as instrumental for its environmental and economic advantages leveraging superior mixing, heat transfer and cost savings through the "scaling out" strategy as opposed to the traditional "scaling up". Herein, we report the reaction of diphenyldiazomethane with p-nitrobenzoic acid in both batch and flow modes. To effectively transfer the reaction from batch to flow mode, it is essential to first conduct the reaction in batch. As a consequence, the reaction of diphenyldiazomethane was first studied in batch as a function of temperature, reaction time, and concentration to obtain kinetic information and process parameters. The glass flow reactor set-up is described and combines two types of reaction modules with "mixing" and "linear" microstructures. Finally, the reaction of diphenyldiazomethane with p-nitrobenzoic acid was successfully conducted in the flow reactor, with up to 95% conversion of the diphenyldiazomethane in 11 min. This proof of concept reaction aims to provide insight for scientists to consider flow technology's competitiveness, sustainability, and versatility in their research.

Dynamics of the F(-) + CH3I → HF + CH2I(-) Proton Transfer Reaction.

Science.gov (United States)

Zhang, Jiaxu; Xie, Jing; Hase, William L

2015-12-17

Direct chemical dynamics simulations, at collision energies Erel of 0.32 and 1.53 eV, were performed to obtain an atomistic understanding of the F(-) + CH3I reaction dynamics. There is only the F(-) + CH3I → CH3F + I(-) bimolecular nucleophilic substitution SN2 product channel at 0.32 eV. Increasing Erel to 1.53 eV opens the endothermic F(-) + CH3I → HF + CH2I(-) proton transfer reaction, which is less competitive than the SN2 reaction. The simulations reveal proton transfer occurs by two direct atomic-level mechanisms, rebound and stripping, and indirect mechanisms, involving formation of the F(-)···HCH2I complex and the roundabout. For the indirect trajectories all of the CH2I(-) is formed with zero-point energy (ZPE), while for the direct trajectories 50% form CH2I(-) without ZPE. Without a ZPE constraint for CH2I(-), the reaction cross sections for the rebound, stripping, and indirect mechanisms are 0.2 ± 0.1, 1.2 ± 0.4, and 0.7 ± 0.2 Å(2), respectively. Discarding trajectories that do not form CH2I(-) with ZPE reduces the rebound and stripping cross sections to 0.1 ± 0.1 and 0.7 ± 0.5 Å(2). The HF product is formed rotationally and vibrationally unexcited. The average value of J is 2.6 and with histogram binning n = 0. CH2I(-) is formed rotationally excited. The partitioning between CH2I(-) vibration and HF + CH2I(-) relative translation energy depends on the treatment of CH2I(-) ZPE. Without a CH2I(-) ZPE constraint the energy partitioning is primarily to relative translation with little CH2I(-) vibration. With a ZPE constraint, energy partitioning to CH2I(-) rotation, CH2I(-) vibration, and relative translation are statistically the same. The overall F(-) + CH3I rate constant at Erel of both 0.32 and 1.53 eV is in good agreement with experiment and negligibly affected by the treatment of CH2I(-) ZPE, since the SN2 reaction is the major contributor to the total reaction rate constant. The potential energy surface and reaction dynamics for F

Ruthenium(II) pincer complexes with oxazoline arms for efficient transfer hydrogenation reactions

KAUST Repository

Chen, Tao

2012-08-01

Well-defined P NN CN pincer ruthenium complexes bearing both strong phosphine and weak oxazoline donors were developed. These easily accessible complexes exhibit significantly better catalytic activity in transfer hydrogenation of ketones compared to their PN 3P analogs. These reactions proceed under mild and base-free conditions via protonation- deprotonation of the \\'NH\\' group in the aromatization-dearomatization process. © 2012 Elsevier Ltd. All rights reserved.

Electron transfer reactions, cyanide and O2 binding of truncated hemoglobin from Bacillus subtilis

DEFF Research Database (Denmark)

Fernandez, Esther; Larsson, Jonas T.; McLean, Kirsty J.

2013-01-01

The truncated hemoglobin from Bacillus subtilis (trHb-Bs) possesses a surprisingly high affinity for oxygen and resistance to (auto)oxidation; its physiological role in the bacterium is not understood and may be connected with its very special redox and ligand binding reactions. Electron transfer...

Transfer of energy from irradiated crystals to redox reactions: iodide/bromate and nitrite/bromate systems

International Nuclear Information System (INIS)

Arnikar, H.J.; Madhava Rao, B.S.; Bedekar, M.J.

1978-01-01

Earlier it had been shown by the authors that some of the redox reactions, which do not take place at room temperature can be induced by γ radiation. The yields are proportional to the dose. Results reported here show that instead of direct irradiation, the energy stored in irradiated crystals in the form of F and hole centres can be available, in part, in effecting redox reactions. The mechanism of such an energy transfer is discussed with reference to reactions in the I - +BrO 3 - and NO 2 - +BrO 3 - systems due to the addition of irradiated NaCl. (author)

Extraordinary Mechanism of the Diels-Alder Reaction: Investigation of Stereochemistry, Charge Transfer, Charge Polarization, and Biradicaloid Formation.

Science.gov (United States)

Sexton, Thomas; Kraka, Elfi; Cremer, Dieter

2016-02-25

The Diels-Alder reaction between 1,3-butadiene and ethene is investigated from far-out in the entrance channel to the very last step in the exit channel thus passing two bifurcation points and extending the range of the reaction valley studied with URVA (Unified Reaction Valley Approach) by 300% compared to previous studies. For the first time, the pre- and postchemical steps of the reaction are analyzed at the same level of theory as the actual chemical processes utilizing the path curvature and its decomposition into internal coordinate or curvilinear coordinate components. A first smaller charge transfer to the dienophile facilitates the rotation of gauche butadiene into its cis form. The actual chemical processes are initiated by a second larger charge transfer to the dienophile that facilitates pyramidalization of the reacting carbon centers, bond equalization, and biradicaloid formation of the reactants. The transition state is aromatically stabilized and moved by five path units into the entrance channel in line with the Hammond-Leffler postulate. The pseudorotation of the boat form into the halfchair of cyclohexene is analyzed. Predictions are made for the Diels-Alder reaction based on a 11-phase mechanism obtained by the URVA analysis.

Intramolecular energy transfer and mode-specific effects in unimolecular reactions of 1,2-difluoroethane

Science.gov (United States)

Raff, Lionel M.

1989-06-01

The unimolecular decomposition reactions of 1,2-difluoroethane upon mode-specific excitation to a total internal energy of 7.5 eV are investigated using classical trajectory methods and a previously formulated empirical potential-energy surface. The decomposition channels for 1,2-difluoroethane are, in order of importance, four-center HF elimination, C-C bond rupture, and hydrogen-atom dissociation. This order is found to be independent of the particular vibrational mode excited. Neither fluorine-atom nor F2 elimination reactions are ever observed even though these dissociation channels are energetically open. For four-center HF elimination, the average fraction of the total energy partitioned into internal HF motion varies between 0.115-0.181 depending upon the particular vibrational mode initially excited. The internal energy of the fluoroethylene product lies in the range 0.716-0.776. Comparison of the present results with those previously obtained for a random distribution of the initial 1,2-difluoroethane internal energy [J. Phys. Chem. 92, 5111 (1988)], shows that numerous mode-specific effects are present in these reactions in spite of the fact that intramolecular energy transfer rates for this system are 5.88-25.5 times faster than any of the unimolecular reaction rates. Mode-specific excitation always leads to a total decomposition rate significantly larger than that obtained for a random distribution of the internal energy. Excitation of different 1,2-difluoroethane vibrational modes is found to produce as much as a 51% change in the total decomposition rate. Mode-specific effects are also seen in the product energy partitioning. The rate coefficients for decomposition into the various channels are very sensitive to the particular mode excited. A comparison of the calculated mode-specific effects with the previously determined mode-to-mode energy transfer rate coefficients [J. Chem. Phys. 89, 5680 (1988)] shows that, to some extent, the presence of mode

Bridge mediated two-electron transfer reactions: Analysis of stepwise and concerted pathways

International Nuclear Information System (INIS)

Petrov, E.G.; May, V.

2004-01-01

A theory of nonadiabatic donor (D)-acceptor (A) two-electron transfer (TET) mediated by a single regular bridge (B) is developed. The presence of different intermediate two-electron states connecting the reactant state D -- BA with the product state DBA -- results in complex multiexponential kinetics. The conditions are discussed at which a reduction to two-exponential as well as single-exponential kinetics becomes possible. For the latter case the rate K TET is calculated, which describes the bridge-mediated reaction as an effective two-electron D-A transfer. In the limit of small populations of the intermediate TET states D - B - A, DB -- A, D - BA - , and DB - A - , K TET is obtained as a sum of the rates K TET (step) and K TET (sup) . The first rate describes stepwise TET originated by transitions of a single electron. It starts at D -- BA and reaches DBA -- via the intermediate state D - BA - . These transitions cover contributions from sequential as well as superexchange reactions all including reduced bridge states. In contrast, a specific two-electron superexchange mechanism from D -- BA to DBA -- defines K TET (sup) . An analytic dependence of K TET (step) and K TET (sup) on the number of bridging units is presented and different regimes of D-A TET are studied

A Stefan model for mass transfer in a rotating disk reaction vessel

KAUST Repository

BOHUN, C. S.

2015-05-04

Copyright © Cambridge University Press 2015. In this paper, we focus on the process of mass transfer in the rotating disk apparatus formulated as a Stefan problem with consideration given to both the hydrodynamics of the process and the specific chemical reactions occurring in the bulk. The wide range in the reaction rates of the underlying chemistry allows for a natural decoupling of the problem into a simplified set of weakly coupled convective-reaction-diffusion equations for the slowly reacting chemical species and a set of algebraic relations for the species that react rapidly. An analysis of the chemical equilibrium conditions identifies an expansion parameter and a reduced model that remains valid for arbitrarily large times. Numerical solutions of the model are compared to an asymptotic analysis revealing three distinct time scales and chemical diffusion boundary layer that lies completely inside the hydrodynamic layer. Formulated as a Stefan problem, the model generalizes the work of Levich (Levich and Spalding (1962) Physicochemical hydrodynamics, vol. 689, Prentice-Hall Englewood Cliffs, NJ) and will help better understand the natural limitations of the rotating disk reaction vessel when consideration is made for the reacting chemical species.

Insights into the mechanisms on chemical reactions: reaction paths for chemical reactions

International Nuclear Information System (INIS)

Dunning, T.H. Jr.; Rosen, E.; Eades, R.A.

1987-01-01

We report reaction paths for two prototypical chemical reactions: Li + HF, an electron transfer reaction, and OH + H 2 , an abstraction reaction. In the first reaction we consider the connection between the energetic terms in the reaction path Hamiltonian and the electronic changes which occur upon reaction. In the second reaction we consider the treatment of vibrational effects in chemical reactions in the reaction path formalism. 30 refs., 9 figs

Analysis of coupled mass transfer and sol-gel reaction in a two-phase system

NARCIS (Netherlands)

Castelijns, H.J.; Huinink, H.P.; Pel, L.; Zitha, P.L.J.

2006-01-01

The coupled mass transfer and chemical reactions of a gel-forming compound in a two-phase system were studied in detail. Tetra-methyl-ortho-silicate (TMOS) is often used as a precursor in sol-gel chemistry to produce silica gels in aqueous systems. TMOS can also be mixed with many hydrocarbons

Stripping of two protons and one alpha particle transfer reactions for 16 O + A Sm and their influence on the fusion cross section

International Nuclear Information System (INIS)

Maciel, A.M.M.; Gomes, P.R.S.

1995-01-01

Transfer cross section angular distribution data for the stripping of two protons and one alpha particle are studied for the 16 O + A Sm systems (A=144, 148, 150, 152 and 154), at near barrier energies. A semiclassical formalism is used to derive the corresponding transfer form factors. For only one channel the analysis shows evidences that the transfer reaction mechanism at backward angles - corresponding to small distances, may behave as a multi-step process leading to fusion. Simplified coupled channel calculations including transfer channels are performed for the study of the sub-barrier of these systems. The influence of short distance transfer reactions on the fusion is discussed. (author)

[Intermediate energy studies of polarization transfer, polarized deuteron scattering, and (p,π+-) reactions: Rapporteur's report

International Nuclear Information System (INIS)

Moss, J.M.

1985-01-01

An overview of intermediate energy (80 to 1000 MeV) study contributions to the International Polarization Symposium in Osaka, Japan, August 1985 is presented in this report. Contributions fall into three categories: polarization transfer, polarized deuteron scattering and polarized (p,π +- ) reactions

Study of transfer reactions (α,t), (α,3He) in the f-p shell: mechanism and spectroscopic use

International Nuclear Information System (INIS)

Roussel, P.

1968-05-01

We describe an experimental study of (α,t), (α, 3 He) reactions at 44 MeV using a solid-state identifier, on the target-nuclei 54 Fe and 58,60,62,64 Ni. A critical study of optical model and of disturbed wave analysis has been performed. We show the complementarity of different transfer-reactions, the ambiguity of spectroscopic factors, the importance of the problem of the reaction mechanism. (author) [fr

Simple Ion Transfer at Liquid|Liquid Interfaces

Directory of Open Access Journals (Sweden)

L. J. Sanchez Vallejo

2012-01-01

Full Text Available The main aspects related to the charge transfer reactions occurring at the interface between two immiscible electrolyte solutions (ITIES are described. The particular topics to be discussed involve simple ion transfer. Focus is given on theoretical approaches, numerical simulations, and experimental methodologies. Concerning the theoretical procedures, different computational simulations related to simple ion transfer are reviewed. The main conclusions drawn from the most accepted models are described and analyzed in regard to their relevance for explaining different aspects of ion transfer. We describe numerical simulations implementing different approaches for solving the differential equations associated with the mass transport and charge transfer. These numerical simulations are correlated with selected experimental results; their usefulness in designing new experiments is summarized. Finally, many practical applications can be envisaged regarding the determination of physicochemical properties, electroanalysis, drug lipophilicity, and phase-transfer catalysis.

Production of 149Tb in deep inelastic transfer reactions: an approach to the angular momentum of fragments

International Nuclear Information System (INIS)

Rivet, M.F.; Bimbot, R.; Gardes, D.; Fleury, A.; Hubert, F.; Llabador, Y.

1978-01-01

The excitation functions for deep inelastic reactions in which two to six charges are transferred from 40 Ar and 63 Cu ions to rare earth targets have been measured using activation techniques, the observed radionuclides being 150 Dy, 151 Dy and 149 gTb. From the comparison of the curves relative to 149 gTb and those relative to 150 Dy, 151 Dy, it was deduced that the low spin isomer 149 gTb was produced with significant probability for low incident energies. Using data from (heavy ions, xn) reactions, it was possible to attribute this production to the deexcitation of Tb fragments formed in deep inelastic transfers with angular momenta lower than 9n. This result is in good agreement with the angular momentum calculations performed under the hypothesis that the initial angular momentum window leading to deep inelastic reactions is situated between the critical angular momentum for fusion and that corresponding to grazing collisions. As far as Cu induced reactions are concerned, both hypothesis of rolling and sticking are consistent with the experimental data. For Ar induced reactions, the results indicate that the stage of sticking is not reached when the incident energy is lower than 200 MeV

Super-multi-nucleon transfer observed in 60Ni+124Sn reaction slightly above the barrier

International Nuclear Information System (INIS)

Tomasi, E.; Pravikoff, M.S.; Nolte, E.; Morinaga, H.

1982-01-01

In order to investigate the behaviour of nucleon transfer near the Coulomb barrier through the produced radioactivities, we have studied the 60 Ni+ 124 Sn system, the residual activity measurements were done at three lab energies of 237, 247 and 258 MeV (Bsub(c)(lab) = 234 MeV). For the highest energy we measured also the angular distribution. In addition to activities corresponding to a few nucleon transfers and evaporation residues, a large number of radioactive nuclei was found, which could be attributed to another class of reaction mechanism. Here, we report on this new phenomenon, which might be due to a super-multi-nucleon transfer, on the basis of the measured angular and mass distributions

Photochemical reactions of electron-deficient olefins with N,N,N',N'-tetramethylbenzidine via photoinduced electron-transfer

International Nuclear Information System (INIS)

Pan Yang; Zhao Junshu; Ji Yuanyuan; Yan Lei; Yu Shuqin

2006-01-01

Photoinduced electron transfer reactions of several electron-deficient olefins with N,N,N',N'-tetramethylbenzidine (TMB) in acetonitrile solution have been studied by using laser flash photolysis technique and steady-state fluorescence quenching method. Laser pulse excitation of TMB yields 3 TMB* after rapid intersystem crossing from 1 TMB*. The triplet which located at 480 nm is found to undergo fast quenching with the electron acceptors fumaronitrile (FN), dimethyl fumarate (DMF), diethyl fumarate (DEF), cinnamonitrile (CN), α-acetoxyacrylonitrile (AAN), crotononitrile (CrN) and 3-methoxyacrylonitrile (MAN). Substituents binding to olefin molecule own different electron-donating/withdrawing powers, which determine the electron-deficient property (π-cloud density) of olefin molecule as well as control the electron transfer rate constant directly. The detection of ion radical intermediates in the photolysis reactions confirms the proposed electron transfer mechanism, as expected from thermodynamics. The quenching rate constants of triplet TMB by these olefins have been determined at 510 nm to avoid the disturbance of formed TMB cation radical around 475 nm. All the k q T values approach or reach to the diffusion-controlled limit. In addition, fluorescence quenching rate constants k q S have been also obtained by calculating with Stern-Volmer equation. A correlation between experimental electron transfer rate constants and free energy changes has been explained by Marcus theory of adiabatic outer-sphere electron transfer. Disharmonic k q values for CN and CrN in endergonic region may be the disturbance of exciplexs formation. e of exciplex formation

Fission fragments mass distributions of nuclei populated by the multinucleon transfer channels of the 18O+232Th reaction

Directory of Open Access Journals (Sweden)

R. Léguillon

2016-10-01

Full Text Available It is shown that the multinucleon transfer reactions is a powerful tool to study fission of exotic neutron-rich actinide nuclei, which cannot be accessed by particle-capture or heavy-ion fusion reactions. In this work, multinucleon transfer channels of the 18O+232Th reaction are used to study fission of fourteen nuclei 231,232,233,234Th, 232,233,234,235,236Pa, and 234,235,236,237,238U. Identification of fissioning nuclei and of their excitation energy is performed on an event-by-event basis, through the measurement of outgoing ejectile particle in coincidence with fission fragments. Fission fragment mass distributions are measured for each transfer channel, in selected bins of excitation energy. In particular, the mass distributions of 231,234Th and 234,235,236Pa are measured for the first time. Predominantly asymmetric fission is observed at low excitation energies for all studied cases, with a gradual increase of the symmetric mode towards higher excitation energy. The experimental distributions are found to be in general agreement with predictions of the fluctuation–dissipation model.

Characterization of ferritin core on redox reactions as a nanocomposite for electron transfer

International Nuclear Information System (INIS)

Shin, Kwang Min; Watt, Richard K.; Watt, Gerald D.; Choi, Sang H.; Kim, Hyug-Han; Kim, Sun I.; Kim, Seon Jeong

2010-01-01

The kinetics of the change in mass related to the release from and deposition onto the cavities of a ferritin in the SWCNT nanocomposite by electrochemical redox reactions, and the effects of the SWCNT on the kinetics of the variation in mass of the ferritin nanocomposite were characterized using an electrochemical quartz crystal microbalance. The change in mass of reconstituted ferritin in the SWCNT nanocomposite shows reversible variation and stability of the ferritin/SWCNT nanocomposite on redox reactions was confirmed by using a coreless apoferritin and a Fe 2+ chelating agent. The ferritin/SWCNT nanocomposite is a good candidate for applications based on electron transfer, such as biosensor, biobatteries and electrodes for biofuel cell.

Spectroscopic factors measurement of the five first energy levels of lead 208 nucleus using the 208Pb(e,e'p207Tl* huge pulse transfer reaction

International Nuclear Information System (INIS)

Medaglia, R.

1999-08-01

In this work, the spectral functions and the spectroscopic factors of the first five energy levels of the lead 208 nucleus have been measured using the 208 Pb(e,e'p) 207 Tl * reaction. The aim is to characterize the effect of the nuclear environment on pulse and energy distributions of protons. In order to minimize the ejected proton-residual nucleus interactions in the final state, the measurement has been performed at 750 and 570 MeV/c pulse transfers, and thus for proton kinetic energies of 263 MeV and 161 MeV, contrarily to a previous measurement performed at 100 MeV. A kinematics with a transverse electromagnetic coupling, instead of a longitudinal one, has been used because of the important coupling dependence observed for medium nuclei. The experiment has been carried out at the NIKHEF electron accelerator and smoothing ring. The pulse distributions of the first five energy levels for a proton pulse range of 0 to 300 MeV/c have been extracted from the (e,e'p) cross sections. An integration of model-dependent distributions gives the spectroscopic factors which indicate the number of protons of each level. These data rae compared to models that include both the proton interactions in the final state and the coulomb distortions. The Pavie model reproduces well the observed distributions and the transfer dependence, while the Ohio model does not. The spectroscopic factors obtained with the Pavie model are the same for both transfers and are 20% higher as an average than the previous experiment performed at 450 MeV/c. However, they are 30% below the shell model. The uncertain estimation of the reaction mechanisms does not allow to consider this reduction as being due exclusively to nuclear structure effects. (J.S.)

Severe immediate allergic reactions to grapes: part of a lipid transfer protein-associated clinical syndrome

NARCIS (Netherlands)

Vassilopoulou, Emilia; Zuidmeer, Laurian; Akkerdaas, Jaap; Tassios, Ioannis; Rigby, Neil R.; Mills, E. N. Clare; van Ree, Ronald; Saxoni-Papageorgiou, Photini; Papadopoulos, Nikolaos G.

2007-01-01

BACKGROUND: Grape allergy is considered rare; grape lipid transfer protein (LTP; Vit v 1), an endochitinase and a thaumatin-like protein (TLP) have been reported as grape allergens. A considerable number of patients have referred to our department for severe reactions to grapes, and several IgE

Modelling excitonic energy transfer in the photosynthetic unit of purple bacteria

International Nuclear Information System (INIS)

Linnanto, J.M.; Korppi-Tommola, J.E.I.

2009-01-01

Molecular mechanics and quantum chemical configuration interaction calculations in combination with exciton theory were used to predict vibronic energies and eigenstates of light harvesting antennae and the reaction centre and to evaluate excitation energy transfer rates in the photosynthetic unit of purple bacteria. Excitation energy transfer rates were calculated by using the transition matrix formalism and exciton basis sets of the interacting antenna systems. Energy transfer rates of 600-800 fs from B800 ring to B850 ring in the LH2 antenna, 3-10 ps from LH2 to LH2 antenna, 2-8 ps from LH2 to LH1 antenna and finally 30-70 ps from LH1 to the reaction centre were obtained. Dependencies of energy transfer rates on lateral and vertical inter-complex distances were determined. The results indicate that a fair amount of spatial heterogeneity of antenna complexes in the photosynthetic membrane is tolerated without much loss in excitation energy transfer efficiency

Modelling excitonic energy transfer in the photosynthetic unit of purple bacteria

Energy Technology Data Exchange (ETDEWEB)

Linnanto, J.M. [Department of Chemistry, P.O. Box 35, FIN-40014 University of Jyvaeskylae, Jyvaeskylae (Finland)], E-mail: juha.m.linnanto@jyu.fi; Korppi-Tommola, J.E.I. [Department of Chemistry, P.O. Box 35, FIN-40014 University of Jyvaeskylae, Jyvaeskylae (Finland)

2009-02-23

Molecular mechanics and quantum chemical configuration interaction calculations in combination with exciton theory were used to predict vibronic energies and eigenstates of light harvesting antennae and the reaction centre and to evaluate excitation energy transfer rates in the photosynthetic unit of purple bacteria. Excitation energy transfer rates were calculated by using the transition matrix formalism and exciton basis sets of the interacting antenna systems. Energy transfer rates of 600-800 fs from B800 ring to B850 ring in the LH2 antenna, 3-10 ps from LH2 to LH2 antenna, 2-8 ps from LH2 to LH1 antenna and finally 30-70 ps from LH1 to the reaction centre were obtained. Dependencies of energy transfer rates on lateral and vertical inter-complex distances were determined. The results indicate that a fair amount of spatial heterogeneity of antenna complexes in the photosynthetic membrane is tolerated without much loss in excitation energy transfer efficiency.

X-ray Crystal Structures Elucidate the Nucleotidyl Transfer Reaction of Transcript Initiation Using Two Nucleotides

Energy Technology Data Exchange (ETDEWEB)

M Gleghorn; E Davydova; R Basu; L Rothman-Denes; K Murakami

2011-12-31

We have determined the X-ray crystal structures of the pre- and postcatalytic forms of the initiation complex of bacteriophage N4 RNA polymerase that provide the complete set of atomic images depicting the process of transcript initiation by a single-subunit RNA polymerase. As observed during T7 RNA polymerase transcript elongation, substrate loading for the initiation process also drives a conformational change of the O helix, but only the correct base pairing between the +2 substrate and DNA base is able to complete the O-helix conformational transition. Substrate binding also facilitates catalytic metal binding that leads to alignment of the reactive groups of substrates for the nucleotidyl transfer reaction. Although all nucleic acid polymerases use two divalent metals for catalysis, they differ in the requirements and the timing of binding of each metal. In the case of bacteriophage RNA polymerase, we propose that catalytic metal binding is the last step before the nucleotidyl transfer reaction.

Leading coordinate analysis of reaction pathways in proton chain transfer: Application to a two-proton transfer model for the green fluorescent protein

International Nuclear Information System (INIS)

Wang Sufan; Smith, Sean C.

2006-01-01

The 'leading coordinate' approach to computing an approximate reaction pathway, with subsequent determination of the true minimum energy profile, is applied to a two-proton chain transfer model based on the chromophore and its surrounding moieties within the green fluorescent protein (GFP). Using an ab initio quantum chemical method, a number of different relaxed energy profiles are found for several plausible guesses at leading coordinates. The results obtained for different trial leading coordinates are rationalized through the calculation of a two-dimensional relaxed potential energy surface (PES) for the system. Analysis of the 2-D relaxed PES reveals that two of the trial pathways are entirely spurious, while two others contain useful information and can be used to furnish starting points for successful saddle-point searches. Implications for selection of trial leading coordinates in this class of proton chain transfer reactions are discussed, and a simple diagnostic function is proposed for revealing whether or not a relaxed pathway based on a trial leading coordinate is likely to furnish useful information

Determination by transfer reaction of alpha widths in fluorine for astrophysical interest

International Nuclear Information System (INIS)

Oliveira Santos, F. de

1995-04-01

The nucleosynthesis of fluorine is not known. Several astrophysical models predict the alpha radiative capture onto N 15 as the main fluorine production reaction. In the expression of the reaction rate, one parameter is missing: the alpha width of the resonance on the E = 4.377 MeV level in fluorine. A direct measurement is excluded due to the very low cross-section expected. We have determined this alpha width using a transfer reaction followed by analyses with FR-DWBA (Finite Range Distorted Wave Born Approximation) in a simple cluster alpha model. This experiment was carried out with a Li 7 beam with E = 28 MeV onto a N 15 gas target. The 16 first levels were studied. Spectroscopic factors were extracted for most of them. Alpha widths for unbound levels were determined. Many alpha width were compared with known values from direct reaction and the differences lie within the uncertainty range (factor 2). The alpha width for the E = 4.377 MeV level was determined (Γ α = 1.5*10 -15 MeV), its value is about 60 times weaker than the used value. The influence of our new rate was studied in AGB (Asymptotic Giant Branch) stars during thermal pulses. In this model the alteration is sensitive. (author)

Mass Transfer and Chemical Reaction Approach of the Kinetics of the Acetylation of Gadung Flour using Glacial Acetic Acid

Directory of Open Access Journals (Sweden)

Andri Cahyo Kumoro

2015-03-01

Full Text Available Acetylation is one of the common methods of modifying starch properties by introducing acetil (CH3CO groups to starch molecules at low temperatures. While most acetylation is conducted using starch as anhidroglucose source and acetic anhydride or vinyl acetate as nucleophilic agents, this work employ reactants, namely flour and glacial acetic acid. The purpose of this work are to study the effect of pH reaction and GAA/GF mass ratio on the rate of acetylation reaction and to determine its rate constants. The acetylation of gadung flour with glacial acetic acid in the presence of sodium hydroxide as a homogenous catalyst was studied at ambient temperature with pH ranging from 8-10 and different mass ratio of acetic acid : gadung flour (1:3; 1:4; and 1:5. It was found that increasing pH, lead to increase the degree of substitution, while increasing GAA/GF mass ratio caused such decreases in the degree of substitution, due to the hydrolysis of the acetylated starch. The desired starch acetylation reaction is accompanied by undesirable hydrolysis reaction of the acetylated starch after 40-50 minutes reaction time. Investigation of kinetics of the reaction observed that the value of mass transfer rate constant (Kcs is smaller than the surface reaction rate constant (k. Thus, it can be concluded that rate controlling step is mass transfer.  © 2015 BCREC UNDIP. All rights reservedReceived: 7th August 2014; Revised: 8th September 2014; Accepted: 14th September 2014How to Cite: Kumoro, A.C., Amelia, R. (2015. Mass Transfer and Chemical Reaction Approach of the Kinetics of the Acetylation of Gadung Flour using Glacial Acetic Acid. Bulletin of Chemical Reaction Engineering & Catalysis, 10 (1: 30-37. (doi:10.9767/bcrec.10.1.7181.30-37Permalink/DOI: http://dx.doi.org/10.9767/bcrec.10.1.7181.30-37

Single-collision studies of hot atom energy transfer and chemical reaction

International Nuclear Information System (INIS)

Valentini, J.J.

1991-01-01

This report discusses research in the collision dynamics of translationally hot atoms, with funding with DOE for the project ''Single-Collision Studies of Hot Atom Energy Transfer and Chemical Reaction,'' Grant Number DE-FG03-85ER13453. The work reported here was done during the period September 9, 1988 through October 31, 1991. During this period this DOE-funded work has been focused on several different efforts: (1) experimental studies of the state-to-state dynamics of the H + RH → H 2 R reactions where RH is CH 4 , C 2 H 6 , or C 3 H 8 , (2) theoretical (quasiclassical trajectory) studies of hot hydrogen atom collision dynamics, (3) the development of photochemical sources of translationally hot molecular free radicals and characterization of the high resolution CARS spectroscopy of molecular free radicals, (4) the implementation of stimulated Raman excitation (SRE) techniques for the preparation of vibrationally state-selected molecular reactants

Structural integrity of callosal midbody influences intermanual transfer in a motor reaction-time task.

Science.gov (United States)

Bonzano, Laura; Tacchino, Andrea; Roccatagliata, Luca; Mancardi, Giovanni Luigi; Abbruzzese, Giovanni; Bove, Marco

2011-02-01

Training one hand on a motor task results in performance improvements in the other hand, also when stimuli are randomly presented (nonspecific transfer). Corpus callosum (CC) is the main structure involved in interhemispheric information transfer; CC pathology occurs in patients with multiple sclerosis (PwMS) and is related to altered performance of tasks requiring interhemispheric transfer of sensorimotor information. To investigate the role of CC in nonspecific transfer during a pure motor reaction-time task, we combined motor behavior with diffusion tensor imaging analysis in PwMS. Twenty-two PwMS and 10 controls, all right-handed, were asked to respond to random stimuli with appropriate finger opposition movements with the right (learning) and then the left (transfer) hand. PwMS were able to improve motor performance reducing response times with practice with a trend similar to controls and preserved the ability to transfer the acquired motor information from the learning to the transfer hand. A higher variability in the transfer process, indicated by a significantly larger standard deviation of mean nonspecific transfer, was found in the PwMS group with respect to the control group, suggesting the presence of subtle impairments in interhemispheric communication in some patients. Then, we correlated the amount of nonspecific transfer with mean fractional anisotropy (FA) values, indicative of microstructural damage, obtained in five CC subregions identified on PwMS's FA maps. A significant correlation was found only in the subregion including posterior midbody (Pearson's r = 0.74, P = 0.003), which thus seems to be essential for the interhemispheric transfer of information related to pure sensorimotor tasks. Copyright © 2010 Wiley-Liss, Inc.

Molecular weight control in emulsion polymerization by catalytic chain transfer : a reaction engineering approach

NARCIS (Netherlands)

Smeets, N.M.B.; Meda, U.S.; Heuts, J.P.A.; Keurentjes, J.T.F.; Herk, van A.M.; Meuldijk, J.

2007-01-01

For the application of catalytic chain transfer in (mini)emulsion polymerization, catalyst partitioning and deactivation are key parameters that govern the actual catalyst concentration at the locus of polymerization and consequently the final molecular weight distribution. A global model, based on

Synthesis and Catalytic Hydrogen Transfer Reaction of Ruthenium(II) Complex

Energy Technology Data Exchange (ETDEWEB)

Son, Jung Ik; Kim, Aram; Noh, Hui Bog; Lee, Hyun Ju; Shim, Yoon Bo; Park, Kang Hyun [Pusan National University, Busan (Korea, Republic of)

2012-01-15

The ruthenium(II) complex [Ru(bpy){sub 2}-(PhenTPy)] was synthesized, and used for the transfer hydrogenation of ketones and the desired products were obtained in good yield. Based on the presented results, transition-metal complexes can be used as catalysts for a wide range of organic transformations. The relationship between the electro-reduction current density and temperature are being examined in this laboratory. Attempts to improve the catalytic activity and determine the transfer hydrogenation mechanism are currently in progress. The catalytic hydrogenation of a ketone is a basic and critical process for making many types of alcohols used as the final products and precursors in the pharmaceutical, agrochemical, flavor, fragrance, materials, and fine chemicals industries. The catalytic hydrogenation process developed by Noyori is a very attractive process. Formic acid and 2-propanol have been used extensively as hydrogenation sources. The advantage of using 2-propanol as a hydrogen source is that the only side product will be acetone, which can be removed easily during the workup process. Hydrogen transfer (HT) catalysis, which generates alcohols through the reduction of ketones, is an attractive protocol that is used widely. Ruthenium(II) complexes are the most useful catalysts for the hydrogen transfer (HT) of ketones. In this method, a highly active catalytic system employs a transition metal as a catalyst to synthesize alcohols, and is a replacement for the hydrogen-using hydrogenation process. The most active system is based on Ru, Rh and Ir, which includes a nitrogen ligand that facilitates the formation of a catalytically active hydride and phosphorus.

Synthesis and Catalytic Hydrogen Transfer Reaction of Ruthenium(II) Complex

International Nuclear Information System (INIS)

Son, Jung Ik; Kim, Aram; Noh, Hui Bog; Lee, Hyun Ju; Shim, Yoon Bo; Park, Kang Hyun

2012-01-01

The ruthenium(II) complex [Ru(bpy) 2 -(PhenTPy)] was synthesized, and used for the transfer hydrogenation of ketones and the desired products were obtained in good yield. Based on the presented results, transition-metal complexes can be used as catalysts for a wide range of organic transformations. The relationship between the electro-reduction current density and temperature are being examined in this laboratory. Attempts to improve the catalytic activity and determine the transfer hydrogenation mechanism are currently in progress. The catalytic hydrogenation of a ketone is a basic and critical process for making many types of alcohols used as the final products and precursors in the pharmaceutical, agrochemical, flavor, fragrance, materials, and fine chemicals industries. The catalytic hydrogenation process developed by Noyori is a very attractive process. Formic acid and 2-propanol have been used extensively as hydrogenation sources. The advantage of using 2-propanol as a hydrogen source is that the only side product will be acetone, which can be removed easily during the workup process. Hydrogen transfer (HT) catalysis, which generates alcohols through the reduction of ketones, is an attractive protocol that is used widely. Ruthenium(II) complexes are the most useful catalysts for the hydrogen transfer (HT) of ketones. In this method, a highly active catalytic system employs a transition metal as a catalyst to synthesize alcohols, and is a replacement for the hydrogen-using hydrogenation process. The most active system is based on Ru, Rh and Ir, which includes a nitrogen ligand that facilitates the formation of a catalytically active hydride and phosphorus

Studies of Nuclei Close to 132Sn Using Single-Neutron Transfer Reactions

International Nuclear Information System (INIS)

Jones, K.L.; Pain, S.D.; Kozub, R.L.; Adekola, Aderemi S.; Bardayan, Daniel W.; Blackmon, Jeff C.; Catford, Wilton N.; Chae, K.Y.; Chipps, K.; Cizewski, J.A.; Erikson, Luke; Gaddis, A.L.; Greife, U.; Grzywacz, R.K.; Harlin, Christopher W.; Hatarik, Robert; Howard, Joshua A.; James, J.; Kapler, R.; Krolas, W.; Liang, J. Felix; Ma, Zhanwen; Matei, Catalin; Moazen, Brian; Nesaraja, Caroline D.; O'Malley, Patrick; Patterson, N.P.; Paulauskas, Stanley; Shapira, Dan; Shriner, J.F. Jr.; Sikora, M.; Sissom, D.J.; Smith, Michael Scott; Swan, T.P.; Thomas, J.S.; Wilson, Gemma L.

2009-01-01

Neutron transfer reactions were performed in inverse kinematics using radioactive ion beams of 132Sn, 130Sn, and 134Te and deuterated polyethylene targets. Preliminary results are presented. The Q-value spectra for 133Sn, 131Sn and 135Te reveal a number of previously unobserved peaks. The angular distributions are compatible with the expected lf7/2 nature of the ground state of 133Sn, and 2p3/2 for the 3.4 MeV state in 131Sn.

Kinetic mechanism of molecular energy transfer and chemical reactions in low-temperature air-fuel plasmas.

Science.gov (United States)

Adamovich, Igor V; Li, Ting; Lempert, Walter R

2015-08-13

This work describes the kinetic mechanism of coupled molecular energy transfer and chemical reactions in low-temperature air, H2-air and hydrocarbon-air plasmas sustained by nanosecond pulse discharges (single-pulse or repetitive pulse burst). The model incorporates electron impact processes, state-specific N(2) vibrational energy transfer, reactions of excited electronic species of N(2), O(2), N and O, and 'conventional' chemical reactions (Konnov mechanism). Effects of diffusion and conduction heat transfer, energy coupled to the cathode layer and gasdynamic compression/expansion are incorporated as quasi-zero-dimensional corrections. The model is exercised using a combination of freeware (Bolsig+) and commercial software (ChemKin-Pro). The model predictions are validated using time-resolved measurements of temperature and N(2) vibrational level populations in nanosecond pulse discharges in air in plane-to-plane and sphere-to-sphere geometry; temperature and OH number density after nanosecond pulse burst discharges in lean H(2)-air, CH(4)-air and C(2)H(4)-air mixtures; and temperature after the nanosecond pulse discharge burst during plasma-assisted ignition of lean H2-mixtures, showing good agreement with the data. The model predictions for OH number density in lean C(3)H(8)-air mixtures differ from the experimental results, over-predicting its absolute value and failing to predict transient OH rise and decay after the discharge burst. The agreement with the data for C(3)H(8)-air is improved considerably if a different conventional hydrocarbon chemistry reaction set (LLNL methane-n-butane flame mechanism) is used. The results of mechanism validation demonstrate its applicability for analysis of plasma chemical oxidation and ignition of low-temperature H(2)-air, CH(4)-air and C(2)H(4)-air mixtures using nanosecond pulse discharges. Kinetic modelling of low-temperature plasma excited propane-air mixtures demonstrates the need for development of a more accurate

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

Science.gov (United States)

Soudackov, Alexander V; Hammes-Schiffer, Sharon

2015-11-21

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

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

International Nuclear Information System (INIS)

Soudackov, Alexander V.; Hammes-Schiffer, Sharon

2015-01-01

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

Enantioselective syntheses of aeruginosin 298-A and its analogues using a catalytic asymmetric phase-transfer reaction and epoxidation.

Science.gov (United States)

Ohshima, Takashi; Gnanadesikan, Vijay; Shibuguchi, Tomoyuki; Fukuta, Yuhei; Nemoto, Tetsuhiro; Shibasaki, Masakatsu

2003-09-17

We developed a versatile synthetic process for aeruginosin 298-A as well as several attractive analogues, in which all stereocenters were controlled by a catalytic asymmetric phase-transfer reaction and epoxidation. Furthermore, drastic counteranion effects in phase-transfer catalysis were observed for the first time, making it possible to three-dimensionally fine-tune the catalyst (ketal part, aromatic part, and counteranion).

Treatment for the recoil effects of the multi-step heavy-ion nucleon transfers with the orthogonalized coupled-reaction-channel theory

International Nuclear Information System (INIS)

Misono, S.; Imanishi, B.

1997-02-01

We have investigated recoil effects in heavy-ion reactions for the nucleon transfers, and the validity of the spatially local approximation for the non-local transfer interaction defined by the orthogonalized coupled-reaction-channel (OCRC) theory. This approximation makes it easier to treat multi-step transfer processes with the coupled channel method and makes it possible to define the nucleon molecular orbitals with the inclusion of the recoil effects. The transfer interaction is expanded in a power series of the momentum operator, and is approximated by the first order term, i.e., the spatially local term. The numerical calculation for the core-symmetric systems 12 C+ 13 C and 16 O+ 17 O with this approximation shows that the recoil effects are well included in the results at energies lower than a few MeV/nucleon. Furthermore, the OCRC formalism allows us even to employ the complete no-recoil approximation for the calculation of cross sections, even though it is not adequate to use this approximation in the distorted wave Born approximation (DWBA) method. As to polarization, however, the no-recoil approximation is not good even in the OCRC formalism. We discuss the recoil effects on nucleon molecular-orbital states. It is shown that states of the covalent molecular orbitals of the valence (transferred) nucleon are little affected by the recoil effects, as already suggested by Korotky et al. in the full finite-range DWBA analysis of the transfer reaction, 13 C( 13 C, 12 C) 14 C. (author). 59 refs

Salt-assisted clean transfer of continuous monolayer MoS2 film for hydrogen evolution reaction

Science.gov (United States)

Cho, Heung-Yeol; Nguyen, Tri Khoa; Ullah, Farman; Yun, Jong-Won; Nguyen, Cao Khang; Kim, Yong Soo

2018-03-01

The transfer of two-dimensional (2D) materials from one substrate to another is challenging but of great importance for technological applications. Here, we propose a facile etching and residue-free method for transferring a large-area monolayer MoS2 film continuously grown on a SiO2/Si by chemical vapor deposition. Prior to synthesis, the substrate is dropped with water- soluble perylene-3, 4, 9, 10-tetracarboxylic acid tetrapotassium salt (PTAS). The as-grown MoS2 on the substrate is simply dipped in water to quickly dissolve PTAS to yield the MoS2 film floating on the water surface, which is subsequently transferred to the desired substrate. The morphological, optical and X-ray photoelectron spectroscopic results show that our method is useful for fast and clean transfer of the MoS2 film. Specially, we demonstrate that monolayer MoS2 film transferred onto a conducting substrate leads to excellent performance for hydrogen evolution reaction with low overpotential (0.29 V vs the reversible hydrogen electrode) and Tafel slope (85.5 mV/decade).

Graphene Charge Transfer, Spectroscopy, and Photochemical Reactions

Energy Technology Data Exchange (ETDEWEB)

Brus, Louis [Columbia Univ., New York, NY (United States)

2017-01-31

This project focused on the special electronic and optical properties of graphene and adsorbed molecular species. Graphene makes an excellent substrate for current collection in nanostructured photovoltaic designs. Graphene is almost transparent, and can be used as a solar cell window. It also has no surface states, and thus current is efficiently transported over long distances. Progress in graphene synthesis indicates that there will soon be practical methods for making large pieces of graphene for devices. We now need to understand exactly what happens to both ground state and electronically excited molecules and Qdots near graphene, if we are going to use them to absorb light in a nano-structured photovoltaic device using graphene to collect photocurrent. We also need to understand how to shift the graphene Fermi level, to optimize the kinetics of electron transfer to graphene. And we need to learn how to convert local graphene areas to semiconductor structure, to make useful spatially patterned graphenes. In this final report, we describe how we addressed these goals. We explored the question of possible Surface Enhanced Raman spectroscopy from molecular Charge Transfer onto Graphene substrates. We observed strong hole doping of graphene by adsorbed halogens as indicated by the shift of the graphene G Raman band. In the case of iodine adsorption, we also observed the anionic species made by hole doping. At low frequency in the Raman spectrum, we saw quite intense lines from I₃^- and I₅^- , suggesting possible SERS. We reported on Fresnel calculations on this thin film system, which did not show any net electromagnetic field enhancement.

A new pathway for transmembrane electron transfer in photosynthetic reaction centers of Rhodobacter sphaeroides not involving the excited special pair.

NARCIS (Netherlands)

van Brederode, M.E.; Jones, M.R.; van Mourik, F.; van Stokkum, I.H.M.; van Grondelle, R.

1997-01-01

It is generally accepted that electron transfer in bacterial photosynthesis is driven by the first singlet excited state of a special pair of bacteriochlorophylls (P*). We have examined the first steps of electron transfer in a mutant of the Rhodobacter sphaeroides reaction center in which charge

A new pathway for transmembrane electron transfer in photosyntetic reaction centers of Rhodobacter sphaeroides not involving the excited special pair.

NARCIS (Netherlands)

van Brederode, M.E.; Jones, M.R.; van Mourik, F.; van Stokkum, I.H.M.; van Grondelle, R.

1997-01-01

It is generally accepted that electron transfer in bacterial photosynthesis is driven by the first singlet excited state of a special pair of bacteriochlorophylls (P*). We have examined the first steps of electron transfer in a mutant of the Rhodobacter sphaeroides reaction center in which charge

Efficient and Adaptive Methods for Computing Accurate Potential Surfaces for Quantum Nuclear Effects: Applications to Hydrogen-Transfer Reactions.

Science.gov (United States)

DeGregorio, Nicole; Iyengar, Srinivasan S

2018-01-09

We present two sampling measures to gauge critical regions of potential energy surfaces. These sampling measures employ (a) the instantaneous quantum wavepacket density, an approximation to the (b) potential surface, its (c) gradients, and (d) a Shannon information theory based expression that estimates the local entropy associated with the quantum wavepacket. These four criteria together enable a directed sampling of potential surfaces that appears to correctly describe the local oscillation frequencies, or the local Nyquist frequency, of a potential surface. The sampling functions are then utilized to derive a tessellation scheme that discretizes the multidimensional space to enable efficient sampling of potential surfaces. The sampled potential surface is then combined with four different interpolation procedures, namely, (a) local Hermite curve interpolation, (b) low-pass filtered Lagrange interpolation, (c) the monomial symmetrization approximation (MSA) developed by Bowman and co-workers, and (d) a modified Shepard algorithm. The sampling procedure and the fitting schemes are used to compute (a) potential surfaces in highly anharmonic hydrogen-bonded systems and (b) study hydrogen-transfer reactions in biogenic volatile organic compounds (isoprene) where the transferring hydrogen atom is found to demonstrate critical quantum nuclear effects. In the case of isoprene, the algorithm discussed here is used to derive multidimensional potential surfaces along a hydrogen-transfer reaction path to gauge the effect of quantum-nuclear degrees of freedom on the hydrogen-transfer process. Based on the decreased computational effort, facilitated by the optimal sampling of the potential surfaces through the use of sampling functions discussed here, and the accuracy of the associated potential surfaces, we believe the method will find great utility in the study of quantum nuclear dynamics problems, of which application to hydrogen-transfer reactions and hydrogen

Proton transfer reaction-mass spectrometry volatile organic compound fingerprinting for monovarietal extra virgin olive oil identification

NARCIS (Netherlands)

Ruiz-Samblas, C.; Tres, A.; Koot, A.H.; Ruth, van S.M.; Gonzalez-Casado, A.; Cuadros-Rodriguez, L.

2012-01-01

Proton transfer reaction-mass spectrometry (PTR-MS) is a relatively new technique that allows the fast and accurate qualification of the volatile organic compound (VOC) fingerprint. This paper describes the analysis of thirty samples of extra virgin olive oil, of five different varieties of olive

Tunable, Chemo- and Site-Selective Nitrene Transfer Reactions through the Rational Design of Silver(I) Catalysts.

Science.gov (United States)

Alderson, Juliet M; Corbin, Joshua R; Schomaker, Jennifer M

2017-09-19

Carbon-nitrogen (C-N) bonds are ubiquitous in pharmaceuticals, agrochemicals, diverse bioactive natural products, and ligands for transition metal catalysts. An effective strategy for introducing a new C-N bond into a molecule is through transition metal-catalyzed nitrene transfer chemistry. In these reactions, a metal-supported nitrene can either add across a C═C bond to form an aziridine or insert into a C-H bond to furnish the corresponding amine. Typical catalysts for nitrene transfer include Rh 2 L n and Ru 2 L n complexes supported by bridging carboxylate and related ligands, as well as complexes based on Cu, Co, Ir, Fe, and Mn supported by porphyrins and related ligands. A limitation of metal-catalyzed nitrene transfer is the ability to predictably select which specific site will undergo amination in the presence of multiple reactive groups; thus, many reactions rely primarily on substrate control. Achieving true catalyst-control over nitrene transfer would open up exciting possibilities for flexible installation of new C-N bonds into hydrocarbons, natural product-inspired scaffolds, existing pharmaceuticals or biorenewable building blocks. Silver-catalyzed nitrene transfer enables flexible control over the position at which a new C-N bond is introduced. Ag(I) supported by simple N-donor ligands accommodates a diverse range of coordination geometries, from linear to tetrahedral to seesaw, enabling the electronic and steric parameters of the catalyst to be tuned independently. In addition, the ligand, Ag salt counteranion, Ag/ligand ratio and the solvent all influence the fluxional and dynamic behavior of Ag(I) complexes in solution. Understanding the interplay of these parameters to manipulate the behavior of Ag-nitrenes in a predictable manner is a key design feature of our work. In this Account, we describe successful applications of a variety of design principles to tunable, Ag-catalyzed aminations, including (1) changing Ag/ligand ratios to influence

On the ultrafast kinetics of the energy and electron transfer reactions in photosystem I

Energy Technology Data Exchange (ETDEWEB)

Slavov, Chavdar Lyubomirov

2009-07-09

The subject of the current work is one of the main participants in the light-dependent phase of oxygenic photosynthesis, Photosystem I (PS I). This complex carries an immense number of cofactors: chlorophylls (Chl), carotenoids, quinones, etc, which together with the protein entity exhibit several exceptional properties. First, PS I has an ultrafast light energy trapping kinetics with a nearly 100% quantum efficiency. Secondly, both of the electron transfer branches in the reaction center are suggested to be active. Thirdly, there are some so called 'red' Chls in the antenna system of PS I, absorbing light with longer wavelengths than the reaction center. These 'red' Chls significantly modify the trapping kinetics of PS I. The purpose of this thesis is to obtain better understanding of the above-mentioned, specific features of PS I. This will not merely cast more light on the mechanisms of energy and electron transfer in the complex, but also will contribute to the future developments of optimized artificial light-harvesting systems. In the current work, a number of PS I complexes isolated from different organisms (Thermosynechococcus elongatus, Chlamydomonas reinhardtii, Arabidopsis thaliana) and possessing distinctive features (different macroorganisation, monomers, trimers, monomers with a semibelt of peripheral antenna attached; presence of 'red' Chls) is investigated. The studies are primarily focused on the electron transfer kinetics in each of the cofactor branches in the PS I reaction center, as well as on the effect of the antenna size and the presence of 'red' Chls on the trapping kinetics of PS I. These aspects are explored with the help of several ultrafast optical spectroscopy methods: (i) time-resolved fluorescence ? single photon counting and synchroscan streak camera; and (ii) ultrafast transient absorption. Physically meaningful information about the molecular mechanisms of the energy trapping in PS I is

Heterogeneous electron transfer and oxygen reduction reaction at nanostructured iron(II) phthalocyanine and its MWCNTs nanocomposites

CSIR Research Space (South Africa)

Mamuru, SA

2010-05-01

Full Text Available species within the porous layers of MWCNTs. Electron transfer process is much easier at the EPPGE-MWCNT and EPPGE-MWCNT-nanoFePc compared to the other electrodes. The best response for oxygen reduction reaction was at the EPPGE-MWCNTnanoFePc, yielding a 4...

Stripping of two protons and one alpha particle transfer reactions for {sup 16} O + {sup A} Sm and their influence on the fusion cross section

Energy Technology Data Exchange (ETDEWEB)

Maciel, A.M.M.; Gomes, P.R.S

1995-12-31

Transfer cross section angular distribution data for the stripping of two protons and one alpha particle are studied for the {sup 16} O + {sup A} Sm systems (A=144, 148, 150, 152 and 154), at near barrier energies. A semiclassical formalism is used to derive the corresponding transfer form factors. For only one channel the analysis shows evidences that the transfer reaction mechanism at backward angles - corresponding to small distances, may behave as a multi-step process leading to fusion. Simplified coupled channel calculations including transfer channels are performed for the study of the sub-barrier of these systems. The influence of short distance transfer reactions on the fusion is discussed. (author) 16 refs., 5 figs., 5 tabs.

Study of the 18F(p,α)15O reaction by transfer reaction for application to γ-ray emission from Novae

International Nuclear Information System (INIS)

Sereville, N. de

2003-12-01

The gamma emission from novae at/or below 511 keV is due to the annihilation of the positrons produced in the beta + decay of F 18 . The interpretation of this emission through observations made by the Integral satellite for instance, requires a good knowledge of F 18 nucleosynthesis. The reaction rate of the F 18 (p,α)O 15 is the least known because of 2 resonances corresponding to the levels 6.419 and 6.449 MeV of Ne 19 whose proton widths are completely unknown. We have determined these proton widths via the study of one-nucleon transfer reaction D(F 18 ,pα)N 15 populating equivalent levels in F 19 . We have used a 14 MeV F 18 radioactive beam on a CD 2 target for inverse kinematics studies and the multi-track silicon detector LEDA. A DWBA (Distorted Wave Bound Approximation) has enabled us to determine the proton width of both resonances and has showed that they have an impact in the calculation of the reaction rate. A thorough study of the remaining uncertainties of the reaction rate has been undertaken, particularly for those concerning interferences between these resonances and a higher resonance of Ne 19 . The reaction rate that we have obtained is very similar to the previous rate used but now it rests on a more solid basis

The TDF System for Thermonuclear Plasma Reaction Rates, Mean Energies and Two-Body Final State Particle Spectra

International Nuclear Information System (INIS)

Warshaw, S I

2001-01-01

The rate of thermonuclear reactions in hot plasmas as a function of local plasma temperature determines the way in which thermonuclear ignition and burning proceeds in the plasma. The conventional model approach to calculating these rates is to assume that the reacting nuclei in the plasma are in Maxwellian equilibrium at some well-defined plasma temperature, over which the statistical average of the reaction rate quantity σv is calculated, where σ is the cross-section for the reaction to proceed at the relative velocity v between the reacting particles. This approach is well-understood and is the basis for much nuclear fusion and astrophysical nuclear reaction rate data. The Thermonuclear Data File (TDF) system developed at the Lawrence Livermore National Laboratory (Warshaw 1991), which is the topic of this report, contains data on the Maxwellian-averaged thermonuclear reaction rates for various light nuclear reactions and the correspondingly Maxwellian-averaged energy spectra of the particles in the final state of those reactions as well. This spectral information closely models the output particle and energy distributions in a burning plasma, and therefore leads to more accurate computational treatments of thermonuclear burn, output particle energy deposition and diagnostics, in various contexts. In this report we review and derive the theoretical basis for calculating Maxwellian-averaged thermonuclear reaction rates, mean particle energies, and output particle spectral energy distributions for these reactions in the TDF system. The treatment of the kinematics is non-relativistic. The current version of the TDF system provides exit particle energy spectrum distributions for two-body final state reactions only. In a future report we will discuss and describe how output particle energy spectra for three- and four-body final states can be developed for the TDF system. We also include in this report a description of the algorithmic implementation of the TDF

In Situ Solid-State Reactions Monitored by X-ray Absorption Spectroscopy: Temperature-Induced Proton Transfer Leads to Chemical Shifts.

Science.gov (United States)

Stevens, Joanna S; Walczak, Monika; Jaye, Cherno; Fischer, Daniel A

2016-10-24

The dramatic colour and phase alteration with the solid-state, temperature-dependent reaction between squaric acid and 4,4'-bipyridine has been probed in situ with X-ray absorption spectroscopy. The electronic and chemical sensitivity to the local atomic environment through chemical shifts in the near-edge X-ray absorption fine structure (NEXAFS) revealed proton transfer from the acid to the bipyridine base through the change in nitrogen protonation state in the high-temperature form. Direct detection of proton transfer coupled with structural analysis elucidates the nature of the solid-state process, with intermolecular proton transfer occurring along an acid-base chain followed by a domino effect to the subsequent acid-base chains, leading to the rapid migration along the length of the crystal. NEXAFS thereby conveys the ability to monitor the nature of solid-state chemical reactions in situ, without the need for a priori information or long-range order. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Study of the reaction of astrophysical interest 60Fe(n,γ)61Fe via (d,pγ) transfer reaction

International Nuclear Information System (INIS)

Giron, S.

2011-12-01

60 Fe is of special interest in nuclear astrophysics. Indeed the recent observations of 60 Fe characteristic gamma-ray lines by the RHESSI and INTEGRAL spacecrafts allowed to measure the total flux of 60 Fe over the Galaxy. Moreover the observation in presolar grains of an excess of the daughter-nuclei of 60 Fe, 60 Ni, gives constraints on the conditions of formation of the early solar system. However, the cross-sections of some reactions involved in 60 Fe nucleosynthesis and included to stellar models are still uncertain. The destruction reaction of 60 Fe, 60 Fe(n, γ) 61 Fe, is one of them. The total cross-section can be separate into two contributions: the direct one, involving states below the neutron separation threshold of 61 Fe, and the resonant one.We improved 61 Fe spectroscopy in order to evaluate the direct capture part of the 60 Fe(n, γ) 61 Fe reaction cross-section. 60 Fe(n, γ) 61 Fe was thus studied via d( 60 Fe, pγ) 61 Fe transfer reaction with the CATS/MUST2/EXOGAM setup at LISE-GANIL. DWBA analysis of experimental proton differential cross-sections allowed to extract orbital angular momentum and spectroscopic factors of different populated states identified below the neutron threshold. A comparison of experimental results for 61 Fe with experimental results for similar nuclei and with shell-model calculations was also performed. (author) [fr

The Electronic Flux in Chemical Reactions. Insights on the Mechanism of the Maillard Reaction

Science.gov (United States)

Flores, Patricio; Gutiérrez-Oliva, Soledad; Herrera, Bárbara; Silva, Eduardo; Toro-Labbé, Alejandro

2007-11-01

The electronic transfer that occurs during a chemical process is analysed in term of a new concept, the electronic flux, that allows characterizing the regions along the reaction coordinate where electron transfer is actually taking place. The electron flux is quantified through the variation of the electronic chemical potential with respect to the reaction coordinate and is used, together with the reaction force, to shed light on reaction mechanism of the Schiff base formation in the Maillard reaction. By partitioning the reaction coordinate in regions in which different process might be taking place, electronic reordering associated to polarization and transfer has been identified and found to be localized at specific transition state regions where most bond forming and breaking occur.

Investigation of the decomposition reaction and dust explosion characteristics of crystalline benzoyl peroxides

International Nuclear Information System (INIS)

Lu, K.-T.; Chen, T.-C.; Hu, K.-H.

2009-01-01

The benzoyl peroxide (BPO) is widely used in the chemical industry. Many catastrophes have been caused by its thermal instability or reactive incompatibility in storage or thermal decomposition reaction. Thus, its hazard characteristics have to be clearly identified. First of all, the differential scanning calorimeter (DSC) is used to measure the heat of decomposition reaction, which can contribute to understanding the reaction characteristics of benzoyl peroxide. The accelerating rate calorimeter (ARC) is used to measure the rates of temperature and pressure rises of decomposition reaction, and then the kinetics parameters are estimated. Furthermore, the MIKE 3 apparatus and the 20-l-Apparatus are used to measure and analyze the dust explosion characteristics of benzoyl peroxide under room temperature and atmospheric pressure. Finally, Semenov's thermal explosion theory is applied to investigate the critical runaway condition and the stability criterion of decomposition reaction, and to build the relationship of critical temperature, convective heat transfer coefficient, heat transfer surface area and ambient temperature. These results contribute to improving the safety in the reaction, transportation and storage processes of benzoyl peroxide

Mass transfer rate through liquid membranes: interfacial chemical reactions and diffusion as simultaneous permeability controlling factors

International Nuclear Information System (INIS)

Danesi, P.R.; Horwitz, E.P.; Vandegrift, G.F.; Chiarizia, R.

1981-01-01

Equations describing the permeability of a liquid membrane to metal cations have been derived taking into account aqueous diffusion, membrane diffusion, and interfacial chemical reactions as simultaneous permeability controlling factors. Diffusion and chemical reactions have been coupled by a simple model analogous to the one previously described by us to represent liquid-liquid extraction kinetics. The derived equations, which make use of experimentally determined interfacial reaction mechanisms, qualitatively fit unexplained literature data regarding Cu 2+ transfer through liquid membranes. Their use to predict and optimize membrane permeability in practical separation processes by setting the appropriate concentration of the membrane carrier [LIX 64 (General Mills), a commercial β-hydroxy-oxime] and the pH of the aqueous copper feed solution is briefly discussed. 4 figures

Computer-assisted mechanistic evaluation of organic reactions

Energy Technology Data Exchange (ETDEWEB)

Gushurst, A.J.

1988-01-01

CAMEO, an interactive computer program which predicts the products of organic reactions given starting materials and conditions, has been refined and extended in the area of base-catalyzed and nucleophilic processes. The present capabilities of the program are outlined including brief discussion on the major segments in CAMEO: graphics, perception, and reaction evaluation. The implementation of general algorithms for predicting the acidities of a vast number of organic compounds to within 2 pK{sub a} units in dimethylsulfoxide and water are then described, followed by a presentation of the reactivity rules used by the program to evaluate nucleophilc reactions. Finally, a treatment of sulfur and phosphorus ylides, iminophosphoranes, and P=X-activated anions is given illuminating the various competitions available for these reagents, such as between proton transfer and addition, 1,2- and 1,4-addition, and the Peterson, Wittig, and Horner-Emmons olefination reactions.

A treatment of the final-state interaction for photonuclear reactions

International Nuclear Information System (INIS)

Eden, J.A.; Thompson, M.N.

1991-01-01

The final state interaction is considered for the Gottfried factorized cross section. Numerical examples are presented for the 40 Ca(γ,pn) and 40 Ca(γ,n) reactions. The surface refraction process, allowing photonucleons to refract as they emerge from the nuclear potential well, cannot change the magnitude of the total cross section, but may redistribute the strength in the angular dependence of the differential cross section. The absorption process accounts for the loss of photonucleons as a result of inelastic collisions while escaping the nucleus. The surface refraction correction is calculated in a plane-wave Born approximation and the absorption correction is presented as a simple development of earlier phenomenological treatments. 12 refs., 7 figs

A simple approach to the solvent reorganisation Gibbs free energy in electron transfer reactions of redox metalloproteins

DEFF Research Database (Denmark)

Ulstrup, Jens

1999-01-01

We discuss a simple model for the environmental reorganisation Gibbs free energy, E-r, in electron transfer between a metalloprotein and a small reaction partner. The protein is represented as a dielectric globule with low dielectric constant, the metal centres as conducting spheres, all embedded...

Comparison between proton transfer reaction mass spectrometry and near infrared spectroscopy for the authentication of Brazilian coffee

NARCIS (Netherlands)

Monteiro, Pablo Inocêncio; Santos, Jânio Sousa; Alvarenga Brizola, Vitor Rafael; Pasini Deolindo, Carolina Turnes; Koot, Alex; Boerrigter-Eenling, Rita; Ruth, van Saskia; Georgouli, Konstantia; Koidis, Anastasios; Granato, Daniel

2018-01-01

In this study, proton-transfer reaction mass spectrometry (PTR-MS) and near-infrared spectroscopy (NIRS) were compared for the authentication of geographical and farming system origins of Brazilian coffees. For this purpose, n = 19 organic (ORG) and n = 26 conventional (CONV) coffees from

On final-state interaction in d - NN reaction in the (1236) - resonance region

International Nuclear Information System (INIS)

Aznauryan, I.G.; Nagorskaya, I.A.

1975-01-01

The spectator model is corrected due to scattering of particles in the final state. It is shown that the discrepancies between the data for γd→u 0 π + uu and γd→u 0 pn and the predictions from the spectator model are mainly due to the nucleon-nucleon scattering in the final state. By means of a generally used evaluation procedure for the experimental data it is shown that the reaction cross sections of γu→π 0 u and γu→ - p, which are obtained from the experiments with deuterons, are not very sensitive to these corrections will have no influence on conclusions concerning the exotic properties of the electromagnetic current

Transfer of a wave packet in double-well potential

Science.gov (United States)

Yang, Hai-Feng; Hu, Yao-Hua; Tan, Yong-Gang

2018-04-01

Energy potentials with double-well structures are typical in atoms and molecules systems. A manipulation scheme using Half Cycles Pulses (HCPs) is proposed to transfer a Gaussian wave packet between the two wells. On the basis of quantum mechanical simulations, the time evolution and the energy distribution of the wave packet are evaluated. The effect of time parameters, amplitude, and number of HCPs on spatial and energy distribution of the final state and transfer efficiency are investigated. After a carefully tailored HCPs sequence is applied to the initial wave packet localized in one well, the final state is a wave packet localized in the other well and populated at the lower energy levels with narrower distribution. The present scheme could be used to control molecular reactions and to prepare atoms with large dipole moments.

Energy transfer and reaction dynamics of matrix-isolated 1,2-difluoroethane-d4

Science.gov (United States)

Raff, Lionel M.

1990-09-01

The molecular dynamics of vibrationally excited 1,2-difluoroethane-d4 isolated in Ar, Kr, and Xe matrices at 12 K are investigated using trajectory methods. The matrix model is an fcc crystal containing 125 unit cells with 666 atoms in a cubic (5×5×5) arrangement. It is assumed that 1,2-difluoroethane-d4 is held interstitially within the volume bounded by the innermost unit cell of the crystal. The transport effects of the bulk are simulated using the velocity reset method introduced by Riley, Coltrin, and Diestler [J. Chem. Phys. 88, 5934 (1988)]. The system potential is written as the separable sum of a lattice potential, a lattice-molecule interaction and a gas-phase potential for 1,2-difluoroethane. The first two of these are assumed to have pairwise form while the molecular potential is a modified form of the global potential previously developed for 1,2-difluoroethane [J. Phys. Chem. 91, 3266 (1987)]. Calculated sublimation energies for the pure crystals are in good accord with the experimental data. The distribution of metastable-state energies for matrix-isolated 1,2-difluoroethane-d4 is Gaussian in form. In krypton, the full width at half maximum for the distribution is 0.37 eV. For a total excitation energy of 6.314 eV, the observed dynamic processes are vibrational relaxation, orientational exchange, and four-center DF elimination reactions. The first of these processes is characterized by a near linear, first-order decay curve with rate coefficients in the range 1.30-1.48×1011 s-1. The average rates in krypton and xenon are nearly equal. The process is slightly slower in argon. The decay curves exhibit characteristic high-frequency oscillations that are generally seen in energy transfer studies. It is demonstrated that these oscillations are associated with the frequencies for intramolecular energy transfer so that the entire frequency spectrum for such transfer processes can be obtained from the Fourier transform of the decay curve. Orientational

Large momentum transfer phenomena

International Nuclear Information System (INIS)

Imachi, Masahiro; Otsuki, Shoichiro; Matsuoka, Takeo; Sawada, Shoji.

1978-01-01

The large momentum transfer phenomena in hadron reaction drastically differ from small momentum transfer phenomena, and are described in this paper. Brief review on the features of the large transverse momentum transfer reactions is described in relation with two-body reactions, single particle productions, particle ratios, two jet structure, two particle correlations, jet production cross section, and the component of momentum perpendicular to the plane defined by the incident protons and the triggered pions and transverse momentum relative to jet axis. In case of two-body process, the exponent N of the power law of the differential cross section is a value between 10 to 11.5 in the large momentum transfer region. The breaks of the exponential behaviors into the power ones are observed at the large momentum transfer region. The break would enable to estimate the order of a critical length. The large momentum transfer phenomena strongly suggest an important role of constituents of hadrons in the hard region. Hard rearrangement of constituents from different initial hadrons induces large momentum transfer reactions. Several rules to count constituents in the hard region have been proposed so far to explain the power behavior. Scale invariant quark interaction and hard reactions are explained, and a summary of the possible types of hard subprocess is presented. (Kato, T.)

Effects of specific adsorption of copper (II) ion on charge transfer reaction at the thin film LiMn2O4 electrode/aqueous electrolyte interface

International Nuclear Information System (INIS)

Nakayama, N.; Yamada, I.; Huang, Y.; Nozawa, T.; Iriyama, Y.; Abe, T.; Ogumi, Z.

2009-01-01

This study investigated the effect of a specific adsorption ion, copper (II) ion, on the kinetics of the charge transfer reaction at a LiMn 2 O 4 thin film electrode/aqueous solution (1 mol dm -3 LiNO 3 ) interface. The zeta potential of LiMn 2 O 4 particles showed a negative value in 1 x 10 -2 mol dm -3 LiNO 3 aqueous solution, while it was measured as positive in the presence of 1 x 10 -2 mol dm -3 Cu(NO 3 ) 2 in the solution. The presence of copper (II) ions in the solution increased the charge transfer resistance, and CV measurement revealed that the lithium insertion/extraction reaction was retarded by the presence of small amount of copper (II) ions. The activation energy for the charge transfer reaction in the solution with Cu(NO 3 ) 2 was estimated to be 35 kJ mol -1 , which was ca. 10 kJ mol -1 larger than that observed in the solution without Cu(NO 3 ) 2 . These results suggest that the interaction between the lithium ion and electrode surface is a factor in the kinetics of charge transfer reaction

Modeling of mass transfer and chemical reactions in a bubble column reactor using a discrete bubble model

NARCIS (Netherlands)

Darmana, D.; Deen, N.G.; Kuipers, J.A.M.

2004-01-01

A 3D discrete bubble model is adopted to investigate complex behavior involving hydrodynamics, mass transfer and chemical reactions in a gas-liquid bubble column reactor. In this model a continuum description is adopted for the liquid phase and additionally each individual bubble is tracked in a

Chemical Evolution of Groundwater Near a Sinkhole Lake, Northern Florida: 2. Chemical Patterns, Mass Transfer Modeling, and Rates of Mass Transfer Reactions

Science.gov (United States)

Katz, Brian G.; Plummer, L. Niel; Busenberg, Eurybiades; Revesz, Kinga M.; Jones, Blair F.; Lee, Terrie M.

1995-06-01

Chemical patterns along evolutionary groundwater flow paths in silicate and carbonate aquifers were interpreted using solute tracers, carbon and sulfur isotopes, and mass balance reaction modeling for a complex hydrologic system involving groundwater inflow to and outflow from a sinkhole lake in northern Florida. Rates of dominant reactions along defined flow paths were estimated from modeled mass transfer and ages obtained from CFC-modeled recharge dates. Groundwater upgradient from Lake Barco remains oxic as it moves downward, reacting with silicate minerals in a system open to carbon dioxide (CO2), producing only small increases in dissolved species. Beneath and downgradient of Lake Barco the oxic groundwater mixes with lake water leakage in a highly reducing, silicate-carbonate mineral environment. A mixing model, developed for anoxic groundwater downgradient from the lake, accounted for the observed chemical and isotopic composition by combining different proportions of lake water leakage and infiltrating meteoric water. The evolution of major ion chemistry and the 13C isotopic composition of dissolved carbon species in groundwater downgradient from the lake can be explained by the aerobic oxidation of organic matter in the lake, anaerobic microbial oxidation of organic carbon, and incongruent dissolution of smectite minerals to kaolinite. The dominant process for the generation of methane was by the CO2 reduction pathway based on the isotopic composition of hydrogen (δ2H(CH4) = -186 to -234‰) and carbon (δ13C(CH4) = -65.7 to -72.3‰). Rates of microbial metabolism of organic matter, estimated from the mass transfer reaction models, ranged from 0.0047 to 0.039 mmol L-1 yr-1 for groundwater downgradient from the lake.

Energy transfer in structured and unstructured environments

DEFF Research Database (Denmark)

Iles-Smith, Jake; Dijkstra, Arend G.; Lambert, Neill

2016-01-01

of motion over a wide range of parameters. Furthermore, we show that the Zusman equations, which may be obtained in a semiclassical limit of the reaction coordinate model, are often incapable of describing the correct dynamical behaviour. This demonstrates the necessity of properly accounting for quantum......We explore excitonic energy transfer dynamics in a molecular dimer system coupled to both structured and unstructured oscillator environments. By extending the reaction coordinate master equation technique developed by Iles-Smith et al. [Phys. Rev. A 90, 032114 (2014)], we go beyond the commonly...... correlations generated between the system and its environment when the Born-Markov approximations no longer hold. Finally, we apply the reaction coordinate formalism to the case of a structured environment comprising of both underdamped (i.e., sharply peaked) and overdamped (broad) components simultaneously...

Characterisation of the semi-volatile component of Dissolved Organic Matter by Thermal Desorption - Proton Transfer Reaction - Mass Spectrometry

NARCIS (Netherlands)

Materić, Dušan; Peacock, Mike; Kent, Matthew; Cook, Sarah; Gauci, Vincent; Röckmann, Thomas; Holzinger, Rupert

2017-01-01

Proton Transfer Reaction - Mass Spectrometry (PTR-MS) is a sensitive, soft ionisation method suitable for qualitative and quantitative analysis of volatile and semi-volatile organic vapours. PTR-MS is used for various environmental applications including monitoring of volatile organic compounds

B-side charge separation in bacterial photosynthetic reaction centers: nanosecond time scale electron transfer from HB- to QB.

Science.gov (United States)

Kirmaier, Christine; Laible, Philip D; Hanson, Deborah K; Holten, Dewey

2003-02-25

We report time-resolved optical measurements of the primary electron transfer reactions in Rhodobacter capsulatus reaction centers (RCs) having four mutations: Phe(L181) --> Tyr, Tyr(M208) --> Phe, Leu(M212) --> His, and Trp(M250) --> Val (denoted YFHV). Following direct excitation of the bacteriochlorophyll dimer (P) to its lowest excited singlet state P, electron transfer to the B-side bacteriopheophytin (H(B)) gives P(+)H(B)(-) in approximately 30% yield. When the secondary quinone (Q(B)) site is fully occupied, P(+)H(B)(-) decays with a time constant estimated to be in the range of 1.5-3 ns. In the presence of excess terbutryn, a competitive inhibitor of Q(B) binding, the observed lifetime of P(+)H(B)(-) is noticeably longer and is estimated to be in the range of 4-8 ns. On the basis of these values, the rate constant for P(+)H(B)(-) --> P(+)Q(B)(-) electron transfer is calculated to be between approximately (2 ns)(-)(1) and approximately (12 ns)(-)(1), making it at least an order of magnitude smaller than the rate constant of approximately (200 ps)(-)(1) for electron transfer between the corresponding A-side cofactors (P(+)H(A)(-) --> P(+)Q(A)(-)). Structural and energetic factors associated with electron transfer to Q(B) compared to Q(A) are discussed. Comparison of the P(+)H(B)(-) lifetimes in the presence and absence of terbutryn indicates that the ultimate (i.e., quantum) yield of P(+)Q(B)(-) formation relative to P is 10-25% in the YFHV RC.

Photochemical reactions of electron-deficient olefins with N,N,N',N'-tetramethylbenzidine via photoinduced electron-transfer

Energy Technology Data Exchange (ETDEWEB)

Pan Yang [Laboratory of Bond-selective Chemistry, Department of Chemical Physics, University of Science and Technology of China, No. 96 of Jinzhai Road, Hefei, Anhui 230026 (China); Zhao Junshu [Laboratory of Bond-selective Chemistry, Department of Chemical Physics, University of Science and Technology of China, No. 96 of Jinzhai Road, Hefei, Anhui 230026 (China); Ji Yuanyuan [Laboratory of Bond-selective Chemistry, Department of Chemical Physics, University of Science and Technology of China, No. 96 of Jinzhai Road, Hefei, Anhui 230026 (China); Yan Lei [Laboratory of Bond-selective Chemistry, Department of Chemical Physics, University of Science and Technology of China, No. 96 of Jinzhai Road, Hefei, Anhui 230026 (China); Yu Shuqin [Laboratory of Bond-selective Chemistry, Department of Chemical Physics, University of Science and Technology of China, No. 96 of Jinzhai Road, Hefei, Anhui 230026 (China)], E-mail: sqyu@ustc.edu.cn

2006-01-05

Photoinduced electron transfer reactions of several electron-deficient olefins with N,N,N',N'-tetramethylbenzidine (TMB) in acetonitrile solution have been studied by using laser flash photolysis technique and steady-state fluorescence quenching method. Laser pulse excitation of TMB yields {sup 3}TMB* after rapid intersystem crossing from {sup 1}TMB*. The triplet which located at 480 nm is found to undergo fast quenching with the electron acceptors fumaronitrile (FN), dimethyl fumarate (DMF), diethyl fumarate (DEF), cinnamonitrile (CN), {alpha}-acetoxyacrylonitrile (AAN), crotononitrile (CrN) and 3-methoxyacrylonitrile (MAN). Substituents binding to olefin molecule own different electron-donating/withdrawing powers, which determine the electron-deficient property ({pi}-cloud density) of olefin molecule as well as control the electron transfer rate constant directly. The detection of ion radical intermediates in the photolysis reactions confirms the proposed electron transfer mechanism, as expected from thermodynamics. The quenching rate constants of triplet TMB by these olefins have been determined at 510 nm to avoid the disturbance of formed TMB cation radical around 475 nm. All the k{sub q}{sup T} values approach or reach to the diffusion-controlled limit. In addition, fluorescence quenching rate constants k{sub q}{sup S} have been also obtained by calculating with Stern-Volmer equation. A correlation between experimental electron transfer rate constants and free energy changes has been explained by Marcus theory of adiabatic outer-sphere electron transfer. Disharmonic k{sub q} values for CN and CrN in endergonic region may be the disturbance of exciplexs formation. e of exciplex formation.

Pion-transfer (n,d) and (d, 3He) reactions leading to deeply bound pionic atoms

International Nuclear Information System (INIS)

Toki, H.; Hirenzaki, S.; Yamazaki, T.

1990-11-01

Theoretical studies are given on the (n,d) and (d, 3 He) reactions leading to deeply bound pionic atoms in heavy nuclei of configuration [(nl) π ·j n -1 ]J. The cross sections for various pionic and neutron-hole configurations in the case of a 208 Pb target are calculated at incident energies 300-1000 MeV/u by using the effective number approach and the eikonal approximation for distortion. The effective number with a pion in the 1s or 2p state and a neutron hole in the i 13/2 orbit peaks around the same incident energy (T n =600 MeV) as the elementary cross section n+n→d+π - , where the momentum transfer matches the angular-momentum transfer of L=5∼7. The DWIA cross section for (n,d) producing a pion in the 1s or 2p orbit at T n =600 MeV is found to be around 42 or 75 μb/sr, respectively. At T n =350 MeV, where the momentum transfer is small, quasi-substitutional states of configurations [(2p) π (3p 1/2 ) n -1 ]L=0 and [(2p) π (3p 3/2 ) n -1 ]L=0 are preferentially populated with cross sections of 190 and 380 μb/sr, respectively. The (d, 3 He) cross sections are estimated to be an order of magnitude smaller than the (n,d) cross sections. Thus, the (n,d) and (d, 3 He) reactions are found to be suited for the production of deeply bound pionic atoms. (author)

Hydrogen Transfer during Liquefaction of Elbistan Lignite to Biomass; Total Reaction Transformation Approach

Science.gov (United States)

Koyunoglu, Cemil; Karaca, Hüseyin

2017-12-01

Given the high cost of the tetraline solvent commonly used in liquefaction, the use of manure with EL is an important factor when considering the high cost of using tetraline as a hydrogen transfer source. In addition, due to the another cost factor which is the catalyst prices, red mud (commonly used, produced as a byproduct in the production of aluminium) is reduced cost in the work of liquefaction of coal, biomass, even coal combined biomass, corresponding that making the EL liquefaction an agenda for our country is another important factor. Conditions for liquefaction experiments conducted for hydrogen transfer from manure to coal; Catalyst concentration of 9%, liquid/solid ratio of 3/1, reaction time of 60 min, fertilizer/lignite ratio of 1/3, and the reaction temperature of 400 °C, the stirred speed of 400 rpm and the initial nitrogen pressure of 20 bar was fixed. In order to demonstrate the hydrogen, transfer from manure to coal, coal is used solely, by using tetraline (also known as a hydrogen carrier) and distilled water which is not hydrogen donor as a solvent in the co-liquefaction of experiments, and also the liquefaction conditions are carried out under an inert (N2) gas atmosphere. According to the results of the obtained liquefaction test; using tetraline solvent the total liquid product conversion percentage of the oil + gas conversion was 38.3 %, however, the results of oil+gas conversion obtained using distilled water and EL combined with manure the total liquid product conversion percentage was 7.4 %. According to the results of calorific value and elemental analysis, only the ratio of (H/C)atomic of coal obtained by using tetraline increased with the liquefaction of manure and distilled water. The reason of the increase in the amount of hydrogen due to hydrogen transfer from the manure on the solid surface of the coal, and also on the surface of the inner pore of the coal during the liquefaction, brings about the evaluation of the coal as a

Reactions of guanine with methyl chloride and methyl bromide: O6-methylation versus charge transfer complex formation

Science.gov (United States)

Shukla, P. K.; Mishra, P. C.; Suhai, S.

Density functional theory (DFT) at the B3LYP/6-31+G* and B3LYP/AUG-cc-pVDZ levels was employed to study O6-methylation of guanine due to its reactions with methyl chloride and methyl bromide and to obtain explanation as to why the methyl halides cause genotoxicity and possess mutagenic and carcinogenic properties. Geometries of the various isolated species involved in the reactions, reactant complexes (RCs), and product complexes (PCs) were optimized in gas phase. Transition states connecting the reactant complexes with the product complexes were also optimized in gas phase at the same levels of theory. The reactant complexes, product complexes, and transition states were solvated in aqueous media using the polarizable continuum model (PCM) of the self-consistent reaction field theory. Zero-point energy (ZPE) correction to total energy and the corresponding thermal energy correction to enthalpy were made in each case. The reactant complexes of the keto form of guanine with methyl chloride and methyl bromide in water are appreciably more stable than the corresponding complexes involving the enol form of guanine. The nature of binding in the product complexes was found to be of the charge transfer type (O6mG+ · X-, X dbond Cl, Br). Binding of HCl, HBr, and H2O molecules to the PCs obtained with the keto form of guanine did not alter the positions of the halide anions in the PCs, and the charge transfer character of the PCs was also not modified due to this binding. Further, the complexes obtained due to the binding of HCl, HBr, and H2O molecules to the PCs had greater stability than the isolated PCs. The reaction barriers involved in the formation of PCs were found to be quite high (?50 kcal/mol). Mechanisms of genotoxicity, mutagenesis and carcinogenesis caused by the methyl halides appear to involve charge transfer-type complex formation. Thus the mechanisms of these processes involving the methyl halides appear to be quite different from those that involve the

Phosphorus-31 NMR magnetization transfer measurements of metabolic reaction rates in the rat heart and kidney in vivo

International Nuclear Information System (INIS)

Koretsky, A.P.

1984-01-01

31 P NMR is a unique tool to study bioenergetics in living cells. The application of magnetization transfer techniques to the measurement of steady-state enzyme reaction rates provides a new approach to understanding the regulation of high energy phosphate metabolism. This dissertation is concerned with the measurement of the rates of ATP synthesis in the rat kidney and of the creatine kinase catalyzed reaction in the rat heart in situ. The theoretical considerations of applying magnetization transfer techniques to intact organs are discussed with emphasis on the problems associated with multiple exchange reactions and compartmentation of reactants. Experimental measurements of the ATP synthesis rate were compared to whole kidney oxygen consumption and Na + reabsorption rates to derive ATP/O values. The problems associated with ATP synthesis rate measurements in kidney, e.g. the heterogeneity of the inorganic phosphate resonance, are discussed and experiments to overcome these problems proposed. In heart, the forward rate through creatine kinase was measured to be larger than the reverse rate. To account for the difference in forward and reverse rates a model is proposed based on the compartmentation of a small pool of ATP

Study of nuclear isovector spin responses from polarization transfer in (p,n) reactions at intermediate energies

International Nuclear Information System (INIS)

Wakasa, Tomotsugu

1997-01-01

We have measured a complete set of polarization transfer observables has been measured for quasi-free (p vector, n vector) reactions on 2 H, 6 Li, 12 C, 40 Ca, and 208 Pb at a bombarding energy of 346MeV and a laboratory scattering angle of 22deg (q=1.7 fm -1 ). The polarization transfer observables for all five targets are remarkably similar. These polarization observables yield separated spin-longitudinal (σ·q) and spin-transverse (σxq) nuclear responses. These results are compared to the spin-transverse responses measured in deep-inelastic electron scattering as well as to nuclear responses based on the random phase approximation. Such a comparison reveals an enhancement in the (p vector, n vector) spin-transverse channel, which masks the effect of pionic correlations in the response ratio. Second, the double differential cross sections at θ lab between 0deg and 12.3deg and the polarization transfer D NN at 0deg for the 90 Zr(p,n) reaction are measured at a bombarding energy of 295MeV. The Gamow-Teller(GT) strength B(GT) in the continuum deduced from the L=0 cross section is compared both with the perturbative calculation by Bertsch and Hamamoto and with the second-order random phase approximation calculation by Drozdz et al. The sum of B(GT) values up to 50MeV excitation becomes S β- =28.0±1.6 after subtracting the contribution of the isovector spin-monopole strength. This S β- value of 28.0±1.6 corresponds to about (93±5)% of the minimum value of the sum-rule 3(N-Z)=30. Last, first measurements of D NN (0deg) for (p vector, n vector) reactions at 295MeV yield large negative values up to 50MeV excitation for the 6 Li, 11 B, 12 C, 13 C(p vector, n vector) reactions. DWIA calculations using the Franey and Love (FL) 270MeV interaction reproduce differential cross sections and D NN (0deg) values, while the FL 325MeV interaction yield D NN (0deg) values less negative than the experimental values. (J.P.N.)

Electron transfer in proteins

DEFF Research Database (Denmark)

Farver, O; Pecht, I

1991-01-01

Electron migration between and within proteins is one of the most prevalent forms of biological energy conversion processes. Electron transfer reactions take place between active centers such as transition metal ions or organic cofactors over considerable distances at fast rates and with remarkable...... specificity. The electron transfer is attained through weak electronic interaction between the active sites, so that considerable research efforts are centered on resolving the factors that control the rates of long-distance electron transfer reactions in proteins. These factors include (in addition......-containing proteins. These proteins serve almost exclusively in electron transfer reactions, and as it turns out, their metal coordination sites are endowed with properties uniquely optimized for their function....

Transport Visualization for Studying Mass Transfer and Solute Transport in Permeable Media

International Nuclear Information System (INIS)

Roy Haggerty

2004-01-01

first such experiments that show mass transfer in porous media in great detail. Experimental and theoretical work in media with pore-scale heterogeneity showed the temporal scale-dependency of mass transfer. Extension of the work into reactive transport, where mass transfer is very important to mixing, suggests a number of promising research directions for constructing better models of reactive transport and provides the experimental tools to develop and test these models. In particular, it is important to determine how the different solute spreading mechanisms in heterogeneous conductivity fields affect the rate and spatial pattern of chemical reaction. The project was conducted collaboratively between Oregon State University, Sandia National Laboratories, and the Massachusetts Institute of Technology. While each institution is submitting a copy of this final report for administrative purposes, the report is the largely the same since the project was a joint effort. This final report will outline the results of work completed and summarize publications and presentations. Manuscripts published or in press are attached, and subsequent publications will follow once published

Multinucleon-Transfer Reactions as a Gateway to Neutron-Rich Actinides and Nuclei near the N=82 and Z=50 Shell Closures

OpenAIRE

Vogt, Andreas Günter Heinz

2017-01-01

In the present work, reaction products in the 136Xe+238U multinucleon-transfer reaction at 1 GeV were investigated employing the high-resolution position-sensitive gamma-ray tracking array AGATA coupled to the large-solid-angle mass spectrometer PRISMA at the Laboratori Nazionali di Legnaro (INFN, Italy). Beam-like reaction products were identified and selected by the PRISMA spectrometer. Recoils and fission fragments were tagged by DANTE micro-channel plate detectors installed within the sca...

Kinetics of elementary atom and radical reactions

International Nuclear Information System (INIS)

Gordon, R.J.

1990-06-01

During the past three years we have been working on four problems in the general area of gas phase kinetics and energy transfer of small molecules. These are: (1) measurements of the fine structure populations of ground state oxygen atoms produced in photodissociation reactions; (2) quenching of the Rydberg B ( 1 Σ + ) state of CO; (3) vibrational relaxation of highly excited molecules; and (4) kinetics of hydrogen molecules. The first two topics, which involve transitions between different electronic states of the parent molecule, are a departure from our previous research interests. In the accompanying renewal proposal we discuss plans to pursue these new topics vigorously during the coming year. The third topic is a continuation of our long interest in the energy dependence of the rates laws governing vibrational-to-translational energy transfer of molecules having large initial amounts of vibrational excitation. The final topic is a continuation of our studies of the reaction of O( 3 P) + H 2 . In this work we measured the rate constant for the reaction O( 3 P) with deuterium and also analyzed spectroscopically different sources of vibrationally excited hydrogen for possible future work. We discuss each of these four studies in the following sections

Multi-nucleon transfer reaions with heavy ions

International Nuclear Information System (INIS)

Nadkarni, D.M.

1975-01-01

The reaction mechanisms of multinucleon transfer reactions with heavy ions such as O 16 , Ne 22 , Ar 40 , Ge 74 , Kr 84 and Xe 136 are discussed. As an example, the transfer reactions of Th 232 bombarded with O 16 , Ne 22 and Ar 40 ions are described. Some general features and a semiclassical picture of these reactions are presented. Cross sections, energy spectra and angular distributions are derived for the products of these reactions. The energy dependence of nucleon transfer cross sections in the interaction of Ge 74 with Th 232 is discussed. The importance of the study of multinucleon transfer reactions in the production of neutron-rich isotopes and transuranium elements is pointed out. (A.K.)

Spectrophotometric determination of quetiapine fumarate in pharmaceuticals and human urine by two charge-transfer complexation reactions

Directory of Open Access Journals (Sweden)

Vinay K.B.

2012-01-01

Full Text Available Two simple, rapid and accurate spectrophotometric procedures are proposed for the determination of quetiapine fumarate (QTF in pharmaceuticals and in spiked human urine. The methods are based on charge transfer complexation reactions of free base form of the drug (quetiapine, QTP, as n-electron donor (D, with either p-chloranilic acid (p-CAA (method A or 2,3-dichloro-5,6-dicyanoquinone (DDQ (method B as π-acceptors (A. The coloured charge transfer complexes produced exhibit absorption maxima at 520 and 540 nm, in method A and method B, respectively. The experimental conditions such as reagent concentration, reaction solvent and time have been carefully optimized to achieve the maximum sensitivity. Beer’s law is obeyed over the concentration ranges of 8.0 - 160 and 4.0 - 80.0 μg ml-1, for method A and method B, respectively. The calculated molar absorptivity values are 1.77 × 103 and 4.59 × 103 l mol-1cm-1, respectively, for method A and method B. The Sandell sensitivity values, limits of detection (LOD and quantification (LOQ have also been reported. The stoichiometry of the reaction in both cases was accomplished adopting the limiting logarithmic method and was found to be 1: 2 (D: A. The accuracy and precision of the methods were evaluated on intra-day and inter-day basis. The proposed methods were successfully applied for the determination of QTF in pharmaceutical formulations and spiked human urine.

Bimolecular reactions of carbenes: Proton transfer mechanism

Science.gov (United States)

Abu-Saleh, Abd Al-Aziz A.; Almatarneh, Mansour H.; Poirier, Raymond A.

2018-04-01

Here we report the bimolecular reaction of trifluoromethylhydroxycarbene conformers and the water-mediated mechanism of the 1,2-proton shift for the unimolecular trans-conformer by using quantum chemical calculations. The CCSD(T)/cc-pVTZ//MP2/cc-pVDZ potential-energy profile of the bimolecular reaction of cis- and trans-trifluoromethylhydroxycarbene, shows the lowest gas-phase barrier height of 13 kJ mol-1 compared to the recently reported value of 128 kJ mol-1 for the unimolecular reaction. We expect bimolecular reactions of carbene's stereoisomers will open a valuable field for new and useful synthetic strategies.

Detailed modeling of hydrodynamics mass transfer and chemical reactions in a bubble column using a discrete bubble model

NARCIS (Netherlands)

Darmana, D.; Deen, N.G.; Kuipers, J.A.M.

2005-01-01

A 3D discrete bubble model is adopted to investigate complex behavior involving hydrodynamics, mass transfer and chemical reactions in a gas–liquid bubble column reactor. In this model a continuum description is adopted for the liquid phase and additionally each individual bubble is tracked in a

Positive photocatalysis of a Diels-Alder reaction by quenching of excited naphthalene-indole charge-transfer complex with cyclohexadiene.

Science.gov (United States)

Gonzalez-Béjar, María; Stiriba, Salah-Eddine; Miranda, Miguel A; Pérez-Prieto, Julia

2007-02-01

[reaction: see text] Naphthalene photo-catalyzes formation of cyclohexadiene-indole cycloadducts in a wavelength-dependent process. Steady-state irradiation and time-resolved fluorescence studies agree well with NP-InH ground-state charge transfer (CT) complexes as the key species responsible for the photo-catalyzed process.

In vitro and in vivo volatile flavour analysis of red kidney beans by proton transfer reaction-mass spectrometry

NARCIS (Netherlands)

Ruth, van S.M.; Dings, L.; Buhr, K.; Posthumus, M.A.

2004-01-01

The volatile flavour released from red kidney beans was evaluated in vitro (in a model mouth system) and in vivo (in-nose). The dynamic release of the volatile flavour compounds was analysed by proton transfer reaction¿mass spectrometry. The flavour compounds were identified by gas

Study on charge transfer reaction of several organic molecules with accelerated rare gas ions

International Nuclear Information System (INIS)

Takahasi, Makoto; Okuda, Sachiko; Arai, Eiichi; Ichinose, Akira; Takakubo, Masaaki.

1984-01-01

Observing the charge transfer mass spectra of ethylbenzene, cyclobutane and methanol in Ar and Xe ion impacts, we investigated the dependence of the secondary ion peak intensities (normalized to primary ion current and target pressure) on the translational energy of primary ions (0-3500 eV).In the case of ethylbenzene, several maxima of the secondary i on peak intensities were observed in Ar and Xe ion impacts. The correlation between the maxima and the primary ion energy was examined in terms of near adiabatic theory of Massey. Supplementary studies on the energy distribution of primary ion, charge transfer cross section between methanol and Xe ion, and final product analysis in rare gas ion irradiation on cyclobutane were described. (author)

Investigation of reactions and species dominating low temperature combustion - Final report

Energy Technology Data Exchange (ETDEWEB)

Gerber, T.; Radi, P.; Knopp, G.; Tulej, M.

2007-07-01

This final report for the Swiss Federal Office of Energy (SFOE), reports on work done in 2007 at the Paul Scherrer Institute PSI in Switzerland on the quantitative description of ignition. processes and the influence of peroxy radicals that determine ignition and speciation of the intermediates initially present and, thereby, the progress of subsequent reactions. The authors note that for the preparation of peroxy radicals, a dedicated molecular beam apparatus has been built by the PSI's 'Molecular Dynamics' group. A novel radical source is operational. In many cases, specific radicals can be prepared with high selectivity. A description of flame chemistry is being worked on that can reliably predict the speciation of intermediate products during ignition. Laser-based measurement techniques are being applied at PSI to measure the static and dynamic properties of alkyl peroxy radicals in order to accurately describe their reaction behaviour in combustion processes. A dedicated synchrotron beam line is installed at the Swiss Light Source (SLS) that extends the available range of spectroscopic measurements into the VUV (vacuum-ultraviolet) wavelength domain. The results obtained are presented and discussed.

Some aspects of the use of deep inelastic transfer reactions to produce nuclei far from stability and nuclei with large angular momenta

International Nuclear Information System (INIS)

Volkov, V.V.

1980-01-01

Some experimental data are considered that indicate the validity of the Q/sub gg/ systematics of cross sections for production of isotopes in multinucleon transfer reactions for any target-projectile combination. The effect of the nuclear structure of the light fragment on the evolution and disintegration of the double nuclear system formed in deep inelastic collisions of complex nuclei is discussed. Predominance of the α-particle emission over all other channels of the disintegration of the double nuclear system is demonstrated. It is shown that deep inelastic transfer reactions can be used to study the deformation of nuclei with large angular momenta. 9 figures

Spectroscopy of particle-phonon coupled states in $^{133}$Sb by the cluster transfer reaction of $^{132}$Sn on $^{7}$Li

CERN Multimedia

We propose to investigate, with MINIBALL coupled to T-REX, the one-valence-proton $^{133}$Sb nucleus by the cluster transfer reaction of $^{132}$Sn on $^{7}$Li. The excited $^{133}$Sb will be populated by transfer of a triton into $^{132}$Sn, followed by the emission of an $\\alpha$-particle (detected in T-REX) and 2 neutrons. The aim of the experiment is to locate states arising from the coupling of the valence proton of $^{133}$Sb to the collective low-lying phonon excitations of $^{132}$Sn (in particular the 3$^−$). According to calculations in the weak-coupling approach, these states lie in the 4$\\, - \\,$5 MeV excitation energy region and in the spin interval 1/2$\\, - \\,$ 19/2, i.e., in the region populated by the cluster transfer reaction. The results will be used to perform advanced tests of different types of nuclear interactions, usually employed in the description of particle-phonon coupled excitations. States arising from couplings of the proton with simpler core excitations, involving few nucleons...

Theory of nuclear reactions, with applications to heavy ion scattering reactions

International Nuclear Information System (INIS)

Youssef, M.S.A.

1981-01-01

Nuclear science to day, has gained its stature through the pioneer work of both theorists and experimentalists within its two main divisions, Nuclear Reaction and Nuclear Structure theories. Our main interest in this theoretical work in nuclear reaction theory is focused on three topics, come under the headings of three parts which are the constituents of the present paper. Part 1 is concerned with ''Contributions to the theory of Threshold phenomena in nuclear reactions; cluster threshold states in heavy ion reactions''. Part II is devoted to ''Hermiticity of the Laplacian operator, R-matrix theories and direct interaction theory'', while part xII is ascribed to ''Heavy ion transfer reactions and scattering''. The aforementioned selected topics are the backbones of this thesis, which starts with general introduction giving a brief account about the material included in. In each part, investiqations are given in an extended manner through several chapters. Finally, the thesis is ended eith the chapter on ''General Discussions and Conclusions''. Appendices, references, and figure captions are found at the end of each part, the matter which we believe to facilitate much the reading through of the thesis. The first two parts are based (to some extent) on the same formal background (R-matrix, Kapur-Peierls-theories) and they converge to solve some physical problems originating from flux conservation laws in nuclear reactions, while the third part is indirect related to the first two; in principle it joins the other two parts under computational aspects. All of them after all, form the solidarity of the material included in the thesis. (author)

Study of breakup and transfer of weakly bound nucleus 6Li to explore the low energy reaction dynamics

Science.gov (United States)

Zhang, G. L.; Zhang, G. X.; Hu, S. P.; Zhang, H. Q.; Gomes, P. R. S.; Lubian, J.; Guo, C. L.; Wu, X. G.; Yang, J. C.; Zheng, Y.; Li, C. B.; He, C. Y.; Zhong, J.; Li, G. S.; Yao, Y. J.; Guo, M. F.; Sun, H. B.; Valiente-Dobòn, J. J.; Goasduff, A.; Siciliano, M.; Galtarosa, F.; Francesco, R.; Testov, D.; Mengoni, D.; Bazzacco, D.; John, P. R.; Qu, W. W.; Wang, F.; Zheng, L.; Yu, L.; Chen, Q. M.; Luo, P. W.; Li, H. W.; Wu, Y. H.; Zhou, W. K.; Zhu, B. J.; Li, E. T.; Hao, X.

2017-11-01

Investigation of the breakup and transfer effect of weakly bound nuclei on the fusion process has been an interesting research topic in the past several years. However, owing to the low intensities of the presently available radioactive ion beam (RIB), it is difficult to clearly explore the reaction mechanisms of nuclear systems with unstable nuclei. In comparison with RIB, the beam intensities of stable weakly bound nuclei such as 6,7Li and 9Be, which have significant breakup probability, are orders of magnitude higher. Precise fusion measurements have already been performed with those stable weakly bound nuclei, and the effect of breakup of those nuclei on the fusion process has been extensively studied. Those nuclei indicated large production cross sections for particles other than the α + x breakup. The particles are originated from non-capture breakup (NCBU), incomplete fusion (ICF) and transfer processes. However, the conclusion of reaction dynamics was not clear and has the contradiction. In our previous experiments we have performed 6Li+96Zr and 154Sm at HI-13 Tandem accelerator of China Institute of Atomic Energy (CIAE) by using HPGe array. It is shown that there is a small complete fusion (CF) suppression on medium-mass target nucleus 96Zr different from about 35% suppression on heavier target nucleus 154Sm at near-barrier energies. It seems that the CF suppression factor depends on the charge of target nuclei. We also observed one neutron transfer process. However, the experimental data are scarce for medium-mass target nuclei. In order to have a proper understanding of the influence of breakup and transfer of weakly bound projectiles on the fusion process, we performed the 6Li+89Y experiment with incident energies of 22 MeV and 34 MeV on Galileo array in cooperation with Si-ball EUCLIDES at Legnaro National Laboratory (LNL) in Italy. Using particle-particle and particle-γ coincidences, the different reaction mechanisms can be clearly explored.

Detailed modeling of hydrodynamics mass transfer and chemical reactions in a bubble column using a discrete bubble model

NARCIS (Netherlands)

Darmana, D.; Deen, N.G.; Kuipers, J.A.M.

2005-01-01

A 3D discrete bubble model is adopted to investigate complex behavior involving hydrodynamics, mass transfer and chemical reactions in a gas¿liquid bubble column reactor. In this model a continuum description is adopted for the liquid phase and additionally each individual bubble is tracked in a

Detailed modelling of hydrodynamics, mass transfer and chemical reactions in a bubble column using a discrete bubble model: Chemisorption of CO2 into NaOH solution, numerical and experimental study

NARCIS (Netherlands)

Darmana, D.; Henket, R.L.B.; Deen, N.G.; Kuipers, J.A.M.

2007-01-01

This paper describes simulations that were performed with an Euler–Lagrange model that takes into account mass transfer and chemical reaction reported by Darmana et al. (2005. Detailed modelling of hydrodynamics, mass transfer and chemical reactions in a bubble column using a discrete bubble model.

Two-Centre Close-Coupling method in charge transfer

Directory of Open Access Journals (Sweden)

Reza Bagheri

2017-09-01

Full Text Available In the present work, the transition matrix elements as well as differential and total scattering cross-sections for positronium formation in Positron-Hydrogen atom collision and hydrogen formation in Positronium-Hydrogen ion collision, through the charge transfer channel by Two-Centre Close-Coupling method up to a first order approximation have been calculated. The charge transfer collision is assumed to be a three-body reaction, while the projectile is a plane wave. Additionally, the hydrogen and positronium atoms are assumed, initially, to be in their ground states. For the case of charge transfer in the scattering of positron by hydrogen atoms, the differential cross sections are plotted for the energy range of 50eV to 10keV, where the Thomas peak is clearly observable. Finally, the total scattering cross-section for the charge transfer in the collision of Positron-Hydrogen and Positronium-Hydrogen ion are plotted as a function of projectile energies and compared with other methods in the literature.

Oxidoreduction reactions involving the electrostatic and the covalent complex of cytochrome c and plastocyanin: Importance of the protein rearrangement for the intracomplex electron-transfer reaction

International Nuclear Information System (INIS)

Peerey, L.M.; Kostic, N.M.

1989-01-01

Horse heart cytochrome c and French bean plastocyanin are cross-linked one-to-one by a carbodiimide in the same general orientation in which they associate electrostatically. The reduction potentials of the Fe and Cu atoms in the covalent diprotein complex are respectively 245 and 385 mV vs NHE; the EPR spectra of the two metals are not perturbed by cross-linking. For isomers of the covalent diprotein complex, which probably differ slightly from one another in the manner of cross-linking, are separated efficiently by cation-exchange chromatography. Stopped-flow spectrophotometric experiments with the covalent diprotein complex show that the presence of plastocyanin somewhat inhibits oxidation of ferrocytochrome c by [Fe(CN) 6 ] 3- and somewhat promotes oxidation of this protein by [Fe(C 5 H 5 ) 2 ] + . These changes in reactivity are explained in terms of electrostatic and steric effects. Pulse-radiolysis experiments with the electrostatic diprotein complex yield association constants of ≥5 x 10 6 and 1 x 10 5 M -1 at ionic strengths of 1 and 40 mM, respectively, and the rate constant of 1.05 x 10 3 s -1 , regardless of the ionic strength, for the intracomplex electron-transfer reaction. Analogous pulse-radiolysis experiments with each of the four isomers of the covalent diprotein complex, at ionic strengths of both 2 and 200 mM, show an absence of the intracomplex electron-transfer reaction. A rearrangement of the proteins for this reaction seems to be possible (or unnecessary) in the electrostatic complex but impossible in the covalent complex

Eddy covariance emission and deposition flux measurements using proton transfer reaction – time of flight – mass spectrometry (PTR-TOF-MS): comparison with PTR-MS measured vertical gradients and fluxes

NARCIS (Netherlands)

Park, J.H.; Goldstein, A.H.; Timkovsky, J|info:eu-repo/dai/nl/330541676; Fares, S.; Weber, R.; Karlik, J.; Holzinger, R.|info:eu-repo/dai/nl/337989338

2013-01-01

During summer 2010, a proton transfer reaction – time of flight – mass spectrometer (PTR-TOF-MS) and a quadrupole proton transfer reaction mass spectrometer (PTR-MS) were deployed simultaneously for one month in an orange orchard in the Central Valley of California to collect continuous data

Characterisation of the volatile profiles of infant formulas by proton transfer reaction-mass spectrometry and gas chromatography-mass spectrometry

NARCIS (Netherlands)

Ruth, van S.M.; Floris, V.; Fayoux, S.

2006-01-01

The volatile profiles of 13 infant formulas were evaluated by proton transfer reaction-mass spectrometry (PTR-MS) and gas chromatography¿mass spectrometry (GC¿MS). The infant formulas varied in brand (Aptamil, Cow & Gate, SMA), type (for different infant target groups) and physical form

Kinematical coincidence method in transfer reactions

Energy Technology Data Exchange (ETDEWEB)

Acosta, L.; Amorini, F. [INFN—Laboratori Nazionali del Sud, Via S. Sofia, Catania (Italy); Auditore, L. [INFN Gruppo Collegato di Messina and Dipartimento di Fisica, Università di Messina (Italy); Berceanu, I. [Institute for Physics and Nuclear Engineering, Bucharest (Romania); Cardella, G., E-mail: cardella@ct.infn.it [INFN—Sezione di Catania, Via S. Sofia, 95123 Catania (Italy); Chatterjiee, M.B. [Saha Institute for Nuclear Physics, Kolkata (India); De Filippo, E. [INFN—Sezione di Catania, Via S. Sofia, 95123 Catania (Italy); Francalanza, L.; Gianì, R. [INFN—Laboratori Nazionali del Sud, Via S. Sofia, Catania (Italy); Dipartimento di Fisica e Astronomia, Università di Catania, Via S. Sofia, Catania (Italy); Grassi, L. [INFN—Sezione di Catania, Via S. Sofia, 95123 Catania (Italy); Rudjer Boskovic Institute, Zagreb (Croatia); Grzeszczuk, A. [Institut of Physics, University of Silesia, Katowice (Poland); La Guidara, E. [INFN—Sezione di Catania, Via S. Sofia, 95123 Catania (Italy); Centro Siciliano di Fisica Nucleare e Struttura della Materia, Catania (Italy); Lanzalone, G. [INFN—Laboratori Nazionali del Sud, Via S. Sofia, Catania (Italy); Facoltà di Ingegneria e Architettura, Università Kore, Enna (Italy); Lombardo, I. [INFN—Laboratori Nazionali del Sud, Via S. Sofia, Catania (Italy); Dipartimento di Scienze Fisiche, Università Federico II and INFN Sezione di Napoli (Italy); Loria, D.; Minniti, T. [INFN Gruppo Collegato di Messina and Dipartimento di Fisica, Università di Messina (Italy); Pagano, E.V. [INFN—Laboratori Nazionali del Sud, Via S. Sofia, Catania (Italy); Dipartimento di Fisica e Astronomia, Università di Catania, Via S. Sofia, Catania (Italy); and others

2013-07-01

A new method to extract high resolution angular distributions from kinematical coincidence measurements in binary reactions is presented. Kinematics is used to extract the center of mass angular distribution from the measured energy spectrum of light particles. Results obtained in the case of {sup 10}Be+p→{sup 9}Be+d reaction measured with the CHIMERA detector are shown. An angular resolution of few degrees in the center of mass is obtained. The range of applicability of the method is discussed.

Electron emission from transfer ionization reaction in 30 keV amu‑1 He 2+ on Ar collision

Science.gov (United States)

Amaya-Tapia, A.; Antillón, A.; Estrada, C. D.

2018-06-01

A model is presented that describes the transfer ionization process in H{e}2++Ar collision at a projectile energy of 30 keV amu‑1. It is based on a semiclassical independent-particle close-coupling method that yields a reasonable agreement between calculated and experimental values of the total single-ionization and single-capture cross sections. It is found that the transfer ionization reaction is predominantly carried out through simultaneous capture and ionization, rather than by sequential processes. The transfer-ionization differential cross section in energy that is obtained satisfactorily reproduces the global behavior of the experimental data. Additionally, the probabilities of capture and ionization as function of the impact parameter for H{e}2++A{r}+ and H{e}++A{r}+ collisions are calculated, as far as we know, for the first time. The results suggest that the model captures essential elements that describe the two-electron transfer ionization process and could be applied to systems and processes of two electrons.

Electronic interactions decreasing the activation barrier for the hydrogen electro-oxidation reaction

International Nuclear Information System (INIS)

Santos, Elizabeth; Schmickler, Wolfgang

2008-01-01

A unified model for electrochemical electron transfer reactions which explicitly accounts for the electronic structure of the electrode recently proposed by us is applied to the hydrogen oxidation reaction at different metal electrocatalysts. We focus on the changes produced in the transition state (saddle point) as a consequence of the interactions with d-bands. We discuss different empirical correlations between properties of the metal and catalytic activity proposed in the past. We show which role is played by the band structure of the different metals and its interaction with the molecule for decreasing the activation barrier. Finally, we demonstrate why some metals are better electrocatalysts for the hydrogen electro-oxidation reaction than others

Oxygen atom transfer reactions from Mimoun complexes to sulfides and sulfoxides. A bonding evolution theory analysis.

Science.gov (United States)

González-Navarrete, Patricio; Sensato, Fabricio R; Andrés, Juan; Longo, Elson

2014-08-07

In this research, a comprehensive theoretical investigation has been conducted on oxygen atom transfer (OAT) reactions from Mimoun complexes to sulfides and sulfoxides. The joint use of the electron localization function (ELF) and Thom's catastrophe theory (CT) provides a powerful tool to analyze the evolution of chemical events along a reaction pathway. The progress of the reaction has been monitored by structural stability domains from ELF topology while the changes between them are controlled by turning points derived from CT which reveal that the reaction mechanism can be separated in several steps: first, a rupture of the peroxo O1-O2 bond, then a rearrangement of lone pairs of the sulfur atom occurs and subsequently the formation of S-O1 bond. The OAT process involving the oxidation of sulfides and sulfoxides is found to be an asynchronous process where O1-O2 bond breaking and S-O1 bond formation processes do not occur simultaneously. Nucleophilic/electrophilic characters of both dimethyl sulfide and dimethyl sulfoxide, respectively, are sufficiently described by our results, which hold the key to unprecedented insight into the mapping of electrons that compose the bonds while the bonds change.

Lifetime and g-factor measurements of excited states using Coulomb excitation and alpha transfer reactions

Energy Technology Data Exchange (ETDEWEB)

Guevara, Z. E., E-mail: zjguevaram@unal.edu.co; Torres, D. A., E-mail: datorresg@unal.edu.co [Physics Department, Universidad Nacional de Colombia, Bogotá D.C. (Colombia)

2016-07-07

In this contribution the challenges in the use of a setup to simultaneously measure lifetimes and g-factor values will be presented. The simultaneous use of the transient field technique and the Doppler Shift Attenuation Method, to measure magnetic moments and lifetimes respectively, allows to obtain a complete characterization of the currents of nucleons and the deformation in excited states close to the ground state. The technique is at the moment limited to Coulomb excitation and alpha-transfer reactions, what opens an interesting perspective to consider this type of experiments with radioactive beams. The use of deep-inelastic and fusion-evaporation reactions will be discussed. An example of a setup that makes use of a beam of {sup 106}Cd to study excited states of {sup 110}Sn and the beam nuclei itself will be presented.

Final State Interactions and Polarization Observables in the Reaction pp → pKΛ

Directory of Open Access Journals (Sweden)

Röder Matthias

2012-12-01

Full Text Available Due to the lack of high quality hyperon beams, final state interactions in hyperon production reactions are a compelling tool to study hyperon-nucleon interactions. The COSY-TOF experiment has recently been upgraded in order to reconstruct the pK+Λ final state with sufficient precision to determine the spin triplet pΛ scattering length with a polarized proton beam. We find an unexpected behavior of the K+ analyzing power which prevents the extraction method to be used with the available statistics. A theoretical explanation is pending. Furthermore, the polarized beam together with the self analyzing decay of the Λ allows us to determine the Λ depolarization. This is especially sensitive to K+ and π exchange in the production mechanism. Our finding verifies, to a large extent, the result from DISTO [2] that has so far been the only measurement close to the production threshold.

Nucleon transfer between heavy nuclei

International Nuclear Information System (INIS)

Von Oertzen, W.

1984-02-01

Nucleon transfer reactions between heavy nuclei are characterized by the classical behaviour of the scattering orbits. Thus semiclassical concepts are well suited for the description of these reactions. In the present contribution the characteristics of single and multinucleon transfer reactions at energies below and above the Coulomb barrier are shown for systems like Sn+Sn, Xe+U and Ni+Pb. The role of the pairing interaction in the transfer of nucleon pairs is illustrated. For strong transitions the coupling of channels and the absorption into more complicated channels is taken into account in a coupled channels calculation

Influence of mass transfer and chemical reaction on ozonation of azo dyes

Energy Technology Data Exchange (ETDEWEB)

Choi, I.S.; Wiesmann, U. [Dept. of Environmental Engineering, Technical Univ. of Berlin, Berlin (Germany)

2003-07-01

Azo dyes can be only mineralised by chemical oxidation. In this paper the oxidation of reactive black 5 (RB 5) and reactive orange 96 (RO 96) with concentrations between 35 and 5700 mgL{sup -1} (RB 5) and between 20 and 2050 mgL{sup -1} (RO 96) is investigated. A lab scale bubble column was used, which was gassed by a mixture of O{sub 2} and O{sub 3}. The oxidation rate was influenced by mass transfer for all dye concentrations used. For lower dye concentrations mass transfer alone was decisive for reaction rate showing an enhancement factor of E {approx} 1. However, in the region of higher dye concentrations, the slope of the decreasing ozone concentration inside the liquid boundary layer increases more and more with increasing dye concentration as a result of a chemical oxidation. Therefore, the enhancement factor depends on the kind and concentration of the azo dyes. For RB 5 as an diazo dye an enhancement factor of E = 9 was observed for 3800 mgL{sup -1}, RO 96 as a mono azo dye with a remarkable higher chemical oxidation rate shows an E = 17 already for 2050 mgL{sup -1}. (orig.)

Two-Dimensional Free Energy Surfaces for Electron Transfer Reactions in Solution

Directory of Open Access Journals (Sweden)

Shigeo Murata

2008-01-01

Full Text Available Change in intermolecular distance between electron donor (D and acceptor (A can induce intermolecular electron transfer (ET even in nonpolar solvent, where solvent orientational polarization is absent. This was shown by making simple calculations of the energies of the initial and final states of ET. In the case of polar solvent, the free energies are functions of both D-A distance and solvent orientational polarization. On the basis of 2-dimensional free energy surfaces, the relation of Marcus ET and exciplex formation is discussed. The transient effect in fluorescence quenching was measured for several D-A pairs in a nonpolar solvent. The results were analyzed by assuming a distance dependence of the ET rate that is consistent with the above model.

The reaction 12C + 12C at bombarding energies from 5 to 10 MeV per nucleon

International Nuclear Information System (INIS)

Morsad, A.

1986-01-01

The reaction 12 C + 12 C has been studied for energies ranging from E LAB = 60 to 120 MeV. The excitation functions and angular distributions were obtained for the elastic (0 + , 0 + ) and inelastic (2 + , 0 + ), (2 + , 2 + ) channels as well as for the transfer channels of one and two nucleons. For the transfer reactions, the feeding of the final bound states was very selective. Narrow correlated structures were found in the transfer and especially in the elastic and inelastic channels. In this energy range, there appears to be a transition from surface transparency to interference phenomena. The optical model in its simplest form is unable to describe the elastic scattering at large angles. This has been interpreted as a consequence of the coupling between the elastic and inelastic channels which is particularly strong of these energies. 80 refs [fr

Transient core characteristics of small molten salt reactor coupling problem between heat transfer/flow and nuclear fission reaction

International Nuclear Information System (INIS)

Yamamoto, Takahisa; Mitachi, Koshi

2004-01-01

This paper performed the transient core analysis of a small Molten Salt Reactor (MSR). The emphasis is that the numerical model employed in this paper takes into account the interaction among fuel salt flow, nuclear reaction and heat transfer. The model consists of two group diffusion equations for fast and thermal neutron fluexs, balance equations for six-group delayed neutron precursors and energy conservation equations for fuel salt and graphite moderator. The results of transient analysis are that (1) fission reaction (heat generation) rate significantly increases soon after step reactivity insertion, e.g., the peak of fission reaction rate achieves about 2.7 times larger than the rated power 350 MW when the reactivity of 0.15% Δk/k 0 is inserted to the rated state, and (2) the self-control performance of the small MSR effectively works under the step reactivity insertion of 0.56% Δk/k 0 , putting the fission reaction rate back on the rated state. (author)

Theoretical study on production of heavy neutron-rich isotopes around the N=126 shell closure in radioactive beam induced transfer reactions

Directory of Open Access Journals (Sweden)

Long Zhu

2017-04-01

Full Text Available In order to produce more unknown neutron-rich nuclei around N=126, the transfer reactions 136Xe + 198Pt, 136–144Xe + 208Pb, and 132Sn + 208Pb are investigated within the framework of the dinuclear system (DNS model. The influence of neutron excess of projectile on production cross sections of target-like products is studied through the reactions 136,144Xe + 208Pb. We find that the radioactive projectile 144Xe with much larger neutron excess is favorable to produce neutron-rich nuclei with charge number less than the target rather than produce transtarget nuclei. The incident energy dependence of yield distributions of fragments in the reaction 132Sn + 208Pb are also studied. The production cross sections of neutron-rich nuclei with Z=72–77 are predicted in the reactions 136–144Xe + 208Pb and 132Sn + 208Pb. It is noticed that the production cross sections of unknown neutron-rich nuclei in the reaction 144Xe + 208Pb are at least two orders of magnitude larger than those in the reaction 136Xe + 208Pb. The radioactive beam induced transfer reactions 139,144Xe + 208Pb, considering beam intensities proposed in SPIRAL2 (Production System of Radioactive Ion and Acceleration On-Line project as well, for production of neutron-rich nuclei around the N=126 shell closure are investigated for the first time. It is found that, in comparison to the stable beam 136Xe, the radioactive beam 144Xe shows great advantages for producing neutron-rich nuclei with N=126 and the advantages get more obvious for producing nuclei with less charge number.

Geographical provenancing of purple grape juices from different farming systems by proton transfer reaction mass spectrometry using supervised statistical techniques

NARCIS (Netherlands)

Granato, Daniel; Koot, Alex; Ruth, van S.M.

2015-01-01

BACKGROUND: Organic, biodynamic and conventional purple grape juices (PGJ; n = 79) produced in Brazil and Europe were characterized by volatile organic compounds (m/z 20-160) measured by proton transfer reaction mass spectrometry (PTR-MS), and classification models were built using supervised

An experimental approach to angular momentum transfer in heavy ion reactions

International Nuclear Information System (INIS)

Babinet, R.

1980-01-01

The current experimental status on angular momentum transfer status in heavy ion reactions is reviewed. After a short presentation of the basic theoretical concepts that are underlying all the research works in this field, the experimental techniques that have been commonly used are presented. Results obtained by the γ-multiplicity method are discussed first. Then come, for the very heavy systems, the sequential fission data, followed by the results of a recent experiment on light charged particles. The simple theoretical concepts that are introduced first are continuously used as guidelines to discuss the following results. The respective advantages but also the basic limitations of the above three experimental techniques are exposed. Although they are expected to work best in different regions of the mass table, it is shown, that they give complementary informations which have been most useful in improving our understanding of the tangential friction mechanism

Modelling of simultaneous mass and heat transfer with chemical reaction using the Maxwell-Stefan theory II. Non-isothermal study

NARCIS (Netherlands)

Frank, M.J.W.; Kuipers, J.A.M.; Krishna, R.; van Swaaij, W.P.M.

1995-01-01

In Part I a general applicable model has been developed which calculates mass and heat transfer fluxes through a vapour/gas-liquid interface in case a reversible chemical reaction with associated heat effect takes place in the liquid phase. In this model the Maxwell-Stefan theory has been used to

31P NMR saturation-transfer measurements in Saccharomyces cerevisiae: characterization of phosphate exchange reactions by iodoacetate and antimycin A inhibition

International Nuclear Information System (INIS)

Campbell-Burk, S.L.; Jones, K.A.; Shulman, R.G.

1987-01-01

31 P nuclear magnetic resonance (NMR) saturation-transfer (ST) techniques have been used to measure steady-state flows through phosphate-adenosine 5'-triphosphate (ATP) exchange reactions in glucose-grown derepressed yeast. The results have revealed that the reactions catalyzed by glyceraldehyde-3-phosphate dehydrogenase/phosphoglycerate kinase (GAPDH/PGK) and by the mitochondrial ATPase contribute to the observed ST. Contributions from these reactions were evaluated by performing ST studies under various metabolic conditions in the presence and absence of either iodoacetate, a specific inhibitor of GAPDH, or the respiratory chain inhibitor antimycin A. Intracellular phosphate (P/sub i/) longitudinal relaxation times were determined by performing inversion recovery experiments during steady-state ATP/sub λ/ saturation and were used in combination with ST data to determine P/sub i/ consumption rates. 13 C NMR and O 2 electrode measurements were also conducted to monitor changes in rates of glucose consumption and O 2 consumption, respectively, under the various metabolic conditions examined. The results suggest that GAPDH/PGK-catalyzed P/sub i/-ATP exchange is responsible for antimycin-resistant saturation transfer observed in anaerobic and aerobic glucose-fed yeast. Kinetics through GAPDH/PGK were found to depend on metabolic conditions. The coupled system appears to operate in a unidirectional manner during anaerobic glucose metabolism and bidirectionally when the cells are respiring on exogenously supplied ethanol. Additionally, mitochondrial ATPase activity appears to be responsible for the transfer observed in iodoacetate-treated aerobic cells supplied with either glucose or ethanol, with synthesis of ATP occurring unidirectionally

Cold transfer between deformed, Coulomb excited nuclei

International Nuclear Information System (INIS)

Bauer, H.

1998-01-01

The scattering system 162 Dy → 116 Sn has been examined at energies in the vicinity of the Coulomb barrier using the Heidelberg-Darmstadt Crystal Ball spectrometer combined with 5 Germanium-CLUSTER detectors. In order to study pairing correlations as a function of angular momentum cold events were selected in the 2n stripping channel by identifying and suppressing the dominant hot part of the transfer with the Crystal Ball. The CLUSTER detectors with their high γ-efficiency were used to identify the transfer channel and to resolve individual final states. Cross sections for the population of individual yrast states in a cold transfer reaction have been measured for the first time indicating the strong influence of higher transfer multipolarities. At small surface distances Coulomb-nuclear interferences were found to be responsible for the stronger decline of the population of higher yrast states in the transfer channel as compared to the Coulex channel. As a preparatory study for 2n transfer measurements between high spin yrast states in the backbending region of deformed nuclei the Coulomb excitation process in the crossing region of two bands in 162 Dy has been analyzed. The gross properties of the measured population probabilities could be interpreted in a simple band mixing model. (orig.)

Manganese-Oxygen Intermediates in O-O Bond Activation and Hydrogen-Atom Transfer Reactions.

Science.gov (United States)

Rice, Derek B; Massie, Allyssa A; Jackson, Timothy A

2017-11-21

Biological systems capitalize on the redox versatility of manganese to perform reactions involving dioxygen and its derivatives superoxide, hydrogen peroxide, and water. The reactions of manganese enzymes influence both human health and the global energy cycle. Important examples include the detoxification of reactive oxygen species by manganese superoxide dismutase, biosynthesis by manganese ribonucleotide reductase and manganese lipoxygenase, and water splitting by the oxygen-evolving complex of photosystem II. Although these enzymes perform very different reactions and employ structurally distinct active sites, manganese intermediates with peroxo, hydroxo, and oxo ligation are commonly proposed in catalytic mechanisms. These intermediates are also postulated in mechanisms of synthetic manganese oxidation catalysts, which are of interest due to the earth abundance of manganese. In this Account, we describe our recent efforts toward understanding O-O bond activation pathways of Mn III -peroxo adducts and hydrogen-atom transfer reactivity of Mn IV -oxo and Mn III -hydroxo complexes. In biological and synthetic catalysts, peroxomanganese intermediates are commonly proposed to decay by either Mn-O or O-O cleavage pathways, although it is often unclear how the local coordination environment influences the decay mechanism. To address this matter, we generated a variety of Mn III -peroxo adducts with varied ligand environments. Using parallel-mode EPR and Mn K-edge X-ray absorption techniques, the decay pathway of one Mn III -peroxo complex bearing a bulky macrocylic ligand was investigated. Unlike many Mn III -peroxo model complexes that decay to oxo-bridged-Mn III Mn IV dimers, decay of this Mn III -peroxo adduct yielded mononuclear Mn III -hydroxo and Mn IV -oxo products, potentially resulting from O-O bond activation of the Mn III -peroxo unit. These results highlight the role of ligand sterics in promoting the formation of mononuclear products and mark an important

Engineering of RuMb: Toward a Green Catalyst for Carbene Insertion Reactions.

Science.gov (United States)

Wolf, Matthew W; Vargas, David A; Lehnert, Nicolai

2017-05-15

The small, stable heme protein myoglobin (Mb) was modified through cofactor substitution and mutagenesis to develop a new catalyst for carbene transfer reactions. The native heme was removed from wild-type Mb and several Mb His64 mutants (H64D, H64A, H64V), and the resulting apoproteins were reconstituted with ruthenium mesoporphyrin IX (RuMpIX). The reconstituted proteins (RuMb) were characterized by UV-vis and circular dichroism spectroscopy and were used as catalysts for the N-H insertion of aniline derivatives and the cyclopropanation of styrene derivatives. The best catalysts for each reaction were able to achieve turnover numbers (TON) up to 520 for the N-H insertion of aniline, and 350 TON for the cyclopropanation of vinyl anisole. Our results show that RuMb is an effective catalyst for N-H insertion, with the potential to further increase the activity and stereoselectivity of the catalyst in future studies. Compared to native Mb ("FeMb"), RuMb is a more active catalyst for carbene transfer reactions, which leads to both heme and protein modification and degradation and, hence, to an overall much-reduced lifetime of the catalyst. This leads to lower TONs for RuMb compared to the iron-containing analogues. Strategies to overcome this limitation are discussed. Finally, comparison is also made to FeH64DMb and FeH64AMb, which have not been previously investigated for carbene transfer reactions.

Determination of minor actinides fission cross sections by means of transfer reactions

Energy Technology Data Exchange (ETDEWEB)

Jurado, B.; Aiche, M.; Barreau, G.; Boyer, S.; Czajkowski, S.; Dassie, D.; Grosjean, C.; Guiral, A.; Haas, B.; Osmanov, B.; Petit, M. [CENBG - UMR 5795 CNRS/IN2P3-Univ. Bordeaux 1- Le Haut Vigneau, 33175 Gradignan (France); Berthoumieux, E.; Gunsing, F.; Perrot, L.; Theisen, Ch. [CEN Saclay, DSM/DAPNIA/SPhN, 91191 Gif-sur-Yvette cedex (France); Bauge, E. [CEA, SPhN, BP12 91680 Bruyeres-le-Chatel (France); Michel-Sendis, F. [IPN, 15 rue G. Clemenceau, 91406 Orsay cedex (France); Billebaud, A. [LPSC, 53 Avenue des Martyrs, 38026 Grenoble cedex (France); Wilson, J. N. [IPN, 15 rue G. Clemenceau, 91406 Orsay cedex (France); LPSC, 53 Avenue des Martyrs, 38026 Grenoble cedex (France); Ahmad, I.; Greene, J.P.; Janssens, R. V. F. [ANL, 9700 S. Cass Avenue, Argonne, IL 60439 (United States)

2005-07-01

We present an original method that allows to determine neutron-induced cross sections of very short-lived minor actinides. This indirect method, based on the use of transfer reactions, has already been applied with success for the determination of the neutron-induced fission and capture cross section of {sup 233}Pa, a key nucleus in the {sup 232}Th - {sup 233}U fuel cycle. A recent experiment using this technique has been performed to determine the neutron-induced fission cross sections of {sup 242,243,244}Cm and {sup 241}Am which are present in the nuclear waste of the current U-Pu fuel cycle. These cross sections are highly relevant for the design of reactors capable to incinerate minor actinides. The first results will be illustrated. (authors)

Low energy ion-molecule reactions

Energy Technology Data Exchange (ETDEWEB)

Farrar, J.M. [Univ. of Rochester, NY (United States)

1993-12-01

This project is concerned with elucidating the dynamics of elementary ion-molecule reactions at collision energies near and below 1 eV. From measurements of the angular and energy distributions of the reaction products, one can infer intimathe details about the nature of collisions leading to chemical reaction, the geometries and lifetimes of intermediate complexes that govern the reaction dynamics, and the collision energy dependence of these dynamical features. The author employs crossed-beam low energy mass spectrometry technology developed over the last several years, with the focus of current research on proton transfer and hydrogen atom transfer reactions of te O{sup {minus}} ion with species such as HF, H{sub 2}O, and NH{sub 3}.

Experimental and numerical reaction analysis on sodium-water chemical reaction field

International Nuclear Information System (INIS)

Deguchi, Yoshihiro; Takata, Takashi; Yamaguchi, Akira; Kikuchi, Shin; Ohshima, Hiroyuki

2015-01-01

In a sodium-cooled fast reactor (SFR), liquid sodium is used as a heat transfer fluid because of its excellent heat transport capability. On the other hand, it has strong chemical reactivity with water vapor. One of the design basis accidents of the SFR is the water leakage into the liquid sodium flow by a breach of heat transfer tubes. This process ends up damages on the heat transport equipment in the SFR. Therefore, the study on sodium-water chemical reactions is of paramount importance for security reasons. This study aims to clarify the sodium-water reaction mechanisms using an elementary reaction analysis. A quasi one-dimensional flame model is applied to a sodium-water counter-flow reaction field. The analysis contains 25 elementary reactions, which consist of 17 H_2-O_2 and 8 Na-H_2O reactions. Temperature and species concentrations in the counter-flow reaction field were measured using laser diagnostics such as LIF and CARS. The main reaction in the experimental conditions is Na+H_2O → NaOH+H and OH is produced by H_2O+H → H_2+OH. It is demonstrated that the reaction model in this study well explains the structure of the sodium-water counter-flow diffusion flame. (author)

Numerical study for melting heat transfer and homogeneous-heterogeneous reactions in flow involving carbon nanotubes

Science.gov (United States)

Hayat, Tasawar; Muhammad, Khursheed; Alsaedi, Ahmed; Asghar, Saleem

2018-03-01

Present work concentrates on melting heat transfer in three-dimensional flow of nanofluid over an impermeable stretchable surface. Analysis is made in presence of porous medium and homogeneous-heterogeneous reactions. Single and multi-wall CNTs (carbon nanotubes) are considered. Water is chosen as basefluid. Adequate transformations yield the non-linear ordinary differential systems. Solution of emerging problems is obtained using shooting method. Impacts of influential variables on velocity and temperature are discussed graphically. Skin friction coefficient and Nusselt number are numerically discussed. The results for MWCNTs and SWCNTs are compared and examined.

Role of pendant proton relays and proton-coupled electron transfer on the hydrogen evolution reaction by nickel hangman porphyrins

Science.gov (United States)

Bediako, D. Kwabena; Solis, Brian H.; Dogutan, Dilek K.; Roubelakis, Manolis M.; Maher, Andrew G.; Lee, Chang Hoon; Chambers, Matthew B.; Hammes-Schiffer, Sharon; Nocera, Daniel G.

2014-01-01

The hangman motif provides mechanistic insights into the role of pendant proton relays in governing proton-coupled electron transfer (PCET) involved in the hydrogen evolution reaction (HER). We now show improved HER activity of Ni compared with Co hangman porphyrins. Cyclic voltammogram data and simulations, together with computational studies using density functional theory, implicate a shift in electrokinetic zone between Co and Ni hangman porphyrins due to a change in the PCET mechanism. Unlike the Co hangman porphyrin, the Ni hangman porphyrin does not require reduction to the formally metal(0) species before protonation by weak acids in acetonitrile. We conclude that protonation likely occurs at the Ni(I) state followed by reduction, in a stepwise proton transfer–electron transfer pathway. Spectroelectrochemical and computational studies reveal that upon reduction of the Ni(II) compound, the first electron is transferred to a metal-based orbital, whereas the second electron is transferred to a molecular orbital on the porphyrin ring. PMID:25298534

Prediction of Support Reaction Forces of ITA via Response Spectrum Analysis

Energy Technology Data Exchange (ETDEWEB)

Kwak, Jin Sung; Jeong, Joon Ho; Lee, Sang Jin; Oh, Jin Ho; Lee, Jong Min [KAERI, Daejeon (Korea, Republic of)

2016-05-15

The irradiation targets are transferred along pipes between TTS (Target Transfer Station) and ITA (Irradiation Tube Assembly) by hydraulic forces. The ITA corresponds to the vertical guide tube for irradiation targets inside a reactor, and it penetrates the reactor structure. Because the ITA is classified into seismic category II, its structural integrity must be evaluated by the seismic analysis. To approach more realistic problem, the interaction between the ITA and the reactor structure must be considered. However, this paper is focused on the preliminary analysis, and it is simplified that only the response of the ITA caused by earthquake affects the reactor structure. The response of the ITA is predicted by the spectrum response analysis based on the FDRS (Floor Design Response Spectra) of KJRR. Finally, the reaction forces corresponding to the load transfer into the reactor structure are estimated by using ANSYS. In this study, the reaction forces due to the earthquake are estimated by the response spectrum analysis. For the saving computational time and resource required, the FE model with beam element is constructed, and it is confirmed that the accuracy of the solution is acceptable by comparing the results of the solid model.

Spin dynamics and zero-field splitting constants of the triplet exciplex generated by photoinduced electron transfer reaction between erythrosin B and duroquinone

OpenAIRE

Tachikawa, Takashi; Kobori, Yasuhiro; Akiyama, Kimio; Katsuki, Akio; Steiner, Ulrich; Tero-Kubota, Shozo

2002-01-01

The spin dynamics of the duroquinone anion radical generated by photoinduced electron transfer reactions from triplet erythrosin B to duroquinone has been studied by using transient absorption and pulsed FT-EPR spectroscopy. Triplet exciplex formation as the reaction intermediate is verified by the observation of spin orbit coupling induced electron spin polarization. The kinetic parameters for exciplex formation and the intrinsic enhancement factors of electron spin polarization are determin...

The influence of transfer reactions on the sub-barrier fusion enhancement in the systems {sup 58.64}Ni +, {sup 92,100}Mo

Energy Technology Data Exchange (ETDEWEB)

Rehm, K.E.; Jiang, C.L.; Esbensen, H. [and others

1995-08-01

High resolution experiments performed during the past few years demonstrated that the various reaction modes occurring in heavy ion collisions can strongly influence each other. This interrelation of the different reaction modes brings a nuclear structure dependence to the fusion and deep-inelastic channels that were previously described in the framework of pure statistical models. In order to fully understand the interrelation between these reaction channels, a complete set of measurements including elastic and inelastic scattering, few-nucleon transfer and fusion is required. In continuation of our earlier measurements of the fusion cross sections in the system {sup 58,64}Ni + {sup 92,100}Mo we finished the studies of the quasielastic process in these systems. The experiments were done in inverse reaction kinematics using the split-pole spectrograph with its hybrid focal-plane detector for particle identification. The experiments with {sup 100}Mo beams were performed previously. First test runs with {sup 92}Mo showed the possible interference with {sup 98}Mo ions which could be eliminated by using the 13{sup +} charge state from the ECR source. The data from these experiments were completely analyzed. The smallest transfer cross sections are observed for the systems {sup 64}Ni + {sup 100}Mo and {sup 58}Ni + {sup 92}Mo, i.e., the most neutron-rich and neutron-deficient systems, respectively. For the other systems, {sup 64}Ni + {sup 92}Mo and {sup 58}Ni + {sup 100}Mo, the transfer cross sections at energies close to the barrier are about of equal magnitude. This observation does not correlate with the deviation of the experimental fusion cross sections from the coupled-channels predictions. While for {sup 58}Ni + {sup 100}Mo discrepancies between the experimental and theoretical fusion cross sections are observed, the system {sup 64}Ni + {sup 92}Mo which shows about the same transfer yields, is quite well described by the coupled-channels calculations.

/sup 58,60,62/Ni (. cap alpha. ,p) three--nucleon transfer reactions and. cap alpha. optical potential ambiguities

Energy Technology Data Exchange (ETDEWEB)

Yuanda, Wang; Xiuming, Bao; Zhiqiang, Mao; Rongfang, Yuan; Keling, Wen; Binyin, Huang; Zhifu, Wang; Shuming, Li; Jianan, Wang; Zuxun, Sun; others, and

1985-11-01

The differential cross sections are measured using 26.0 MeV ..cap alpha.. particle for /sup 58,62/Ni(..cap alpha.., ..cap alpha..) /sup 58,62/Ni and /sup 58,62/Ni(..cap alpha..,p) /sup 61,65/Cu reactions as well as 25.4 MeV ..cap alpha.. particle for /sup 60/Ni(..cap alpha.., ..cap alpha..)/sup 69/Ni and /sup 60/Ni(..cap alpha.., p)/sup 63/Cu reactions. Consistent calculations with optical model and ZR DWBA are made for (..cap alpha.., ..cap alpha..) and (..cap alpha.., p) reactions by using of single, two, three and four nucleon optical potential parameters. For elastic scattering due to the ..cap alpha.. optical potential ambiguities, all the above optical potential can reproduce the experimental angular distributions. However, the single, two and three nucleon potential, including the Baird's mass systematics and the Chang's energy systematics of ..cap alpha.. potentials, obviously can not provide a reasonable fitting with the (..cap alpha..,p) reaction experimental data. Only the results from the four nucleon potential is in good agreement with the (..cap alpha..,p) reaction experimental data. This reveals that in the ..cap alpha..-particle induced transfer reactions, the real depth of the ..cap alpha..-nucleus optical potential should be rather deep.

Uranium reactions with water vapor. Final progress report

International Nuclear Information System (INIS)

Condon, J.B.; Cristy, S.S.; Kirkpatrick, J.R.

1983-01-01

The reaction kinetics and ion microprobe mass analyzer (IMMA) depth-profile data for water-oxygen-uranium reaction is explained in terms of the perfusive-precipitation model. This model is reviewed extensively enough to deal with this interacting, 3-element reaction system. The model, based on simultaneous diffusion and product precipitation, can be applied to several systems in a parameterless fashion. It is applied to the uranium-water reaction in the absence and presence of the oxygen inhibitor. The results of the calculations of the model are compared to the experimental rates and the IMMA depth profiles obtained when 18 O-labeled water is used. The predictions are excellent for the pressure dependence of the rates, the activation energies for both the oxygen-poisoned and oxygen-free reactions, the absolute rates for the oxygen-poisoned case, and the IMMA depth profiles. The prediction of the absolute rate for the oxygen-free case is only within a factor of five due to the approximations made for the thermodynamics of the product layer that fixes the oxygen activity. Comparison of the model to experimental data for other metal-oxidation systems such as iron, silicon, copper, zirconium with oxygen, and thorium with water, is also presented to lend credibility to the modeling technique

Nicotinamide-NAD sequence: redox process and related behavior, behavior and properties of intermediate and final products

International Nuclear Information System (INIS)

Elving, P.J.; Schmakel, C.O.; Santhanam, K.S.V.

1976-01-01

Illustrations of the application of analytical chemical techniques to the study of chemical phenomena are given. In particular, electrochemical techniques and methodology and, to a lesser extent, spectrophotometry were used to investigate the solution behavior, adsorption, redox processes including coupled chemical reactions, and allied aspects of biologically significant compounds and of their intermediate and final redox products, e.g., the behavior of the free radicals produced by initial one-electron processes. This approach is illustrated by the consideration of the behavior in aqueous and nonaqueous media of a sequence of compounds ranging from nicotinamide (3-carbamoylpyridine) to NAD + and NADP + ; the latter compounds function as coenzymes for the pyridinoproteins which are principal components in the Krebs citric acid cycle and in the electron transport chain in biological redox reactions. The discussion is presented under the following section headings: interpretation of electrochemical behavior; mechanistic patterns; kinetic aspects of charge-transfer and chemical reactions; correlation with theoretically calculated parameters; and, mechanisms of biological oxidation-reduction reactions. The use of pulse radiolysis, chronopotentiometric, and cyclic voltammetric methods in studies on free radical dimerization rates is reviewed in the discussion of the kinetic aspects of charge-transfer and chemical reactions. (188 references)

Study of shell evolution around the doubly magic $^{208}$Pb via a multinucleon transfer reaction with an unstable beam

CERN Multimedia

This proposal aims at the study of the neutron-rich region around the doubly-magic nucleus $^{208}$Pb populated via a multinucleon transfer reaction. An unstable $^{94}$Rb beam will be delivered by HIE-ISOLDE at 5.5 MeV$\\cdot$u onto a $^{208}$Pb 13.0 mg/cm$^{2}$ target. The $\\gamma$- rays will be recorded by the MINIBALL $\\gamma$-ray spectrometer. The aim of the experiment is twofold: \\\\ \\\\ i) firstly it will represent the proof of principle that multinucleon transfer reactions with neutron-rich unstable beams is efficient to populate neutron-rich heavy binary partners and represents a competitive method to cold fragmentation \\\\ ii) secondly we aim at populating medium- to high-spin states in $^{212;214}$Pb and $^{208;210}$Hg to elucidate the existence of the 16$^{+}$ isomer in the lead isotopes and at the same time to disentangle the puzzling case of a very low energy 3$^{-}$ state in $^{210}$Hg not described by any nuclear model. \\\\ \\\\ The experimental results will be compared with large-scale shell-model ...

Humidity independent mass spectrometry for gas phase chemical analysis via ambient proton transfer reaction.

Science.gov (United States)

Zhu, Hongying; Huang, Guangming

2015-03-31

In this work, a humidity independent mass spectrometric method was developed for rapid analysis of gas phase chemicals. This method is based upon ambient proton transfer reaction between gas phase chemicals and charged water droplets, in a reaction chamber with nearly saturate humidity under atmospheric pressure. The humidity independent nature enables direct and rapid analysis of raw gas phase samples, avoiding time- and sample-consuming sample pretreatments in conventional mass spectrometry methods to control sample humidity. Acetone, benzene, toluene, ethylbenzene and meta-xylene were used to evaluate the analytical performance of present method. The limits of detection for benzene, toluene, ethylbenzene and meta-xylene are in the range of ∼0.1 to ∼0.3 ppbV; that of benzene is well below the present European Union permissible exposure limit for benzene vapor (5 μg m(-3), ∼1.44 ppbV), with linear ranges of approximately two orders of magnitude. The majority of the homemade device contains a stainless steel tube as reaction chamber and an ultrasonic humidifier as the source of charged water droplets, which makes this cheap device easy to assemble and facile to operate. In addition, potential application of this method was illustrated by the real time identification of raw gas phase chemicals released from plants at different physiological stages. Copyright © 2015 Elsevier B.V. All rights reserved.

Transient Exciplex Formation Electron Transfer Mechanism

Directory of Open Access Journals (Sweden)

Michael G. Kuzmin

2011-01-01

Full Text Available Transient exciplex formation mechanism of excited-state electron transfer reactions is analyzed in terms of experimental data on thermodynamics and kinetics of exciplex formation and decay. Experimental profiles of free energy, enthalpy, and entropy for transient exciplex formation and decay are considered for several electron transfer reactions in various solvents. Strong electronic coupling in contact pairs of reactants causes substantial decrease of activation energy relative to that for conventional long-range ET mechanism, especially for endergonic reactions, and provides the possibility for medium reorganization concatenated to gradual charge shift in contrast to conventional preliminary medium and reactants reorganization. Experimental criteria for transient exciplex formation (concatenated mechanism of excited-state electron transfer are considered. Available experimental data show that this mechanism dominates for endergonic ET reactions and provides a natural explanation for a lot of known paradoxes of ET reactions.

Bis(pentamethylcyclopentadienyl) ytterbium: Electron-transfer reactions with organotransition metal complexes

Energy Technology Data Exchange (ETDEWEB)

Matsunaga, P.T.

1991-11-01

The divalent lanthanide complex, (Me{sub 5}C{sub 5}){sub 2}Yb, reacts with methylcopper to produce the base-free, ytterbium-methyl complex, (Me{sub 5}C{sub 5}){sub 2}YbMe. This product forms a asymmetric, methyl-bridged dimer in the solid state. The bulky alkyl complex, (Me{sub 5}C{sub 5}){sub 2}YbCH(SiMe{sub 3}){sub 2}, displays similar chemistry to (Me{sub 5}C{sub 5}){sub 2}YbMe, but at a reduced reaction rate due to the limited accessibility of the metal in (Me{sub 5}C{sub 5}){sub 2}YbCH(SiMe{sub 3}){sub 2}. Copper and silver halide salts react with (Me{sub 5}C{sub 5}){sub 2}V to produce the trivalent halide derivatives, (Me{sub 5}C{sub 5}){sub 2}VX (X + F, Cl, Br, I). The chloride complex, (Me{sub 5}C{sub 5}){sub 2}VCl, reacts with lithium reagents to form the phenyl and borohydride species. Nitrous oxide transfers an oxygen atom to (Me{sub 5}C{sub 5}){sub 2}V producing the vanadium-oxo complex, (Me{sub 5}Ce{sub 5}){sub 2}VO. The trivalent titanium species, (Me{sub 5}C{sub 5}){sub 2}TiX (X = Cl, Br, Me, BH{sub 4}), form bimetallic coordination complexes with (Me{sub 5}C{sub 5}){sub 2}Yb. The magnetic behavior of the products indicates that electron transfer has not occurred. The solid state structures of the chloride and bromide complexes show unusual bend angles for the halide bridges between ytterbium and titanium. A model based on frontier orbital theory has been proposed to account for the bending behavior in these species. The bimetallic methyl complex contains a linear methyl bridge between ytterbium and titanium.

Single-particle states in neutron-rich 69,71Cu by means of the (d,3He) transfer reaction

International Nuclear Information System (INIS)

Morfouace, Pierre

2014-01-01

In two (d, 3 He) transfer reactions with MUST2 at GANIL and the split-pole at Orsay, we have determined the position of the proton-hole states in the neutron-rich 71 Cu (N=42) and 69 Cu (N=40) isotopes. We have found that in 71 Cu the hole strength of the f7/2 orbital lies at higher excitation energies than expected. From beta-decay and laser spectroscopy, the f5/2 first excited particle state in these isotopes was known to come down rapidly in energy when passing N=40 and even become the ground state in 75 Cu. This sudden energy shift has been explained in a number of theoretical works. The prediction for the f7/2 spin-orbit partner was that it would change in energy too through a related effect. Experimentally, the f7/2 proton-hole state is not known for N≥40. In 71 Cu two 7/2- states around 1 MeV are candidates to be a proton-hole. The experiment at GANIL took place in March 2011. A secondary beam of 72 Zn at 38 AMeV was produced by fragmentation and purified through the LISE spectrometer. The transfer reaction in inverse kinematics was studied with the MUST2 detectors plus four 20 micrometer silicon detector to identified the 3 He of low kinetic energy. The excitation spectrum of 71 Cu was reconstruct thanks to the missing mass method and the angular distributions were extracted and compared with a reaction model using the DWUCK4 and DWUCK5 code. From this work no states have been populated around 1 MeV concluding that the centroid of the f7/2 lies at higher excitation energy. We then remeasured the single-particle strength in 69 Cu in the corresponding (d, 3 He) reaction at Orsay in March 2013 in order to extend the existing data where 60% of the f7/2 strength is missing and make sure that there is a consistent analysis of spectroscopic factors between both isotopes in order to well understood and well quantify the evolution of the f7/2 orbital when we start filling the g9/2 orbital. In this second experiment we have performed the reaction in direct

Furfural to Furfuryl Alcohol: Computational Study of the Hydrogen Transfer on Lewis Acidic BEA Zeolites and Effects of Cation Exchange and Tetravalent Metal Substitution.

Science.gov (United States)

Prasertsab, Anittha; Maihom, Thana; Probst, Michael; Wattanakit, Chularat; Limtrakul, Jumras

2018-06-04

The hydrogen transfer of furfural to furfuryl alcohol with i-propanol as the hydrogen source over cation-exchanged Lewis acidic BEA zeolite has been investigated by means of density functional calculations. The reaction proceeds in three steps. First the O-H bond of i-propanol is broken to form a propoxide intermediate. After that, the furylmethoxy intermediate is formed via hydrogen transfer process, and finally furylmethoxy abstracts the proton to form the furfuryl alcohol product. The second step is rate-determining by requiring the highest activation energy (23.8 kcal/mol) if the reaction takes place on Li-Sn-BEA zeolite. We find that the catalytic activity of various cation-exchanged Sn-BEA zeolites is in the order Li-Sn-BEA > Na-Sn-BEA > K-Sn-BEA. The lower activation energy for Li-Sn-BEA compared to Na-Sn-BEA and K-Sn-BEA can be explained by the larger charge transfer from the carbonyl bond to the catalyst, leading to its activation and to the attraction of the hydrogen being transferred. The larger charge transfer in turn is due to the smaller gap between the energies of furfural HOMO and the zeolite LUMO in Li-Sn-BEA, compared to both Na-Sn-BEA and K-Sn-BEA. In a similar way, we also compare the catalytic activity of tetravalent metal centers (Sn, Zr, and Hf) substituted into BEA and find in the order Zr ≥ Hf > Sn, based on activation energies. Finally we investigate statistically which property of the reactants is a suitable descriptor for an approximative prediction of the reaction rate in order to be able to quickly screen promising catalytic materials for this reaction.

Energy transfers between N_2(A"3Σ) nitrogen metastable molecules and oxygen atoms and molecules

International Nuclear Information System (INIS)

De Souza, Antonio Rogerio

1985-01-01

This research thesis aims at determining reaction coefficients for energy transfers between nitrogen in its metastable status and oxygen atoms and molecules, the variation of these coefficients with respect to temperature (mainly in the 200-400 K range), products formed and more particularly branching rates of O("1S) oxygen and of NO_2. Reaction coefficients are experimentally determined by using the technique of post-discharge in flow. The experimental set-up is described and the study of the best operating conditions is reported. In the next part, the author reports the study of the energy transfer between nitrogen in its metastable status N_2(A) and oxygen molecules. Reaction coefficients are determined for the first three vibrational levels. The author then reports the study of the transfer of N_2(A) molecules on oxygen atoms in their fundamental status. Reactions coefficients and their variations are determined for the three first vibrational levels. The author describes the dissociation method and the method of detection of atomic oxygen. A kinetic model is proposed for the analysis of formed products during a post-discharge in flow, and the branching rate for the formation of O("1S) oxygen between 190 and 365 K is determined. The author finally discusses publications on the role of these reactions in the interpretation of some atmospheric phenomena

Investigation of Na-CO2 Reaction with Initial Reaction in Various Reacting Surface

International Nuclear Information System (INIS)

Kim, Hyun Su; Park, Gunyeop; Kim, Soo Jae; Park, Hyun Sun; Kim, Moo Hwan; Wi, Myung-Hwan

2015-01-01

The reaction products that cause oxidation and erosion are threaten the heat transfer tubes so that it is necessary to investigate Na-CO 2 reaction according to various experimental parameter. Unlike SWR, Na-CO 2 reaction is more complex to deal with reaction kinetics. Since a comprehensive understanding of Na-CO 2 reaction mechanism is crucial for the safety analysis, the reaction phenomenon under the various conditions was investigated. The current issue is to make a database for developing computational code for CO 2 gas leak situation because it is experimentally difficult to analyze the actual accident situation. Most studies on Na-CO 2 interaction reports that chemical reaction is getting vigorous as temperature increased and reactivity is sensitive as temperature change between 400 .deg. C and 600 .deg. C. Therefore, temperature range is determined based on the operating condition (450 - 500 .deg. C) of KALIMER-600 employed as supercritical CO 2 brayton cycle energy conversion system for Na-CO 2 heat exchanger. And next parameter is sodium surface area which contact between sodium and CO 2 when CO 2 is injected into sodium pool in the accident situation. So, the fundamental surface reaction is experimentally studied in the range of 8 - 12cm 2 . Additionally, it has been reported in recent years that CO 2 Flow rate affects reactivity less significantly and CO 2 flow rate is assumed that 5 SLPM (standard liter per minute) is suitable as a basis for a small leakage. The finally selected control parameters is sodium temperature and reacting surface area with constant CO 2 flow rate. Na-CO 2 reaction test is performed for investigating risk of potential accident which contacts with liquid sodium and CO 2 . Amount of reaction is saturated as time passed because of kept a balance between production of solid phase reaction products and amount of diffusivity. These results contribute to make a database for the SFR safety analysis and additional experiments are needed

Identification of mechanisms in heavy ion reactions by measurement of angular correlations

International Nuclear Information System (INIS)

Carlin Filho, N.

1987-01-01

The identification of reaction mechanisms in light heavy-ion collisions has been performed within the framework of the three body kinematics, by means of angular correlation measurements. The 16 O+ 27 Al, 16 +O+ 28 Si and 10 B+ 27 Al reactions were investigated at Laboratory bombarding energies of 64 MeV, 64 and 48 MeV, respectively. Contributions of transfer-reemission and projectile sequential decay mechanisms were identified by the analysis of the relative kinetic energy of the final state components, excitation energies of the system at the intermediate stages, and also by means of fits to theoretical predictions for the angular correlations. (author) [pt

Cornish heat transfer experiment - final report

International Nuclear Information System (INIS)

Bourke, P.J.; Hodgkinson, D.P.

1985-01-01

The transfer of heat released in an in-site heating experiment simulating high level radioactive waste packages in granite in Cornwall has been found to be mainly by conduction but some appreciable convection does occur. Interim analysis of the data suggests that the latter may account for about 20% of the total. (author)

Five-nucleon simultaneous and sequential transfer in the 12C(11B,6Li)17O and 12C(d,7Li)7Be reactions

International Nuclear Information System (INIS)

Jarczyk, L.; Kamys, B.; Kistryn, M.; Magiera, A.; Rudy, Z.; Strzal/kowski, A.; Barna, R.; DAmico, V.; De Pasquale, D.; Italiano, A.; Licandro, M.

1996-01-01

Measurements of the angular distributions of the 12 C( 11 B, 6 Li) 17 O reaction were performed at three energies of a 11 B beam: 28, 35, and 40 MeV. The results were analyzed in the frame of the exact finite range distorted wave Born approximation of the first and the second order assuming the simultaneous and sequential transfer of the neutron and the α particle. Such an analysis was also performed for previously measured angular distributions of the 12 C(d, 7 Li) 7 Be reaction at E lab = 78 MeV. In both reactions under investigation dominance was found of the simultaneous transfer of the α particle and the nucleon correlated to the 5 He ( 5 Li) cluster in the ground or the first excited state. copyright 1996 The American Physical Society

The lithiation and acyl transfer reactions of phosphine oxides, sulfides and boranes in the synthesis of cyclopropanes

DEFF Research Database (Denmark)

Clarke, Celia; Fox, David J; Pedersen, Daniel Sejer

2009-01-01

Phosphine oxides are lithiated much faster than phosphine sulfides and phosphine boranes. Phosphine sulfides are in turn lithiated much more readily than phosphine boranes. It was possible to trap a phosphine sulfide THF in one case which upon treatment with t-BuOK gave cyclopropane, showing...... that phosphine sulfides readily undergo both phosphinoyl transfer and cyclopropane ring closure just like their phosphine oxide counterparts. The obtained data show that phosphine oxides are easily lithiated and undergo phosphoryl transfer much more readily and faster than phosphine sulfides and phosphine...... boranes. The observations suggest that it would be possible to perform reactions involving phosphine oxides in the presence of phosphine boranes or phosphine sulfides, potentially allowing regioselective alkylation of phosphine oxides in the presence of phosphine boranes or phosphine sulfides....

Low energy cross section data for ion-molecule reactions in hydrogen systems and for charge transfer of multiply charged ions with atoms and molecules

International Nuclear Information System (INIS)

Okuno, Kazuhiko

2007-04-01

Systematic cross section measurements for ion-molecule reactions in hydrogen systems and for charge transfer of multiply charged ions in low energy collisions with atoms and molecules have been performed continuously by the identical apparatus installed with an octo-pole ion beam guide (OPIG) since 1980 till 2004. Recently, all of accumulated cross section data for a hundred collision systems has been entered into CMOL and CHART of the NIFS atomic and molecular numerical database together with some related cross section data. In this present paper, complicated ion-molecule reactions in hydrogen systems are revealed and the brief outlines of specific properties in low energy charge transfer collisions of multiply charged ions with atoms and molecules are introduced. (author)

LiHe{sup +} IN THE EARLY UNIVERSE: A FULL ASSESSMENT OF ITS REACTION NETWORK AND FINAL ABUNDANCES

Energy Technology Data Exchange (ETDEWEB)

Bovino, Stefano; Tacconi, Mario; Gianturco, Francesco A. [Department of Chemistry, Universita degli Studi di Roma ' La Sapienza' , Piazzale A. Moro 5, 00185 Roma (Italy); Curik, Roman [J. Heyrovsky Institute of Physical Chemistry, Dolejskova 3, Prague (Czech Republic); Galli, Daniele, E-mail: fa.gianturco@caspur.it [INAF-Osservatorio Astrofisico di Arcetri, Largo E. Fermi 5, 50125 Firenze (Italy)

2012-06-10

We present the results of quantum calculations based on entirely ab initio methods for a variety of molecular processes and chemical reactions involving the LiHe{sup +} ionic polar molecule. With the aid of these calculations, we derive accurate reaction rates and fitting expressions valid over a range of gas temperatures representative of the typical conditions of the pregalactic gas. With the help of a full chemical network, we then compute the evolution of the abundance of LiHe{sup +} as function of redshift in the early universe. Finally, we compare the relative abundance of LiHe{sup +} with that of other polar cations formed in the same redshift interval.

Symmetric charge transfer cross section of uranium

International Nuclear Information System (INIS)

Shibata, Takemasa; Ogura, Koichi

1995-03-01

Symmetric charge transfer cross section of uranium was calculated under consideration of reaction paths. In the charge transfer reaction a d 3/2 electron in the U atom transfers into the d-electron site of U + ( 4 I 9/2 ) ion. The J value of the U atom produced after the reaction is 6, 5, 4 or 3, at impact energy below several tens eV, only resonant charge transfer in which the product atom is ground state (J=6) takes place. Therefore, the cross section is very small (4-5 x 10 -15 cm 2 ) compared with that considered so far. In the energy range of 100-1000eV the cross section increases with the impact energy because near resonant charge transfer in which an s-electron in the U atom transfers into the d-electron site of U + ion. Charge transfer cross section between U + in the first excited state (289 cm -1 ) and U in the ground state was also obtained. (author)

MHD Heat and Mass Transfer of Chemical Reaction Fluid Flow over a Moving Vertical Plate in Presence of Heat Source with Convective Surface Boundary Condition

Directory of Open Access Journals (Sweden)

B. R. Rout

2013-01-01

Full Text Available This paper aims to investigate the influence of chemical reaction and the combined effects of internal heat generation and a convective boundary condition on the laminar boundary layer MHD heat and mass transfer flow over a moving vertical flat plate. The lower surface of the plate is in contact with a hot fluid while the stream of cold fluid flows over the upper surface with heat source and chemical reaction. The basic equations governing the flow, heat transfer, and concentration are reduced to a set of ordinary differential equations by using appropriate transformation for variables and solved numerically by Runge-Kutta fourth-order integration scheme in association with shooting method. The effects of physical parameters on the velocity, temperature, and concentration profiles are illustrated graphically. A table recording the values of skin friction, heat transfer, and mass transfer at the plate is also presented. The discussion focuses on the physical interpretation of the results as well as their comparison with previous studies which shows good agreement as a special case of the problem.

Quenching reactions of electronically excited atoms

International Nuclear Information System (INIS)

Setser, D.W.

2001-01-01

The two-body, thermal quenching reactions of electronically excited atoms are reviewed using excited states of Ar, Kr, and Xe atoms as examples. State-specific interstate relaxation and excitation-transfer reactions with atomic colliders are discussed first. These results then are used to discuss quenching reactions of excited-state atoms with diatomic and polyatomic molecules, the latter have large cross sections, and the reactions can proceed by excitation transfer and by reactive quenching. Excited states of molecules are not considered; however, a table of quenching rate constants is given for six excited-state molecules in an appendix

Advances in electron transfer chemistry

CERN Document Server

Mariano, Patrick S

1995-01-01

Advances in Electron Transfer Chemistry, Volume 4 presents the reaction mechanisms involving the movement of single electrons. This book discusses the electron transfer reactions in organic, biochemical, organometallic, and excited state systems. Organized into four chapters, this volume begins with an overview of the photochemical behavior of two classes of sulfonium salt derivatives. This text then examines the parameters that control the efficiencies for radical ion pair formation. Other chapters consider the progress in the development of parameters that control the dynamics and reaction p

Polarization transfer in the 3H(rvec p,rvec n)3He reaction and the 0- level in 4He

International Nuclear Information System (INIS)

Walston, J.R.; Gould, C.R.; Haase, D.G.; Raichle, B.W.; Seely, M.L.; Walston, J.R.; Keith, C.D.; Gould, C.R.; Haase, D.G.; Raichle, B.W.; Seely, M.L.; Tornow, W.; Wilburn, W.S.; Keith, C.D.; Tornow, W.; Wilburn, W.S.; Hoffmann, G.W.; Penttilae, S.I.

1998-01-01

Longitudinal polarization-transfer coefficients for the 3 H(rvec p,rvec n) 3 He reaction have been measured at zero degrees for proton energies of 1.3 endash 2.8 MeV. The results show a striking resonance behavior for energies corresponding to excitation of the 0 - level in 4 He at 21.0 MeV. In agreement with R-matrix calculations, the value approaches unity at 1.52 MeV, the peak of the resonance. Near this same energy, at 1.62 MeV, the transverse polarization-transfer coefficient was measured to be consistent with zero. copyright 1998 The American Physical Society

Handbook of heat and mass transfer. Volume 2

International Nuclear Information System (INIS)

Cheremisinoff, N.P.

1986-01-01

This two-volume series, the work of more than 100 contributors, presents advanced topics in industrial heat and mass transfer operations and reactor design technology. Volume 2 emphasizes mass transfer and reactor design. Some of the contents discussed are: MASS TRANSFER PRINCIPLES - Effect of turbulence promoters on mass transfer. Mass transfer principles with homogeneous and heterogeneous reactions. Convective diffusion with reactions in a tube. Transient mass transfer onto small particles and drops. Modeling heat and mass transport in falling liquid films. Heat and mass transfer in film absorption. Multicomponent mass transfer: theory and applications. Diffusion limitation for reaction in porous catalysts. Kinetics and mechanisms of catalytic deactivation. DISTILLATION AND EXTRACTION - Generalized equations of state for process design. Mixture boiling. Estimating vapor pressure from normal boiling points of hydrocarbons. Estimating liquid and vapor molar fractions in distillation columns. Principles of multicomponent distillation. Generalized design methods for multicomponent distillation. Interfacial films in inorganic substances extraction. Liquid-liquid extraction in suspended slugs. MULTIPHASE REACTOR SYSTEMS - Reaction and mass transport in two-phase reactors. Mass transfer and kinetics in three-phase reactors. Estimating liquid film mass transfer coefficients in randomly packed columns. Designing packed tower wet scrubbers - emphasis on nitrogen oxides. Gas absorption in aerated mixers. Axial dispersion and heat transfer in gas-liquid bubble columns. Operation and design of trickle-bed reactors

Ion-molecule reactions: their role in radiation chemistry

International Nuclear Information System (INIS)

Lias, S.G.; Ausloos, P.

1975-01-01

A comprehensive review of ion--molecule reactions is presented, including information from mass spectrometric, organic chemistry, and NMR studies, from theoretical calculations, and from gas and liquid phase radiation chemistry. Special emphasis is placed on interpreting the role of ion--molecule reactions in systems under high energy irradiation. The discussion is presented under the following chapter headings: ion--molecule reactions and their role in radiation chemistry; unimolecular processes: the nature and structure of ionic intermediates in radiolysis; ion lifetimes and the fate of unreactive ions; kinetics and mechanisms of ion--molecule reactions; proton transfer reactions; negative atom and two-atom transfer reactions; condensation reactions; and, association or clustering reactions

Intramolecular Energy Transfer, Charge Transfer & Hydrogen Bond

Indian Academy of Sciences (India)

Ultrafast Dynamics of Chemical Reactions in Condensed Phase: Intramolecular Energy Transfer, Charge Transfer & Hydrogen Bond · PowerPoint Presentation · Slide 3 · Slide 4 · Slide 5 · Slide 6 · Slide 7 · Slide 8 · Slide 9 · Slide 10 · Slide 11 · Slide 12 · Slide 13 · Slide 14 · Slide 15 · Slide 16 · Slide 17 · Slide 18 · Slide 19.

Study of one-nucleon transfer reactions with polarized deuterons of 20 MeV

International Nuclear Information System (INIS)

Seichert, N.

1983-01-01

In this thesis the results of the study of (d vector,p), (d vector,t), and (d vector, 3 He) reactions at Esub(d)approx.=20 MeV on the target nuclei 16 O, 18 O, 28 Si, 36 Ar, 40 Ca, 48 Ca, 54 Cr, 65 Cu, 90 Zr, 144 Sm, and 208 Pb in the framework of a DWBA analysis are presented. The collection of the results of the analysis over this wide mass range shall permit a survey, how well the conventional DWBA describes the measured angular distributions of dsigma/dΩ(theta) and iT 11 (theta). Furthermore in justified cases the contribution of higher order processes (inelastic transfer) are studied by means of a CCBA analysis. The spectroscopical possibilities given by the measurement of the analyzing power iT 11 (theta) are presented in detail on the example of the reaction 144 Sm (d vector,p) 145 Sm. The analysis of the tensor analyzing power T 21 (theta) in the framework of a finite range DWBA in the last part of the thesis permits quantitative statements about the D state amplitude in the relative wave function of the deuteron, the triton, and of 3 He. (orig./HSI) [de

Curly arrows meet electron density transfers in chemical reaction mechanisms: from electron localization function (ELF) analysis to valence-shell electron-pair repulsion (VSEPR) inspired interpretation.

Science.gov (United States)

Andrés, Juan; Berski, Sławomir; Silvi, Bernard

2016-07-07

Probing the electron density transfers during a chemical reaction can provide important insights, making possible to understand and control chemical reactions. This aim has required extensions of the relationships between the traditional chemical concepts and the quantum mechanical ones. The present work examines the detailed chemical insights that have been generated through 100 years of work worldwide on G. N. Lewis's ground breaking paper on The Atom and the Molecule (Lewis, G. N. The Atom and the Molecule, J. Am. Chem. Soc. 1916, 38, 762-785), with a focus on how the determination of reaction mechanisms can be reached applying the bonding evolution theory (BET), emphasizing how curly arrows meet electron density transfers in chemical reaction mechanisms and how the Lewis structure can be recovered. BET that combines the topological analysis of the electron localization function (ELF) and Thom's catastrophe theory (CT) provides a powerful tool providing insight into molecular mechanisms of chemical rearrangements. In agreement with physical laws and quantum theoretical insights, BET can be considered as an appropriate tool to tackle chemical reactivity with a wide range of possible applications. Likewise, the present approach retrieves the classical curly arrows used to describe the rearrangements of chemical bonds for a given reaction mechanism, providing detailed physical grounds for this type of representation. The ideas underlying the valence-shell-electron pair-repulsion (VSEPR) model applied to non-equilibrium geometries provide simple chemical explanations of density transfers. For a given geometry around a central atom, the arrangement of the electronic domain may comply or not with the VSEPR rules according with the valence shell population of the considered atom. A deformation yields arrangements which are either VSEPR defective (at least a domain is missing to match the VSEPR arrangement corresponding to the geometry of the ligands), VSEPR compliant

Lettuce Allergy Is a Lipid Transfer Syndrome-Related Food Allergy With a High Risk of Severe Reactions.

Science.gov (United States)

Muñoz-García, E; Luengo-Sánchez, O; Moreno-Pérez, N; Cuesta-Herranz, J; Pastor-Vargas, C; Cardona, V

Lipid transfer protein (LTP) sensitization is the most common cause of food allergy in the Mediterranean area, with peach allergy acting as the primary sensitizer in most cases. Lettuce has been described as a common offending food in patients with LTP syndrome. The aim of the study was to investigate the frequency and clinical expression of LTP syndrome in a sample of lettuceallergic patients. We determined specific IgE to Pru p 3 and lettuce in a sample of 30 patients with a diagnosis of lettuce allergy. Symptoms elicited by other LTP-containing plant-derived foods and the presence of cofactors were assessed. The clinical symptoms of lettuce allergy were frequently severe, with 18 of the 30 patients experiencing anaphylaxis. All the patients had allergic reactions to other plant foods. Cofactors were involved in the clinical reactions of 13 of the 30 patients. Sensitization to pollens was found in 90% of patients. Lettuce allergy is found not as an isolated condition but in the context of LTP syndrome and it is characterized by severe reactions and frequent cofactor association.

Electron transfer reactions in microporous solids. Progress report, September 1990--January 1993

Energy Technology Data Exchange (ETDEWEB)

Mallouk, T.E.

1993-01-01

Basic thrust the research program involves use of microporous solids (zeolites, clays, layered and tunnel structure oxide semiconductors) as organizing media for artificial photosynthetic systems. Purpose of the microporous solid is twofold. First, it induces spatial organization of photoactive and electroactive components (sensitizers, semiconductor particles, electron relays, and catalysts) at the solid-solution interface, enhancing the quantum efficiency of charge separation and separating physically the ultimate electron donor and acceptor in the electron transport chain. Second, since the microcrystalline solid admits only molecules of a certain charge and size, it is possible to achieve permanent charge separation by sieving chemical photoproducts (e.g., H{sub 2} and I{sub 3}{sup {minus}}, or H{sub 2} and O{sub 2)} from each other. Spectroscopic and electrochemical methods are used to study the kinetics of electron transfer reactions in these hybrid molecular/solid state assemblies.

On the intramolecular proton transfer of 3-hydroxyflavone in the first singlet excited state: A theoretical study

International Nuclear Information System (INIS)

Casadesus, Ricard; Vendrell, Oriol; Moreno, Miquel; Lluch, Jose M.; Morokuma, Keiji

2006-01-01

The intramolecular proton-transfer reaction in 3-hydroxyflavone (3HF) is theoretically studied both in the ground (S 0 ) and first singlet excited (S 1 ) electronic states. In S 0 the proton-transfer reaction is shown to be quite unfavorable at the DFT (B3LYP) level. However, the back proton transfer is found to be a feasible process with a small energy barrier, both results being in qualitative agreement with known experimental facts. Different theoretical levels are considered and compared for S 1 . The ab initio configuration interaction singles (CIS) method overestimates the energy of S 1 and give too high energy barriers for the proton-transfer reaction. The complete active space SCF (CASSCF) method gives a more reasonable value but the inclusion of the dynamical correlation through second-order perturbation theory (CASPT2) upon CASSCF geometries or the use of the time-dependent DFT (TDDFT) method upon CIS geometries gives a barrierless process. Optimization of geometries (minima and transition-state structures) at the TDDFT level leads to a small but non-negligible energy barrier for the proton-transfer reaction in S 1 and global energies that fit quite well with the known experimental (spectroscopic and femtochemistry) data. Finally the effect of a polar environment is analyzed through a continuum model, which gives only a small difference from the previous gas-phase results. This points out that the remarkable changes in the photochemistry of 3HF observed experimentally are not to be solely attributed to the polarity of the surrounding media

On the intramolecular proton transfer of 3-hydroxyflavone in the first singlet excited state: A theoretical study

Energy Technology Data Exchange (ETDEWEB)

Casadesus, Ricard [Departament de Quimica, Universitat Autonoma de Barcelona, 08193 Bellaterra, Barcelona (Spain); Cherry L. Emerson Center for Scientific Computation and Department of Chemistry, Emory University, Atlanta, GA 30322 (United States); Vendrell, Oriol [Departament de Quimica, Universitat Autonoma de Barcelona, 08193 Bellaterra, Barcelona (Spain); Moreno, Miquel [Departament de Quimica, Universitat Autonoma de Barcelona, 08193 Bellaterra, Barcelona (Spain)], E-mail: mmf@klingon.uab.es; Lluch, Jose M. [Departament de Quimica, Universitat Autonoma de Barcelona, 08193 Bellaterra, Barcelona (Spain); Morokuma, Keiji [Cherry L. Emerson Center for Scientific Computation and Department of Chemistry, Emory University, Atlanta, GA 30322 (United States)

2006-06-20

The intramolecular proton-transfer reaction in 3-hydroxyflavone (3HF) is theoretically studied both in the ground (S{sub 0}) and first singlet excited (S{sub 1}) electronic states. In S{sub 0} the proton-transfer reaction is shown to be quite unfavorable at the DFT (B3LYP) level. However, the back proton transfer is found to be a feasible process with a small energy barrier, both results being in qualitative agreement with known experimental facts. Different theoretical levels are considered and compared for S{sub 1}. The ab initio configuration interaction singles (CIS) method overestimates the energy of S{sub 1} and give too high energy barriers for the proton-transfer reaction. The complete active space SCF (CASSCF) method gives a more reasonable value but the inclusion of the dynamical correlation through second-order perturbation theory (CASPT2) upon CASSCF geometries or the use of the time-dependent DFT (TDDFT) method upon CIS geometries gives a barrierless process. Optimization of geometries (minima and transition-state structures) at the TDDFT level leads to a small but non-negligible energy barrier for the proton-transfer reaction in S{sub 1} and global energies that fit quite well with the known experimental (spectroscopic and femtochemistry) data. Finally the effect of a polar environment is analyzed through a continuum model, which gives only a small difference from the previous gas-phase results. This points out that the remarkable changes in the photochemistry of 3HF observed experimentally are not to be solely attributed to the polarity of the surrounding media.

Reaction channels of 6,7Li+28Si at near-barrier energies

International Nuclear Information System (INIS)

Pakou, A; Rusek, K; Nicolis, N G; Alamanos, N; Doukelis, G; Gillibert, A; Kalyva, G; Kokkoris, M; Lagoyannis, A; Musumarra, A; Papachristodoulou, C; Perdikakis, G; Pierroutsakou, D; Pollacco, E C; Spyrou, A; Zarkadas, Ch

2005-01-01

The production of α-particles in the reactions 6,7 Li+ 28 Si was studied as a means to disentangle the various reaction channels at near-barrier energies. The competition between compound and direct reactions was determined by using the shape of angular distributions and statistical model calculations. DWBA calculations were also performed to probe the various direct channels. It was found that, approaching barrier, transfer channels are the most dominant for both reactions. For 7 Li+ 28 Si d-transfer is one of the contributing channels without excluding t-transfer, while for 6 Li+ 28 Si, n-transfer and p-transfer have substantial contribution but without excluding d-transfer

Energy transfer in structured and unstructured environments: Master equations beyond the Born-Markov approximations

Energy Technology Data Exchange (ETDEWEB)

Iles-Smith, Jake, E-mail: Jakeilessmith@gmail.com [Controlled Quantum Dynamics Theory, Imperial College London, London SW7 2PG (United Kingdom); Photon Science Institute and School of Physics and Astronomy, The University of Manchester, Oxford Road, Manchester M13 9PL (United Kingdom); Department of Photonics Engineering, DTU Fotonik, Ørsteds Plads, 2800 Kongens Lyngby (Denmark); Dijkstra, Arend G. [Max Planck Institute for the Structure and Dynamics of Matter, Luruper Chaussee 149, 22761 Hamburg (Germany); Lambert, Neill [CEMS, RIKEN, Saitama 351-0198 (Japan); Nazir, Ahsan, E-mail: ahsan.nazir@manchester.ac.uk [Photon Science Institute and School of Physics and Astronomy, The University of Manchester, Oxford Road, Manchester M13 9PL (United Kingdom)

2016-01-28

We explore excitonic energy transfer dynamics in a molecular dimer system coupled to both structured and unstructured oscillator environments. By extending the reaction coordinate master equation technique developed by Iles-Smith et al. [Phys. Rev. A 90, 032114 (2014)], we go beyond the commonly used Born-Markov approximations to incorporate system-environment correlations and the resultant non-Markovian dynamical effects. We obtain energy transfer dynamics for both underdamped and overdamped oscillator environments that are in perfect agreement with the numerical hierarchical equations of motion over a wide range of parameters. Furthermore, we show that the Zusman equations, which may be obtained in a semiclassical limit of the reaction coordinate model, are often incapable of describing the correct dynamical behaviour. This demonstrates the necessity of properly accounting for quantum correlations generated between the system and its environment when the Born-Markov approximations no longer hold. Finally, we apply the reaction coordinate formalism to the case of a structured environment comprising of both underdamped (i.e., sharply peaked) and overdamped (broad) components simultaneously. We find that though an enhancement of the dimer energy transfer rate can be obtained when compared to an unstructured environment, its magnitude is rather sensitive to both the dimer-peak resonance conditions and the relative strengths of the underdamped and overdamped contributions.

Fluorination reaction uranium dioxide by fluorine

International Nuclear Information System (INIS)

Ogata, Shinji; Homma, Shunji; Koga, Jiro; Matsumoto, Shiro; Sasahira, Akira; Kawamura, Fumio

2004-01-01

Kinetics of the fluorination reaction of uranium dioxide is studied using un-reacted core model with shrinking particles. The model includes the film mass transfer of fluorine gas and its diffusion in the particle. The rate constants of the model are determined by fitting the experimental data for 370-450degC. The model successfully represents the fluorination in this temperature range. The rate control step is identified by examining the rate constants of the model for 300-1,800degC. For temperature range up to 900degC, the fluorination reaction is rate controlling. For over 900degC, both mechanisms of the mass transfer of fluorine and the fluorination reaction control the rate of the fluorination. With further increase of the temperature, however, the fluorination reaction becomes so fast that the mass transfer of fluorine eventually controls the rate of the fluorination. (author)

Theoretical aspects of electron transfer reactions of complex molecules

DEFF Research Database (Denmark)

Kuznetsov, A. M.; Ulstrup, Jens

2001-01-01

Features of electron transfer involving complex molecules are discussed. This notion presently refers to molecular reactants where charge transfer is accompanied by large molecular reorganization, and commonly used displaced harmonic oscillator models do not apply. It is shown that comprehensive...... theory of charge transfer in polar media offers convenient tools for the treatment of experimental data for such systems, with due account of large-amplitude strongly anharmonic intramolecular reorganization. Equations for the activation barrier and free energy relationships are provided, incorporating...

Processing development for ceramic structural components: the influence of a presintering of silicon on the final properties of reaction bonded silicon nitride. Final technical report

Energy Technology Data Exchange (ETDEWEB)

1982-03-01

The influence of a presintering of silicon on the final properties of reaction bonded silicon nitride has been studied using scanning electron and optical microscopy, x-ray diffraction analysis, 4 pt. bend test, and mecury intrusion porosimetry. It has been shown that presintering at 1050/sup 0/C will not affect the final nitrided properties. At 1200/sup 0/C, the oxide layer is removed, promoting the formation of B-phase silicon nitride. Presintering at 1200/sup 0/C also results in compact weight loss due to the volatilization of silicon, and the formation of large pores which severely reduce nitrided strength. The development of the structure of sintered silicon compacts appears to involve a temperature gradient, with greater sintering observed near the surface.

Study of breakup and transfer of weakly bound nucleus 6Li to explore the low energy reaction dynamics

Directory of Open Access Journals (Sweden)

Zhang G. L.

2017-01-01

In order to have a proper understanding of the influence of breakup and transfer of weakly bound projectiles on the fusion process, we performed the 6Li+89Y experiment with incident energies of 22 MeV and 34 MeV on Galileo array in cooperation with Si-ball EUCLIDES at Legnaro National Laboratory (LNL in Italy. Using particle-particle and particle-γ coincidences, the different reaction mechanisms can be clearly explored.

75 FR 9120 - Electronic Fund Transfers

Science.gov (United States)

2010-03-01

... FEDERAL RESERVE SYSTEM 12 CFR Part 205 [Regulation E; Docket No. R-1343] Electronic Fund Transfers... implements the Electronic Fund Transfer Act, and the official staff commentary to the regulation. The final..., the Board adopted a final rule under Regulation E, which implements the Electronic Fund Transfer Act...

Method and apparatus for obtaining enhanced production rate of thermal chemical reactions

Science.gov (United States)

Tonkovich, Anna Lee Y [Pasco, WA; Wang, Yong [Richland, WA; Wegeng, Robert S [Richland, WA; Gao, Yufei [Kennewick, WA

2003-04-01

The present invention is a method and apparatus (vessel) for providing a heat transfer rate from a reaction chamber through a wall to a heat transfer chamber substantially matching a local heat transfer rate of a catalytic thermal chemical reaction. The key to the invention is a thermal distance defined on a cross sectional plane through the vessel inclusive of a heat transfer chamber, reaction chamber and a wall between the chambers. The cross sectional plane is perpendicular to a bulk flow direction of the reactant stream, and the thermal distance is a distance between a coolest position and a hottest position on the cross sectional plane. The thermal distance is of a length wherein the heat transfer rate from the reaction chamber to the heat transfer chamber substantially matches the local heat transfer rate.

Watching proton transfer in real time: Ultrafast photoionization-induced proton transfer in phenol-ammonia complex cation.

Science.gov (United States)

Shen, Ching-Chi; Tsai, Tsung-Ting; Wu, Jun-Yi; Ho, Jr-Wei; Chen, Yi-Wei; Cheng, Po-Yuan

2017-10-28

In this paper, we give a full account of our previous work [C. C. Shen et al., J. Chem. Phys. 141, 171103 (2014)] on the study of an ultrafast photoionization-induced proton transfer (PT) reaction in the phenol-ammonia (PhOH-NH 3 ) complex using ultrafast time-resolved ion photofragmentation spectroscopy implemented by the photoionization-photofragmentation pump-probe detection scheme. Neutral PhOH-NH 3 complexes prepared in a free jet are photoionized by femtosecond 1 + 1 resonance-enhanced multiphoton ionization via the S 1 state. The evolving cations are then probed by delayed pulses that result in ion fragmentation, and the ionic dynamics is followed by measuring the parent-ion depletion as a function of the pump-probe delay time. By comparing with systems in which PT is not feasible and the steady-state ion photofragmentation spectra, we concluded that the observed temporal evolutions of the transient ion photofragmentation spectra are consistent with an intracomplex PT reaction after photoionization from the initial non-PT to the final PT structures. Our experiments revealed that PT in [PhOH-NH 3 ] + cation proceeds in two distinct steps: an initial impulsive wave-packet motion in ∼70 fs followed by a slower relaxation of about 1 ps that stabilizes the system into the final PT configuration. These results indicate that for a barrierless PT system, even though the initial PT motions are impulsive and ultrafast, the time scale to complete the reaction can be much slower and is determined by the rate of energy dissipation into other modes.

New aspects of high energy heavy-ion transfer reactions

International Nuclear Information System (INIS)

Scott, D.K.

1975-03-01

New aspects of heavy ion reactions at incident energies in the region of 10 MeV/nucleon are discussed with an emphasis on the peripheral nature of the collisions, which leads to simplicities in the differential cross sections. The distortion of the peripheral distribution through the interference of direct and multistep processes is used to illustrate aspects of high energy reactions unique to heavy ions. The simplicities of the distributions for reactions on lighter nuclei are exploited to give new information about nuclear structure from direct and compound reactions at high energy. (16 figures, 32 references) (U.S.)

Domino reactions initiated by intramolecular hydride transfers from tri(di)arylmethane fragments to ketenimine and carbodiimide functions.

Science.gov (United States)

Alajarin, Mateo; Bonillo, Baltasar; Ortin, Maria-Mar; Sanchez-Andrada, Pilar; Vidal, Angel; Orenes, Raul-Angel

2010-10-21

The ability of triarylmethane and diarylmethane fragments to behave as hydride donors participating in thermal [1,5]-H shift/6π-ERC tandem processes involving ketenimine and carbodiimide functions is disclosed. C-Alkyl-C-phenyl ketenimines N-substituted by a triarylmethane substructure convert into a variety of 3,3,4,4-tetrasubstituted-3,4-dihydroquinolines, as structurally related carbodiimides transform into 3,4,4-trisubstituted-3,4-dihydroquinazolines via transient ortho-azaxylylenes. The first step of these one-pot conversions, the [1,5]-H shift, is considered to be a hydride migration on the basis of the known hydricity of the tri(di)arylmethane fragment and the electrophilicity of the central heterocumulenic carbon atom, whereas the final electrocyclization involves the formation of a sterically congested C-C or C-N bond. In the cases of C,C-diphenyl substituted triarylmethane-ketenimines the usual 6π-ERC becomes prohibited by the presence of two phenyl rings at each end of the azatrienic system. This situation opens new reaction channels: (a) following the initial hydride shift, the tandem sequence continues with an alternative electrocyclization mode to give 9,10-dihydroacridines, (b) the full sequence is initiated by a rare 1,5 migration of an electron-rich aryl group, followed by a 6π-ERC which leads to 2-aryl-3,4-dihydroquinolines, or (c) a different [1,5]-H shift/6π-ERC sequence involving the initial migration of a hydrogen atom from a methyl group at the ortho position to the nitrogen atom of the ketenimine function. Diarylmethane-ketenimines bearing a methyl group at the benzylic carbon atom experience a tandem double [1,5]-H shift, the first one being the usual benzylic hydride transfer whereas the second one involves the methyl group at the initial benzylic carbon atom, the reaction products being 2-aminostyrenes. Diarylmethane-ketenimines lacking such a methyl group convert into 3,4-dihydroquinolines by the habitual tandem [1,5]-H shift/6�

Quasi-steady-state voltammetry of rapid electron transfer reactions at the macroscopic substrate of the scanning electrochemical microscope.

Science.gov (United States)

Nioradze, Nikoloz; Kim, Jiyeon; Amemiya, Shigeru

2011-02-01

We report on a novel theory and experiment for scanning electrochemical microscopy (SECM) to enable quasi-steady-state voltammetry of rapid electron transfer (ET) reactions at macroscopic substrates. With this powerful approach, the substrate potential is cycled widely across the formal potential of a redox couple while the reactant or product of a substrate reaction is amperometrically detected at the tip in the feedback or substrate generation/tip collection mode, respectively. The plot of tip current versus substrate potential features the retraceable sigmoidal shape of a quasi-steady-state voltammogram although a transient voltammogram is obtained at the macroscopic substrate. Finite element simulations reveal that a short tip-substrate distance and a reversible substrate reaction (except under the tip) are required for quasi-steady-state voltammetry. Advantageously, a pair of quasi-steady-state voltammograms is obtained by employing both operation modes to reliably determine all transport, thermodynamic, and kinetic parameters as confirmed experimentally for rapid ET reactions of ferrocenemethanol and 7,7,8,8-tetracyanoquinodimethane at a Pt substrate with ∼0.5 μm-radius Pt tips positioned at 90 nm-1 μm distances. Standard ET rate constants of ∼7 cm/s were obtained for the latter mediator as the largest determined for a substrate reaction by SECM. Various potential applications of quasi-steady-state voltammetry are also proposed.

Bis(pentamethylcyclopentadienyl) ytterbium: Electron-transfer reactions with organotransition metal complexes

Energy Technology Data Exchange (ETDEWEB)

Matsunaga, Phillip Thomas [Univ. of California, Berkeley, CA (United States)

1991-11-01

The divalent lanthanide complex, (Me₅C₅)₂Yb, reacts with methylcopper to produce the base-free, ytterbium-methyl complex, (Me₅C₅)₂YbMe. This product forms a asymmetric, methyl-bridged dimer in the solid state. The bulky alkyl complex, (Me₅C₅)₂YbCH(SiMe₃)₂, displays similar chemistry to (Me₅C₅)₂YbMe, but at a reduced reaction rate due to the limited accessibility of the metal in (Me₅C₅)₃YbCH(SiMe₅)₂. Copper and silver halide salts react with (Me₅C₅)₂V to produce the trivalent halide derivatives, (Me₅C₅)₂VX (X + F, Cl, Br, I). The chloride complex, (Me₅C₅)₂VCl, reacts with lithium reagents to form the phenyl and borohydride species. Nitrous oxide transfers an oxygen atom to (Me₅C₅)₂V producing the vanadium-oxo complex, (Me₅Ce₅)₂VO. The trivalent titanium species, (Me₅C₅)₂TiX (X = Cl, Br, Me, BH₄), form bimetallic coordination complexes with (Me₅C₅)₂Yb. The magnetic behavior of the products indicates that electron transfer has not occurred. The solid state structures of the chloride and bromide complexes show unusual bend angles for the halide bridges between ytterbium and titanium. A model based on frontier orbital theory has been proposed to account for the bending behavior in these species. The bimetallic methyl complex contains a linear methyl bridge between ytterbium and titanium.

Study of the alpha+12C →16O capture via 12C(16O,12C)16O transfer reaction

International Nuclear Information System (INIS)

Morais, M.C.; Lichtenthaeler, R.; Arazi, A.; Hojman, D.; Cardona, M.A.; Fimiani, L.; Carnelli, P.F.; Marti, G.V.; Pacheco, A.J.; Heimann, D. Martinez; Negri, A.E.; Capurro, O.A.; Niello, J.O. Fernandez; Montero, P.

2009-01-01

Full text: The 12 C(α γ) 16 O reaction is one of the most important in nuclear astrophysics. The rate of this reaction influences the subsequent nucleosynthesis of heavier elements in massive stars and consequently determines the stellar evolution. The 12 C(α γ) 16 O reaction cross section is extremely small at stellar temperature, this is mainly due to the Gamow energy (∼ 300KeV at T= 2x10 8 K) be much lower than the Coulomb barrier, E C.B. : = 3:142MeV. The α+ 12 C → 16 O at low energies is dominated by subthreshold states (1 - , 7:12MeV) and (2 + , 6:92MeV) of the 16 O, thus spectroscopic factors measurements of these states are very important. We propose to use the α-transfer reaction 12 C( 16 O, 12 C) 16 O * at very forward angles to obtain those spectroscopic factors. In this way, measurements of elastic and inelastic angular distributions for the 12 C+ 16 O system were performed at the TANDAR Laboratory in Buenos Aires, using an 16 O beam of E lab = 46.3MeV. These angular distributions were obtained using 8 adjacent surface barrier detectors and the measurements were performed from 5 deg to 48.5 deg with steps of 1 deg. The scattering chamber has an angular precision better than 0.1 deg. The transfer angular distributions are being analysed by DWBA using the computer code FRESCO in order to obtain the two spectroscopic factors. (author)

Direct electron transfer based enzymatic fuel cells

International Nuclear Information System (INIS)

Falk, Magnus; Blum, Zoltan; Shleev, Sergey

2012-01-01

In this mini-review we briefly describe some historical developments made in the field of enzymatic fuel cells (FCs), discussing important design considerations taken when constructing mediator-, cofactor-, and membrane-less biological FCs (BFCs). Since the topic is rather extensive, only BFCs utilizing direct electron transfer (DET) reactions on both the anodic and cathodic sides are considered. Moreover, the performance of mostly glucose/oxygen biodevices is analyzed and compared. We also present some unpublished results on mediator-, cofactor-, and membrane-less glucose/oxygen BFCs recently designed in our group and tested in different human physiological fluids, such as blood, plasma, saliva, and tears. Finally, further perspectives for BFC applications are highlighted.

Kinetics of the reactions of hydrated electrons with metal complexes

International Nuclear Information System (INIS)

Korsse, J.

1983-01-01

The reactivity of the hydrated electron towards metal complexes is considered. Experiments are described involving metal EDTA and similar complexes. The metal ions studied are mainly Ni 2+ , Co 2+ and Cu 2+ . Rates of the reactions of the complexes with e - (aq) were measured using the pulse radiolysis technique. It is shown that the reactions of e - (aq) with the copper complexes display unusually small kinetic salt effects. The results suggest long-range electron transfer by tunneling. A tunneling model is presented and the experimental results are discussed in terms of this model. Results of approximate molecular orbital calculations of some redox potentials are given, for EDTA chelates as well as for series of hexacyano and hexaquo complexes. Finally, equilibrium constants for the formation of ternary complexes are reported. (Auth./G.J.P.)

Chemical Reactions at Surfaces. Final Progress Report

Energy Technology Data Exchange (ETDEWEB)

Freud, Hans-Joachim [Max-Planck-Gesellschaft, Berlin (Germany). Fritz-Haber-Inst.

2003-02-21

The Gordon Research Conference (GRC) on Chemical Reactions at Surfaces was held at Holiday Inn, Ventura, California, 2/16-21/03. Emphasis was placed on current unpublished research and discussion of the future target areas in this field.

Mechanistic photodecarboxylation of pyruvic acid: Excited-state proton transfer and three-state intersection

Science.gov (United States)

Chang, Xue-Ping; Fang, Qiu; Cui, Ganglong

2014-10-01

Photodissociation dynamics of pyruvic acid experimentally differs from that of commonly known ketones. We have employed the complete active space self-consistent field and its multi-state second-order perturbation methods to study its photodissociation mechanism in the S0, T1, and S1 states. We have uncovered four nonadiabatic photodecarboxylation paths. (i) The S1 system relaxes via an excited-state intramolecular proton transfer (ESIPT) to a hydrogen-transferred tautomer, near which an S1/S0 conical intersection funnels the S1 to S0 state. Then, some trajectories continue completing the decarboxylation reaction in the S0 state; the remaining trajectories via a reverse hydrogen transfer return to the S0 minimum, from which a thermal decarboxylation reaction occurs. (ii) Due to a small S1 -T1 energy gap and a large S1/T1 spin-orbit coupling, an efficient S1 → T1 intersystem crossing process happens again near this S1/S0 conical intersection. When decaying to T1 state, a direct photodecarboxylation proceeds. (iii) Prior to ESIPT, the S1 system first decays to the T1 state via an S1 → T1 intersystem crossing; then, the T1 system evolves to a hydrogen-transferred tautomer. Therefrom, an adiabatic T1 decarboxylation takes place due to a small barrier of 7.7 kcal/mol. (iv) Besides the aforementioned T1 ESIPT process, there also exists a comparable Norrish type I reaction in the T1 state, which forms the ground-state products of CH3CO and COOH. Finally, we have found that ESIPT plays an important role. It closes the S1-T1 and S1-S0 energy gaps, effecting an S1/T1/S0 three-state intersection region, and mediating nonadiabatic photodecarboxylation reactions of pyruvic acid.

High-efficiency pump for space helium transfer. Final Technical Report

International Nuclear Information System (INIS)

Hasenbein, R.; Izenson, M.G.; Swift, W.L.; Sixsmith, H.

1991-12-01

A centrifugal pump was developed for the efficient and reliable transfer of liquid helium in space. The pump can be used to refill cryostats on orbiting satellites which use liquid helium for refrigeration at extremely low temperatures. The pump meets the head and flow requirements of on-orbit helium transfer: a flow rate of 800 L/hr at a head of 128 J/kg. The overall pump efficiency at the design point is 0.45. The design head and flow requirements are met with zero net positive suction head, which is the condition in an orbiting helium supply Dewar. The mass transfer efficiency calculated for a space transfer operation is 0.99. Steel ball bearings are used with gas fiber-reinforced teflon retainers to provide solid lubrication. These bearings have demonstrated the longest life in liquid helium endurance tests under simulated pumping conditions. Technology developed in the project also has application for liquid helium circulation in terrestrial facilities and for transfer of cryogenic rocket propellants in space

Catalytic biorefining of plant biomass to non-pyrolytic lignin bio-oil and carbohydrates through hydrogen transfer reactions.

Science.gov (United States)

Ferrini, Paola; Rinaldi, Roberto

2014-08-11

Through catalytic hydrogen transfer reactions, a new biorefining method results in the isolation of depolymerized lignin--a non-pyrolytic lignin bio-oil--in addition to pulps that are amenable to enzymatic hydrolysis. Compared with organosolv lignin, the lignin bio-oil is highly susceptible to further hydrodeoxygenation under low-severity conditions and therefore establishes a unique platform for lignin valorization by heterogeneous catalysis. Overall, the potential of a catalytic biorefining method designed from the perspective of lignin utilization is reported. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Covalent electron transfer chemistry of graphene with diazonium salts.

Science.gov (United States)

Paulus, Geraldine L C; Wang, Qing Hua; Strano, Michael S

2013-01-15

Graphene is an atomically thin, two-dimensional allotrope of carbon with exceptionally high carrier mobilities, thermal conductivity, and mechanical strength. From a chemist's perspective, graphene can be regarded as a large polycyclic aromatic molecule and as a surface without a bulk contribution. Consequently, chemistries typically performed on organic molecules and surfaces have been used as starting points for the chemical functionalization of graphene. The motivations for chemical modification of graphene include changing its doping level, opening an electronic band gap, charge storage, chemical and biological sensing, making new composite materials, and the scale-up of solution-processable graphene. In this Account, we focus on graphene functionalization via electron transfer chemistries, in particular via reactions with aryl diazonium salts. Because electron transfer chemistries depend on the Fermi energy of graphene and the density of states of the reagents, the resulting reaction rate depends on the number of graphene layers, edge states, defects, atomic structure, and the electrostatic environment. We limit our Account to focus on pristine graphene over graphene oxide, because free electrons in the latter are already bound to oxygen-containing functionalities and the resulting chemistries are dominated by localized reactivity and defects. We describe the reaction mechanism of diazonium functionalization of graphene and show that the reaction conditions determine the relative degrees of chemisorption and physisorption, which allows for controlled modulation of the electronic properties of graphene. Finally we discuss different applications for graphene modified by this chemistry, including as an additive in polymer matrices, as biosensors when coupled with cells and biomolecules, and as catalysts when combined with nanoparticles.

Final Report: Geoelectrical Measurement of Multi-Scale Mass Transfer Parameters

Energy Technology Data Exchange (ETDEWEB)

Haggerty, Roy [Oregon State Univ., Corvallis, OR (United States); Day-Lewis, Fred [U.S. Geological Survey, Storrs, CT (United States); Singha, Kamini [Colorado School of Mines, Golden, CO (United States); Johnson, Timothy [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Binley, Andrew [Lancaster Univ. (United Kingdom); Lane, John [U.S. Geological Survey, Storrs, CT (United States)

2014-03-20

Mass transfer affects contaminant transport and is thought to control the efficiency of aquifer remediation at a number of sites within the Department of Energy (DOE) complex. An improved understanding of mass transfer is critical to meeting the enormous scientific and engineering challenges currently facing DOE. Informed design of site remedies and long-term stewardship of radionuclide-contaminated sites will require new cost-effective laboratory and field techniques to measure the parameters controlling mass transfer spatially and across a range of scales. In this project, we sought to capitalize on the geophysical signatures of mass transfer. Previous numerical modeling and pilot-scale field experiments suggested that mass transfer produces a geoelectrical signature—a hysteretic relation between sampled (mobile-domain) fluid conductivity and bulk (mobile + immobile) conductivity—over a range of scales relevant to aquifer remediation. In this work, we investigated the geoelectrical signature of mass transfer during tracer transport in a series of controlled experiments to determine the operation of controlling parameters, and also investigated the use of complex-resistivity (CR) as a means of quantifying mass transfer parameters in situ without tracer experiments. In an add-on component to our grant, we additionally considered nuclear magnetic resonance (NMR) to help parse mobile from immobile porosities. Including the NMR component, our revised study objectives were to: 1. Develop and demonstrate geophysical approaches to measure mass-transfer parameters spatially and over a range of scales, including the combination of electrical resistivity monitoring, tracer tests, complex resistivity, nuclear magnetic resonance, and materials characterization; and 2. Provide mass-transfer estimates for improved understanding of contaminant fate and transport at DOE sites, such as uranium transport at the Hanford 300 Area. To achieve our objectives, we implemented a 3

Theoretical characterizations of novel C2H5O+ reactions

Science.gov (United States)

Hudson, Charles E.; McAdoo, David J.

2004-03-01

Assorted reactions of C2H5O+ isomers are characterized by theory, including tracing their courses by means of intrinsic reaction coordinate computations. We establish that CH3CH=OH+ eliminates methane by transferring H from oxygen to a methyl hydrogen and then to the CC bond to produce CHO++CH4. This adds to the limited knowledge of the involvement of hypervalent structures in the reactions of cations in the gas phase. Second, we characterized the course of CH3CH=OH+-->H3O++HC[triple bond; length as m-dash]CH. In this dissociation, H first migrates from the methyl to the oxygen to give O-protonated vinyl alcohol, a stable intermediate. Then the H2O swings outward to over the middle of the CC bond while one of the two hydrogens on the non-O-bearing carbon revolves to between the oxygen and the two carbons, leading to formation of a [H3O+ HC[triple bond; length as m-dash]CH] complex. This complex contains sufficient energy to dissociate its partners because a high barrier is crossed in its formation. Third, we found that methane elimination from CH3O+=CH2 involves stretching of the CH3---O bond and then rotation of the methyl so that a methyl hydrogen is pointed directly toward the oxygen. This reaction is completed by further rotation of the methyl to abstract a methylene hydrogen to the opposite side of the methyl from that initially bonded to oxygen. This clearly establishes that this dissociation takes place through an ion-neutral complex. Each of the reaction coordinates for the three preceding reactions traverses a novel bonding stage involving H, evidence that such are not unusual in gas phase ion chemistry. Finally, we showed that in the rearrangement CH3O+=CH2-->CH2=O+CH3, before Ht is transferred CH2 rotates around the C=C bond from being in the skeletal plane to being perpendicular to it, and Ht remains in the skeletal plane throughout its transfer. This pathway appears to balance avoiding an orbital symmetry-forbidden suprafacial transition state with

Effects of mass transfer on MHD flow of casson fluid with chemical reaction and suction

Directory of Open Access Journals (Sweden)

S. A. Shehzad

2013-03-01

Full Text Available Effect of mass transfer in the magnetohydrodynamic flow of a Casson fluid over a porous stretching sheet is addressed in the presence of a chemical reaction. A series solution for the resulting nonlinear flow is computed. The skin friction coefficient and local Sherwood number are analyzed through numerical values for various parameters of interest. The velocity and concentration fields are illustrated for several pertinent flow parameters. We observed that the Casson parameter and Hartman number have similar effects on the velocity in a qualitative sense. We further analyzed that the concentration profile decreases rapidly in comparison to the fluid velocity when we increased the values of the suction parameter.

Study of multi nucleon transfer in "9","1"1Li + "2"0"8Pb reactions

International Nuclear Information System (INIS)

Vinodkumar, A.M.

2014-01-01

One of the most active areas of research with radioactive beams is the study of the fusion of weakly bound nuclei, such as the halo nuclei. The central issue is whether the fusion cross section will be enhanced due to the large nuclear size of the halo nucleus or whether fusion-limiting breakup of the weakly bound valence nucleons will lead to a decreased fusion cross section. The fusion of "9","1"1Li with "2"0"8Pb were reported. These measurements were carried out at TRIUMF, Canada. These measurements suggests at above barrier energies, fusion hindrance is taking place in the case of "1"1Li projectile. However, sub barrier fusion measurement need a lower energy measurement. These measurements also suggest need for further measurement of transfer and breakup channels in these reactions. So we suggest a measurement of multi nucleon transfer in the case of "9Li + "2"0"8Pb. Also, these measurement will be able to produce the same nuclei as suggested in the ISOLDE experiment by, where "2"1"2","2"1"4Pb and "2"0"8","2"1"0Hg nuclei for studying the spectroscopy of these nuclei. (author)

Model-Independent Analysis of the Neutron-Proton Final-State Interaction Region in the $\\pi\\pi \\to pn\\pi^+$ Reaction

CERN Document Server

Uzikov, Yu N

2001-01-01

Experimental data on the \\pi\\pi\\to pn\\pi^+ reaction measured in an exclusive two-arm experiment at 800 MeV show a narrow peak arising from the strong proton-neutron final-state interaction. It was claimed, within the framework of a certain model, that this peak contained up to a 25 % spin-singlet final-state contribution. By comparing the data with those of \\pi\\pi\\to d\\pi^+ in a largely model-independent way, it is here demonstrated that at all the angles measured the whole of the peak could be explained as being due to spin-triplet final states, with the spin-singlet being at most a few percent. Good qualitative agreement with the measured proton analysing power is also found within this approach.

Experimental study of bound states in ¹²Be through low-energy ¹¹Be(d,p)-transfer reactions

DEFF Research Database (Denmark)

Johansen, Jacob S.; Bildstein, V.; Borge, M. J. G.

2013-01-01

The bound states of 12Be have been studied through a 11Be(d,p)12Be transfer reaction experiment in inverse kinematics. A 2.8 MeV/u beam of 11Be was produced using the REX-ISOLDE facility at CERN. The outgoing protons were detected with the T-REX silicon detector array. The MINIBALL germanium arra...

The 58606264Ni(p,α)55575961Co reactions and their description by the semi-microscopic model for three-nucleon transfer

International Nuclear Information System (INIS)

Smits, J.W.; Siemssen, R.H.; Werf, S.Y. van der; Woude, A. van der

1979-01-01

The (p,α) reaction on the even-A nickel isotopes has been studied at an incident proton energy of 30 MeV. Between 14 and 26 states, or groups of states, were analysed for each of the residual cobalt isotopes. For these transitions angular distributions were determined from thetasub(lab) = 7.5 0 to 70 0 . In all reactions the proton-hole states (0fsub(7/2), 1ssub(1/2) and 0dsub(3/2)) stand out in the spectra. Also, states formed by the weak-coupling of the proton-holes to excitations of the neutron core were seen. Differences in the relative strengths of the positive-parity hole states between the proton pickup and the (p,α) data can be explained by a semi-microscopic model for three-nucleon transfer. Also the strength distribution of the transitions to the lowest weak-coupling quintuplet is correctly predicted. These results underline the importance of the inclusion of non-zero coupled neutron pairs into the description of (p, α) reactions. Several T> states are observed in the 58 Ni(p, α) 55 Co reactions

Transferência e complexo de édipo, na obra de Freud: notas sobre os destinos da transferência Transference and oedipus complex, within Freud's theory: notes about the transference destiny

Directory of Open Access Journals (Sweden)

Lara Cristina d'Avila Lourenço

2005-04-01

Full Text Available Este artigo comunica algumas considerações sobre o conceito de transferência, na teoria freudiana. Especial atenção é voltada para as relações entre transferência, complexo de Édipo e complexo de castração. Partindo dessas relações e da hipótese segundo a qual Freud não apresenta um final possível para o complexo de Édipo, o presente trabalho entende que esse autor não fornece uma teoria sobre o final da transferência. Esse pensamento evoca o impasse freudiano em relação aos términos das análises. Nesse ponto, é feita uma breve referência à teoria lacaniana sobre a castração e a transferência ao final de análise.This article discloses some considerations about the transference conception situated within Freud's theory. The relations between transference, Oedipus complex and castration complex are highlighted. Starting from these relations and from the allegedly in wich Freud doesn't reveal a possible ending to Oedipus complex, this current work perceives that this author does not provide a theory about the transference ending. This idea drives into Freud's impasse, as far as the analysis ending is concerned. In this issue, a short reference is produced on Lacan's castration theory and on that of the transference at end of the analysis.

Probing the semi-magicity of $^{68}$Ni via the $^{3}$H($^{66}$Ni,$^{68}$Ni)p two-neutron transfer reaction in inverse kinematics

CERN Multimedia

Reiter, P; Blazhev, A A; Kruecken, R; Franchoo, S; Mertzimekis, T; Darby, I G; Van de walle, J; Raabe, R; Elseviers, J; Gernhaeuser, R A; Sorlin, O H; Georgiev, G P; Bree, N C F; Habs, D; Chapman, R; Gaudefroy, L; Diriken, J V J; Jenkins, D G; Kroell, T; Axiotis, M; Huyse, M L; Patronis, N

We propose to perform the two-neutron transfer reaction $^{3}$H($^{66}$Ni, $^{68}$Ni)$p$ using the ISOLDE radioactive ion beam at 2.7 $A$ MeV and the MINIBALL + T-REX setup to characterize the 0$^{+}$ and 2$^{+}$ states in $^{68}$Ni.

Exploring possible reaction pathways for the o-atom transfer reactions to unsaturated substrates catalyzed by a [Ni-NO2 ] ↔ [Ni-NO] redox couple using DFT methods.

Science.gov (United States)

Tsipis, Athanassios C

2017-07-15

The (nitro)(N-methyldithiocarbamato)(trimethylphospane)nickel(II), [Ni(NO 2 )(S 2 CNHMe)(PMe 3 )] complex catalyses efficiently the O-atom transfer reactions to CO and acetylene. Energetically feasible sequence of elementary steps involved in the catalytic cycle of the air oxidation of CO and acetylene are proposed promoted by the Ni(NO 2 )(S 2 CNHMe)(PMe 3 )] ↔ Ni(NO 2 )(S 2 CNHMe)(PMe 3 ) redox couple using DFT methods both in vacuum and dichloromethane solutions. The catalytic air oxidation of HC≡CH involves formation of a five-member metallacycle intermediate, via a [3 + 2] cyclo-addition reaction of HC≡CH to the Ni-N = O moiety of the Ni(NO 2 )(S 2 CNHMe)(PMe 3 )] complex, followed by a β H-atom migration toward the C α carbon atom of the coordinated acetylene and release of the oxidation product (ketene). The geometric and energetic reaction profile for the reversible [Ni( κN1-NO 2 )(S 2 CNHMe)(PMe 3 )] ⇌ [Ni( κO,O2-ONO)(S 2 CNHMe)(PMe 3 )] linkage isomerization has also been modeled by DFT calculations. © 2017 Wiley Periodicals, Inc. © 2017 Wiley Periodicals, Inc.

C2-symmetric bisamidines: Chiral Brønsted bases catalysing the Diels-Alder reaction of anthrones

Directory of Open Access Journals (Sweden)

2008-08-01

Full Text Available C2-symmetric bisamidines 8 have been tested as chiral Brønsted bases in the Diels-Alder reaction of anthrones and N-substituted maleimides. High yields of cycloadducts and significant asymmetric inductions up to 76% ee are accessible. The proposed mechanism involves proton transfer between anthrone and bisamidine, association of the resulting ions and finally a cycloaddition step stereoselectively controlled by the chiral ion pair.

Nitrogen-doped graphene prepared by a transfer doping approach for the oxygen reduction reaction application

Science.gov (United States)

Mo, Zaiyong; Zheng, Ruiping; Peng, Hongliang; Liang, Huagen; Liao, Shijun

2014-01-01

Well defined nitrogen-doped graphene (NG) is prepared by a transfer doping approach, in which the graphene oxide (GO) is deoxidized and nitrogen doped by the vaporized polyaniline, and the GO is prepared by a thermal expansion method from graphite oxide. The content of doped nitrogen in the doped graphene is high up to 6.25 at% by the results of elements analysis, and oxygen content is lowered to 5.17 at%. As a non-precious metal cathode electrocatalyst, the NG catalyst exhibits excellent activity toward the oxygen reduction reaction, as well as excellent tolerance toward methanol. In 0.1 M KOH solution, its onset potential, half-wave potential and limiting current density for the oxygen reduction reaction reach 0.98 V (vs. RHE), 0.87 V (vs. RHE) and 5.38 mA cm-2, respectively, which are comparable to those of commercial 20 wt% Pt/C catalyst. The well defined graphene structure of the catalyst is revealed clearly by HRTEM and Raman spectra. It is suggested that the nitrogen-doping and large surface area of the NG sheets give the main contribution to the high ORR catalytic activity.

Investigation of Na-CO{sub 2} Reaction with Initial Reaction in Various Reacting Surface

Energy Technology Data Exchange (ETDEWEB)

Kim, Hyun Su; Park, Gunyeop; Kim, Soo Jae; Park, Hyun Sun; Kim, Moo Hwan [POSTECH, Pohang (Korea, Republic of); Wi, Myung-Hwan [KAERI, Daejeon (Korea, Republic of)

2015-10-15

The reaction products that cause oxidation and erosion are threaten the heat transfer tubes so that it is necessary to investigate Na-CO{sub 2} reaction according to various experimental parameter. Unlike SWR, Na-CO{sub 2} reaction is more complex to deal with reaction kinetics. Since a comprehensive understanding of Na-CO{sub 2} reaction mechanism is crucial for the safety analysis, the reaction phenomenon under the various conditions was investigated. The current issue is to make a database for developing computational code for CO{sub 2} gas leak situation because it is experimentally difficult to analyze the actual accident situation. Most studies on Na-CO{sub 2} interaction reports that chemical reaction is getting vigorous as temperature increased and reactivity is sensitive as temperature change between 400 .deg. C and 600 .deg. C. Therefore, temperature range is determined based on the operating condition (450 - 500 .deg. C) of KALIMER-600 employed as supercritical CO{sub 2} brayton cycle energy conversion system for Na-CO{sub 2} heat exchanger. And next parameter is sodium surface area which contact between sodium and CO{sub 2} when CO{sub 2} is injected into sodium pool in the accident situation. So, the fundamental surface reaction is experimentally studied in the range of 8 - 12cm{sup 2}. Additionally, it has been reported in recent years that CO{sub 2} Flow rate affects reactivity less significantly and CO{sub 2} flow rate is assumed that 5 SLPM (standard liter per minute) is suitable as a basis for a small leakage. The finally selected control parameters is sodium temperature and reacting surface area with constant CO{sub 2} flow rate. Na-CO{sub 2} reaction test is performed for investigating risk of potential accident which contacts with liquid sodium and CO{sub 2}. Amount of reaction is saturated as time passed because of kept a balance between production of solid phase reaction products and amount of diffusivity. These results contribute to make a

Determination of nn scattering length from data on nn final state interaction in nd-breakup reaction

International Nuclear Information System (INIS)

Konobeevski, E.S.; Mordovskoy, M.V.; Sergeev, V.A.; Potashev, S.I.; Zuev, S.V.

2006-01-01

Full text: An experiment is proposed for the high-precision determination of the neutron-neutron scattering length investigating the nn final state interaction in the nd breakup reaction. The singlet pp and nn scattering lengths are very sensitive probes of the NN-interaction, and their difference is a direct measure of charge-symmetry breaking (CSB) of the nuclear force. However CSB is a small effect, and accurate values of the scattering lengths are needed for a theoretical analysis. The proton-proton scattering length is well known from pp-scattering data (a pp = -17.3± 0.4 fm), and its uncertainty is mainly due to a model-dependent procedure of removing Coulomb effects. The neutron-neutron scattering length is determined from the following processes n+d→p+n+n, π - + d → γ +n+n, d+d→ 2 He+n+n by investigating the kinematic region of the nn final-state interaction (FSI) where two neutrons fly with low relative energy. The results obtained by now are characterized by a significant uncertainty in values of a nn ; they are grouped near -16 and -19 fm [1,2], so even the sign of the difference a nn - a pp is uncertain. In this experiment neutron-neutron scattering length is determined by measuring the yield of the nd breakup reaction as a function of the relative energy ε nn =(E 1 +E 2 -2(E 1 E 2 ) 1/2 cosθ)/2 of two neutrons in the FSI region (two neutrons fly in a narrow angular cone) where nn-interaction is strongly revealed. The theory of reactions in 3N system predicts the ε nn dependence of the FSI cross section being sensitive to the value of a nn . The measurements will be made using the neutron channel RADEX at Moscow meson factory of the Institute for Nuclear Research. The momenta and angles of the two emitted neutrons and the energy of the proton will be measured for each breakup event. The measured dependence of the reaction yield on the relative energy of the two neutrons will be compared to results of the Monte Carlo simulation that includes

One-nucleon pickup reactions and compound-nuclear decays

Science.gov (United States)

Escher, J. E.; Burke, J. T.; Casperson, R. J.; Hughes, R. O.; Scielzo, N. D.

2018-05-01

One-nucleon transfer reactions, long used as a tool to study the structure of nuclei, are potentially valuable for determining reaction cross sections indirectly. This is significant, as many reactions of interest to astrophysics and other applications involve short-lived isotopes and cannot be measured directly. We describe a procedure for obtaining constraints for calculations of neutron capture cross sections using observables from experiments with transfer reactions. As a first step toward demonstrating the method, we outline the theory developments used to properly describe the production of the compound nucleus 88Y* via the one-nucleon pickup reaction 89Y(p,d)88Y* and test the description with data from a recent experiment. We indicate how this development can be used to extract the unknown 87Y(n,γ) cross section from 89Y(p,dγ) data. The example illustrates a more generally applicable method for determining unknown cross sections via a combination of theory and transfer (or inelastic scattering) experiments.

Relations between the simultaneous and sequential transfer of two nucleons

International Nuclear Information System (INIS)

Satchler, G.R.

1982-01-01

The transfer of two nucleons between projectile and target in a direct or peripheral reaction such as (p,t) or ( 16 O, 14 C) may occur in one-step or two-steps. These we refer to as simultaneous and sequential transfers, respectively. In the former, the interaction acts once and both nucleons are transferred. In the latter, the interaction acts once to transfer one nucleon, the system then propagates in one or more intermediate states and is followed by a second action of the interaction to transfer the second nucleon. This process may be symbolized for the examples as (p,d; d,t) and ( 16 O, 15 N; 15 N, 14 C), implying the intermediate formation of a deuteron or the nucleus 15 N. In terms of a perturbation theory expansion, such as the distorted-wave Born series, simultaneous transfer is possible in first order while sequential transfer requires second order. The nuclear forces are predominantly two-body in character; hence, in first-order only one of the two nucleons experiences an interaction. The possibility of finding that the other nucleon has also transferred arises only because its state within the projectile is not orthogonal to the state in the target into which it transfers. In the two-step process each nucleon is transferred under the direct influence of an interaction with the target. The one-step and two-step amplitudes are frequently comparable in magnitude for light-ion reactions while the two-step may dominate in reactions with heavy ions. Our purpose here is to gain some insight into the relationship between the two amplitudes by using a simple approximate form of the theory. For simplicity, we shall discuss a light-ion reaction and, to be specific, we choose the (t,p) reaction (or the inverse (p,t) reaction)

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

Science.gov (United States)

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

2016-03-01

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

Electron transfer between a zinc porphyrin photo-sensitized in the visible, and various acceptors, in aqueous and micellar solutions

International Nuclear Information System (INIS)

Le Roux, Dominique

1983-01-01

This research thesis addresses the study of reactions occurring during the transformation of solar energy in chemical energy, and more precisely the search for photochemical systems allowing the dissociation of water into hydrogen and oxygen. In this study on water photolysis, the author chose to use a porphyrin soluble in water, the zinc tetra-meta-N-methylpyridinium porphyrin, as one of its isomer provided a good efficiency in hydrogen formation. Before reporting the study of electron photo-transfer, the author reports the study of photo-physical and photochemical properties of this porphyrin. Then, in the case of a well known electron acceptor (methyl viologen), he studied the influence of Coulomb effects on the kinetics of direct electron transfer, and on the kinetics of recombination of formed species. He also studied the influence of organised systems (cationic micelles) on these reactions when using a viologen with long chains. He finally reports the study of reactions of the triplet state of this porphyrin with metallic complexes

Computational study of chain transfer to monomer reactions in high-temperature polymerization of alkyl acrylates.